Analysis of carbohydrates and glycoconjugates by matrixassisted laser desorption/ionization mass spectrometry: an update for the period 20052006

ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATESBY MATRIX-ASSISTED LASER DESORPTION/IONIZATION MASSSPECTROMETRY: AN UPDATE FOR THE PERIOD 2005–2006 David J. Harvey*Department of Biochemistry, Oxford Glycobiology Institute,University of Oxford, Oxford OX1 3QU, UK Received 01 December 2008; received (revised) 26 June 2009; accepted 13 July 2009 Published online 10 March 2010 in Wiley Online Library (wileyonlinelibrary.com). DOI 10.1002/mas.20265 This review is the fourth update of the original review, published (Mechref & Novotny, 2006), solid-phase tools such as micro- in 1999, on the application of MALDI mass spectrometry to the arrays (Larsen et al., 2006), capillary electrophoresis-MS analysis of carbohydrates and glycoconjugates and brings (Campa et al., 2006; Huck et al., 2006), atmospheric pressure coverage of the literature to the end of 2006. The review covers MALDI (Creaser & Ratcliffe, 2006). More specific reviews fundamental studies, fragmentation of carbohydrate ions, include those on the analysis of polysaccharides (Cui, 2005), method developments, and applications of the technique to the glycoproteins and attached glycans (Aitken, 2005; Morelle & analysis of different types of carbohydrate. Specific compound Michalski, 2005; Budnik, Lee, & Steen, 2006; Geiser, Silvescu, classes that are covered include carbohydrate polymers from & Reinhold, 2006; Geyer & Geyer, 2006; Harvey, Dwek, plants, N- and O-linked glycans from glycoproteins, glycated & Rudd, 2006; Haslam, Khoo, & Dell, 2006a; Haslam, North, & proteins, glycolipids from bacteria, glycosides, and various other Dell, 2006b; Kondo et al., 2006; Morelle et al., 2006a), natural products. There is a short section on the use of MALDI- N- (Harcum, 2005; Harvey, 2005d,e; Medzihradszky, 2005; TOF mass spectrometry for the study of enzymes involved in Bardor et al., 2006; Jang-Lee et al., 2006) and O-linked glycan processing, a section on industrial processes, particularly (Peter-Katalinic, 2005) glycosylation, bacterial glycoproteomics the development of biopharmaceuticals and a section on the use (Hitchen & Dell, 2005), protein glycation (Lapolla et al., 2006; of MALDI–MS to monitor products of chemical synthesis of Niwa, 2006; Silva´n et al., 2006), GPI anchors (Baldwin, 2005), carbohydrates. Large carbohydrate–protein complexes and proteoglycans (Didraga, Barroso, & Bischoff, 2006), glycosyla- glycodendrimers are highlighted in this final section. # 2010 minoglycans (Gama & Hsieh-Wilson, 2005; Pojasek, Raman, & Wiley Periodicals, Inc., Mass Spec Rev 30:1–100, 2011 Sasisekharan, 2005; Sasisekharan et al., 2006), glycosphingoli- Keywords: MALDI; carbohydrates; glycoproteins; glycolipids pids (Levery, 2005; Zheng, Wu, & Hancock, 2006b), andflavonoids (de Rijke et al., 2006). The book on mass spectrometryin biophysics by Kaltashov and Eyles (2005) also containsinformation.
This review is a continuation of the four earlier ones in this series(Harvey, 1999, 2006, 2009) on the application of MALDI mass spectrometry to the analysis of carbohydrates andglycoconjugates and is intended to bring the coverage of the Knochenmuss (2006) has summarized ion formation mecha- literature to the end of 2006. MALDI continues to be a major nisms in UV MALDI and emphasized that a two-step mechanism technique for the analysis of carbohydrates although electrospray of ionization during or shortly after the laser pulse, followed is becoming increasingly popular. Figure 1 shows the year-by- by secondary reactions in the expanding plume of desorbed year increase in articles reporting use of MALDI for the period material is gaining acceptance. He concludes by saying that: ‘‘To 1991–2006. As the review is designed to complement the earlier the extent that local thermal equilibrium is approached in the work, structural formulae, etc. that were presented earlier are not plume, the mass spectra may be straightforwardly interpreted in repeated. However, a citation to the structure in the earlier work is terms of charge transfer thermodynamics.'' indicated by its number with the prefix ‘‘1'' (i.e., 1/x refers to Gas-phase cationization has been demonstrated in an structure x in the first review and 2/x to the second). Other reviews experiment in which two target spots were prepared and and review-type articles directly concerned with, or including illuminated simultaneously with the laser. One spot contained MALDI analysis of glycoconjugates to have been published polyethylene glycol (PEG) and dihydroxybenzoic acid (DHB, during the review period include general reviews on miniatur- 1/26), whereas the other contained DHB and lithium hydroxide.
ized separation techniques including LC/MALDI-TOF/TOF Even though the PEG and lithium did not come into contact on thetarget, [M þ Li]þ ions were observed in the spectrum. However,because of difficulties in removing residual Naþ and Kþ from the DHB, the authors could not conclude that gas-phase cationization *Correspondence to: David J. Harvey, Department of Biochemistry,Oxford Glycobiology Institute, University of Oxford, Oxford OX1 was the only or major process operating under normal MALDI 3QU, UK. E-mail: [email protected] conditions (Erb, Hanton, & Owens, 2006).
Mass Spectrometry Reviews, 2011, 30, 1– 100# 2010 by Wiley Periodicals, Inc.
A. High-Pressure and Atmospheric PressureMALDI (AP-MALDI) Atmospheric pressure MALDI produces ions with less internalenergy than vacuum MALDI and has been used to producespectra of sialylated N- and O-linked glycans and gangliosideswithout substantial loss of the sialic acid that is a regular featureof vacuum MALDI (Zhang, Fu, & Ning, 2005a). A mixture ofDHB and 2,5-dihydroxyacetophenone (DHA, 1/43) was used asthe matrix and spectra were recorded with an FT-ICR massspectrometer.
A. Theory of Matrix Action FIGURE 1. Number of articles published on the application of Although incorporation of the analyte into the crystal has been MALDI–MS to carbohydrate research by year.
thought to be necessary for the MALDI process to occur, a recentstudy has shown that this probably is not the case and thatintimate contact between analyte and the crystal surface is more Sodium cation affinities of hydroxybenzoic acid isomers important. The study showed that the strength of the MALDI have been published (Chinthaka et al., 2006). In general the most signal was approximately inversely proportional to crystal size stable binding conformations involved formation of a hexacyclic suggesting that contact between the analyte and the matrix chelation ring involving the carboxyl carbonyl group and a surface was more important (Trimpin, Ra¨der, & Mu¨llen, 2006).
hydroxy group in the 2-position. Proton affinities and gas-phasebasicities for the DHB isomers have been calculated usingdensity functional theory and shown to be in good agreement with B. Simple Matrices values obtained by FT-ICR (Rebber et al., 2006). Mesaros et al.
(2006) have studied the photophysics of common MALDI matrices and found that 2,4,6-trihydroxyacetophenone (THAP, ononitrile (DCTB, 1) has been shown to be an effective matrix for 1/44) and DHB release heat to the medium more efficiently than hydrophobic compounds but less so for compounds soluble in matrices such as harmane (1/34) and nor-harmane (1/35) and water. Nevertheless, derivatized sugars and glycosides could be behave as ‘‘hotter'' matrices.
induced to fly with the formation of the normal [M þ metal]þ ions The observation that thin MALDI samples can perform (Wyatt, Stein, & Brenton, 2006).
differently than thicker samples on metal substrates has beeninvestigated by Knochenmuss, McCombie, and Faderl (2006) forthree electrosprayed matrixes, DHB, sinapinic acid (SA, 1/48),and a-cyano-4-hydroxycinnamic acid (CHCA, 1/23), on stain-less steel and gold substrates. Thin sample enhancement wasfound in both polarities for all three matrices on a steel substrate.
Pencil ‘‘lead'' (a mixture of graphite, clay, and waxes) has On gold, only CHCA showed enhancement. Two models were been shown to be an effective matrix for several types of used to evaluate the data. The first was based on one-photon compound including cyclodextrin. The matrix has the advantage photoelectron emission from the metal, and the second on two- of the absence of low mass matrix ions that characterize the photon matrix ionization at the metal interface. The surface- spectra recorded from most other matrices making it ideal for enhanced matrix photoionization model best fitted the evidence, small molecules although carbon clusters are often seen and, including the fluence-dependence of electron emission from depending on the pencil, various constituents of the ‘‘lead'' can DHB on steel.
give signals (Black et al., 2006).
Carbon nanotubes were reported in 2003 as effective matrices for carbohydrates (Xu et al., 2003). However, a problemwas keeping them on the MALDI target. This problem has III. INSTRUMENTATION been solved by attaching them to the target with polyurethaneadhesive prior to adding the glycan solution (Ren et al., 2005).
A pyroelectric lead–lanthanum–zirconate–titanate ceramic This procedure retained the property of the matrix to produce plate has been developed as a MALDI target which allows signals without the low-mass matrix ions. Oxidized carbon spectra of thermally unstable compounds such as carbohydrates nanotubes have been reported to give better results than carbon to be obtained without the use of a matrix (Sato et al., 2005). a- nanotubes themselves because of their greater solubility in water (4/24) and b-cyclodextrins (4/6) in the presence of sodium iodide (Pan et al., 2005). They have been used to record MALDI spectra gave strong [M þ Na]þ ions with no sign of fragmentation.
from honeysuckle constituents (Chen et al., 2006c).
Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES Schulz et al. (2006) have compared the degree of analyte liquid matrices 1-methylimidazolium (4 þ 1/23) a-cyano-4- fragmentation in AP-MALDI as a function of the matrix and hydroxycinnamate and tetrabutylammonium (Bu4N þ 1/26) laser fluence. Several analytes were employed and the matrix 2,5-dihydroxybenzoic acid have produced signals from sucrose hardness/softness was found to be consistent when comparing octasulfate (5) and an octasulfated pentasaccharide as their the analytes. The consensus ranking from hardest to softest sodium salts. No ion pairing was necessary but some loss of was: CHCA
DHB>SA THAP > 6-azo-2-thiothymine (ATT, sulfate was seen (Laremore et al., 2006).
1/45) > hydroxypicolinic acid (HPA, 1/60) although the exactranking could be fluence dependent. Of several matrix properties,sublimation or decomposition temperature (determined usingthermogravimetry), analyte initial velocity, and matrix protonaffinity, the best correlation was found with the matrix protonaffinity.
C. Binary Matrices Lewandrowski, Resemann, and Sickmann (2005) have noted thata mixed matrix of DHB and ATTwas useful in reducing in-sourcefragmentation of sialylated glycans. A novel MALDI matrixconsisting of DHB and aniline has been reported to produce asignificant increase in signal for N-linked glycans compared withthe signal obtained with DHB alone (Snovida, Chen, & Perreault, E. Negative Ions from Neutral Glycans 2006). The presence of aniline produced an on-target derivatiza-tion of the glycans via Schiff base formation with the reducing In general, neutral carbohydrates do not give negative ions with end GlcNAc residue without the need for prolonged incubation the common matrices such as DHB. However, they can be made to periods and elevated temperatures. The reaction appeared to be form adducts with anions such as chloride with b-carboline occurring slowly even after the sample-matrix spot had dried and matrices, such as nor-harmane (1/35) if ammonium chloride is could be used to differentiate glycans and peptides because the added (Suzuki, Yamagaki, & Tachibana, 2006). These authors latter compounds did not react.
(Suzuki, Yamagaki, & Tachibana, 2005) have also used The use of added quaternary ammonium or phosphonium ammonium chloride with a harmine (1/36) matrix to produce salts to matrices has allowed fragile sulfated and sialylat- [M þ Cl] ions and noted that the best results were obtained when ed carbohydrates to be analyzed without decomposition.
the ammonium chloride was added in the same amount as the heparin disaccharide matrix. A layered target consisting of matrix, analyte and additive (1 ! 4)GlcNS-6S), the combination of 2-amino-5-nitropyridine gave the best results. Although addition of salts is usually (2/20) and tetraphenylphosphonium bromide (2) gave the best detrimental to signal strength in positive ion mode, the authors of results. Signals were produced both in positive and negative ion this work report that the ionization efficiency for the production of modes. In positive ion mode, species such as [M þ P [M þ Cl] ions increases in the presence of an excess of observed where n ¼ the number of acid groups. For sialylated ammonium chloride. Lasˇtovickova´ and Chmelı´k (2006) have glycans such as gangliosides, a combination of THAP with obtained negative ion spectra of carbohydrates such as inulin (6) dimethylpalmitylammonium bromide (3) was the system of directly from the five matrices DHB, THAP, CHCA, 3-amino- choice (Ueki & Yamaguchi, 2005).
quinoline (3-AQ, 1/24) and HABA. Of these, THAP was by far thebest. 3-AQ gave a spectrum displaying smaller carbohydrates.
Spectra were recorded with a 4700 TOF/TOF instrument.
Carbohydrates such as inulin without a reducing terminus gave[M  H] ions but reducing sugars could be identified by forma-tion of an [M-120] ion as the result of a cross-ring fragmentation.
D. Liquid Matrices Two reviews on ionic liquid matrices have appeared (Koel,2005; Tholey & Heinzle, 2006) and two other more generalreviews (Jain et al., 2005; Liu, Jo¨nsson, & Jiang, 2005)have included their use. Although polysulfated sugars usuallydo not give signals under conventional MALDI conditions, the Mass Spectrometry Reviews DOI 10.1002/mas Derivatization of carbohydrates, mainly of the reducing terminalby reductive amination, has been reviewed (Anumula, 2006).
A. Reducing Terminal Derivatives Sekiya et al. (2005b) have reported that N-linked glycans, whenderivatized with 2-aminpyridine (2-AP, 1/52) but not with 2-aminobenzamide (2-AB, 1/56) and when ionized from DHB,produce, in addition to the normal [M þ Na]þ ions, additional[M þ H]þ ions that are accompanied by another ion two massunits higher. This apparently reduced product does notaccompany the [M þ Na]þ ion, is not seen with nor-harmane asthe matrix or on electrospray ionization. However, the abundanceof the [M þ H þ H2]þ ion was enhanced when the reductive Xia et al. (2005a) have derivatized a range of glycans with matrix 1,5-diaminonaphthalene (1/70) was used. The authors 2,6-diaminopyridine (10) by reductive amination to give a proposed, on the basis that all ions in the MS/MS spectra were fluorescent derivative with a free amino group that could be shifted by two mass units from their positions in the spectra of the conjugated with a range of other compounds such as N- [M þ H]þ ions, that the reaction involved reduction of the hydroxysuccinimide-activated glass slides, maleimide-activated pyridine ring of the 2-AP derivative.
proteins, carboxylated microspheres and biotin (10). Products A comparison of ions formed by three different derivatives were ionized by MALDI-TOF–MS.
have shown that 2-AB and phenylhydrazone derivativesproduced [M þ Na]þ under MALDI conditions whereas 1-phenyl-3-methyl-5-pyrazolone (PMP, 7) produced a mixture of[M þ Na]þ, [M þ H]þ and [M  H þ 2Na]þ ions. Phenylhydra-zones and PMP derivatives produced more abundant cross-ringcleavage ions in the PSD spectra of complex glycans whereas, forhigh-mannose glycans, more informative spectra were provided A method for removing the derivative from reductively by the 2-AB derivatives and phenylhydrazones (Lattova´ et al., aminated glycans has been reported and involves incubation at 2005). Formation of phenylhydrazones, either ‘‘in-tube'' or on 308C with a solution of hydrogen peroxide/acetic acid.
the MALDI target has been reported to improve detection of Recoveries were in the region of 90% (Suzuki, Fujimori, & released glycans in the presence of peptides (Lattova´ et al., 2006).
Yodoshi, 2006).
The spectra of a mixture of these compounds showed both anincrease in the signal from the glycans and a decrease in theabundance of the peptide signals.
B. Reducing-Terminal Derivatives Prepared byOther Methods N-glycans are released with protein-N-glycosidase F (PNGase F)as glycosylamines that are rapidly hydrolyzed to the nativesugars, particularly at low pH. Consequently, if the reaction isperformed rapidly, they can be labeled by reaction with carbonylcompounds in what is essentially the reverse of the normalreductive amination procedure. Kamoda et al. (2005) have madeuse of this reaction to prepare in situ Fmoc derivatives by reactionwith 9-fluorenylmethyl chloroformate (11) which they claim A multifunctional tag combining UV activity with bio- gave a fivefold increase in fluorescence detection compared with affinity has been described (Hsu, Chang, & Franz, 2006). The tag 2-aminobenzoic acid (2-AA, 1/57) derivatives. Furthermore, the (8) was synthesized by activating biotin (9) with 1,10-carbonyl free sugars could be recovered by incubation with morpholine in diimidazole and coupled to one of the aminomethyl groups of dimethylformamide. The derivatives gave good MALDI-TOF xylylenediamine. The other amino group was available for spectra from DHB.
reductive amination of the carbohydrate. The tag was used forlabeling linear oligosaccharides, milk sugars, and high-mannoseglycans from ribonuclease B. Quaternization of the amino groupwith methyl iodide gave a positively charged species and anincrease in sensitivity of 10-fold such that amounts as little as100 fmol on-probe could be detected. The presence of the tagdid not affect fragmentation which occurred by cleavage ofthe sugar.
Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES C. Derivatives of Other Sites 0.5 mg) in 2H2O (200 mL) containing 10% 2H3-acetonitrile (theacetonitrile was necessary to ensure the complete solubility of the A solid-phase method for permethylation of small amounts of matrix). The solution was lyophilized and redissolved in 2H carbohydrates has been developed and consists of microcolumns packed with sodium hydroxide powder through which is passed a 3-acetonitrile (25 mL) immediately prior to spotting 0.5 mL onto an ice-cold, stainless steel target. The target solution of the carbohydrates in DMSO containing traces of was stored in an airtight polyethylene container at 208C over water. Effective permethylation was reported to take less than Dryrite and, after 24 hr, was transferred to the spectrometer inlet.
1 min and both oxidative degradation and peeling reactions To minimize the condensation of atmospheric water onto the cold were minimized. The need for excessive clean-up was also target, this transfer was made with the inlet to the mass avoided although the glycans had to be separated from the DMSO spectrometer enclosed inside a nitrogen-flushed glovebox. The with chloroform in the conventional manner. MALDI-TOF method was applied to several sugars including malto- and xylo- spectra were then obtained directly from DHB (Kang et al., pyranoses, a- (4/24) and b-cyclodextrins (4/6), stachyose (1/19), chitotetraose (13), and erythromycin (4/4).
Permethylation of carbohydrates frequently produces com- pounds 30 mass units higher than that of the product which,until now have not been characterized. These compounds havenow been identified as containing a methoxy-methyl group inplace of one of the methyl groups, its source being reaction withiodomethyl methyl ether produced as a by-product of themethylating reagents (Robinson, Routledge, & Thomas-Oates,2005). Permethylation in general has been reviewed by Ciucanu VI. CLEAN-UP OF SAMPLES PRIOR TO The problem of signal suppression of small glycopeptides in the presence of larger peptides has been successfully addressed A. Trapping of Glycans and Glycoproteins by formation of derivatives with 6-aminoquinolyl-N-hydroxy-succinimidyl carbamate (AQC). Glycopeptides from human Lee et al. (2005e) have prepared magnetic beads linked to 4- antithrombin, chicken ovalbumin, and bovine a1-acid glyco- aminophenylboronic acid (14) and used the ability of the boronic protein could be detected in low fmol amounts (Ullmer, Plematl, acid to form cyclic boroxanes with carbohydrates to isolate & Rizzi, 2006).
glycoproteins from solution. The bound glycoproteins were Sialic acids have been stabilized for MALDI analysis by removed with a magnet and transferred directly to the MALDI conversion to amides by reaction with ammonium bicarbonate/ target from which spectra were recorded from sinapinic acid.
ammonium chloride in the presence of 4-(4,6-dimethoxy-1,2,3- CHCA was used for tryptic peptides derived directly from the triazil-2-yl)-4-methylmorpholinium chloride (DMT-MM, 12) bound glycoproteins. Similar beads have been used to enrich for 24 hr at 508C (Sekiya, Wada, & Tanaka, 2005). Masses were glycated insulin (Farah et al., 2005). Sparbier, Wenzel, and 1 unit/sialic acid less than those of the underivatized molecules Kostrzewa (2006) have used magnetic beads functionalized with and their MS/MS spectra (positive ion) were very informative ConA, wheat germ agglutinin (WGA) or 3-aminophenyl-boronic with a wealth of B- and Y-type glycosidic cleavage products.
acid to extract glycoproteins from human serum. Analysis of the Methyl ester formation can achieve similar stabilization; this enriched serum proteins by tryptic digestion and MALDI-TOF/ reaction, or its equivalent, has been proposed as a necessary step TOF MS/MS analyses revealed the specific binding of nine for detecting sialylated glycans with the Shimadzu quadrupole glycosylated proteins by ConA, eight glycosylated proteins by ion trap-TOF (QIT-TOF) instrument where there is considerable WGA and eight glycoproteins by boronic acid. Only four non- loss of sialic acid (1/11) as the result of post-source decay glycosylated peptides were identified. Each bead type presented (Mandato et al., 2006).
its own individual binding profile overlapping with the profilesof the two others. A method has been reported for enrichment ofO-GlcNAc-modified peptides by use of lectin affinity chroma-tography with wheat-germ agglutinin as the lectin (Vosselleret al., 2006). The method was successfully used to enrich 145unique O-GlcNAc-modified peptides from a post-synapticdensity preparation.
D. Carbohydrates Labeled with Stable Isotopes Hydrogen–deuterium exchange can be used for studies ofcarbohydrate structure and carbohydrate–protein interaction buthas been plagued by back-exchange of deuterium by hydrogen.
Price (2006) has now reported a method for optimization of thedeuteration reaction and for minimizing back exchange.
Typically, the exchange reactions involved mixing the carbohy- Nanoparticles whose surfaces have aminooxyl groups have drate sample (0.2–0.3 mg) and DHB (0.5 mg; oxalic acid, been developed for extracting carbohydrates from biological Mass Spectrometry Reviews DOI 10.1002/mas matrices (Niikura et al., 2005). Reducing carbohydrates reacted amine stock solution and a 10% acetic anhydride solution in with the amino groups of the nanoparticles to form oximes dioxane. Treatment of the reaction mixture with 10 mL of a 26% and the complexes were isolated by centrifugation. The glycans aqueous ammonia solution resulted in the hydrolysis of O-acetyl were then released under acidic conditions. The method was groups and gave N-acetylglucosamine-6P as a single product.
demonstrated with N-glycans released from ovalbumin. Before Spectra were recorded in negative ion reflectron mode with nanoparticle treatment, no glycans were observed in the reaction THAP as the matrix and good linearity and reproducibility were mixture but after treatment, only signals from the glycans were A method for trapping released glycans by chemical reaction with a water-soluble polymer carrying reactive aminogroups has been developed (Nishimura et al., 2005). Afterisolating the complex, the sugars could be released and examinedby MALDI-TOF. Experiments were conducted with N-glycansreleased from human immunoglobin (IgG) and profiles similar tothose obtained by HPLC were observed.
VIII. FRAGMENTATION Yu et al. (2005c) from Waters Corporation, Milford, MA, havereported the use of hydrophilic interaction chromatography By use of an enzymatic reaction, biantennary N-linked glycans (HILIC) sorbent to clean sugars after PNGase release. The have been prepared in which one of the galactose rings contain- sorbent was packed into a 96-well microelution device which was ed 13C. Positive ion fragmentation with a MALDI-QIT-TOF operated with a vacuum manifold. Each well was washed with instrument showed preferential elimination of Gal-GlcNAc Milli Q water and conditioned with 200 mL of 90% MeCN. The moieties from the 6-antenna. This represents one of the few deglycosylated sample was diluted with MeCN (20 mL glycan studies in which stable isotope labeling has been used to study solution to 180 mL MeCN to bring the organic concentration to details of the fragmentation mechanisms undergone by N-linked 90%) and loaded onto the HILIC plate. Salts, detergent, and glycans (Kato et al., 2004).
protein residues were washed out with 200 mL of 90% MeOH/water after which the glycans were eluted with 20–50 mL 10 mM A. Post-Source Decay (PSD) ammonium citrate in 25% MeCN (pH 8). Recovery wasestimated to be 70% using a RapiGest surfactant to denature Post-source decay (PSD) studies on isomeric trehaloses have the glycoproteins prior to enzymatic glycan release (see below) shown that Y-type fragments are most abundant from the and both MALDI-TOF and MALDI-Q-TOF spectra were a,a-isomer (3/39) as predicted from theoretical calculations.
reported from DHB for folate-binding protein, ovalbumin and Use of hydroxy-deuterated trehaloses showed an isotope effect IgG glycans. HILIC clean-up has also been demonstrated by that was greatest for the b,b-isomer (17) but this could not be Thaysen-Andersen and Højrup (2006) for glycopeptides from explained purely on vibrational effects and was probably related bovine fetuin.
to molecular conformation (Yamagaki, Fukui, & Tachibana, Many other resins have been used in the review period; some 2006). Takashiba et al. (Takashiba, Chiba, & Jigami, 2006) have of these are C18 to remove peptides (Parry et al., 2006b), studied the fragmentation of phosphorylated high-mannose cellulose cartridges (Higai et al., 2005) and GlycoClean H glycans from yeast mannan and noted that, whereas the HPO3- cartridges (Prozyme, San Leandro, CA), (Wong, Yap, & Wang, Man bond is stable, the mannose-a-1-PO3 (18) bond is not. The 2006) for N-glycans. High salt content has been removed with a position of the phosphate residue in the 3-antenna could be Microcon YM-10 centrifugal filtering device with a low-binding, determined by the masses of Y-type fragments (positive ion anisotropic, hydrophilic cellulose membrane with a nominal mode). PSD spectra of g-cyclodextrin (1/65) and the isomeric mass limit of 10,000 (Mechref, Muzikar, & Novotny, 2005).
maltosyl-a-cyclodextrin (19) contained fragment ions at thesame masses (loss of glucose fragments) but at different relativeabundances, allowing the isomers to be differentiated (Yamagaki,2005).
VII. QUANTIFICATION A method for quantification of glucosamine-6-phosphate (15) asan assay for glucosamine-6-phosphate synthase has beendeveloped (Maillard et al., 2006). N-(13C2)-acetylglucosamine-6-phosphate (16) was used as the internal standard becauseit could be prepared with use of the commercially available13C2-acetic anhydride. However, this method necessitatedN-acetylation of the analyte in the enzyme-buffered mixtureunder conditions that were compatible with MALDI analysis.
The adopted conditions involved the use of a 0.7 M trimethyl- Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES B. Collision-Induced Dissociation (CID) dissociation (LID) gave spectra dominated by C and cross-ringfragments reminiscent of those from PSD spectra of [M þ Cl] High-energy CID spectra obtained with a TOF/TOF instrument ions reported by Yamagaki, Suzuki, and Tachibana (2005) and have again been shown to produced enhanced abundance of low-energy electrospray-CID spectra of various adducts reported cross-ring cleavage, particularly X-type, ions (Lewandrowski, by Harvey (2005a,b,c). Fragments from these negative ions Resemann, & Sickmann, 2005; Yu, Wu, & Khoo, 2006). Some provide much more informative spectra than those in positive ion protonated fragment ions were observed in the CID spectra of sodiated precursors when DHB was used as the matrix but the Comparisons of the MS2 fragmentation of [M þ H]þ and reason for their formation was unclear. Kurogochi and Nishimura [M þ Na]þ ions from 2-AP-labeled complex N-linked glycans (2004) had previously reported the formation of such ions and in a MALDI-QIT instrument have shown that, whereas the observed that they could be suppressed with CHCA. However, [M þ H]þ ions yielded mainly Y-type cleavage ions, the it was also noted that this matrix suppressed formation of the [M þ Na]þ ions gave a wealth of B-, Y- and cross-ring product ions that provided much more structural information. Isomeric Mechref, Kang, and Novotny (2006) have used permethy- monogalactosylated biantennary glycans (21, 22) could be lation and the high-energy fragmentation available with the 4700 differentiated by relative intensity differences in some of the TOF/TOF instrument to produce cross-ring fragments from fragment ions in the MS2 spectra of the [M þ Na]þ ions (Ojima sialylated glycans and have reported that 0,4A2, 3,5A2, and et al., 2005). MSn spectra recorded with this instrument have A3/2,4X1 ions at m/z 458.2, 486.3, and 588.4 are present only in also allowed isomeric milk sugars to be differentiated (Suzuki the spectra of glycans containing an a-(2 ! 6)-linked sialic acid.
et al., 2005b).
In branched structures, ions were found that enabled branch-specific linkage to be determined.
A TOF instrument with a curved field reflectron has been modified by the inclusion of a collision cell to enable high-energyspectra to be obtained (Belgacem et al., 2006). The resultingspectrum of Man8GlcNAc2 (20) contained abundant X-typecleavage fragments that were not seen in the low energy Fukui et al. (2006) have performed quantum-mechanical calculations on sodiated ions of small oligosaccharides and haveattempted to compare their results with the observed spectra withan AXIMA QIT instrument to determine the Naþ affinity forseveral binding positions and the dependence of fragmentationon the location of sodium. The Na position was less crucial interms of the resulting fragment ions for the loss of Fucp andNeup5Ac because of the acidic functionality and electro-negativity of the Neup5Ac and Fucp residues. The calculated Most fragmentation of neutral glycans is acquired in positive structures for the oligosaccharides containing Manp as a ion mode because of the reluctance of the compounds to form reducing end and GlcpNAc indicated an increase in stability negative ions. However, Wuhrer and Deelder (2005) have with an increasing number of oxygen atoms interacting with the reported that N-glycans labeled with 2-AB give strong [M  H] Naþ ion. The preferred calculated position of Na was in the ions in negative ion mode from an ATT matrix. Fragmentation of vicinity of GlcNAc residues, which was consistent with the these ions in a TOF/TOF mass spectrometer by laser-induced Mass Spectrometry Reviews DOI 10.1002/mas 1. Multiple Successive Fragmentation (MSn) the Gal-b-(1 ! 4)-[Fuc-a-(1 ! 3-]-GlcNAc-b-1 ! or GalNAc-b-(1 ! 4)-[Fuc-a-(1 ! 3-]-GlcNAc-b-1 ! antennae, free or 2- Takemori, Komori, and Matsumoto (2006) have developed a AB labeled, showed migration of fucose between antennae so method for glycoprotein analysis that involves in-gel tryptic that difucosylated antennae could be deduced erroneously. The digestion and analysis of the resulting tryptic glycopeptides with transfer did not occur from the core fucose, and was not observed a MALDI-QIT-TOF MS. Fragmentation at the MS2 and MS3 for sodiated adducts or for permethylated glycans.
stages involved mainly the glycan portion of the molecules andthe technique was used to characterize N-linked glycopeptidesfrom Drosophila cuticle protein.
E. Fragmentation of Negative Ions The advantages of using negative ion MS/MS for sugar In-source decay (ISD) of [M  H] ions from small neutral analysis have been stressed and applied to the ion-trap MSn carbohydrates can be produced from the matrix nor-harmane and fragmentation of mono-to hexa-saccharides that mimic the these ions fragment to give abundant cross-ring cleavage terminal epitopes of the O-antigens from Vibrio cholerae O:1, products yielding linkage information. PSD fragmentation of serotypes Ogawa and Inaba. The two strains are differentiated by [M þ Cl] ions is similar with all fragments being deprotonated the presence of a methoxy group at C2, the chain linkage position, following loss of HCl (Yamagaki, Suzuki, & Tachibana, 2005).
in the Ogawa strain. The fragmentation patterns allowed the two PSD fragmentation of the [M þ Cl] ion from lactooligosac- serotypes to be differentiated (Bekesova´ et al., 2006). The charides (e.g., 23, 24) produces prominent A-type cross-ring compounds could also be differentiated in positive ion mode with cleavage ions from the reducing-terminal glucose residues a TOF/TOF instrument (Kova´cik et al., 2006). Reinhold's group whereas CID fragmentation in an ion trap is dominated by C- have made considerable use of this technique. Several examples type glycosidic cleavages similar to those seen with Q-TOF are included in the tables below and, in addition, they have instruments. The differences have been attributed to collisional developed software for analysis of the resulting spectra as cooling of the [M þ Cl] ions in the trap and the possibility that described in the section on Computer Analysis of Spectra.
these ions decompose in the flight tube in the PSD experiment togive deprotonated molecules that then rapidly decompose (Yamagaki, Suzuki, & Tachibana, 2006a,c). The very specificfragmentation processes occurring in the negative ion spectra of Laser-induced (157 nM) photofragmentation has been compared neutral sugars results in ions that are specific to certain isomers.
with CID with a TOF/TOF instrument. Cation-derivatized Yamagaki, Suzuki, and Tachibana (2006b) have shown that carbohydrates (e.g., derivatized with Girard's T reagent, 1/55) measurements of the ratio of such ions in mixtures of isomers can produced spectra containing abundant cross-ring cleavage ions be used to estimate the percentage of each because there is a with better coverage than provided by low or high energy CID.
linear relationship between ion abundance and percent of a On the other hand, native (underivatized) carbohydrates gave compound in a mixture. Furthermore, it was noted that C ions are better results by CID (Devakumar, Thompson, & Reilly, 2005).
often very abundant adjacent to HexNAc residues and a Normal-phase HPLC coupled off-line to MALDI-TOF/TOF mechanism involving transfer of the amide proton to the negative MS/MS has been reported to be a good method for isomer site at the cleaved oxygen was proposed.
differentiation (Maslen et al., 2006). The TOF/TOF instrumentproduced abundant cross-ring fragment ions revealing linkageinformation. Two ions were found from 2-AA-derivatized F. Infrared Multiphoton Dissociation (IRMPD) paucimannosidic glycans that were diagnostic for the presence A comparison of the CID and IRMPD spectra of 39 mucin-type of an a-(1 ! 3)-linked fucose residue. Formation of one of these O-glycans has shown that they yield nearly identical spectra was proposed to involve direct interaction of the acid group of the corresponding to the lowest energy fragmentation pathways derivative with the fucose as proposed in Scheme 1.
(Zhang, Fu, & Ning, 2005b). However, fragmentation efficiencyof IRMPD was reported to be better that that for CID for the largerglycans (above m/z 1400). Both IRMPD and CID produced D. Internal Residue Losses similar fragmentation patterns from N-glycans although IRMPD Additional problems have been reported for fragmentation of has been reported to yield more cross-ring cleavage products with protonated glycans as the result of internal rearrangements the mannose branch points being particularly susceptible to (Wuhrer et al., 2006c). Biantennary glycans (4/23) with either cleavage (Lancaster et al., 2006).
Mass Spectrometry Reviews DOI 10.1002/mas

ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES H. Computer Analysis of Spectra Kamekawa et al. (2006) have investigated a combination of Following the demise of CarbBank, there have been several frontal affinity chromatography (FAC) and MALDI LIFT-TOF/ initiatives to construct glycan databases and tools for glycomics.
TOF MS of four groups of the 2-AP derivatives of structural One such source is the Kyoto Encyclopedia of Genes and isomers and have shown that most can be differentiated by mass Genomes (KEGG, http://www.genome.jp/kegg/glycan). This spectrometry. However, two pairs, lacto-N-tetraose/lacto-N-neo- resource contains a database of carbohydrate structures tetraose (LNT/LNnT, 23/24) and lacto-N-hexaose/lacto-N-neo- (GLYCAN), glycan-related biochemical pathways and a map hexaose (LNH/LNnH, 25/26) that differed in having either a illustrating all possible variations of carbohydrate structures b-(1 ! 3)- or b-(1 ! 4)-linked galactose residue at the reducing within organisms (composite structure map, CSM). GLYCAN terminus (type 1 and type 2 chains, respectively) could not. FAC, also includes a structure drawing tool (KegDraw) and a glycan however, did differentiate these isomers; a galectin from the search and alignment tool (KEGG Carbohydrate matcher, marine sponge Geodia cydonium (GC1) and a plant seed lectin KCaM) (Hashimoto et al., 2006). A similar web source is from Ricinus communis (RCA-I) were used for identification of GLYCOSCIENCES.de portal (http://www.glycosciences.de). Its these chains, respectively emphasizing the importance of the database contains references, structures, compositions, NMR combination of FAC with mass spectrometry.
shifts, mass spectral fragments (theoretically calculated), andprotein database references (Lu¨tteke et al., 2006). Similarinformation can be found from the Consortium for FunctionalGlycomics (http://www.functionalglycomics.org) (Raman et al.,2006). Reviews of available databases relating to glycomics havebeen published (Raman et al., 2005; von der Lieth, Lu¨tteke, &Frank, 2006) and web-based tools available for glycan analysisare discussed in a review by Pe´rez and Mulloy (2005).
A program called ‘‘Cartoonist'' has been developed to annotate MALDI spectra with structures chosen from a library.
The software takes account of the biosynthetic pathwaysinvolved and gives each plausible structure a confidence score(Goldberg et al., 2005). ‘‘CartoonistTwo'' proposes structures for X-Type fragments have also been reported from 2-AB- O-linked glycans by automatically analyzing fragmentation derivatized tetra-, penta-, and hexa-saccharides recorded on a spectra and is reported to be an improvement on previous TOF/TOF instrument with LIFT technology (Morelle et al., versions of the software because of its scoring function which is 2005b). Weak X-type fragments were also present in fragmenta- more able to differentiate similar structures. In an evaluation with tion spectra of permethylated glycans studied by Wuhrer and O-glycans from Xenopus egg jelly, the software's predictions Deelder (2006) in experiments that involved the CID fragmenta- agreed with manual determination in 50% of the spectra. The tion of ISD fragments produced in the ion-source of a LIFT MS/ first or second highest scoring structure agreed with manual MS instrument. Permethylation allowed distinction between determination 90% of the time (Goldberg et al., 2006).
terminal, monosubstituted and disubstituted monosaccharides The StrOligo algorithm (Ethier et al., 2002, 2003) for and indicated the oligosaccharide sequence. Substitution posi- assigning structures to N-linked glycans, developed by the Manitoba group and described in the earlier review (Harvey, fragmentation induced by the high-energy collision-induced 2008a), has been compared with more conventional techniques in fragmentation. As an example of the results, fragmentation of the an investigation of N-glycans, as 2AB derivatives, from human B-ion ion resulting from loss of the reducing terminal GlcNAc integrin a5b1 (Ethier et al., 2005). The algorithm identified many residue enabled two isomeric Man3GlcNAc2 N-linked isomers of the constituent glycans but polysialylated glycans were (27, 28) to be differentiated. LIFT-TOF spectra of [M  H] ions problematic and isomeric compounds could not be resolved.
generated from N-acetylheparosan (29) oligosaccharides have The authors recommended using it in combination with more been shown to produce mainly C, Z, and B, Y glycosidic traditional techniques such as exoglycosidase digestion and cleavages with some low abundance cross-ring fragments multistage MS/MS.
(Minamisawa, Suzuki, & Hirabayashi, 2006).
The program GlycoX is designed to predict the composi- tions of glycans and glycosylation sites of glycans attached tosmall peptides of the type obtained by pronase digestion (Anet al., 2006b). The program takes, as input, the exact mass of thepeptide and the glycan spectra in the form of a mass/intensitytable and computes both the site and the glycans attached to thatsite. It has predicted correct glycan compositions for severalmodel glycoproteins. N-glycosylation sites can be predictedwith the NetNGlyc server at http://www.cbs.dtu.dk/services/NetNGlyc/.
In a series of three articles from Reinhold's laboratory, a MSn method is described for structural analysis of permethylated Mass Spectrometry Reviews DOI 10.1002/mas glycans whose fragmentation spectra are recorded with a particular, cross-ring and internal cleavages are accommodated QIT spectrometer (Ashline et al., 2005; Lapadula et al., 2005; to a greater extent than in other algorithms. The program first Zhang, Singh, & Reinhold, 2005). An algorithm named Oligo- applies a scoring scheme to identify potential bond linkages saccharide Subtree Constraint Algorithm (OSCAR) uses a data- between monosaccharides, based on the appearance pattern of base of the masses of 12,378 glycans containing hexose(0–12), cross-ring ions. Next, it uses a dynamic programming algorithm HexNAc(0–12), dHex(0–5), and Neu5Ac(0–5) and 4,542,720 pos- to determine the most probable oligosaccharide structures from sible fragments. Masses of ions from various fragmentation the mass spectrum and, finally, it re-evaluates these oligosac- pathways are used as the input and the algorithm computes and charide structures, taking into account the double (internal) presents the one or more structures that satisfy the fragmentation fragmentation ions. The algorithm appears to work best for linear structures but is still under development. A copy of the software is A strategy for combined MS3 and library search procedures available from the authors.
has been developed by Kameyama et al. (2005) for structural Lewandrowski, Resemann, and Sickmann (2005) have analysis of N-glycans. The library consists of MS2 and MS3 shown that the high-energy CID spectra obtained with a TOF/ spectra of all fragment ions from the MS2 spectra. In use, the TOF instrument gave better scoring than spectra produced by computer selects which fragment ion from the MS2 spectrum LID when using existing glycan databases such as GlycoSuitDB would yield the most informative MS3 spectrum and the method and Glycosciences DB.
was used to assign structures to N-glycans from human IgG.
Kameyama et al. (2006) have constructed a library of simulated fragmentation spectra in an attempt to overcome theneed for a large number of reference compounds. Di-, tri-, and IX. STUDIES ON SPECIFIC CARBOHYDRATE TYPES tetra-antennary N-glycans were labeled in each antenna with13C6-D-galactose to identify characteristic fragment patterns for A. Polysaccharides each branch type of N-linked oligosaccharides. On the basis ofthe resulting characteristic fragment patterns, the authors could Most of the applications articles relating to this large group of simulate CID spectra for isomeric oligosaccharides and were compounds are summarized in Tables 1–3. Only a few reports able to use the library to identify an N-linked glycan with containing information on specific methods are described below.
Analysis of most compounds by MALDI–MS is only possible The biosynthetic pathways of N-linked glycans involve a after depolymerization; methods are given in column 3 of the relatively small number of enzymes and monosaccharides. Many of the enzymes can use multiple N-glycans as substrates, thus Of several matrices (b-carboline, nor-harmane-DHB, generating a large number of glycan intermediates and making THAP and sinapinic acid) tested for UV-MALDI-TOF analysis the biosynthetic pathway resemble a network with diverging and of b-(1 ! 3)- and b-(1 ! 4)-xylans from the red seaweed converging paths. Thus, the N-glycans on any one particular Nothogenia fastigiata, only nor-harmane gave satisfactory glycoprotein include not only terminal glycans, but also signals (positive ion mode) but with distribution profiles lower intermediates from the biosynthetic pathway. The program than those determined earlier by NMR suggesting a decrease in GlycoVis has been designed to assess the glycan distribution ionization efficiency with increasing molecular weight. Because and potential biosynthetic route to each N-glycan taking into the glycans retain a small amount of calcium, the influence of account the substrate specificities of the enzymes involved. The Ca2þ was investigated. Added sodium chloride was shown not to input to the program is the glycan distribution data and the change the distribution profile whereas calcium chloride sup- program outputs a reaction pathway map which labels the relative pressed the signals (Fukuyama et al., 2005). Choi and Ha (2006) abundance levels of different glycans with different colors. The report that the relative abundance of the [M þ Na]þ ion from the program also traces all possible reaction paths leading to each malto-oligosaccharides containing from three to seven residues glycan and identifies each pathway on the map. Use of the increases to a maximum for the hexamer and attribute their program is illustrated with MALDI-TOF data from permethy- findings to the increased chance for sodium bridges to form lated glycans from IgG and tissue plasminogen activator (TPA) between adjacent sugar rings for the larger oligomers.
(Hossler et al., 2006).
Continuous spray deposition of aqueous solutions of A Glycan Finder program written in Igor Pro version 5.04B partially depolymerized methyl cellulose (30) from an HPLC software available from WaveMetrics, Inc., Portland, OR, for column has been reported to improve sensitivity of detection by assigning compositions to milk oligosaccharides has been up to an order of magnitude compared with standard preparation developed (Ninonuevo et al., 2006). The algorithm examines a techniques (Momcilovic et al., 2005b). Furthermore, the analyte list of experimentally measured masses and searches for all was more evenly distributed over the target surface, resulting in possible monosaccharide combinations matching the experimen- higher reproducibility. However, it provided a less accurate tal mass within a specified tolerance level (mass error). In addition estimation of average molar masses than the droplet deposition to providing information regarding the possible monosaccharide technique. A MALDI-TOF–MS method has been developed for composition, the program sorts each measured mass on the basis ofits HPLC retention time and relative intensity.
An algorithm GLYCH has been developed to interpret the high-energy MS/MS spectra of carbohydrates based on theirfragmentation spectra (Tang, Mechref, & Novotny, 2005). In Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES Mass Spectrometry Reviews DOI 10.1002/mas Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES Mass Spectrometry Reviews DOI 10.1002/mas Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES Mass Spectrometry Reviews DOI 10.1002/mas TABLE 3. Use of MALDI –MS for examination of carbohydrate polymers from fungi, algae, etc.
1 Instrument type (matrix), other techniques.
the evaluation of the degree of substitution (DS) in partially TOF–MS and ESI–MSn were also compared. They could be depolymerized carboxymethyl cellulose. A matrix of ammonium used either instead of, additionally to, or coupled either off line to sulfate and DHB gave good quality spectra without the usual HPAEC or online to RP–HPLC or CE–MS. CE with laser- ‘‘sweet-spots'' at the crystalline rim of the MALDI target. It was induced fluorescence proved to be the fastest way to quantify shown that the degrees of substitution calculated from spectra xyloglucan oligomers but MALDI-TOF–MS could be used for acquired from the center region of the MALDI target spot fast oligosaccharide profiling, because many samples could were in better agreement with those provided by the supplier be analyzed in a short time. For structural characterization than were the values obtained from the large crystals at the ESI–MSn outclassed PSD (Hilz et al., 2006).
target spot rim. This observation could be one explanation for the Oligosaccharides produced by depolymerization of hydro- higher DS values reported in other publications (Enebro & xypropylmethyl cellulose, hydroxypropyl cellulose or methyl- Karlsson, 2006).
cellulose with endoglucanase from Bacillus agaradhaerens A new method for structural investigations of rhamnoga- have been reacted with dimethyl-, diethyl-, and dipropyl-amine lacturonans involves methyl esterification of the GalA groups by reductive amination. All three derivatives produced a with tetrabutylammonium fluoride and iodomethane in DMSO considerable increase in sensitivity, especially for small allowing cleavage at the esterified moieties by b-elimination (DP < 3) oligosaccharides, thus partially overcoming low mass at elevated temperature. Oligosaccharide fragments containing discrimination often seen with MALDI-TOF instruments a single side chain were generated, providing a means to (Momcilovic et al., 2005a). Dimethylamine was the preferred thoroughly characterize the structural features of these complex compounds. The degree of methyl esterification was estimated by Chan, Chan, and Tang (2006) have compared MALDI-TOF, the use of 13C-methyl groups introduced from 13C-MeI. Products direct refractometric analysis, UV–vis absorption analysis of the were monitored by MALDI-TOF–MS and NMR (Deng, O'Neill, Aniline Blue-stained sample and GC/MS analysis of the hydro- & York, 2006).
lyzed and trimethylsilyl (TMS)-derivatized sample for estimat- Several techniques for the analysis of xyloglucan oligosac- ing the molecular weight of the extracellular polysaccharide charides from black currents have been compared. All three Curdlan (4/25). All samples were fractionated by gel permeation separation techniques (HPAEC, RP–HPLC, and CE) showed chromatography. Even so, the results showed that results from the different elution orders for the oligomers obtained after enzyme MALDI measurements underestimated the molecular weight and degradation. HPAEC and CE showed similar separation profiles, polydispersity of water-insoluble Curdlan (with and without while RP–HPLC was not able to separate all oligomers. MALDI- GPC fractionation) and were unreliable.
Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES 1. Cyclodextrins (CD) and Related Compounds beam across the analyte bands. A liquid composite matrix ofglycerol and the ultraviolet (UV) MALDI matrix, CHCA, allow- Matrix-assisted laser desorption/ionization (MALDI)-TOF and ed direct HPTLC–MALDI–MS analysis with a 337 nm-UV HPLC have been used to characterize a new class of methylated laser but with a 10-fold reduction in sensitivity.
b-cyclodextrins (Jacquet et al., 2005). A thin layer of CHCA was Using a library of lectins, Nakajima et al. (2006) have iden- used as the matrix and CDs with from two to eight methyl groups tified several oligosaccharides from bovine colostrum. Two were found. The thin layer method of sample preparation was compounds that evaded identification by the lectins were reported to give much more reproducible spectra than targets characterized as GalNAc-b-(1 ! ?)-Gal-b-(1 ! 4)-Glc, where prepared by the dried droplet method which produced increased ? represents an undetermined linkage, and GalNAc-a-(1 ! 3)- signals for the more highly methylated CDs. The effect was (Fuc-a-(1 ! 2)-Gal-b-(1 ! 4)-Glc by MALDI–QIT-TOF–MS.
attributed to the properties of the analyte-matrix crystals.
Bifidobacterium infantis has been shown to ferment purified The ability of cyclodextrins to form inclusion complexes has human milk oligosaccharides as a sole carbon source, while been used by Zhang et al. (2006) to obtain molecular weights of another gut commensal, Lactobacillus gasseri, did not ferment explosives. The inclusion complexes were produced by stirring a the carbohydrates (Ward et al., 2006). MALDI spectra were mixture of the two components at 508C for 72 hr followed by recorded with an FT-ICR instrument. A unique sialylated 48 hr at 08C. MALDI-TOF spectra were recorded from sinapinic (GalNAc-b-(1 ! 4)-[Neu5Ac-a-(2 ! 3)]-Gal- b-(1 ! 4)-Glc and several other carbohydrates have been Amphiphilic b-cyclodextrins with alkylthio chains at identified in the colostrum of the bottlenose dolphin (Tursiops the primary-hydroxyl side and galactosylthio-oligo-(ethylene truncatus) by HPLC, NMR, and MALDI–QIT–MS (DHB) glycol) units at the secondary-hydroxyl side have been (Uemura et al., 2005). Although these glycans have not been synthesized and shown to form nanoparticles and vesicles reported from natural sources in the free state, they are common (Mazzaglia et al., 2004). These compounds were shown by constituents of gangliosides.
MALDI-TOF to bind to the galactose-binding lectin fromPseudomonas aeruginosa (PA-1) which was chosen for its lowmolecular weight which is only three times that of the 3. Other Polysaccharides cyclodextrin. The spectrum of an equimolar mixture of lectin Enzymatically digested kappa-, iota-, and hybrid iota/nu and the cyclodextrin derivative gave peaks for the individual carrageenans, sulfated polymers of 4-linked a- and b-linked constituents and the 1:1 CD:PA-1 (m/z 16,588, sodium adduct) D-galactose, from red algae have been examined by MALDI- and 2:1 complexes showing that the binding of CD to the lectin is TOF–MS in negative mode with nor-harmane as the matrix but relatively strong, and involves effects other than inclusion by the loss of sulfate meant that kappa- and iota carrageenans could not CD of lectin lipophilic side chains. A MALDI mass spectrum easily be distinguished from each other as they differ only in under the same conditions for the glucosylated CD showed a substitution position (Antonopoulos et al., 2005). The iota/nu barely detectable peak corresponding to lectin–CD complex, and carrageenans, however, could be distinguished because their no evidence for a 1:2 complex.
repeating units were different. For all compounds, fragmentationinvolved loss of anhydrogalactose from the non-reducing end 2. Milk Oligosaccharides of the molecules. Autohydrolysis products of partially cyclizedmu/nu-carrageenan from Gigartina skottsbergii, recorded by For a recent review of milk oligosaccharides, see Mehra and MALDI-TOF from nor-harmane, have shown a uinmodal Kelly (2006). Several methods for structural determination of distribution of even and odd peaks suggesting fragmentation of human milk oligosaccharides have been compared by Ninonuevo et al. (2006). MALDI–FTICR and IRMPD were used to analyzeHPLC fractions and another system employed a microfluidic HPLC-Chip/MS device from Agilent, Foster City, CA. Onehundred eighty-three sugars were identified; many had large The growing use of chromatographic and electrophoretic amounts of fucose. The authors concluded that HPLC-Chip/MS methods in combination with MALDI-TOF and TOF/TOF and profiling of oligosaccharides provides a rapid and accurate on-line permethylation techniques for glycan analysis have been method for determining the number of milk oligosaccharide reviewed (Novotny & Mechref, 2005). A large number of studies components and those that contain fucosylated and sialylated have been published in this area; most are summarized in Tables 4 residues in the low femtomole range. The microfluidic HPLC- (specific glycoproteins) and 5 (whole organisms or tissues).
Chip/MS device was found to be both robust and to givereproducible results.
1. Intact Glycoproteins A method has been developed for examination of milk oligosaccharides separated on high-performance (HP) TLC Glycoproteins have been extracted from biological matrices plates and applied to human and elephant milk with a limit of by use of magnetic beads coated with either Concanavalin A or detection of approximately 10 pmol (Dreisewerd et al., 2006).
di-boronic acid. The beads were employed specifically to bind Glycerol was used as a liquid matrix, to provide a homogeneous model proteins containing N-glycans of different oligosaccharide wetting of the silica gel and an infrared laser was used for volume types. Thus, Con A beads successfully isolated RNase B from material ablation and particular soft desorption/ionization condi- human serum but were less efficient at isolating glycoproteins tions. ‘‘Mobility profiles'' were acquired by scanning the laser with complex glycans. No binding of glycoproteins to the Mass Spectrometry Reviews DOI 10.1002/mas Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES Mass Spectrometry Reviews DOI 10.1002/mas Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES Mass Spectrometry Reviews DOI 10.1002/mas Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES Mass Spectrometry Reviews DOI 10.1002/mas Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES Mass Spectrometry Reviews DOI 10.1002/mas beads was observed under competing conditions in the presence Caenorhabditis elegans using a proteomics approach. These of an excess of free mannose. Similarly, the use of di-boronic yielded 195 glycopeptides containing 199 Asn-linked glycans.
acid-functionalized beads was validated by the capturing of Attachment sites were identified by MALDI-TOF by utilizing the different model glycoproteins (Sparbier et al., 2005). A con- Asn–Asp conversion after deglycosylation with PNGase F. The canavalin A-immobilized affinity column has been developed for glycans themselves were not identified (Fan et al., 2005b).
glycoprotein/glycopeptide extraction and demonstrated with Similar studies using the Asn–Asp conversion has determined ribonuclease B containing high-mannose glycans. Optimum that four of the six potential sites of lysosomal hydrolase separation was obtained with a-methyl-D-mannopyranoside in mannose 6-phosphate uncovering enzyme are glycosylated the mobile phase.
(Wei et al., 2005b), that folate binding protein is glycosylated Mu¨ller and Allmaier (2006) have evaluated the ability of at Asn-49 and -141 (Chen, Lee, & Stapels, 2006), that all three MALDI-TOF–MS to measure the mass of intact polyclonal sites (Asn-211, -262, and -303) are glycosylated in decorin from human IgM which consists of a cluster of individual glycosylated human lung (Didraga et al., 2006b), that human recombinant molecules. The sample was extensively desalted with a C18 sRAGE is glycosylated at the two predicted N-glycosylation ZipTip and the best MALDI matrix was found to be THAP. Ions sites, Asn-25 (completely glycosylated) and Asn-81 (partially in charge states of 3–9 were found (Fig. 2), the possible lower glycosylated) (Ostendorp et al., 2006), that five of the six charge stated being above the mass range of the instrument. An potential sites of the sGP glycoprotein of Ebola virus (Asn-40, average mass of 1025.3  28.2 kDa was determined for the intact -204, -228, -57, and -268) are glycosylated with the remaining molecular cluster, which turned out to be in good agreement with one (Asn-238) being glycosylated only infrequently (Falzarano published data.
et al., 2006) and that Asn-79, -99, and -127 from the allergens Vesv 2 from Vespula vulgaris wasp venom are glycosylated (Skovet al., 2006). The Asn to Asp conversion, coupled with the use of 2. N-Linked Glycans 18O labeling and MALDI-TOF–MS was used by Tie et al. (2006) Mechref, Muzikar, and Novotny (2005) have stressed the to show that vitamin K-dependent carboxylase is N-glycosylated importance of a multimethodological approach to the structural at Asn-459, -605, and -627.
identification of these compounds, for example, MALDI, ESI, Okuyama et al. (2005) have determined glycosylation sites and FAB mass spectrometry do not provide information on of a-glucosidase from Schizosaccharomyses pombe by cleaving the constituent monosaccharides; such information needs to the glycans with Endo F to leave a GlcNAc residue at the be obtained with parallel data from exoglycosidase digestion or glycosylation site and observing a 203 mass unit increment from the mass of the tryptic or V8 peptide that contained the putativeN-glycosylation site. Glycosylation was detected at seven of a. Site occupancy. One hundred seventeen hydrophobic N- the potential 27 sites. Some information on site occupancy and glycosylated glycoproteins have been identified from extracts of the types of glycan attached has similarly been obtained byuse of the endoglycosidase, Endo-H which also cleaves thechitobiose core leaving the reducing terminal GlcNAc residueattached to the protein or the peptide following tryptic digestion.
Using this approach, Liou et al. (2006) have shown that, of thethree potential glycosylation sites of NPC2, the proteindeficient in Niemann-Pick C2 disease, Asn-19 is not glycosy-lated, Asn-39 is linked to Endo-H-sensitive glycans whereasAsn-116 is variably glycosylated. Similarly, Utz et al. (2006)have used Endo-H to determine that procyclin from the protozoanparasite Trypanosoma congolense has 13 N-linked sites; ESI MSwas used to show that these were occupied by high-mannoseglycans.
Glycosylation sites have been identified by diagonal chromatography which involves two successive identical chro-matographic steps with a chemical or enzymatic (in this casePNGase F), step between. The different elution pattern ofthe second step allows modified peptides to be identified(Ghesquie re et al., 2006). The method was demonstrated witha1-acid glycoprotein and used to identify 117 sites in glyco-proteins from depleted mouse serum.
b. N-linked glycan composition from glycopeptide analysis. Anew acid labile surfactant (RapiGest SF, sodium 3-[(2-methyl-2-undecyl-1,3-dioxolan-4-yl)methoxyl]-1-propanesulfonate), pro- FIGURE 2. Positive ion MALDI-TOF spectrum of intact polyclonalhuman IgM recorded from THAP. From Mu¨ller and Allmaier (2006) with duced by Waters Corporation has been introduced for denaturing permission from John Wiley and Sons Ltd.
proteins prior to trypsin digestion (Yu et al., 2005b,c). It can Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES easily be degraded with acid after digestion and the products onto the MALDI target but, in this case, the electrode was a metal do not interfere with subsequent MALDI analysis. Imre et al.
tube surrounding the fused silica capillary with the current being (2005) have shown by MALDI-TOF analysis that complete maintained through a liquid junction.
digestion of human a1-acid glycoprotein (AGP) occurred withRapiGest in the incubation mixture enabling very different c. Glycan release. Still the most popular method of analysis of glycan profiles to be seen at each of the five glycosylation sites by N-glycans is to release them from the glycoprotein, either chemically, usually with hydrazine, or enzymatically and to use Thermal-assisted partial acid hydrolysis and TFA used to either mass spectrometry (MALDI, ESI, FAB) or HPLC after produce glycopeptide ladders from horseradish peroxide tryptic peptides is described in two very similar articles (Lee et al., i. Chemical release. Hydrazine release requires re-acety- 2005a,c). Hydrolysis occurred mainly on the carbohydrate lation of the amino-sugars with acetic anhydride in the presence portion; thus the ladders gave information on composition by of an excess of sodium hydrogen carbonate which later has to be MALDI-TOF analysis. The ladders shifted to lower m/z values removed. Tanabe and Ikenaka (2006) have developed an in- with increasing reaction times. The method was later extended column method for hydrazine removal and re-N-acetylation to the glycoproteins ribonuclease B, avidin, human a1-acid simultaneously using a single graphitic carbon column which glycoprotein, and bovine fetuin (Lee et al., 2005b). Ladders they claim overcomes many of the problems with the standard were obtained from ribonuclease B and avidin with one method. After loading the hydrazine reaction solution, the glycosylation site but very little resolution of the hydrolysis column was washed with 15 mL of 50 mM ammonium acetate products could be observed from the larger glycoproteins with buffer and the glycans were eluted with 5 mL triethylamine several N-linked sites.
acetate buffer/acetonitrile (pH 7) containing 2% acetic anhy- A new method based on a two-stage proteolytic digestion dride. Yields were comparable to those of the standard method has been described for characterization of glycosylated proteins whereas they were lower if an ammonium acetate buffer was used separated by gel electrophoresis (Larsen, Højrup, & Roepstorff, for the re-N-acetylation step.
2005). The first stage involved in-gel proteolysis using a ii. Enzymatic release. Protein N-glycosidase F (PNGase F) sequence-specific endoproteinase such as trypsin and a small remains the most commonly used enzyme for glycan release, aliquot of the derived peptide mixture was analyzed by mass with PNGase A being used if glycans are fucosylated at the 3- spectrometry for protein identification based on peptide mass position of the core GlcNAc residue. However, some glyco- mapping. The remaining peptides/glycopeptides were then in- proteins show resistance to both enzymes as with N-glycans from cubated with a non-specific proteinase, such as proteinase K C. elegans with the unusual Gal-b-(1 ! 4)-Fuc at the 3- and 6- which cleaves the majority of the tryptic peptides into smaller positions. In this case, hydrazine was used instead (Hanneman peptides. The presence of a glycan created steric hindrance that et al., 2006). Endo D from Streptococcus pneumoniae has been resulted in a small peptide tag attached to the glycan. Masses reported to hydrolyze the core of complex N-glycans between were typically around 1,200 Da. Remaining peptides were the GlcNAc residues, unlike Endo-H that preferentially hydro- removed with a Poros R2 microcolumn packed into a GELoader lyzed high-mannose structures (Yamamoto, Muramatsu, & tip (glycopeptides pass through) and the glycopeptides were Muramatsu, 2005).
trapped on a second GELoader tip microcolumn packed with As an alternative to endoglycosidase release, Liu et al.
graphite powder. These glycopeptides could efficiently be (2006a) have used pronase E at high concentration and at washed to remove low molecular weight contaminants and extended time periods (up to 72 hr) to reduce the protein or subsequently eluted using 30% acetonitrile, 0.2% formic acid.
glycoproteins to single amino acids with only Asn attached to the The method, combined with MALDI-TOF monitoring of the N-glycans. The resulting glycopeptides were then permethylated glycopeptides was used to examine N-glycans from ovalbumin, under which conditions the Asn underwent b-elimination to give ovomucoid, and ovoglycoprotein.
a stable product. Pronase is much cheaper than PNGase, the usual Glycopeptides are often difficult to detect in the presence of enzyme used for glycan release and the method produced peptides; thus, when no tryptic peptides with predicted N- excellent results with ribonuclease B, chicken ovalbumin and glycosylation sites were detected from the human CB1 avidin. New linear glycans were also identified from Campylo- cannabinoid receptor expressed in Pichia pastoris. Kim et al.
bacter jejuini. Another high-throughput method for release and (2005b) suggested that the glycosylation sites were occupied.
analysis, with full experimental details has been described by Nevertheless, MALDI-TOF spectra of two glycosylated peptides Keck, Briggs, and Jones (2005).
have been recorded from tryptic digests of arylphorin from the In-gel methods: A method for examination of N-glycans Chinese oak silkworm (Jung, Kim, & Kim, 2005). A method for from plasma glycoproteins has been reported (Sagi et al., 2005), separating sialylated tryptic glycopeptides from peptides using basically following the in-gel method earlier described by Ku¨ster capillary electrophoresis has been described (Snovida et al., et al. (1997) but with a few modifications. Clean-up of the glycans 2006a). The glycopeptides were first fractionated with a short was effected with graphatized carbon mini-cartridges rather than C18 column and then by CE with the effluent deposited directly with the three-bed resin technique described by Ku¨ster et al. and onto the steel MALDI target which acted as the electrode. The the method was shown to be compatible with silver-stained technique was applied to glycopeptides from a1-acid glycopro- SDS–PAGE gels. Sialylated glycans were examined in linear tein and allowed the four glycosylation sites to be characterized.
TOF mode to minimize observed losses of sialic acids and THAP Amon, Plematl, and Rizzi (2006) have developed a similar was shown to be the best matrix, broadly in line with previous system for deposition of the effluent from a CE column directly observations. Alternatively, the acids were stabilized by methyl Mass Spectrometry Reviews DOI 10.1002/mas ester formation (Powell & Harvey, 1996). Quantitation was examples suggesting that commercial serum-free media appears initially performed by HPAEC-PAD but the glycan profiles of the to contain glycoproteins that are also sequestered by T cells.
methyl esters were shown to be comparable with the exception of Although the masses measured by MALDI analysis lead the trisialo-triantennary glycan that gave a weaker signal by directly to the glycan composition in terms of its monosaccharide MALDI analysis. The method was applied to investigations of content, information on the nature of the monosaccharides, many congenital disorders of glycosylation.
of which are isobaric, is lacking from MALDI spectra and must On-target methods: High-mannose glycans have been be obtained by additional techniques such as exoglycosidase detected and characterized from endo-polygalacturonase A from sequencing. Although usually performed as a separate operation, Aspergillus niger by MALDI-TOF mass measurements before some investigators carry out such digestions directly on the and after on-target digestion with Endo-H and/or a-mannosidase MALDI target. Thus, for example, Faid et al. (2006) have (Woosley et al., 2006a,b) and a MALDI-TOF profile of performed digestions in sodium phosphate buffer and DHB glycoforms of recombinant human thyrotropin (31 kDa) has matrix. Reactions terminated by addition of the matrix.
been obtained after enzymatic desialylation on the MALDI plate Sulfated and phosphorylated glycans have the same nominal (Morelle et al., 2006b) with DHB as the matrix.
mass and are not resolved with low resolution TOF instruments.
Other enzymatic release methods: Palm and Novotny (2005) However, it has been reported that they can be differentiated by have immobilized PNGase F on a porous polymer-based MALDI-TOF because sulfated glycans are invariably detected as monolithic capillary column that included N-acryloxysuccini- their sodium salts (the free sulfates presumably having been mide for enzyme immobilization. The reduced, but not alkylated, eliminated) whereas phosphates can be observed as the free acids glycoproteins, ribonuclease B, asialofetuin and ovalbumin, were (Fig. 3) (Harvey & Bousfield, 2005).
passed through the column and deglycosylation was reported tobe complete in seconds to a few minutes from 0.1 to 20 mg of e. Applications of MALDI to the detailed structural determi- glycoprotein. The enzyme activity was reported to be reprodu- nation of N-linked glycans. Most of this work is summarized in cible for at least 8 weeks. No cleanup was needed for the Tables 4 and 5 and in the section on biopharmaceuticals released glycans to give good signals when examined by (Table 16). Only work leading to the identification of some of MALDI-TOF from DHB. Although the system worked well for the more unusual glycans is reported here.
small and medium-sized glycoproteins, the authors had some Long fucosylated poly-N-acetyllactosamine chains have been reservations about its effectiveness for larger glycoproteins.
characterized in tetra-antennary glycans of mannan-binding lectin However the possibility of direct interfacing with HPLC was on the surface of human colorectal carcinoma SW1116 cells. They were thought to be responsible for binding to microbes (Teradaet al., 2005). In-source fragmentation and MALDI-Q-TOF CID d. N-glycan profiling. Matrix-assisted laser desorption/ioniza- analyses were used in their structural identification. Geyer et al.
tion (MALDI), with its production of only singly charged ions (2005) have identified several novel N-glycans from keyhole from N-glycans remains the best mass spectrometric method for limpet hemocyanine in a study of cross-reactivity with glyco- glycan profiling. Although some investigators prefer ESI or LC/ conjugates from Schistosoma mansoni. Most glycans were MS-based methods, claiming that they provide more consistent paucimannosidic, high-mannose, or hybrid but unusual features long-term reproducibility and are able to record spectra of included one and two galactose residues attached to the a-(1 ! 6)- sialylated glycans, ESI spectra can present the analyst with linked core fucose (31, 32) and galactose attached directly to the several problems. Frequently, multiple ions, such as [M þ H]þ antennae-mannose residues (33). Glycans from the worm stage and [M þ Na]þ are produced in positive ion mode and a number of this parasite have been found to be biantennary with the of anionic adducts, some not identified, are frequently formed antennae consisting of repeats of GalNAc-b-(1 ! 4)[Fuc-a- when negative ion spectra are acquired. Furthermore, ESI spectra (1 ! 3)]GlcNAc-b(1 ! 3) (Wuhrer et al., 2006b). C. elegans has can also contain multiply charged ions and abundant in-source N-glycans with Gal-b-(1 ! 4)-Fuc in both 3- and 6-positions of fragments, some of which (Y-type ions) are isobaric with native the core GlcNAc (Hanneman et al., 2006), as determined by MSn glycans. MALDI-TOF spectra of neutral glycans, on the other fragmentation with a MALDI-Q-TOF instrument. The glycans hand, although often containing [M þ K]þ ions in addition to the also contain phosphorylcholine (3/11) substitution. MALDI-Q- normal [M þ Na]þ species, are usually free of these problems TOF–MS/MS and PSD have shown that glycan profiles in this although it should be noted that acidic glycans can still present species are different at each developmental stage (Cipollo et al., problems as the result of in- and post-source fragmentation.
2005). Young larvae were shown to possess N-acetyllactosamine Many examples of the use of MALDI analyses are listed in extensions to the antennae not seen in adults. PSD analysis showed Tables 4 and 5. Following analysis by MALDI-TOF–MS, Monk that phosphocholine could be substituted on either core or termi- et al. (2006) have added a word of caution about the true nally linked GlcNAc, structures not yet seen in any other organism.
glycosylation of T cells when they noted that, despite stringentwashing, CD25þ and CD25 CD4þ T cells may sequesterglycans from the culture medium, thereby yielding unrepre-sentative N-glycan profiles and false inferences about endoge-nous glycosylation patterns. Some glycans appeared to originatefrom glycoproteins in fetal calf serum and were absent from cellsprepared in phosphate-buffered saline (PBS). Glycans from cellsgrown in serum-free media were intermediate between these two Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES FIGURE 3. Positive ion MALDI-TOF spectra of (a) N-glycans from equine luteinizing hormone recordedfrom DHB and (b) the same sample after incubation with alkaline phosphatase. Key to symbols: (&)GlcNAc, (*) mannose, (}) galactose, ( ) fucose, ( ) GalNAc. From Harvey and Bousfield (2005) withpermission from John Wiley and Sons Ltd.
Linear glycans of Glc1GalNAc5 attached to Asn by dermis and epidermis. The dermal glycans were labeled with the D-glucose 34) have H3 version of the derivative while the epidermal glycans been identified in the bacterium Campylobacter jejuni 11168H received the protonated form. High-mannose glycans were found (Liu et al., 2006a). The enzyme PglC has been shown to be to be characteristic of epidermal glycoproteins.
responsible for synthesizing undecaprenyl pyrophosphate bacil-losamine, an intermediate in the biosynthesis of N-linked glycansin this bacterium (Glover et al., 2006) and the compound has beensynthesized (Weerapana et al., 2005). Sulfated high-mannoseglycans have been identified by negative ion MALDI-TOFanalysis with nor-harmane as the matrix for the first time inTrypanosomatids; they were found in the glycoprotein crusipainfrom Trypanosoma cruzi (Barboza et al., 2005). Biantennaryglycans with N-acetyllactosamine extensions to the antennaewere also found. The nematode Trichinella spiralis has beenfound to synthesizes tetra-antennary glycans whose antennae arecapped with tyvelose (3,6-dideoxy-arabino-hexose, 1/15) (Bruce 3. O-Linked glycans & Gounaris, 2006).
a. Determination of site occupancy. New methods for thedetermination of the site of attachment of O-glycans have beenreported. Thus, a method based on the ladder sequencingtechnique developed by Chait et al. (1993) has been developedby Suzuki et al. (2006d). The glycopeptides were reacted with amixture of phenylisocyanate and phenylisothiocyanate andthen reacted with TFA in methanol under mild conditions f. Glycoproteomics. Uematsu et al. (2005) have developed a to remove the terminal residue from the phenylisothionate deuterated reagent, caoWR, Na-((aminooxy)acetyl)tryptophanyl- derivative (the phenylisocyanate derivative was stable). The arginine methyl ester (35) for labeling N-glycans for proteomic cycle was then repeated several times to produce a ladder of studies and used it to compare glycans released from murine glycopeptides/peptides capped with phenylisocyanate which Mass Spectrometry Reviews DOI 10.1002/mas

FIGURE 4. MALDI-TOF –MS spectra of a synthetic glycopeptide after five repeated ladder sequencingcycles under mild acid hydrolysis conditions. The ions with and indicate methylated ions and sodiumadduct ions, respectively. From Suzuki et al. (2006d) with permission from the American Chemical Society.
were examined by MALDI-TOF to give a spectrum from which the sperm flagella of sea urchin contains glycosylation at eight of the peptide sequence and glycosylation could be determined the possible twelve sites. The glycans consist of three a2 ! 9- linked sialic acids (Neu5Ac), terminating in sulfate and attached The O-linked site of adenovirus type 5 fiber protein has been at the 6-position to a GalNAc residue which is attached to the located by a two-stage process. Proteolysis with trypsin and Glu protein (Miyata et al., 2006). MALDI-TOF analysis was used C localized the site to the Ile101–Glu110 peptide and subsequent to define the glycosylation sites after desialylation. Two new b-elimination of the attached GlcNAc with a mixture of O-glycans, GalNAc and Gal-b-(1 ! 3)-GalNAc carrying 2- 2-propanol/dimethylamine/ethanethiol indicated Ser-109 as the aminoethyl-phosphate on the 6-position of the GalNAc group attachment site. The b-elimination procedure added 44 mass have been identified in glycoproteins from the nests of the units to the originally glycosylated amino acid which was common wasp (Vespula germanica) (Maes et al., 2005). Bovine detected by MALDI-TOF–MS (Cauet et al., 2005).
lens MP20 has been found to contain hexoses that are resistant toenzymatic cleavage. Tryptic glycopeptides were examined by b. Release of O-linked glycans. b-Elimination is still the MALDI-TOF/TOF–MS and their fragmentation spectra were preferred method for releasing O-glycans. The classical consistent with the presence of a hexose with a C-glycosidic link technique, involving sodium hydroxide, gives a solution from to tryptophan (Ervin et al., 2005). Bacterial glycoproteins are which much sodium must be removed. A modification, using rare but MALDI-TOF–MS has assisted in the identification of ammonium hydroxide as the base, introduced by Huang et al.
heptose residues in the autotransporter protein Ag43 from E. coli (2002) gives a cleaner product and has been used by Steiner (Sherlock et al., 2006).
et al. (2006) to release S-layer O-glycans from Geobacillus i. Glycosaminoglycans (GAGS) and related compounds.
stearothermophilus. Clean-up was with a carbon column. Taylor, MALDI-TOF–MS has been used to determine nanogram Holst, and Thomas-Oates (2006) have developed a method for amounts of defined hyaluronan oligomers obtained by enzymatic reductive b-elimination to release O-glycans from within SDS– digestion of high molecular weight hyaluronan with testicular PAGE gels, stained either with Coomassie blue or silver. The hyaluronate lyase (Busse et al., 2006). Stronger signals were glycans were released with sodium borohydride and sodium obtained in negative ion mode than positive but the signal-to- hydroxide at 508C for 16 hr before being extracted with water.
noise (S/N) ratio in both modes was found to be a reliable Glycans from as little as 5 mg of glycoprotein could be analyzed.
measure of the amount deposited onto the target. An amount as The method was developed with bovine submaxillary gland low as approximately 40 fmol could be determined and there was glycoproteins and then applied to glycans from Mycobacterium a linear correlation between the S/N ratio and analyte between avium capsular proteins.
approximately 0.8 pmol and 40 fmol. However, the detectionlimits depended considerably on the size of the oligomer with c. Applications of MALDI to the structural determination of larger oligomers being less sensitively detectable. The use of the O-linked glycans. Work on this topic is mainly summarized in liquid matrices consisting of 1-methylimidazolium a-cyano-4- Tables 6 (specific glycoproteins) and 7 (tissues and organisms).
hydroxycinnamate and butylammonium 2,5-dihydroxybenzoate Only a few examples of the more unusual compounds are given for analysis of GAGS (Laremore et al., 2006) has been mentioned here. Thus, a novel glycoprotein, named Flagellasialin, found in above. Other studies are summarized in Table 8.
Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES Mass Spectrometry Reviews DOI 10.1002/mas Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES biantennary glycans and of a-(1 ! 3)-fucosylated glycans ateach site. Increased fucosylation of haptoglobin has been A combination of hydrophilic interaction liquid chromatography identified and proposed as a biomarker for pancreatic cancer and MALDI-Q-TOF has been used to characterize glycosyl- (Okuyama et al., 2006).
phosphatidylinositol (GPI)-anchored peptides (Omaetxebarriaet al., 2006). GPI-anchor-specific diagnostic ions were observedby MS/MS at m/z 162, 286, 422, and 447, corresponding toglucosamine, mannose ethanolamine phosphate, glucosamineinositol phosphate, and mannose ethanolamine phosphate gluco-samine, respectively. This method was used for analysis of GPIpeptides derived from low picomole levels of the porcine kidney Naka et al. (2006) have devised a strategy involving release of N-glycans from cell membrane fractions, labeling with 2-AB,fractionating according to the number of sialic acids by serotoninaffinity chromatography, desialylating, further fractionating by 5. Glycoproteins and Disease normal-phase HPLC and identifying the resulting glycans byMALDI-TOF–MS. Application of the method allowed the Matrix-assisted laser desorption/ionization (MALDI)–MS is investigators to detect glycans with poly-N-acetyllactosamine being increasingly used to detect changes in glycosylation chains from histocytic lymphoma cells and hyperfucosylated accompanying various disease states with the aim of identifying glycans from gastric adenocarcinoma cells. Pochec et al. (2006) possible biomarkers for disease detection and/or monitoring.
have detected increased amounts of sialylated tetra-antennary Thus, Morelle et al. (2006c) have described a method for glycans in a3b1-integrin from a human bladder carcinoma qualitative analysis of N-glycosylation of human serum proteins cell line and shown that the glycoprotein exhibits significantly as a method for detecting disease biomarkers. N-linked higher binding than integrin from normal epithelial cells in a oligosaccharides were released from patient serum glycoproteins ligand-binding assay. N-glycolylneuraminic (37) acid has with PNGase F and cleaned with a graphitized carbon column.
been identified as its 1,2-diamino-4,5-methylenedioxybenzene Half of the sample was desialylated with hot acetic acid and the (DMB, 38) derivative by MALDI-TOF–MS from ferritin other half was reacted with methyl iodide to stabilize the sialic obtained from human hepatocarcinoma tissue. This acid is not acids. Samples are then examined by MALDI-TOF–MS. A synthesized by humans and its origin from some external source parallel structural study of the released oligosaccharides involved was postulated (Asakawa et al., 2006). SELDI protein chip exoglycosidase digestions, linkage analysis, and electrospray technology and its use in proteomic approaches to the detection ionization ion trap mass spectrometry (ESI-IT-MS) of perme- of disease biomarkers, with emphasis on cancer diagnosis has thylated glycans. Twenty-six, mainly complex glycans were been reviewed (Xiao et al., 2005).
identified. Application to patients with cirrhosis showed anincrease in bisecting N-acetylglucosamine residues and corefucosylation.
a. Cancer. Monitoring human serum for glycoproteins thatcould be used as markers for cancer has been investigated by anumber of laboratories. An et al. (2006a) have used MALDI–FTICR–MS to look for glycans specific to ovarian cancer andhave noted at least 15 peaks in their spectra that appear to beassociated with the tumor. Several of the ions, many of whichappear to be fragments, were isolated and fragmented furtherusing IRMPD to determine their structure. Zhao et al. (2006)have used lectins to monitor the distribution of a-(2 ! 3)- and b. Congenital disorders of glycosylation (CDGs). The use of a-(2 ! 6)-linked sialic acid in serum from cancer patients and MALDI-TOF–MS for screening for CDGs has been summarized controls. Changed glycoproteins were identified and the in a review of known diseases of this type (Freeze & Aebi, 2005) glycosylation sites and glycan structures were identified by and Wada (2006) has also published a review on the use of mass LC-MS/MS and MALDI-TOF–MS. The method was applied to spectrometry for studying CDGs. A method for in-gel-release of serum from pancreatic cancer patients where Asn-83 glycosy- N-glycans from plasma glycoproteins from CDG patients has lation of a1-antitrypsin was found to be down-regulated.
been described above and applied to cases of CDG-IIx and Increased a-(1 ! 3)-fucosylation of complex and, in particular, HEMPAS (Sagi et al., 2005).
triantennary glycans (36) from a1-acid glycoprotein have beenobserved in cases of inflammation and the inflammation c. Alcohol abuse. A review including the use of MALDI-TOF associated with conditions such as rheumatoid arthritis and for the detection of carbohydrate-deficient transferrin as a marker cancer (Higai et al., 2005). Glycopeptides were obtained by Glu- of alcohol abuse has been published (Bortolotti, De Paoli, C digestion from the glycoprotein that had been isolated from & Tagliaro, 2006). Elevated levels of carbohydrate-deficient serum and examined by HPLC. Glycans from the five N-linked transferrin have become used as a marker for prolonged over- glycosylation sites were released with PNGase F and MALDI- consumption of alcohol and an immunological test kit (Axis-Shild TOF analysis of desialylated glycans showed an increase in %CDT) is available. However results from the kit differ from Mass Spectrometry Reviews DOI 10.1002/mas those obtained by HPLC. MALDI-TOF analysis of the transferrinshowed a considerable amount of tri-sialo-transferrin that was notsupposed to be present and which probably accounted for thediscrepancy between the two results (Alde´n et al., 2005). Acomparison of MALDI-TOF and ESI-Q-TOF analyses fordetecting glycosylation differences of transferrin in chronicalcohol abuse has concluded that the ESI-Q-TOF approach issuperior on account of its higher resolution (del Castillo Bustoet al., 2005). Other studies are summarized in Table 9.
C. Glycated Proteins (Non-Enzymatic Attachmentof Sugars) A review on the importance of measuring products of non-enzymatic glycation of proteins has been published (Lapolla,Traldi, & Fedele, 2005) and the same group has publishedupdates on the role of mass spectrometry in the study of proteinglycation in diabetes (Lapolla et al., 2006) and related diseases(Lapolla, Fedele, & Traldi, 2005). Although detection of advanc-ed glycation end-products (AGE)-modified proteins is ideallydetected by MALDI-TOF–MS, detailed structural analysis is notpossible because of the broad, usually unresolved peaks. Toovercome the problem, Kislinger et al. (2005) used peptidemapping of Glu C digestion products and have detected, forexample, methylimidazolone (39) and argpyrimidine (40)attached to arginine and carboxyethyl (41) bound to lysine onthe peptide KVFGRCE from lysozyme when incubated withmethylglyoxyl (3/12). Other examples are given in the article.
Glycated peptides also occur naturally as the result of in vivoproteolysis. In a study of such systems, model glycated peptideswere obtained from glycated proteins by proteinase K, endo-LysC or trypsin digests and examined by both MALDI-TOF andLC/MS. Although the two techniques gave comparable results,MALDI detected several products that were not seen by LC/MS (Lapolla et al., 2005b). Glu C digestion and MALDI-TOF analysis were also used by Farah et al. (2005) to show that insulincould be glycated at two sites on exposure to glucose; the glycated insulin was enriched with magnetic beads containing immobilized 3-aminophenylboronic acid (42). Mennella et al.
(2006) have studied the effect of vicinal amino acids on the reactivity of lysine towards various carbohydrates. The presenceof hydrophobic amino acids, such as Ile, Leu, and Phe stronglyincreased reactivity. Contrasting results were obtained with basic residues. The Lys–Arg dipeptide was among the most reactivewhile the Lys–Lys was not. MALDI-TOF–MS was stated to be particularly useful for product monitoring.
Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES automatic sample spotting and applied to a group of 184individuals. Articles relating to more biologically targetedprojects are listed in Table 10.
1. Lipopolysaccharides (LPS) Studies on these compounds are summarized in Table 11.
a. Intact LPS. These complex molecules often require elaboratemethods of sample preparation in order for them to producestrong signals but, even so, spectra can only be obtained from the The fragmentation behavior of D-glucose- (1/4) and D- smaller molecules. Larger compounds are examined after split- ribose- (1/1) derived Amadori peptides as well as D-fructose- ting into smaller fragments; usually the lipid A portion and the (1/7) derived Heynes peptides have been studied by ESI- or repeat units of the O-chain. Because of the normally high amount MALDI-CID (Frolov, Hoffmann, & Hoffmann, 2006). All three of phosphate, spectra are normally recorded in negative ion sugar moieties displayed characteristic fragmentation patterns mode from a variety of matrices although, as with other which could be explained by consecutive losses of water and carbohydrates, DHB appears to be the most popular. However, formaldehyde. Glucose-derived Amadori products showed Choudhury, Carlson, and Goldberg (2005) have found that the losses of 18, 36, 54, 72, and 84 mass units whereas ions from phosphorylated oligosaccharides from P. aeruginosa serogroup- the D-fructose products contained an additional loss of 96 units.
O11 gave better negative ion signals from 3-AQ than from DHB.
Ribose-conjugated peptides lost 18, 36, and 54 units. Each Phosphates can be neutralized by methylation such as with compound yielded diagnostic lysine-derived immonium ions that MeOH/HCl as used by Silipo et al. (2005d) in a study of were successfully used in a precursor ion scan analysis to identify lipooligosaccharides (LOS) from Arenibacter certesii KMM Amadori peptides in a tryptic digest of bovine serum albumin (BSA) glycated with D-glucose on lysines 36, 160, 235, 256, 401, Sturiale et al. (2005b) have optimized conditions for obtaining strong signals from bacterial rough (R-type) LPS and Optimization of conditions for obtaining maximum found that, in addition to [M  H] ions, the spectra contained sequence coverage of proteins for studies of various modifica- abundant ions originating from cleavage between the Kdo moiety tions such as glycation have been performed by Wa, Cerny, and and the lipid A (Fig. 5). Sample preparation involved suspending Hage (2006) with human serum albumin (HSA) as a model the LPS in a mixture of methanol/water (1:1) containing 5 mM protein. A mixture of CHCA and DHB was employed as the final ethylenediaminetetraacetic acid (EDTA, 43) with sonication to matrix. This matrix, when used with a tryptic digest, gave aid dissolution. A few microliters of the solution was desalted on information on only half of the peptides. However, the combined a small piece of Parafilm1 with some grains of Dowex 50WX8- use of three enzyme digests, trypsin, endoproteinase Lys-C, and 200 cation-exchange beads that had been converted into the endoproteinase Glu-C increased this sequence coverage to ammonium form. 0.3 mL of this solution was transferred to the 72.8%. The use of a ZipTip to fractionate peptides in these MALDI target along with the same volume of dibasic ammonium digests increased the sequence coverage to 97.4%. By use of this citrate in a thin layer with the matrix solution that consisted of optimized procedure Lys199 was confirmed as a glycation site on THAP (200 mg/mL) in methanol and nitrocellulose (15 mg/mL normal HSA, whereas Lys-536 and Lys-389 were identified as in acetone/propanol (1:1 by volume)) mixed in a 4:1 ratio. The additional modification sites on minimally glycated HSA.
method was illustrated by spectra of LPS from Shewanella In a study of tryptic peptides from glycated HSA, Brancia pacifica, Xanthomonas campestris, and Pseudoalteromonas et al. (2006) have shown that DHB is a more effective matrix than issachenkonii. A similar method for preparing the MALDI target CHCA leading to an increase in the coverage of the glycated was used by Liparoti et al. (2006) in the first report of b-Kdo in the protein. It was found that, regardless of the high glucose inner core of LPS from Alteromonas macleodii ATCC 27126.
concentration employed for HSA incubation, glycation does not Procedures such as alkaline and acid hydrolysis, mild hydrazi- go to completion. Tandem mass spectrometric data suggested nolysis (de-O-acylation) followed by de-N-acylation with hot that the CID of singly charged glycated peptides leads to specific KOH were used. Another first report is of the discovery of an fragmentation pathways related to the condensed glucose enzyme that hydrolyses one of the two KDO residues that are molecule. The authors suggest that the specific neutral losses attached to the tetra-acylated lipid A precursor of Helicobacter derived from the activated glycated peptides can be used as a pylori LPS (Stead et al., 2005).
signature for establishing the occurrence of glycation processes.
A quantitative method for measuring glycated and gluta- thionylated hemoglobin using linear MALDI-TOF with asinapinic acid matrix has been developed by Biroccio et al.
(2005) and shown to give results in good agreement withHPLC measurements. The method was developed by the use of Mass Spectrometry Reviews DOI 10.1002/mas TABLE 10. Use of MALDI –MS for the study of glycated proteins Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES Mass Spectrometry Reviews DOI 10.1002/mas Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES Mass Spectrometry Reviews DOI 10.1002/mas Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES b. Lipid A. The CID fragmentation of KDO2-lipid A (44) has some other methods for detecting subtle differences in isogenic been briefly reviewed (Murphy et al., 2005). A new method strains of Staphylococcus aureus differing in their resistance for obtaining lipid A from whole bacterial cells involves to methicillin or teicoplanin. More important changes in stirring the cells with isobutyric acid/ammonium hydroxide MALDI-TOF–MS spectra were found with strains differing in for 2 hr at 1008C, washing the product with methanol methicillin than in teicoplanin resistance (Majcherczyk et al., and extracting the lipid A with chloroform/MeOH/water (3:1.5:0.25 by volume) (El Hamidi et al., 2005). Themethod avoids the usual hot phenol extractions and producesvery little decomposition. It was applied to lipid A from 2. Glycosphingolipids (GSL) Haemophilus influenzae and Bordetella holmesii. DHB, THAP,and ATT with ammonium citrate appear to be the preferred These compounds can be examined intact by MALDI–MS or the sugar portion can be removed enzymatically to reduce hetero- (2006) have obtained better spectra with nor-harmane as geneity caused by the lipid as exemplified by the release of matrix than with DHB for studies of Lipid A from Meso- pseudo-LewisY glycolipids of S. mansoni cercaria by endogly- rhizobium loti. Considerable heterogeneity was present in coceramidase II (from Rhodococcus spp.) (Meyer et al., 2005). A the spectra as the result of different chain lengths of the acyl semi-quantitative method for the determination of intact glycosphingolipids using sphingosylphosphorylcholine (45) asthe internal standard and monitoring by MALDI-TOF–MS from c. Medical aspects. Matrix-assisted laser desorption/ioniza- DHB has been developed for detecting GSLs deposited in Fabry tion (MALDI)-TOF–MS has been reported to be better than disease (Fujiwaki et al., 2006). It was used to study deposition of Mass Spectrometry Reviews DOI 10.1002/mas

FIGURE 5. Negative ion MALDI-TOF mass spectrum of native R-type LPS from Pseudoalteromonasissachenkonii. From Sturiale et al. (2005b) with permission from John Wiley and Sons Ltd.
ceramide trihexoside (CTH, 46) in cardiac valves. Deuterated internal energy produced by atmospheric pressure MALDI have standards for quantification of several GSLs have been also been used to advantage to record spectra of intact ganglio- synthesized and evaluated by ESI MS (Mills et al., 2005).
sides without loss of the sialic acid (Zhang et al., 2005c).
Thin-layer chromatography (TLC) has been coupled Nakamura et al. (2006) have also coupled TLC to a MALDI-QIT- directly with a commercial orthogonal-MALDI-TOF instrument TOF instrument and used it to record MS2 and MS3 spectra of for the analysis of gangliosides (Ivleva et al., 2005). The matrix glycosphingolipids. Ions characteristic of both sugar and lipid was sinapinic acid, spotted onto the TLC plate after development portions were obtained. The matrix, DHB, was coated onto a of the plate. Application of a declustering potential during target in 1:1 acetonitrile/water and spectra were recorded from MALDI analysis allowed control of the matrix adducts and the regions that a parallel stained plate indicated contained clusters. Stabilization of these sialylated molecules was provid- sample. TLC plates directly stained with primuline also yielded ed by collisional cooling. Several investigators have developed spectra. Suzuki et al. (2006c) have reported that the use of lithium methods for stabilization of sialic acids in these compounds. A adducts, increased laser power and a cooling gas flow can method, reported by Dreisewerd et al. (2005) used the liquid increase the abundance of the fragment ions in this QIT system.
matrix, glycerol, with ionization involving an Er:Yag infrared Other studies on glycosphingolipids are listed in Table 12.
laser to provide soft ionization conditions. The ions of lower Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES 3. Mycobacterial Glycolipids Glucose monomycolate is synthesized by mycobacteria uponinfection. Enomoto et al. (2005) have shown up-regulation ofsynthesis at 308C. The compounds, with a variety of mycolicacids from Mycobacterium smegmatis were identified byMALDI-TOF–MS after isolation by TLC. Trehalose (3/39) is aprerequisite for the production of mycolates that are importantconstituents of mycobacterial cell walls. Corynebacteriumglutamicum, a mutant that is unable to synthesize trehalose is,nevertheless able to synthesize mycolates when grown on otherglucose-containing oligosaccharides. The compounds, analyzedby MALDI-TOF and NMR contained one mycolic acidchain attached to C6 of the reducing-terminal glucose (Tropiset al., 2005). Cord factor (trehalose-6,60-dimycolate) from ninespecies of mycobacteria has been successfully analyzed byMALDI-TOF–MS (Fujita et al., 2005c). Spectra were verycomplicated (Fig. 6) because of the heterogeneity in both mycolicacid chains.
E. Glycosides and Other Natural Products Much work on glycosides relies on ESI or FAB ionization withfewer applications involving MALDI–MS. However, the tech-nique is still valuable in this context as illustrated by the worksummarized in Tables 13 and 14.
X. GLYCOSYLATION AND OTHERREACTION MECHANISMS Work involving glycosidases and glycosyl-transferases whereMALDI–MS has mainly been used for product characterization,is summarized in Table 15. Freire, D'Alayer, and Bay (2006)have reported that SELDI-TOF is a very convenient analyticalmethod for monitoring bioconjugation reactions. The trans-glycosylation reaction of GlcNAc to a recombinant mucinprotein, MUC6, catalyzed by ppGalNAc transferases were used.
XI. INDUSTRIAL APPLICATIONS A. Biopharmaceuticals The growing trend towards the production of biopharmaceuticals has resulted in studies in a large range of organisms such as the legume Medicago truncatula that has recently been proposed,on the bases of MALDI-TOF analysis, as promising for theproduction of these pharmaceuticals (Abranches et al., 2005).
Some of these organisms produce non-human glycosylation which can be antigenic and much work has been reported on the use of genetic engineering to remove the enzymes responsible forbiosynthesis of antigenic glycans, predominantly those con- taining 1 ! 2-linked xylose and a-galactose, and to introduceenzymes that synthesize human-type glycosylation. Plant andinsect cells are frequently used as bioreactors and a review by Harrison and Jarvis (2006) addresses N-glycosylation inbaculovirus-insect expression systems and the engineering of Mass Spectrometry Reviews DOI 10.1002/mas

FIGURE 6. MALDI-TOF mass spectrum of trehalose 6,60-dimycolate, from Mycobacterium tuberculosisH37Rv recorded from DHB. From Fujita et al. (2005c) with permission from the Society for GeneralMicrobiology.
insect cells to produce ‘‘mammalianized'' recombinant glyco- MALDI-TOF assay was best at identification of afucosylated proteins. Thus, for example, IgG1, human embryonic kidney glycoforms but was inferior to the others for analysis of sialylated (HEK) cells transfected with GlcNAc-TIII produce glycans with compounds. Other work on antibodies is summarized in Table 16.
bisecting GlcNAc (Schuster et al., 2005). LEC10b mutant Several studies on recombinant erythropoietin (EPO) have Chinese hamster ovary (CHO) cells have been shown to be the been reported (see Table 16). EPOs from various manufacturers cell line of choice for producing recombinant glycoproteins differ in several respects, but predominantly in glycosylation.
whose glycans contain a bisecting GlcNAc (Stanley et al., 2005).
All samples contain, as their major N-glycan, sialylated tetra- Production of monoclonal antibodies (IgG) represents a antennary compounds. Aranesp (NESP), however, contains a major investment by many biopharmaceutical companies.
large percentage of O-acetylated sialic acids (Stu¨biger et al., Several new methods have been developed for their analysis.
2005a), unlike EPO from other sources. Stu¨biger et al. (2005b) Thus, Bailey et al. (2005) have described a method for rapid and have also used MALDI-TOF–MS to study the intact molecules high-throughput analysis of recombinant monoclonal antibodies and found that Aranesp has a significantly higher molecular (MAbs) and their post-translational modifications. MAb capture, weight (36.6 kDa) than the other two samples (Erypo and desalting and in situ reduction/alkylation were accomplished by NeoRecormon) used in the experiment as the result of its sequential adsorption of the analyte onto solid-phase beads additional two N-glycosylation sites (Sanz-Nebot et al., 2005).
suspended in microtiter plate wells. The antibodies were eluted The neutral glycoforms could be resolved after desialylation and and digested with trypsin in the presence of the acid-labile after N-glycans had been removed, the MALDI-TOF spectra surfactant RapiGestTM and the resulting peptides were fractio- revealed the profile of the O-glycosylated glycoproteins. Use of nated by stepwise elution from reverse-phase pipette tips. The an ionene-dynamically coated capillary in a CE-MS system has fraction containing Fc N-glycopeptides was isolated and separated three glycoforms of EPO; molecular weights were analyzed by linear MALDI-TOF–MS. The results were in good verified by MALDI-TOF–MS (Yu et al., 2005a). MALDI-TOF agreement with those obtained by normal phase HPLC analysis has also been used to differentiate rhEPO (29 kDa from Research of fluorophore-labeled N-glycans released by PNGase F. A Diagnostics, Flanders, NJ) from darbepoietin (36 kDa, a product comparison of three techniques, ESIMS, MALDI-TOF–MS, from Amgen, Thousand Oaks, CA) in spiked horse plasma and anion-exchange chromatography with fluorescence (2-AA) (Gupta, Sage, & Singh, 2005). Four immunoassay based methods detection for quantitative analysis of the galactosylation present detected both EPOs but could not differentiate them and three on immunoglobulins has been published by Siemiatkoski et al.
also cross-reacted with equine EPO.
(2006). A recombinant monoclonal IgG was enzymatically MALDI-TOF analysis has been used to compare five modified in vitro to produce completely galactosylated and commercial samples of prostate-specific antigen (PSA) with degalactosylated forms of the immunoglobulin. Samples of certified reference material (CRM 613) from the European known galactosylation levels were prepared by mixing the Commission Community Bureau of Reference. All samples modified forms with the native form. Good repeatability and showed a different profile but appeared relatively stable; no linearity were demonstrated for all three assays (RSDs <1.0%, evidence for the presence of degrading enzymes was found correlation coefficients >0.99) which were evaluated in terms of (Satterfield & Welch, 2005). Other work on biopharmaceuticals repeatability, limit of quantitation, selectivity, and linearity. The is summarized in Table 16.
Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES TABLE 13. Use of MALDI –MS for examination of glycosides Mass Spectrometry Reviews DOI 10.1002/mas TABLE 13. (Continued ) hydroxyalkyl groups and enables quantitative determination ofthe oligomer composition after random degradation for the 1. Nodulation (NOD) Factors from Rhizobial Bacteria first time has been developed. The method involves perdeuter-iomethylation; partial acid hydrolysis; reductive amination with The microsymbiont Rhizobium gallicum is a fast-growing propylamine; and, finally, permethylation to yield completely bacterium found in European, Australian, and African soils O- and N-alkylated, permanently charged oligosaccharides.
which is able to nodulate plants of the genus Phaseolus. It Although the methyl pattern can be determined by electrospray produces four extracellular signal molecules, NOD factors (3/31) ionization with an ion trap and MALDI-TOF–MS, only MALDI- whose structures have been elucidated by FAB, LSIMS, and TOF–MS was found to produce quantitative results (Adden et al., MALDI-Q-TOF–MS together with GC/MS. The NOD factors 2006b). Distribution of hydroxyethyl (HE) groups matches with a consist of a linear GlcNAc backbone with an N-methyl group on random distribution calculated from the monomer composition, the reducing terminal and different N-acyl substituents. The four whereas the methyl pattern was heterogeneous to a different acyl-oligosaccharides terminate with a sulfated N-acetylgluco- extent (Adden et al., 2006c). A similar methylation technique has saminitol (Soria-Dı´az et al., 2006). Rhizobium tropici is a been used to investigate hydrolysis of six methylcelluloses by an nodulator of bean growing in areas characterized by highly acidic enzyme preparation from Trichoderma longibrachiatum (Adden soils. In this work, acidity was found to increases rhizobial NOD et al., 2006a). Additional examples of work with large plant factor production. Significant differences were observed between polysaccharides are included in Table 1.
the structures produced at acid and neutral pH: 52 differentmolecules were produced at acid pH, 29 at neutral pH, XII. CARBOHYDRATE SYNTHESIS and only 15 are common to bacteria grown at pH 7.0 or 4.5.
Structural identification was by a combination of MALDI-TOF, Reviews published during the review period include those on FAB, and ESI MS. The results indicate that R. tropici CIAT899 enzymatic polymerization of polysaccharides (Kobayashi & has successfully adapted to life in acidic soils and is a good Ohmae, 2006), glycopeptide synthesis (Buskas, Ingale, & Boons, inoculant for the bean under these conditions (Moro´n et al., 2006) and protein glycosylation (Wong, 2005). Most of the publications in this area relate to routine monitoring of reactionproducts and are summarized in Tables 17–22. Articles reporting work mainly on method development are listed in Table 17. Asmentioned in the previous review, many chemical articles ignore Hydroxyethylmethylcelluloses, prepared from cellulose by the details of the equipment and conditions used to obtain mass action of oxirane and methyl chloride are widely used in industry spectra and frequently demote what minimal, but essential as thickeners and emulsifiers. A new quantitative method for information that is supplied to ‘‘supplementary information.'' locating the methyl and hydroxyethyl groups which overcomes The absence of essential information, such as the matrix used the strong discrimination of relative ion intensities caused by to obtain the MALDI spectra is reflected in Tables 17–21 Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES (with apologies to authors from whose articles this information ESI MS. Peripheral dansyl groups have also been observed to has been missed). In these cases, ‘‘MALDI'' is used for articles undergo some photodecomposition (Baytekin et al., 2006).
omitting to cite the type of instrument used to record the MALDI-TOF analysis from IAA or dithranol of disaccharides attached to aromatic dendrimers have shown that the higher In addition to purely chemical methods, enzymatic methods generation dendrimers tended to aggregate into spherical are used extensively in this area. Shimma et al. (2006) have structures when cross-linked with 1,3-phenylene diisocyanate immobilized 51 human glycosyltransferases to Pir proteins and (47), whereas smaller molecules did not (Numata, Ikeda, & have shown that more than 75% retained their activities. The Shinkai, 2000).
library was used to synthesize several carbohydrates includingsome complex N-linked glycans. In addition to the use ofglycosyltransferases, glycosidases can be used as transglycosi-dases as illustrated by work with human endo-b-N-acetylgluco-saminidase HS (Endo-HS) which is able to transfer intactN-linked glycans to various monosaccharides (Ito et al.,2006). Endo-b-N-acetylglucosaminidase (Endo-M) from Mucorhiemalis expressed in Candida boidinii also has transglycosyla-tion activity and is able to transfer biantennary complex-type A variety of scaffolds have been used to construct these glycan from egg yolk glycoproteins to p-nitrophenyl-N-acetyl-b- compounds as shown in Table 18. These include monosacchar- D-glucosamine in organic solvents such as acetone, DMSO, or ides (Gao et al., 2005b; Lu, Fraser-Reid, & Gowda, 2005; Dubber methanol (Akaike & Yamanoi, 2006). Fujita and Yamamoto et al., 2006a; Dubber, Sperling, & Lindhorst, 2006), cyclo- (2006) have exchanged high-mannose glycans on glycoproteins dextrins (Carpenter & Nepogodiev, 2005; Furuike et al., 2005; by transglycosylation by using Endo-H to remove the high- Go´mez-Garcı´a et al., 2005; Hattori et al., 2006; Yamanoi et al., mannose glycans of ribonuclease B by cleavage of the chitobiose 2005), calix[4]arenes (48) (ten Cate et al., 2005; Dondoni & core and then Endo-M from M. hiemalis to add the complex Marra, 2006; Hocquelet et al., 2006), carbosilanes (Matsuoka glycan. Products were monitored by MALDI-TOF–MS from et al., 2006), phthalocyanines (49) (Alvarez-Mico et al., 2006), sinapinic acid.
poly(amidoamine) (PAMAM) (Ibey et al., 2005; Kubler-Kielb & Another method for monitoring the products of enzymatic Pozsgay, 2005; Mangold et al., 2005; Morgan & Cloninger, 2005; glycosylation reactions involves the use of sugars covalently Wolfenden & Cloninger, 2005; Wolfenden & Cloninger, 2006; linked to the surface of colloidal gold nanoparticles through a Zhu & Marchant, 2006), peptides (Hada et al., 2005; Jin et al., long carbon chain ending in a S–Au bond. Laser irradiation of this 2006; Kantchev, Chang, & Chang, 2006; Sato, Hada, & Takeda, bond caused rupture and release of the attached sugar. Reactions 2006), pentaerythritol (2/33) (Xue et al., 2005; Al-Mughaid & were monitored by enzymatic glycosylation of the attached Grindley, 2006), porphyrins (50) (Laville et al., 2006; Sol et al., sugars and then recording the MALDI spectra with a LIFT-TOF/ 2006), trihydroxybenzoic acid (51) (Fernandez-Megia et al., TOF system directly from the reaction mixture—no matrix was 2006; Joosten et al., 2006), and trimesic acid (4/61) (Patel & necessary (Nagahori & Nishimura, 2006).
Lindhorst, 2006).
As with the previous reviews, the two areas that are particularly suitable for special mention are large moleculessuch as glycodendrimers and glycoprotein conjugates.
A. Synthesis of Multivalent Carbohydrates,Dendrimers, and Glycoclusters Articles reporting work on these compounds are listed inTable 18. Self-assembly of dendrimers towards controllablenanomaterials has been reviewed (Smith et al., 2005). MALDI-TOF spectra of a PAMAM G10 dendrimer has been obtained withTHAP as the matrix (Mu¨ller & Allmaier, 2006). Sample pre-paration involved vacuum drying to remove the methanol and theuse of TFA/MeCN as to solvent to promote charge formationfrom the amine groups. Doubly (m/z 283 kDa) and triply (m/z B. Synthesis of Carbohydrate–Protein Conjugates 193 kDa) charged ions were observed, giving a mass of around570 kDa, considerably less than that of the calculated mass of MALDI-TOF analysis, mainly in linear mode, is used extensively 935 kDa. The difference was attributed to incomplete synthesis to monitor the coupling of carbohydrates to proteins and, in highlighting the usefulness of MALDI for analyses of this type.
particular, to estimate the number of glycans attached. As Although MALDI–MS is usually regarded as the most reliable reported in the previous reviews, the use of squaric acid is a method for characterization of dendrimers, it has now been found popular method for coupling although other linkers such as adipic that dendrimers containing sulfonamide groups at their periphery acid p-nitrophenyl diesters have been used. Work in this area is undergo some decomposition during ionization as shown by summarized in Table 19.
Mass Spectrometry Reviews DOI 10.1002/mas XIII. MISCELLANEOUS STUDIES MALDI-TOF–MS has been used to analyze the speciesinvolved in experiments to measure the binding properties ofvancomycin-type glycopeptide antibiotics using reflectomericinterference spectroscopy (Mehlmann et al., 2005). Althoughthe latter technique is sensitive, it cannot determine which ofthe components of a mixture have bound to the surface, aproblem that is easily solved by MALDI–MS because eachspecies has a unique mass. MALDI-TOF–MS has been usedto measure acid-catalyzed oligomer formation of levoglu-cosan (1,6-anhydro-a-D-glucose), a product of combustionand which can be used to monitor long-range pollution(Holmes & Petrucci, 2006). Oligomers of up to nine residueswere detected and it was proposed that they may contributeto the humic-like substances that are thought to be formedfrom Matrix-assisted laser desorption/ionization MALDI-TOF analysis showed that the antigen recognized by MeningococcalGroup B polysaccharide monoclonal antibodies is a disaccharidecomposed of two a2-8-linked sialic acids of which one containsan N-deacyl residue (Moe, Dave, & Granoff, 2005). Alginateoligosaccharides (AOS), prepared through enzymatic hydrolysisof alginate polymer, linear b-(1 ! 4)-linked glycuronan com-posed mainly of residues of b-D-mannosyluronic acid and its C-5 Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES Mass Spectrometry Reviews DOI 10.1002/mas Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES Mass Spectrometry Reviews DOI 10.1002/mas Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES Mass Spectrometry Reviews DOI 10.1002/mas Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES Mass Spectrometry Reviews DOI 10.1002/mas epimer, and analyzed by MALDI-TOF–MS, have been shown topromote growth of Bifidobacteria, prebiotics that are thought topromote health (Wang et al., 2006d). Oligosaccharides fromhoney have been characterized by size-exclusion chromatog-raphy (SEC) and MALDI-TOF–MS after fractionation withwater/ethanol solutions and activated charcoal (Morales et al.,2006). Di- and tri-saccharides were the main constituents butconstituents with degrees of polymerization to 16 were observedby MALDI-TOF–MS.
Although method development has slowed in recent years, thework reported in this review has shown that applications ofMALDI–MS to carbohydrate and glycoconjugate analysis arevery much alive and growing. The technique has been applied to avery large range of compounds allowing problems to be solvedin many diverse areas of science and commerce. Althoughelectrospray ionization, with its convenient coupling to instru-ments that provide extensive fragmentation is now possiblymore widely used, MALDI-TOF is superior in producing glycanprofiles from mixtures because of its property of producingessentially only singly charged ions. Spectra produced byelectrospray invariably contain multiply charged ions, variousadducts and fragments that can confuse interpretation. On thedown side, however, MALDI-TOF–MS, particularly in reflec-tron-TOF instruments is less attractive for sialylated glycans onaccount of the tendency for the sialic acid to be eliminated eitherwithin the ion source of during the ion's flight through theinstrument. Nevertheless, this problem can be readily overcomeby suitable derivatization.
The past two years have seen some developments in techniques, in particular the growth of negative ion formationfrom neutral glycans by use of anion adduction and specificmatrices such as nor-harmane. Fragmentation of the resultingnegative ions produces much more informative spectra thanfragmentation in positive ion mode, mainly as the result of highlyspecific reaction pathways that produce mainly cross-ringcleavage products. Similar cross-ring product ions can also beproduced using positive ions in TOF-TOF instruments thatproduce high-energy collisions and the use of these instrumentsalso appears to be increasing. The review period has also seensome major advances in the development of software forcarbohydrate analysis and the introduction of new databasescontaining both carbohydrates and their fragment ions.
Although none of these systems is yet able to identify allcompounds, they often provide pointers that considerably aid themanual process.
Although the collection of the increasing number of articles in this area is becoming more time-consuming, the advent ofpowerful search engines such as Google scholar considerably aids the process by highlighting articles in some of the moreobscure journals. Publications on the use of MALDI–MS for the analysis of carbohydrates continue to enter new areas andsome exciting developments are expected in the coming yearswith the advent of new types of mass spectrometer such as those incorporating ion mobility separation. It is intended that Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES Mass Spectrometry Reviews DOI 10.1002/mas Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES TABLE 17. Use of MALDI –MS in the development of synthetic methods Mass Spectrometry Reviews DOI 10.1002/mas TABLE 17. (Continued ) TABLE 18. Use of MALDI mass spectrometry for investigations of glycodendrimers Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES TABLE 18. (Continued ) Mass Spectrometry Reviews DOI 10.1002/mas TABLE 18. (Continued ) Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES TABLE 19. Use of MALDI for the investigation of carbohydrate–protein conjugates TABLE 20. Use of MALDI–MS for the synthesis of carbohydrates from bacteria, fungi, etc.
Mass Spectrometry Reviews DOI 10.1002/mas TABLE 20. (Continued ) Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES TABLE 21. Use of MALDI –MS for the examination of products of carbohydrate synthesis Mass Spectrometry Reviews DOI 10.1002/mas TABLE 21. (Continued ) Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES TABLE 21. (Continued ) Mass Spectrometry Reviews DOI 10.1002/mas TABLE 21. (Continued ) Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES TABLE 21. (Continued ) Mass Spectrometry Reviews DOI 10.1002/mas TABLE 21. (Continued ) TABLE 22. Use of MALDI to study the products combinatorial experiments Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES these updates follow this progress at least into the immediate dihydroxybenzoic acid (2,5-dihydroxy XV. ABBREVIATIONS isomer unless stated otherwise) 2-aminobenzoic acid aminobenzoic acid ethyl ester deoxyribonucleic acid angiotensin I converting enzyme advanced glycation end-products degree of polymerization a1-acid glycoprotein degree of substitution enzyme-linked immunoabsorbent assay alginate oligosaccharide Endo-F (D, H, M) endoglycosidase-F (D, H, M) atmospheric pressure MALDI endoplasmic reticulum electrospray ionization furanose form of sugar ring fast atom bombardment frontal affinity chromatography fibroblast growth factor adenosine triphosphate Fourier transform bovine serum albumin Candida antarctica lipase B galacturonic acid cyclodextrin or circular dichroism congenital disorder of glycosylation gas chromatography/mass spectrometry cystic fibrosis transmembrane conductance Chinese hamster ovary ceramide trihexoside human embryonic kidney hereditary erythroblastic multinuclearity with positive acidified serum lysis test dendritic cell-specific ICAM3-grabbing Mass Spectrometry Reviews DOI 10.1002/mas hydrophilic interaction chromatography mouse myeloma cell line human immunodeficiency virus hydroxypicolinic acid high-performance anion exchange oligosaccharide subtree constraint high-performance liquid chromatography Horseradish peroxidase pyranose form of sugar ring human serum albumin galactose-binding lectin from Pseudomonas indoleacrylic acid intercellular adhesion molecule pulsed amperometric detection ion cyclotron resonance polyacrylamide gel electrophoresis immunoglobulin G (or M) polyethylene glycol infrared multiphoton dissociation ulopyranosonic acid post-source decay pseudaminic acid (5,7-diamino-3,5,7,9- Kyoto Encyclopedia of Genes and Genomes linear (as in linear-TOF) N-acetylpseudaminic acid quadrupole ion trap liquid chromatography reflectron (as in R-TOF) receptor for advanced glycation end- liquid secondary ion mass spectrometry Bacillus anthracis protective antigen lipoteichoic acid relative standard deviation signal-to-noise ratio mass to charge ratio sialic acid transporter monoclonal antibody matrix-assisted laser desorption/ionization sodium dodecyl sulfate mass spectrometry multi-angle light scattering detector surface-enhanced laser desorption/ -T (as GlcNAc-T) transferase mass spectrometry tobacco etch virus trifluoroacetic acid N-acetylneuraminic (sialic) acid trihydroxyacetophenone (normally the 2,4,6-trihydroxy isomer) natural killer T cells nuclear magnetic resonance Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES Allen S, Zaleski A, Johnston JW, Gibson BW, Apicella MA. 2005. Novel sialic acid transporter of Haemophilus influenzae. Infect Immun tissue plasminogen activator Al-Mughaid H, Grindley TB. 2006. Synthesis of a nonavalent mannoside tyvelose (3,6-dideoxy- glycodendrimer based on pentaerythritol. J Org Chem 71:1390–1398.
uridine diphosph(ate)(o) Alvarez-Mico X, Calvete MJF, Hanack M, Thomas Ziegler T. 2006. The first example of anomeric glycoconjugation to phthalocyanines. Tetrahe- dron Lett 47:3283–3286.
wheat germ agglutinin Aly MRE, Rochaix P, Amessou M, Johannes L, Florent J-C. 2006. Synthesis of globo- and isoglobotriosides bearing a cinnamoylphenyl tag as novelelectrophilic thiol-specific carbohydrate reagents. Carbohydr Res341:2026–2036.
Aly MRE, Schmidt RR. 2005. New diacylamino protecting groups for glucosamine. Eur J Org Chem:4382–4392.
Amin MN, Ishiwata A, Ito Y. 2006. Synthesis of asparagine-linked Abe S, Moriyama H, Niikura K, Feng F, Monde K, Nishimura S-I. 2005.
bacillosamine. Carbohydr Res 341:1922–1929.
Versatile synthesis of oligosaccharide-containing fullerenes. Tetrahe- Amon S, Plematl A, Rizzi A. 2006. Capillary zone electrophoresis of dron Asym 16:15–19.
glycopeptides under controlled electroosmotic flow conditions coupled Abranches R, Marcel S, Arcalis E, Altmann F, Fevereiro P, Stoger E. 2005.
to electrospray and matrix-assisted laser desorption/ionization mass Plants as bioreactors: A comparative study suggests that Medicago truncatula is a promising production system. J Biotechnol 120:121– An HJ, Lurie S, Greve LC, Rosenquist D, Kirmiz C, Labavitch JM, Lebrilla CB. 2005a. Determination of pathogen-related enzyme action by mass Adden R, Melander C, Brinkmalm G, Gorton L, Mischnick P. 2006a. New spectrometry analysis of pectin breakdown products of plant cell walls.
approaches to the analysis of enzymatically hydrolyzed methyl Anal Biochem 338:71–82.
cellulose. Part 1. Investigation of the influence of structural parameters An HJ, Ninonuevo M, Aguilan J, Liu H, Lebrilla CB, Alvarenga LS, Mannis on the extent of degradation. Biomacromolecules 7:1399–1409.
MJ. 2005b. Glycomics analyses of tear fluid for the diagnostic detection Adden R, Muller R, Brinkmalm G, Ehrler R, Mischnick P. 2006b.
of ocular rosacea. J Proteome Res 4:1981–1987.
Comprehensive analysis of the substituent distribution in hydroxyethyl An HJ, Miyamoto S, Lancaster KS, Kirmiz C, Li B, Lam KS, Leiserowitz GS, celluloses by quantitative MALDI-ToF-MS. Macromol Biosci 6:435– Lebrilla CB. 2006a. Profiling of glycans in serum for the discovery of potential biomarkers for ovarian cancer. J Proteome Res 5:1626– Adden R, Niedner W, Mu¨ller R, Mischnick P. 2006c. Comprehensive analysis of the substituent distribution in the glucosyl units and along the An HJ, Tillinghast JS, Woodruff DL, Rocke DM, Lebrilla CB. 2006b. A new polymer chain of hydroxyethylmethyl celluloses and statistical computer program (GlycoX) to determine simultaneously the glyco- evaluation. Anal Chem 78:1146–1157.
sylation sites and oligosaccharide heterogeneity of glycoproteins. J Adinolfi M, Galletti P, Giacomini D, Iadonisi A, Quintavalla A, Ravida A.
Proteome Res 5:2800–2808.
2006. Toward novel glyconjugates: Efficient synthesis of glycosylated Ando H, Shimizu H, Katano Y, Koike Y, Koizumi S, Ishida H, Kiso M. 2006.
4-alkylidene-b-lactams. Eur J Org Chem:69–73.
Studies on the a-(1-4)- and a-(1-8)-fucosylation of sialic acid for the Aime S, Gianolio E, Palmisano G, Robaldo B, Barge A, Boffa L, Cravotto G.
total assembly of the glycan portions of complex HPG-series ganglio- 2006. Improved syntheses of bis(b-cyclodextrin) derivatives, new sides. Carbohydr Res 341:1522–1532.
carriers for gadolinium complexes. Org Biomol Chem 4:1124–1130.
Andre´ S, Kojima S, Gundel G, Russwurm R, Schratt X, Unverzagt C, Gabius Aitken A. 2005. Identification of posttranslational modification by mass H-J. 2006. Branching mode in complex-type triantennary N-glycans as spectrometry. In: Walker JM, editor. The Proteomics Protocols regulatory element of their ligand properties. Biochim Biophys Acta Handbook. Totowa, NJ: Humana Press. pp 431–438.
Akaike E, Yamanoi T. 2006. The transglycosylation activity of the Andrianasolo EH, Gross H, Goeger D, Musafija-Girt M, McPhail K, Leal RM, recombinant endo-b-N-acetylglucosaminidase from Mucor hiemalis Mooberry SL, Gerwick WH. 2005. Isolation of swinholide A and in media containing organic solvents. Trends Glycosci Glycotechnol related glycosylated derivatives from two field collections of marine cyanobacteria. Org Lett 7:1375–1378.
Akama TO, Nakagawa H, Wong NK, Sutton-Smith M, Dell A, Morris HR, Antonopoulos A, Hardouin J, Favetta P, Helbert W, Delmas AF, Lafosse M.
Nakayama J, Nishimura S-I, Pai A, Moremen KW, Marth JD, Fukuda 2005. Matrix-assisted laser desorption/ionisation mass spectrometry MN. 2006. Essential and mutually compensatory roles of a-mannosi- for the direct analysis of enzymatically digested kappa- iota- and hybrid dase II and a-mannosidase IIx in N-glycan processing in vivo in mice.
iota/nu-carrageenans. Rapid Commun Mass Spectrom 19:2217– Proc Natl Acad Sci USA 103:8983–8988.
Akamatsu M, Fujimoto Y, Kataoka M, Suda Y, Kusumoto S, Fukase K. 2006.
Anumula KR. 2006. Advances in fluorescence derivatization methods for Synthesis of lipid A monosaccharide analogues containing acidic amino high-performance liquid chromatographic analysis of glycoprotein acid: Exploring the structural basis for the endotoxic and antagonistic carbohydrates. Anal Biochem 350:1–23.
activities. Bioorg Med Chem 14:6759–6777.
Aplander K, Tejler J, Toftered J, Carlsson S, Kahl-Knutsson B, Sundin A, Alde´n A, Ohlson S, Pa˚hlsson P, Ryde´n I. 2005. HPLC analysis of Leffler H, Nilsson UJ. 2006. Synthesis of a 30-naphthamido-LacNAc carbohydrate deficient transferrin isoforms isolated by the Axis-Shield fluorescein conjugate with high selectivity and affinity for galectin-3.
%CDT method. Clin Chim Acta 356:143–146.
Carbohydr Res 341:1363–1369.
Alderwick LJ, Radmacher E, Seidel M, Gande R, Hitchen PG, Morris HR, Arai MA, Matsuo I, Hagihara S, Totani K, Maruyama J-I, Kitamoto K, Ito Y.
Dell A, Sahm H, Eggeling L, Besra GS. 2005. Deletion of Cg-emb 2005. Design and synthesis of oligosaccharides that interfere with in Corynebacterianeae leads to a novel truncated cell wall arabinoga- glycoprotein quality-control systems. ChemBioChem 6:2281–2289.
lactan, whereas inactivation of Cg-ubiA results in an arabinan-deficient Arnold JN, Wallis RR, Willis AC, Harvey DJ, Royle L, Dwek RA, Rudd PM, mutant with a cell wall galactan core. J Biol Chem 280:32362–32371.
Sim RB. 2006. Interaction of mannan binding lectin with a-2 Mass Spectrometry Reviews DOI 10.1002/mas macroglobulin via exposed oligomannose glycans: A conserved feature ides using polysaccharide analysis by carbohydrate gel electrophoresis.
of the thiol-ester protein family? J Biol Chem 281:6955–6963.
Arnold JN, Wormald MR, Suter DM, Radcliffe CM, Harvey DJ, Dwek RA, Bastida A, Hidalgo A, Chiara JL, Torrado M, Corzana F, Pe´rez-Can˜adillas Rudd PM, Sim RB. 2005. Human serum IgM glycosylation: JM, Groves P, Garcia-Junceda E, Gonzalez C, Jimenez-Barbero J, Identification of glycoforms that can bind to mannan-binding lectin. J Asensio JL. 2006. Exploring the use of conformationally locked Biol Chem 280:29080–29087.
aminoglycosides as a new strategy to overcome bacterial resistance. J Asakawa H, Sasabe M, Miyazaki R, Matsuda H, Fukai F, Hanada K, Hirano Am Chem Soc 128:100–116.
H, Takasaki S. 2006. The analysis of N-glycolylneuraminic acid Bauer J, Brandenburg K, Za¨hringer U, Rademann J. 2006. Chemical synthesis (NeuGc) of hepatoma tissue and K562 cell ferritins using HPLC and of a glycolipid library by a solid-phase strategy allows elucidation of the mass spectrometry. Proc Jpn Acad Ser B 82:181–187.
structural specificity of immunostimulation by rhamnolipids. Chem Eur Ashline D, Singh S, Hanneman A, Reinhold V. 2005. Congruent strategies for J 12:7116–7124.
carbohydrate sequencing. 1. Mining structural details by MSn. Anal Bauer S, Vasu P, Mort AJ, Somerville CR. 2005. Cloning, expression, and characterization of an oligoxyloglucan reducing end-specific xyloglu- Aumu¨ller I, Lindhorst TK. 2006. Chromophore-supported purification in canobiohydrolase from Aspergillus nidulans. Carbohydr Res 340: parallel synthesis. Eur J Org Chem:1103–1108.
Avril T, North SJ, Haslam SM, Willison HJ, Crocker PR. 2006. Probing the cis Baytekin B, Werner N, Luppertz F, Engeser M, Bruggemann J, Bitter S, interactions of the inhibitory receptor Siglec-7 with 2,8-disialylated Henkel R, Felder T, Schalley CA. 2006. How useful is mass ligands on natural killer cells and other leukocytes using glycan-specific spectrometry for the characterization of dendrimers? Int J Mass antibodies and by analysis of 2,8-sialyltransferase gene expression. J Leukocyte Biol 80:787–796.
Bazin HG, Bess LS, Livesay MT, Ryter KT, Johnson CL, Arnold JS, Johnson Badi N, Jarroux N, Gue´gan P. 2006. Synthesis of per-2,3-di-O-heptyl-b and g- DA. 2006. New synthesis of glycolipid immunostimulants RC-529 and cyclodextrins: A new kind of amphiphilic molecules bearing hydro- CRX-524. Tetrahedron Lett 47:2087–2092.
phobic parts. Tetrahedron Lett 47:8925–8927.
Beck A, Bussat M-C, Zorn N, Robillard V, Klinguer-Hamour C, Chenu S, Baigude H, Katsuraya K, Tokunaga S, Fujiwara N, Satoyama M, Magome T, Goetsch L, Corvaı¨a N, Van Dorsselaer A, Haeuw J-F. 2005. Character- Okuyama K, Borjihan G, Uryu T. 2005. Synthesis of an oligosacchar- ization by liquid chromatography combined with mass spectrometry of ide-polylysine dendrimer with reducing sugar terminals leading to monoclonal anti-IGF-1 receptor antibodies produced in CHO and NS0 acquired immunodeficiency syndrome vaccine preparation. J Polym Sci cells. J Chromatogr B 819:203–218.
A 43:2195–2206.
Bedini E, Carabellese A, Comegna D, De Castro C, Parrilli M. 2006.
Bailey MJ, Hooker AD, Adams CS, Zhang S, James DC. 2005. A platform for Synthetic oligorhamnans related to the most common O-chain high-throughput molecular characterization of recombinant monoclo- backbone from phytopathogenic bacteria. Tetrahedron 62:8474– nal antibodies. J Chromatogr B 826:177–187.
Bakker H, Rouwendal GJA, Karnoup AS, Florack DEA, Stoopen GM, Bekesova´ S, Kova´cik V, Chmelik J, Kova´c P. 2006. Negative electrospray, ion Helsper JPFG, Van Ree R, Van Die I, Bosch D. 2006. An antibody trap multistage mass spectrometry of synthetic fragments of the O-PS of produced in tobacco expressing a hybrid b-1,4-galactosyltransferase is Vibrio cholerae O:1. Eur J Mass Spectrom 12:43–50.
essentially devoid of plant carbohydrate epitopes. Proc Natl Acad Sci Belgacem O, Bowdler A, Brookhouse I, Brancia FL, Raptakis E. 2006.
Dissociation of biomolecules using a ultraviolet matrix-assisted laser Baldwin MA. 2005. Analysis of glycosylphosphatidylinositol protein desorption/ionisation time-of-flight/curved field reflectron tandem anchors: The prion protein. Methods Enzymol 405:172–187.
mass spectrometer equipped with a differential-pumped collision cell.
Rapid Commun Mass Spectrom 20:1653–1660.
Balen B, Krsnik-Rasol M, Zamfir AD, Milosˇevic J, Vakhrushev SY, Peter- Katalinic J. 2006. Glycoproteomic survey of Mammillaria gracillis Be´lot F, Guerreiro C, Baleux F, Mulard LA. 2005. Synthesis of two linear tissues grown in vitro. J Proteome Res 5:1658–1666.
PADRE conjugates bearing a deca- or pentadecasaccharide B epitope aspotential synthetic vaccines against Shigella flexneri serotype 2a Bao X, Muramatsu T, Sugahara K. 2005. Demonstration of the pleiotrophin- infection. Chem Eur J 11:1625–1635.
binding oligosaccharide sequences isolated from chondroitin sulfate/dermatan sulfate hybrid chains of embryonic pig brains. J Biol Chem Bencu´r P, Steinkellner H, Svoboda B, Mucha J, Strasser R, Kolarich D, Hann S, Ko¨llensperger G, Glo¨ssl J, Altmann F, Mach L. 2005. Arabidopsisthaliana b1,2-xylosyltransferase: An unusual glycosyltransferase with Bao X, Nishimura S, Mikami T, Yamada S, Itoh N, Sugahara K. 2004.
the potential to act at multiple stages of the plant N-glycosylation Chondroitin sulfate/dermatan sulfate hybrid chains from embryonic pig pathway. Biochem J 388:515–525.
brain, which contain a higher proportion of L-iduronic acid than thosefrom adult pig brain, exhibit neuritogenic and growth factor binding Bera A, Herbert S, Jakob A, Vollmer W, Go¨tz F. 2005. Why are pathogenic activities. J Biol Chem 279:9765–9776.
staphylococci so lysozyme resistant? The peptidoglycan O-acetyl-transferase OatA is the major determinant for lysozyme resistance of Bao X, Pava˜o MSG, Cabral dos Santos J, Sugahara K. 2005. A functional Staphylococcus aureus. Mol Microbiol 55:778–787.
dermatan sulfate epitope containing iduronate(2-O-sulfate)a1-3Gal-NAc(6-O-sulfate) disaccharide in the mouse brain. Demonstration Berenson CS, Sayles KB, Huang J, Reinhold VN, Garlipp MA, Yohe HC.
using a novel monoclonal antibody raised against dermatan sulfate of 2005. Nontypeable Haemophilus influenzae-binding gangliosides of ascidian Ascidia nigra. J Biol Chem 280:23184–23193.
human respiratory (HEp-2) cells have a requisite lacto/neolacto core Barboza M, Duschak VG, Fukuyama Y, Nonami H, Erra-Balsells R, Cazzulo structure. FEMS Immunol Med Microbiol 45:171–182.
JJ, Couto AS. 2005. Structural analysis of the N-glycans of the Beyer M, Koch H, Fischer K. 2006. Role of hemicelluloses in the formation of major cysteine proteinase of Trypanosoma cruzi. FEBS J 272:3803– chromophores during heat treatment of bleached chemical pulps.
Macromol Symp 232:98–106.
Bardor M, Cabrera G, Rudd PM, Dwek RA, Cremata JA, Lerouge P. 2006.
Bianchi A, Ferrario D, Bernardi A. 2006. A facile stereoselective synthesis of Analytical strategies to investigate plant N-glycan profiles in the context a-glycosyl ureas. Carbohydr Res 341:1438–1446.
of plant-made pharmaceuticals. Curr Opin Struct Biol 16:576–583.
Bianchi A, Russo A, Bernardi A. 2005. Neo-glycoconjugates: Stereoselective Barton CJ, Tailford LE, Welchman H, Zhang Z, Gilbert HJ, Dupree P, Goubet synthesis of a-glycosyl amides via Staudinger ligation reactions.
F. 2006. Enzymatic fingerprinting of Arabidopsis pectic polysacchar- Tetrahedron Asym 16:381–386.
Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES Bidasee KR, Zhang Y, Shao CH, Wang M, Patel KP, Dincer U ¨ D, Besch HRJ.
Brik A, Ficht S, Yang Y-Y, Bennett CS, Wong C-H. 2006a. Sugar-assisted 2004. Diabetes increases formation of advanced glycation end products ligation of N-linked glycopeptides with broad sequence tolerance at the on sarco(endo)plasmic reticulum Ca2þ-ATPase. Diabetes 53:463– ligation junction. J Am Chem Soc 128:15026–15033.
Brik A, Yang Y-Y, Ficht S, Wong C-H. 2006b. Sugar-assisted glycopeptide Bindscha¨dler P, Noti C, Castagnetti E, Seeberger PH. 2006. Synthesis of a ligation. J Am Chem Soc 128:5626–5627.
potential 10E4 tetrasaccharide antigen involved in scrapie patho- Bruce AF, Gounaris K. 2006. Characterisation of a secreted N-acetyl-b- genesis. Helv Chim Acta 89:2591–2610.
hexosaminidase from Trichinella spiralis. Mol Biochem Parasitol Biroccio A, Urbani A, Massoud R, di Ilio C, Sacchetta P, Bernardini S, Cortese C, Federici G. 2005. A quantitative method for the analysis of Brunner A, Kolarich D, Voglmeir J, Paschinger K, Wilson IBH. 2006.
glycated and glutathionylated hemoglobin by matrix-assisted laser Comparative characterisation of recombinant invertebrate and verte- desorption ionization-time of flight mass spectrometry. Anal Biochem brate peptide O-xylosyltransferases. Glycoconj J 23:543–554.
Buchowiecka A, Bielecki S. 2003. Determination of the regiochemistry of D- Bisht KS, Bhatt S, Muppalla K. 2006. Synthesis of glycolipid analogs via glucal glucosylation by endo-b-1,3-glucanase GA Cellulomonas highly regioselective macrolactonization catalyzed by lipase. Tetrahe- cellulans using CI MS. Biocatal Biotransform 21:1–5.
dron Lett 47:8645–8649.
Budnik BA, Lee RS, Steen JAJ. 2006. Global methods for protein Biskup MB, Mu¨ller JU, Weingart R, Schmidt RR. 2005. New methods for the glycosylation analysis by mass spectrometry. Biochim Biophys Acta generation of carbohydrate arrays on glass slides and their evaluation.
Burguiere A, Hitchen PG, Dover LG, Kremer L, Ridell M, Alexander DC, Liu Black C, Poile C, Langley J, Herniman J. 2006. The use of pencil lead as a J, Morris HR, Minnikin DE, Dell A, Besra GS. 2005. LosA, a key matrix and calibrant for matrix-assisted laser desorption/ionisation.
glycosyltransferase involved in the biosynthesis of a novel family of Rapid Commun Mass Spectrom 20:1053–1060.
glycosylated acyltrehalose lipooligosaccharides from Mycobacterium Blattner R, Furneaux RH, Ludewig M. 2006. Syntheses of oligomannosides marinum. J Biol Chem 280:42124–42133.
in solution and on a soluble polymer support: A comparison. Carbohydr Buskas T, Ingale S, Boons G-J. 2006. Glycopeptides as versatile tools for Res 341:299–321.
glycobiology. Glycobiology 16:113R–136R.
Blixt O, Vasiliu D, Allin K, Jacobsen N, Warnock D, Razi N, Paulson JC, Buskas T, Li Y, Boons G-J. 2005. Synthesis of a dimeric Lewis antigen and the Bernatchez S, Gilbert M, Wakarchu W. 2005. Chemoenzymatic evaluation of the epitope specificity of antibodies elicited in mice. Chem synthesis of 2-azidoethyl-ganglio-oligosaccharides GD3, GT3, GM2, Eur J 11:5457–5467.
GD2, GT2, GM1, and GD1a. Carbohydr Res 340:1963–1972.
Busse K, Averbeck M, Anderegg U, Arnold K, Simon JC, Schiller J. 2006.
Blundell CD, Almond A. 2006. Enzymatic and chemical methods for the The signal-to-noise ratio as a measure of HA oligomer concentration: A generation of pure hyaluronan oligosaccharides with both odd and even MALDI-TOF MS study. Carbohydr Res 341:1065–1070.
numbers of monosaccharide units. Anal Biochem 353:236–247.
Bykova NV, Rampitsch C, Krokhin O, Standing K, Ens W. 2006.
Bodine KD, Gin DY, Gin MS. 2005. Highly convergent synthesis of C3- or Determination and characterization of site-specific N-glycosylation C2-symmetric carbohydrate macrocycles. Org Lett 7:4479–4482.
using MALDI-Qq-TOF tandem mass spectrometry: Case study with aplant protease. Anal Chem 78:1093–1103.
Bohn ML, Colombo MI, Stortz CA, Ru´veda EA. 2006. A comparative study of the influence of some protecting groups on the reactivity of Cabrera JC, Messiaen J, Cambier P, Van Cutsem P. 2006. Size, acetylation and glucosamine acceptors with a galactofuranosyl donor. Carbohydr Res concentration of chitooligosaccharide elicitors determine the switch from defence involving PAL activation to cell death and water peroxideproduction in Arabidopsis cell suspensions. Physiol Plant 127:44–56.
Bollati-Fogolı´n M, Forno G, Nimtz M, Conradt H, Etcheverrigaray M, Kratje R. 2005. Temperature reduction in cultures of hGM-CSF-expressing Cabrera JC, Van Cutsem P. 2005. Preparation of chitooligosaccharides with CHO cells: Effect on productivity and product quality. Biotechnol Prog degree of polymerization higher than 6 by acid or enzymatic degradation of chitosan. Biochem Eng J 25:165–172.
Bondili JS, Castilho A, Mach L, Glo¨ssl J, Steinkellner H, Altmann F, Strasser Cai C, Zhou K, Wu Y, Wu L. 2006. Enhanced liver targeting of 5-fluorouracil R. 2006. Molecular cloning and heterologous expression of b1,2- using galactosylated human serum albumin as a carrier molecule. J xylosyltransferase and core a1,3-fucosyltransferase from maize.
Drug Target 14:55–61.
Cai Y-Z, Xing J, Sun M, Zhan Z-Q, Corke H. 2005. Phenolic antioxidants Bortolotti F, De Paoli G, Tagliaro F. 2006. Carbohydrate-deficient transferrin (hydrolyzable tannins, flavonols, and anthocyanins) identified by LC- (CDT) as a marker of alcohol abuse: A critical review of the literature ESI-MS and MALDI-QIT-TOF MS from Rosa chinensis flowers. J 2001–2005. J Chromatogr B 841:96–109.
Agric Food Chem 53:9940–9948.
Bo¨sch A, Nimtz M, Mischnick P. 2006. Mechanistic studies on cationic ring- Campa C, Coslovi A, Flamigni A, Rossi M. 2006. Overview on advances in opening polymerisation of cyclodextrin derivatives using various Lewis capillary electrophoresis-mass spectrometry of carbohydrates: A acids. Cellulose 13:493–507.
tabulated review. Electrophoresis 27:2027–2050.
Bouillon C, Meyer A, Vidal S, Jochum A, Chevolot Y, Cloarec J-P, Praly J-P, Carpenter C, Nepogodiev SA. 2005. Synthesis of a aMan(1-3)aMan(1- Vasseur J-J, Morvan F. 2006. Microwave assisted ‘‘click'' chemistry for 2)aMan glycocluster presented on a b-cyclodextrin scaffold. Eur J Org the synthesis of multiple labeled-carbohydrate oligonucleotides on solid support. J Org Chem 71:4700–4702.
Carpentier M, Morelle W, Coddeville B, Pons A, Masson M, Mazurier J, Brancia FL, Bereszczak JZ, Lapolla A, Fedele D, Baccarin L, Seraglia R, Legrand D. 2005. Nucleolin undergoes partial N- and O-glycosylations Traldi P. 2006. Comprehensive analysis of glycated human serum in the extranuclear cell compartment. Biochemistry 44:5804–5815.
albumin tryptic peptides by off-line liquid chromatography followed by Casabuono AC, D'Antuono A, Sato Y, Nonami H, Ugalde R, Lepek V, Erra- MALDI analysis on a time-of-flight/curved field reflectron tandem mass Balsells R, Couto AS. 2006. A matrix-assisted laser desorption/ spectrometer. J Mass Spectrom 41:1179–1185.
ionization mass spectrometry approach to the lipid A from Mesorhi- Brecker L, Wicklein D, Moll H, Fuchs EC, Becker W-M, Petersen A. 2005.
zobium loti. Rapid Commun Mass Spectrom 20:2175–2182.
Structural and immunological properties of arabinogalactan polysac- Cato D, Buskas T, Boons G-J. 2005. Highly efficient stereospecific charides from pollen of timothy grass (Phleum pratense L.). Carbohydr preparation of Tn and TF building blocks using thioglycosyl donors Res 340:657–663.
and the Ph2SO/Tf2O. J Carbohydr Chem 24:503–516.
Mass Spectrometry Reviews DOI 10.1002/mas Cauet G, Strub J-M, Leize E, Wagner E, Van Dorsselaer A, Lusky M. 2005.
Choudhury B, Carlson RW, Goldberg JB. 2005. The structure of the Identification of the glycosylation site of the adenovirus type 5 fiber lipopolysaccharide from a galU mutant of Pseudomonas aeruginosa protein. Biochemistry 44:5453–5460.
serogroup-O11. Carbohydr Res 340:2761–2772.
Cavalier DM, Keegstra K. 2006. Two xyloglucan xylosyltransferases catalyze Choudhury B, Leoff C, Saile E, Wilkins P, Quinn CP, Kannenberg EL, the addition of multiple xylosyl residues to cellohexaose. J Biol Chem Carlson RW. 2006. The structure of the major cell wall polysaccharide of Bacillus anthracis is species-specific. J Biol Chem 281:27932– Chait BT, Wang R, Beavis RC, Kent SBH. 1993. Protein ladder sequencing.
Chow LP, Chiu LL, Khoo KH, Peng HJ, Yang SY, Huang SW, Su SN. 2005.
Chaiyaso T, H-kittikun A, Zimmermann W. 2006. Biocatalytic acylation of Purification and structural analysis of the novel glycoprotein allergen carbohydrates with fatty acids from palm fatty acid distillates. J Ind Cyn d 24, a pathogenesis-related protein PR-1, from Bermuda grass Microbiol Biotechnol 33:338–342.
pollen. FEBS J 272:6218–6227.
Chan T-WD, Chan PK, Tang KY. 2006. Determination of molecular weight Christensen B, Nielsen MS, Haselmann KF, Petersen TE, Sorensen ES. 2005.
profile for a bioactive b-(1-3) polysaccharides (Curdlan). Anal Chim Post-translationally modified residues of native human osteopontin are Acta 556:226–236.
located in clusters: Identification of 36 phosphorylation and five O-glycosylation sites and their biological implications. Biochem J Chang R, Vo T-T, Finney NS. 2006. Synthesis of the C1-phosphonate analog of UDP-GlcNAc. Carbohydr Res 341:1998–2004.
Chung S-W, Joo H-S, Jang K-S, Lee H-J, Lee S-G, Kim B-G. 2006.
Chen G, Bai Q, Geng X. 2006. Preparation of a concanavalin A immobilized Galactosylation and sialylation of terminal glycan residues of human affinity column and its application in the structural analysis of immunoglobulin G using bacterial glycosyltransferases with in situ ribonuclease B. Chin J Chromatogr 24:425–432.
regeneration of sugar-nucleotides. Enzyme Microb Technol 39:60–66.
Chen H, Yan X, Zhu P, Lin J. 2006a. Antioxidant activity and hepatoprotective Cid MB, Alfonso F, Martı´n-Lomas M. 2005. A study on the influence of the potential of agaro-oligosaccharides in vitro and in vivo. Nutr J 5:31.
structure of the glycosyl acceptors on the stereochemistry of the Chen L, Zhao X-E, Lai D, Song Z, Kong F. 2006b. A concise and practical glycosylation reactions with 2-azido-2-deoxy-hexopyranosyl trichlor- synthesis of antigenic globotriose, a-D-Gal-(1-4)-b-D-Gal-(1-4)-b-D- oacetimidates. Chem Eur J 11:928–938.
Glc. Carbohydr Res 341:1174–1180.
Cindric M, Bindila L, Cepo T, Peter-Katalinic J. 2006. Mass spectrometry- Chen W, Lee PJ, Stapels M. 2006. The use of mass spectrometry to determine based glycoproteomic approach involving lysine derivatization for location and extent of N-glycosylation on folate binding protein from structural characterization of recombinant human erythropoietin.
bovine milk. Rapid Commun Mass Spectrom 20:313–316.
J Proteome Res 5:3066–3076.
Chen X, Hu L, Su X, Kong L, Ye M, Zou H. 2006c. Separation and detection of Cipollo JF, Awad AM, Costello CE, Hirschberg CB. 2005. N-glycans of compounds in Honeysuckle by integration of ion-exchange chromatog- Caenorhabditis elegans are specific to developmental stages. J Biol raphy fractionation with reversed-phase liquid chromatography- atmospheric pressure chemical ionization mass spectrometer and Ciucanu I. 2006. Per-O-methylation reaction for structural analysis of matrix-assisted laser desorption/ionization time-of-flight mass spec- carbohydrates by mass spectrometry. Anal Chim Acta 576:147–155.
trometry analysis. J Pharm Biomed Anal 40:559–570.
Claridge TDW, Long DD, Baker CM, Odell B, Grant GH, Edwards AA, Chen Y-J, Chen S-H, Chien Y-Y, Chang Y-W, Liao H-K, Chang C-Y, Jan M-D, Tranter GE, Fleet GWJ, Smith MD. 2005. Helix-forming carbohydrate Wang K-T, Lin C-C. 2005a. Carbohydrate-encapsulated gold nano- amino acids. J Org Chem 70:2082–2090.
particles for rapid target-protein identification and binding-epitopemapping. ChemBioChem 6:1169–1173.
Comelli EM, Head SR, Gilmartin T, Whisenant T, Haslam SM, North SJ, Wong N-K, Kudo T, Narimatsu H, Esko JD, Drickamer K, Dell A, Chen Y-L, Leguijt R, Redlich H. 2006. Propane-1,3-diyl dithioacetals of Paulson JC. 2006a. A focused microarray approach to functional carbohydrates; Part 7: Preparation of aminocyclitols and iminosugars glycomics: Transcriptional regulation of the glycome. Glycobiology by intramolecular cyclizations of D-glucosamine propane-1,3-diyl Chen Z, Huang J, Suurs P, Schols HA, Voragen AGJ. 2005b. Granule size Comelli EM, Sutton-Smith M, Yan Q, Amado M, Panico M, Gilmartin T, affects the acetyl substitution on amylopectin populations in potato and Whisenant T, Lanigan CM, Head SR, Goldberg D, Morris HR, Dell A, sweet potato starches. Carbohydr Polym 62:333–337.
Paulson JC. 2006b. Activation of murine CD4þ and CD8þ Tlymphocytes leads to dramatic remodeling of N-linked glycans. J Cheshev P, Marra A, Dondoni A. 2006. Direct epoxidation of D-glucal and D- galactal derivatives with in situ generated DMDO. Carbohydr Res341:2714–2716.
Co´rdova A, IIbrahem I, Casas J, Sunde´n H, Engqvist M, Reyes E. 2005.
Amino acid catalyzed neogenesis of carbohydrates: A plausible ancient Chevalier R, Colsch B, Afonso C, Baumann N, Tabet J-C, Mallet J-M. 2006.
transformation. Chem Eur J 11:4772–4784.
Synthetic sulfated glucuronosyl paragloboside (SGPG) and its use forthe detection of autoimmune peripheral neuropathies. Tetrahedron Corsaro MM, Gambacorta A, Iadonisi A, Lanzetta R, Naldi T, Nicolaus B, Romano I, Ummarino S, Parrilli M. 2006. Structural determination of Chinthaka SDM, Chu Y, Rannulu NS, Rodgers MT. 2006. Sodium cation the O-Chain polysaccharide from the lipopolysaccharide of the affinities of MALDI matrices determined by guided ion beam tandem haloalkaliphilic Halomonas pantelleriensis bacterium. Eur J Org mass spectrometry: Application to benzoic acid derivatives. J Phys Chem A 110:1426–1437.
Coˆte´ GL, Sheng S. 2006. Penta-, hexa-, and heptasaccharide acceptor Choi S-S, Ha S-H. 2006. Characterization of ionized maltooligosaccharides products of alternansucrase. Carbohydr Res 341:2066–2072.
by sodium cation in MALDI-TOFMS depending on the molecular size.
Cottiglia F, Bonsignore L, Casu L, Deidda D, Pompei R, Casu M, Floris C.
Bull Korean Chem Soc 27:1243–1245.
2005. Phenolic constituents from Ephedra nebrodensis. Nat Prod Res Choi SS, Park TH. 2006. Enhancement of sialyltransferase-catalyzed transfer of sialic acid onto glycoprotein oligosaccharides using silkworm Cox KM, Sterling JD, Regan JT, Gasdaska JR, Frantz KK, Peele CG, Black A, hemolymph and its 30K protein. J Mol Catal B Enzym 43:128–132.
Passmore D, Moldovan-Loomis C, Srinivasan M, Cuison S, Cardarelli Choisnard L, Ge ze A, Putaux J-L, Wong Y-S, Wouessidjew D. 2006.
PM, Dickey LF. 2006. Glycan optimization of a human monoclonal Nanoparticles of b-cyclodextrin esters obtained by self-assembling of antibody in the aquatic plant Lemna minor. Nat Biotechnol 24:1591– biotransesterified b-cyclodextrins. Biomacromolecules 7:515–520.
Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES Cozzolino R, Malvagna P, Spina E, Giori A, Fuzzati N, Anelli A, Garozzo del Castillo Busto ME, Montes-Bayo´n M, Blanco-Gonza´lez E, Meija J, Sanz- D, Impallomeni G. 2006. Structural analysis of the polysaccharides Medel A. 2005. Strategies to study human serum transferrin isoforms from Echinacea angustifolia radix. Carbohydr Polym 65:263– using integrated liquid chromatography ICPMS, MALDI-TOF, and ESI-Q-TOF detection: Application to chronic alcohol abuse. Anal Creaser CS, Ratcliffe L. 2006. Atmospheric pressure matrix-assisted laser desorption/ionisation mass spectrometry: A review. Curr Anal Chem Dellagreca M, Previtera L, Zarrelli A. 2005. A new xyloside from Chenopodium album. Nat Prod Res 19:87–90.
Crispin M, Harvey DJ, Chang VT, Yu C, Aricescu AR, Jones EY, Davis SJ, Demelbauer UM, Plematl A, Josic D, Allmaier G, Rizzi A. 2005. On Dwek RA, Rudd PM. 2006. Inhibition of hybrid- and complex-type the variation of glycosylation in human plasma derived antithrombin.
glycosylation reveals the presence of the GlcNAc transferase I- J Chromatogr A 1080:15–21.
independent fucosylation pathway. Glycobiology 16:748–756.
Deng C, O'Neill MA, York WS. 2006. Selective chemical depolymerization Crombez L, Marques B, Lenormand JL, Mouz N, Polack B, Trocme C, of rhamnogalacturonans. Carbohydr Res 341:474–484.
Toussaint B. 2005. High level production of secreted proteins: Example Deng S, Gangadharmath U, Chang C-WT. 2006. Sonochemistry: A powerful of the human tissue inhibitor of metalloproteinases 1. Biochem Biophys way of enhancing the efficiency of carbohydrate synthesis. J Org Chem Res Commun 337:908–915.
Cui SW. 2005. Structural analysis of polysaccharides. In: Cui SW, editor.
Dengjel J, Rammensee H-G, Stevanovic S. 2005. Glycan side chains on Food carbohydrates: Chemistry, physical properties and applications.
naturally presented MHC class II ligands. J Mass Spectrom 40:100– Baca Raton, FL: Taylor and Francis. pp 105–160.
Cumpstey I. 2006. New oligosaccharide analogues: Non-glycosidically Deshayes C, Laval F, Montrozier H, Daffe´ M, Etienne G, Reyrat J-M. 2005.
linked thioether-bridged pseudodisaccharides. Synlett:1711–1714.
A glycosyltransferase involved in biosynthesis of triglycosylated da Silva BP, Campos PO, Parente JP. 2006. Chemical structure and biological glycopeptidolipids in Mycobacterium smegmatis: Impact on surface activity of steroidal saponins from Furcraea gigantea. Chem Nat properties. J Bacteriol 187:7283–7291.
Compd 42:316–321.
Devakumar A, Thompson MS, Reilly JP. 2005. Fragmentation of oligosac- Damager I, Jensen MT, Olsen CE, Blennow A, Møller BL, Svensson B, charide ions with 157 nm vacuum ultraviolet light. Rapid Commun Motawia MS. 2005. Chemical synthesis of a dual branched malto- Mass Spectrom 19:2313–2320.
decaose: A potential substrate for a-amylases. ChemBioChem 6:1224– Di Fabio G, Randazzo A, D'Onofrio J, Ausı´n C, Pedroso E, Grandas A, De Napoli L, Montesarchio D. 2006. Cyclic phosphate-linked oligosac- De Castro C, Carannante A, Lanzetta R, Liparoti V, Molinaro A, Parrilli M.
charides: Synthesis and conformational behavior of novel cyclic 2006. Core oligosaccharide structure from the highly phytopathogenic oligosaccharide analogues. J Org Chem 71:3395–3408.
Agrobacterium tumefaciens TT111 and conformational analysis of the Di Patrizi L, Rosati F, Guerranti R, Pagani R, Gerwig GJ, Kamerling JP. 2006.
putative rhamnan epitope. Glycobiology 16:1272–1280.
Structural characterization of the N-glycans of gpMuc from Mucuna De Castro C, Molinaro A, Lanzetta R, Holst O, Parrilli M. 2005. The linkage pruriens seeds. Glycoconj J 23:599–609.
between O-specific caryan and core region in the lipopolysaccharide of Di Stasio B, Frochot C, Dumas E, Even P, Zwier J, Mu¨ller A, Didelon J, Burkholderia caryophylli is furnished by a primer monosaccharide.
Guillemin F, Viriot M-L, Barberi-Heyob M. 2005. The 2- Carbohydr Res 340:1802–1807.
aminoglucosamide motif improves cellular uptake and photodynamic de Jesu´s Pe´rez J, Jua´rez S, Chen D, Scott CL, Hartweck LM, Olszewski NE, activity of tetraphenylporphyrin. Eur J Med Chem 40:1111–1122.
Garcı´a JA. 2006. Mapping of two O-GlcNAc modification sites in the Dicko MH, Hilhorst R, Traore AS. 2005. Indigenous West African plants as capsid protein of the potyvirus Plum pox virus. FEBS Lett 580:5822– novel sources of polysaccharide degrading enzymes: Application in the reduction of the viscosity of cereal porridges. Afr J Biotechnol 4:1095– de la Salle H, Mariotti S, Angenieux C, Gilleron M, Garcia-Alles L-F, Malm D, Berg T, Paoletti S, Maıˆtre B, Mourey L, Salamero J, Cazenave Didraga M, Barroso B, Bischoff R. 2006. Recent developments in JP, Hanau D, Mori L, Puzo G, De Libero G. 2005. Assistance of proteoglycan purification and analysis. Curr Pharm Anal 2:323–337.
microbial glycolipid antigen processing by CD1e. Science 310:1321– Didraga M, Barroso B, de Vries M, Kerstjens H, Postma D, Bischoff R. 2006.
Purification of decorin core protein from human lung tissue. J De Lorenzo C, Cozzolino R, Carpentieri A, Pucci P, Laccetti P, D'Alessio G.
Chromatogr A 1123:151–159.
2005. Biological properties of a human compact anti-ErbB2 antibody.
Dignam CF, Randall LA, Blacken RD, Cunningham PR, Lester S-KG, Brown MJ, French SC, Aniagyei SE, Wenzel TJ. 2006. Carboxymethylated de Paz JL, Noti C, Seeberger PH. 2006. Microarrays of synthetic heparin cyclodextrin derivatives as chiral NMR discriminating agents. Tetrahe- oligosaccharides. J Am Chem Soc 128:2766–2767.
dron Asym 17:1199–1208.
de Paz J-L, Ojeda R, Barrientos A ´ G, Penade´s S, Martı´n-Lomas M. 2005.
Dinadayala P, Kaur D, Berg S, Amin AG, Vissa VD, Chatterjee D, Brennan Synthesis of a Ley neoglycoconjugate and Ley-functionalized gold PJ, Crick DC. 2006. Genetic basis for the synthesis of the glyconanoparticles. Tetrahedron Asym 16:149–158.
immunomodulatory mannose caps of lipoarabinomannan in Mycobac- de Rijke E, Out P, Niessen WMA, Ariese F, Gooijer C, Brinkman UAT. 2006.
terium tuberculosis. J Biol Chem 281:20027–20035.
Analytical separation and detection methods for flavonoids. J Disney MD, Hook DF, Namoto K, Seeberger PH, Seebach D. 2005. N-linked Chromatogr A 1112:31–63.
glycosylated b-peptides are resistant to degradation by glycoamidase A.
de Segura AG, Alcalde M, Bernabe´ M, Ballesteros A, Plou FJ. 2006.
Chem Biodiversity 2:1624–1634.
Synthesis of methyl a-D-glucooligosaccharides by entrapped dextran- Dmochowska B, Skorupa E, Pellowska-Januszek L, Czarkowska M, Sikorski sucrase from Leuconostoc mesenteroides B-1299. J Biotechnol 124: A, Wisniewski A. 2006. Preparation, single-crystal X-ray diffraction and high-resolution NMR spectroscopic analyses of N-[(1,4-anhydro- DeFrees S, Wang Z-G, Xing R, Scott AE, Wang J, Zopf D, Gouty DL, Sjoberg ER, Panneerselvam K, Brinkman-Van der Linden ECM, Bayer iodide. Carbohydr Res 341:1916–1921.
RJ, Tarp MA, Clausen H. 2006. GlycoPEGylation of recombinant Dondoni A, Catozzi N, Marra A. 2005. Concise and practical synthesis of C- therapeutic proteins produced in Escherichia coli. Glycobiology glycosyl ketones from sugar benzothiazoles and their transformation into chiral tertiary alcohols. J Org Chem 70:9257–9268.
Mass Spectrometry Reviews DOI 10.1002/mas Dondoni A, Marra A. 2006. C-glycoside clustering on calix[4]arene, Enebro J, Karlsson S. 2006. Improved matrix-assisted laser desorption/ adamantane, and benzene scaffolds through 1,2,3-triazole linkers.
ionisation time-of-flight mass spectrometry of carboxymethyl cellu- J Org Chem 71:7546–7557.
lose. Rapid Commun Mass Spectrom 20:3693–3698.
Dondoni A, Massi A, Minghini E. 2006. A facile and general entry to C- Engelmann K, Kinlough CL, Mu¨ller S, Razawi H, Baldus SE, Hughey RP, glycosyl (R)- and (S)-b-amino acid pairs from glycosyl cyanides Hanisch F-G. 2005. Transmembrane and secreted MUC1 probes show through enamino ester intermediates. Synlett:539–542.
trafficking-dependent changes in O-glycan core profiles. Glycobiology Dondoni A, Nuzzi A. 2006. Access to piperidine imino-C-glycosides via stereoselective thiazole-based aminohomologation of pyranoses. J Org Enomoto Y, Sugita M, Matsunaga I, Naka T, Sato A, Kawashima T, Shimizu K, Takahashi H, Norose Y, Yano I. 2005. Temperature-dependent Dreisewerd K, Ko¨lbl S, Peter-Katalinic J, Berkenkamp S, Pohlentz G. 2006.
biosynthesis of glucose monomycolate and its recognition by CD1- Analysis of native milk oligosaccharides directly from thin-layer restricted T cells. Biochem Biophys Res Commun 337:452–456.
chromatography plates by matrix-assisted laser desorption/ionization Erb WJ, Hanton SD, Owens KG. 2006. A study of gas-phase cationization in orthogonal-time-of-flight mass spectrometry with a glycerol matrix. J matrix-assisted laser desorption/ionization time-of-flight mass spec- Am Soc Mass Spectrom 17:139–150.
trometry. Rapid Commun Mass Spectrom 20:2165–2169.
Dreisewerd K, Mu¨thing J, Rohlfing A, Meisen I, Vukelic Z, Peter-Katalinic J, Ernst RK, Adams KN, Moskowitz SM, Kraig GM, Kawasaki K, Stead CM, Hillenkamp F, Berkenkamp S. 2005. Analysis of gangliosides directly Trent S, Miller SI. 2006. The Pseudomonas aeruginosa lipid A from thin-layer chromatography plates by infrared matrix-assisted laser deacylase: Selection for expression and loss within the cystic fibrosis desorption/ionization orthogonal time-of-flight mass spectrometry with airway. J Bacteriol 188:191–201.
a glycerol matrix. Anal Chem 77:4098–4107.
Ervin LA, Ball LE, Crouch RK, Schey KL. 2005. Phosphorylation and Du W, Gervay-Hague J. 2005. Efficient synthesis of a-galactosyl ceramide glycosylation of bovine lens MP20. Invest Ophthalmol Vis Sci 46:627– analogues using glycosyl iodide donors. Org Lett 7:2063–2065.
Du Y, Wei G, Cheng S, Hua Y, Linhardt RJ. 2006. HClO4–SiO2 catalyzed Erwin AL, Allen S, Ho DK, Bonthius PJ, Jarisch J, Nelson KL, Tsao DL, glycosylation using sugar trichloroacetimidates as glycosyl donors.
Unrath WCT, Watson MEJ, Gibson BW, Apicella MA, Smith AL. 2006.
Tetrahedron Lett 47:307–310.
Role of lgtC in resistance of nontypeable Haemophilus influenzae strain Dubber M, Patel A, Sadalapure K, Aumu¨ller I, Lindhorst TK. 2006. Synthesis R2866 to human serum. Infect Immun 74:6226–6235.
of functionalized amphiphilic glycoconjugates and glycoclusters. Eur J Esua MF, Rauwald J-W. 2006. Novel bioactive maloyl glucans from Aloe vera gel: Isolation, structure elucidation and in vitro bioassays. Carbohydr Dubber M, Sperling O, Lindhorst TK. 2006. Oligomannoside mimetics by Res 341:355–364.
glycosylation of octopus glycosides and their investigation as inhibitors Ethier M, Krokhin O, Ens W, Standing KG, Wilkins JA, Perreault H. 2005.
of type 1 fimbriae-mediated adhesion of Escherichia coli. Org Biomol Global and site-specific detection of human integrin a5b1 glycosylation Chem 4:3901–3912.
using tandem mass spectrometry and the StrOligo algorithm. Rapid Duchesne L, Tissot B, Rudd TR, Dell A, Fernig DG. 2006. N-glycosylation of Commun Mass Spectrom 19:721–727.
fibroblast growth factor receptor 1 regulates ligand and heparan sulfate Ethier M, Saba JA, Ens W, Standing KG, Perreault H. 2002. Automated co-receptor binding. J Biol Chem 281:27178–27189.
structural assignment of derivatized complex N-linked oligosaccharides Duffy MS, Morris HR, Dell A, Appleton JA, Haslam SM. 2006. Protein from tandem mass spectra. Rapid Commun Mass Spectrom 16:1743– glycosylation in Parelaphostrongylus tenuis—First description of the Gala1-3Gal sequence in a nematode. Glycobiology 16:854– Ethier M, Saba JA, Spearman M, Krokhin O, Butler M, Ens W, Standing KG, Perreault H. 2003. Application of the StrOligo algorithm for the Dumon C, Bosso C, Utille JP, Heyraud A, Samain E. 2006. Production of automated structure assignment of complex N-linked glycans from Lewis x tetrasaccharides by metabolically engineered Escherichia coli.
glycoproteins using tandem mass spectrometry. Rapid Commun Mass Dziadek S, Kowalczyk D, Kunz H. 2005. Synthetic vaccines consisting of Etienne G, Laval F, Villeneuve C, Dinadayala P, Abouwarda A, Zerbib D, tumor-associated MUC1 glycopeptide antigens and bovine serum Galamba A, Daffe´ M. 2005. The cell envelope structure and properties albumin. Angew Chem Int Ed Engl 44:7624–7630.
of Mycobacterium smegmatis mc2155: Is there a clue for the uniquetransformability of the strain? Microbiology 151:2075–2086.
Edwards KJ, Allen S, Gibson BW, Campagnari AA. 2005a. Characterization of a cluster of three glycosyltransferase enzymes essential for Faid V, Evjen G, Tollersrud O-K, Michalski J-C, Morelle W. 2006. Site- Moraxella catarrhalis lipooligosaccharide assembly. J Bacteriol specific glycosylation analysis of the bovine lysosomal a-mannosidase.
Edwards KJ, Schwingel JM, Datta AK, Campagnari AA. 2005b. Multiplex Faiz JA, Spencer N, Pikramenou Z. 2005. Acetylenic cyclodextrins for PCR assay that identifies the major lipooligosaccharide serotype multireceptor architectures: Cups with sticky ends for the formation of expressed by Moraxella catarrhalis clinical isolates. J Clin Microbiol extension wires and junctions. Org Biomol Chem 3:4239–4245.
Falzarano D, Krokhin O, Wahl-Jensen V, Seebach J, Wolf K, Schnittler H-J, Ehara K, Saka S. 2005. Decomposition behavior of cellulose in supercritical Feldmann H. 2006. Structure-function analysis of the soluble water, subcritical water and their combined treatments. J Wood Sci glycoprotein, sGP, of ebola virus. ChemBioChem 7:1605–1611.
Fan G-T, Pan Y, Lu K-C, Cheng Y-P, Lin W-C, Lin S, Lin C-H, Wong C-H, El Alaoui A, Schmidt F, Monneret C, Florent J-C. 2006. Protecting groups for Fang J-M, Lin C-C. 2005a. Synthesis of a-galactosyl ceramide and the glucuronic acid: Application to the synthesis of new paclitaxel (taxol) related glycolipids for evaluation of their activities on mouse derivatives. J Org Chem 71:9628–9636.
splenocytes. Tetrahedron 61:1855–1862.
El Hamidi A, Tirsoaga A, Novikov A, Hussein A, Caroff M. 2005.
Fan X, She Y-M, Bagshaw RD, Callahan JW, Schachter H, Mahuran DJ.
Microextraction of bacterial lipid A: Easy and rapid method for mass 2005b. Identification of the hydrophobic glycoproteins of Caenorhab- spectrometric characterization. J Lipid Res 46:1773–1778.
ditis elegans. Glycobiology 15:952–964.
Eleute´rio MIP, Schimmel J, Ritter G, Costa MdC, Schmidt RR. 2006.
Faraco V, Palmieri G, Festa G, Monti M, Sannia G, Giardina P. 2005. A new Synthesis of saponins with allobetulin and glycyrrhetic acid as subfamily of fungal subtilases: Structural and functional analysis of a aglycones. Eur J Org Chem:5293–5304.
Pleurotus ostreatus member. Microbiology 151:457–466.
Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES Farah MA, Bose S, Lee J-H, Jung H-C, Kim Y. 2005. Analysis of glycated glycoside hydrolase family of core 1 type O-glycan-specific endo-a-N- insulin by MALDI-TOF mass spectrometry. Biochim Biophys Acta acetylgalactosaminidase from Bifidobacterium longum. J Biol Chem Faure´ R, Saura-Valls M, Brumer H, III, Planas A, Cottaz S, Driguez H. 2006.
Fujita K, Yamamoto K. 2006. A remodeling system for the oligosaccharide Synthesis of a library of xylogluco-oligosaccharides for active-site chains on glycoproteins with microbial endo-b-N-acetylglucosamini- mapping of xyloglucan endo-transglycosylase. J Org Chem 71:5151– dases. Biochim Biophys Acta 1760:1631–1635.
Fujita Y, Naka T, Doi T, Yano I. 2005b. Direct molecular mass determination Fekete A, Hoogerhout P, Zomer G, Kubler-Kielb J, Schneerson R, Robbins of trehalose monomycolate from 11 species of mycobacteria by JB, Pozsgay V. 2006. Synthesis of octa- and dodecamers of D-ribitol-1- MALDI-TOF mass spectrometry. Microbiology 151:1443–1452.
phosphate and their protein conjugates. Carbohydr Res 341:2037– Fujita Y, Naka T, McNeil MR, Yano I. 2005c. Intact molecular character- ization of cord factor (trehalose 6,6'-dimycolate) from nine species of Fenaille F, Parisod V, Visani P, Populaire S, Tabet J-C, Guy PA. 2006.
mycobacteria by MALDI-TOF mass spectrometry. Microbiology Modifications of milk constituents during processing: A preliminary benchmarking study. Int Dairy J 16:728–739.
Fujiwaki T, Tasaka M, Takahashi N, Kobayashi H, Murakami Y, Shimada T, Fernandez-Megia E, Correa J, Rodriguez-Meizoso I, Riguera R. 2006. A click Yamaguchi S. 2006. Quantitative evaluation of sphingolipids using approach to unprotected glycodendrimers. Macromolecules 39:2113– delayed extraction matrix-assisted laser desorption ionization time-of- flight mass spectrometry with sphingosylphosphorylcholine as an Ferrara C, Brunker P, Suter T, Moser S, Puntener U, Umana P. 2006a.
internal standard. J Chromatogr B 832:97–102.
Modulation of therapeutic antibody effector functions by glycosylation Fujiyama K, Misaki R, Katsura A, Tanaka T, Furukawa A, Omasa T, Seki T.
engineering: Influence of Golgi enzyme localization domain and co- 2006. N-linked glycan structures of a mouse monoclonal antibody expression of heterologous b-1, 4-N-acetylglucosaminyltransferase III produced from tobacco BY2 suspension-cultured cells. J Biosci Bioeng and Golgi alpha-mannosidase II. Biotechnol Bioeng 93:851–861.
Ferrara C, Stuart F, Sondermann P, Bru¨nker P, Uman˜a P. 2006b. The Fukui K, Kameyama A, Mukai Y, Takahashi K, Ikeda N, Akiyama Y, carbohydrate at FcgRIIIa Asn-162. An element required for high Narimatsu H. 2006. A computational study of structure-reactivity affinity binding to non-fucosylated IgG glycoforms. J Biol Chem relationships in Na-adduct oligosaccharides in collision-induced dissociation reactions. Carbohydr Res 341:624–633.
Figueroa-Perez I, Stadelmaier A, Deininger S, von Aulock S, Hartung T, Fukuyama Y, Kolender AA, Nishioka M, Nonami H, Matulewicz MC, Erra- Schmidt RR. 2006. Synthesis of Staphylococcus aureus lipoteichoic Balsells R, Cerezo AS. 2005. Matrix-assisted ultraviolet laser acid derivatives for determining the minimal structural requirements for desorption/ionization time-of-flight mass spectrometry of b-(1-3), b- cytokine induction. Carbohydr Res 341:2901–2911.
(1-4)-xylans from Nothogenia fastigiata using nor-harmane as matrix.
Figueroa-Perez I, Stadelmaier A, Morath S, Hartung T, Schmidt RR. 2005.
Rapid Commun Mass Spectrom 19:349–358.
Synthesis of structural variants of Staphylococcus aureus lipoteichoic Fumoto M, Hinou H, Matsushita T, Kurogochi M, Ohta T, Ito T, Yamada K, acid (LTA). Tetrahedron Asym 16:493–506.
Takimoto A, Kondo H, Inazu T, Nishimura S-I. 2005a. Molecular Flieger M, Kantorova´ M, Halada P, Kuzma M, Pazoutova´ S, Stodulkova´ E, transporter between polymer platforms: Highly efficient chemoenzy- Kolı´nska´ R. 2005. Oligosaccharides produced by submerged cultures of matic glycopeptide synthesis by the combined use of solid-phase and Claviceps africana and Claviceps sorghi. Folia Microbiol 50:198– water-soluble polymer supports. Angew Chem Int Ed Engl 44:2534– Fraser-Reid B, Lu J, Jayaprakash KN, Lo´pez JC. 2006. Synthesis of a 28-mer Fumoto M, Hinou H, Ohta T, Ito T, Yamada K, Takimoto A, Kondo H, oligosaccharide core of Mycobacterial lipoarabinomannan (LAM) Shimizu H, Inazu T, Nakahara Y, Nishimura S-I. 2005b. Combinatorial requires only two n-pentenyl orthoester progenitors. Tetrahedron Asym synthesis of MUC1 glycopeptides: Polymer blotting facilitates chemical and enzymatic synthesis of highly complicated mucinglycopeptides. J Am Chem Soc 127:11804–11818.
Fraysse N, Lindner B, Kacynski Z, Sharpova L, Holst O, Niehaus K, Poinot V.
2005. Sinorhizobium meliloti strain 1021 produces a low-molecular- Furneaux RH, Landersjo CL, McCullough JL, Severn WB. 2005. A novel mass capsular polysaccharide that is a homopolymer of 3-deoxy- phosphatidylinositol manno-oligosaccharide (dPIM-8) from Gordonia manno-oct-2-ulosonic acid harboring a phospholipid anchor. Glycobi- sputi. Carbohydr Res 340:1618–1624.
ology 15:101–108.
Furuike T, Sadamoto R, Niikura K, Monde K, Sakairi N, Nishimura S-I. 2005.
Freeze HH, Aebi M. 2005. Altered glycan structures: The molecular basis of Chemical and enzymatic synthesis of glycocluster having seven sialyl congenital disorders of glycosylation. Curr Opin Struct Biol 15:490– lewis X arrays using b-cyclodextrin as a key scaffold material.
Freire T, D'Alayer J, Bay S. 2006. Efficient monitoring of enzymatic Fuse T, Ando H, Imamura A, Sawada N, Ishida H, Kiso M, Ando T, Li S-C, Li Y-T. 2006. Synthesis and enzymatic susceptibility of a series of novel ionization time of flight mass spectrometry for process optimization.
GM2 analogs. Glycoconj J 23:329–343.
Bioconjug Chem 17:559–564.
Gama CI, Hsieh-Wilson LC. 2005. Chemical approaches to deciphering the Fresno S, Jime´nez N, Izquierdo L, Merino S, Corsaro MM, De Castro C, glycosaminoglycan code. Curr Opin Chem Biol 9:609–619.
Parrilli M, Naldi T, Regue´ M, Toma´s JM. 2006. The ionic interaction of Gandolfi-Donadı´o L, Gola G, de Lederkremer RM, Gallo-Rodriguez C. 2006.
Klebsiella pneumoniae K2 capsule and core lipopolysaccharide.
Synthesis of a-D-Galf-(1-2)-D-galactitol and a-D-Galf-(1-2)[b-D-Galf- (1-3)]-D-galactitol, oligosaccharide derivatives from Bacteroides cellu- Frolov A, Hoffmann P, Hoffmann R. 2006. Fragmentation behavior of losolvens glycoproteins. Carbohydr Res 341:2487–2497.
glycated peptides derived from D-glucose, D-fructose and D-ribose in Gao C, Miyoshi E, Uozumi N, Takamiya R, Wang X, Noda K, Gu J, Honke K, tandem mass spectrometry. J Mass Spectrom 41:1459–1469.
Wada Y, Taniguchi N. 2005a. Bisecting GlcNAc mediates the binding of Frolov A, Singer D, Hoffmann R. 2006. Site-specific synthesis of Amadori- annexin V to Hsp47. Glycobiology 15:1067–1075.
modified peptides on solid phase. J Peptide Sci 12:389–395.
Gao Y, Eguchi A, Kakehi K, Lee YC. 2005b. Synthesis and molecular Fujita K, Oura F, Nagamine N, Katayama T, Hiratake J, Sakata K, Kumagai H, recognition of carbohydrate-centered multivalent glycoclusters by a Yamamoto K. 2005a. Identification and molecular cloning of a novel plant lectin RCA120. Bioorg Med Chem 13:6151–6157.
Mass Spectrometry Reviews DOI 10.1002/mas Geiser H, Silvescu C, Reinhold V. 2006. Structural approaches to Goldberg D, Bern M, Li B, Lebrilla CB. 2006. Automatic determination of O- glycoproteomics. In: Smejkal GB, Lazarev A, editors. Separation glycan structure from fragmentation spectra. J Proteome Res 5:1429– methods in proteomics. Boca Raton, FL: CRC Press. pp 321-343.
Gemma E, Lahmann M, Oscarson S. 2006. Synthesis of monodeoxy Goldberg D, Sutton-Smith M, Paulson J, Dell A. 2005. Automatic annotation analogues of the trisaccharide a-D-Glcp-(1-3)-a-D-Manp-(1-2)-a-D- of matrix-assisted laser desorption/ionization N-glycan spectra. Pro- ManpOMe recognised by Calreticulin/Calnexin. Carbohydr Res Gomes RA, Miranda HV, Silva MS, Graca G, Coelho AV, Ferreira AE, Gerlach D, Schlott B, Za¨hringer U, Schmidt K-H. 2005. N-acetyl-D- Cordeiro C, Freire AP. 2006. Yeast protein glycation in vivo by galactosamine/N-acetyl-D-glucosamine-recognizing lectin from the methylglyoxal: Molecular modification of glycolytic enzymes and heat snail Cepaea hortensis: Purification, chemical characterization, cloning shock proteins. FEBS J 273:5273–5287.
and expression in E. coli. FEMS Immunol Med Microbiol 43:223– Gomez SR, Xing DK-L, Corbel MJ, Coote J, Parton R, Yuen C-T. 2006.
Development of a carbohydrate binding assay for the B-oligomer of Geyer H, Geyer R. 2006. Strategies for analysis of glycoprotein glycosyla- pertussis toxin and toxoid. Anal Biochem 356:244–253.
tion. Biochim Biophys Acta 1764:1853–1869.
Go´mez-Garcı´a M, Benito JM, Rodrı´guez-Lucena DR, Yu J-X, Chmurski K, Geyer H, Wuhrer M, Resemann A, Geyer R. 2005. Identification and Mellet CO, Gallego RG, Maestre A, Defaye J, Ferna´ndez JMG. 2005.
characterization of keyhole limpet hemocyanin N-glycans mediating Probing secondary carbohydrate-protein interactions with highly dense cross-reactivity with Schistosoma mansoni. J Biol Chem 280:40731– cyclodextrin-centered heteroglycoclusters: The heterocluster effect. J Am Chem Soc 127:7970–7971.
Ghera BB, Fache F, Parrot-Lopez H. 2006. Use of the olefin metathesis Gormann R, Kaloga M, Ferreira D, Marais JPJ, Kolodziej H. 2006.
reaction for highly efficient b-cyclodextrin modification. Tetrahedron Newbouldiosides A-C, phenylethanoid glycosides from the stem bark of Newbouldia laevis. Phytochemistry 67:805–811.
Ghesquie re B, Van Damme J, Martens L, Vandekerckhove J, Gevaert K. 2006.
Goto K, Miura T, Mizuno M. 2005. Synthesis of peptides and oligosacchar- Proteome-wide characterization of N-glycosylation events by diagonal ides by using a recyclable fluorous tag. Tetrahedron Lett 46:8293–8297.
chromatography. J Proteome Res 5:2438–2447.
Goubet F, Stro¨m A, Que´me´ner B, Stephens E, Williams MAK, Dupree P.
Ghosh P, Ghosal P, Thakur S, Lerouge P, Loutelier-Bourhis CL, Driouich A, 2006. Resolution of the structural isomers of partially methylesterified Ray B. 2005. Polysaccharides from Sesamum indicum meal: Isolation oligogalacturonides by polysaccharide analysis using carbohydrate gel and structural features. Food Chem 90:719–726.
electrophoresis. Glycobiology 16:29–35.
Gibbons HS, Kalb SR, Cotter RJ, Raetz CRH. 2005. Role of Mg2þ and pH in Gray JSS, Montgomery R. 2006. Asymmetric glycosylation of soybean seed the modification of Salmonella lipid A after endocytosis by macrophage coat peroxidase. Carbohydr Res 341:198–209.
tumour cells. Mol Microbiol 55:425–440.
Graziani A, Amer H, Zamyatina A, Hofinger A, Kosma P. 2005. Synthesis of Gibeaut DM, Pauly M, Bacic A, Fincher GB. 2005. Changes in cell wall C-glycosides related to glycero-b-D-manno-heptoses. Tetrahedron polysaccharides in developing barley (Hordeum vulgare) coleoptiles.
Asym 16:167–175.
Greimel P, Jabs S, Storch S, Cherif S, Honke K, Braulke T, Thiem J. 2006. In Gibson KJC, Gilleron M, Constant P, Sichi B, Puzo G, Besra GS, Nigou J.
vitro sulfation of N-acetyllactosaminide by soluble recombinant human 2005. A lipomannan variant with strong TLR-2-dependent pro- b-Gal-30-sulfotransferase. Carbohydr Res 341:918–924.
inflammatory activity in Saccharothrix aerocolonigenes. J Biol Chem Griebl A, Lange T, Weber H, Milacher W, Sixta H. 2006. Xylo- oligosaccharide (XOS) formation through hydrothermolysis of xylan Gilleron M, Garton NJ, Nigou J, Brando T, Puzo G, Sutcliffe IC. 2005.
derived from viscose process. Macromol Symp 232:107–120.
Characterization of a truncated lipoarabinomannan from the actino- Grombe R, Gouzy M-F, Nitschke M, Komber H, Werner C. 2006. Preparation mycete Turicella otitidis. J Bacteriol 187:854–861.
and characterization of glycosylated maleic anhydride copolymer thin Gilleron M, Lindner B, Puzo G. 2006. MS/MS Approach for characterization films. Colloids Surf A 284–285:295–300.
of the fatty acid distribution on mycobacterial phosphatidyl-myo- Gru¨n CH, van Vliet SJ, Schiphorst WECM, Bank CMC, Meyer S, van Die I, inositol mannosides. Anal Chem 78:8543–8548.
van Kooyk Y. 2006. One-step biotinylation procedure for carbohydrates Gilleron M, Nigou J, Nicolle D, Quesniaux V, Puzo G. 2006. The acylation to study carbohydrate-protein interactions. Anal Biochem 254:54–63.
state of mycobacterial lipomannans modulates innate immunity Gu G, Liu H, Pinto BM. 2006. Facile synthesis of sulfonium ion derivatives of response through toll-like receptor 2. Chem Biol 13:39–47.
1,5-anhydro-5-thio-L-fucitol as potential a-L-fucosidase inhibitors.
Glebko LI, Krasovskaj NP, Strigina LI, Ulanova KP, Denisenko VA, Carbohydr Res 341:2478–2486.
Dmitrenok PS. 2002. Triterpene glycosides from Pulsatilla chinensis.
Gu L, Lin Y, Qu L, Sun Y-P. 2006. Carbon nanotubes as a scaffold to display Russ Chem Bull 51:1945–1950.
paired sugars in solution. Biomacromolecules 7:400–402.
Glover KJ, Weerapana E, Chen MM, Imperiali B. 2006. Direct biochemical Gue´rardel Y, Chang L-Y, Maes E, Huang C-J, Khoo K-H. 2006. Glycomic evidence for the utilization of UDP-bacillosamine by PglC, an essential survey mapping of zebrafish identifies unique sialylation pattern.
glycosyl-1-phosphate transferase in the Campylobacter jejuni N-linked glycosylation pathway. Biochemistry 45:5343–5350.
Gue´rardel Y, Leleu D, Coppin A, Lie´nard L, Slomianny C, Strecker G, Ball S, Glover KJ, Weerapana E, Imperiali B. 2005. In vitro assembly of the Tomavo S. 2005. Amylopectin biogenesis and characterization in undecaprenylpyrophosphate linked heptasaccharide for prokaryotic the protozoan parasite Toxoplasma gondii, the intracellular develop- N-linked glycosylation. Proc Natl Acad Sci USA 102:14255– ment of which is restricted in the HepG2 cell line. Microbes Infect Glover KJ, Weerapana E, Numao S, Imperiali B. 2005. Chemoenzymatic Guerrini M, Guglieri S, Santarsiero R, Vismara E. 2005. Synthesis and synthesis of glycopeptides with PglB, a bacterial oligosaccharyl characterisation of hexa- and tetrasaccharide mimics from acetobro- transferase from Campylobacter jejuni. Chem Biol 12:1311–1315.
momaltotriose and acetobromomaltose, and of C-disaccharide mimics Godevac D, Mandic B, Vajs V, Tesˇevic V, Menkovic N, Janackovic P, from acetobromoglucose, obtained by electrochemical reduction on Milosavljevic S. 2006. Triterpenoid saponins and iridoid glycosides silver. Tetrahedron Asym 16:243–253.
from the aerial parts of Cephalaria pastricensis. Biochem Syst Ecol Guillaumie F, Justesen SFL, Mutenda KE, Roepstorff P, Jensen KJ, Thomas ORT. 2006. Fractionation, solid-phase immobilization and chemical Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES degradation of long pectin oligogalacturonides. Initial steps towards Haneda K, Takeuchi M, Tagashira M, Inazu T, Toma K, Isogai Y, Hori M, sequencing of oligosaccharides. Carbohydr Res 341:118–129.
Kobayashi K, Takeuchi M, Takegawa M, Yamamoto M. 2006. Chemo- Gupta S, Sage A, Singh AK. 2005. Screening and confirmation of enzymatic synthesis of eel calcitonin glycosylated at two sites with the recombinant human erythropoietin and darbepoietin-a in spiked same and different carbohydrate structures. Carbohydr Res 341:181– plasma samples from drug-free horses. Anal Chim Acta 552:96– Hanneman AJ, Rosa JC, Ashline D, Reinhold VN. 2006. Isomer and glycomer Gur'yanov O, Gorshkova T, Kabel M, Schols H, Van Dam JEG. 2006.
complexities of core GlcNAcs in Caenorhabditis elegans. Glycobiol- Structural characterization of tissue-specific galactan from flax fibers by ogy 16:874–890.
1H NMR and MALDI TOF mass spectrometry. Russ J Bioorg Chem Haque A, Kotake T, Tsumuraya Y. 2005. Mode of action of b-glucuronidase from Aspergillus niger on the sugar chains of arabinogalactan-protein.
Gustavsson MT, Persson PV, Iversen T, Martinelle M, Hult K, Teeri TT, Biosci Biotechnol Biochem 69:2170–2177.
Brumer H III. 2005. Modification of cellulose fiber surfaces by use of a Harcum SW. 2005. Protein glycosylation. In: Ozturk SS, Hu W-S, editors.
lipase and a xyloglucan endotransglycosylase. Biomacromolecules Cell culture technology for pharmaceutical and cell-based therapies.
Boca Raton, FL: CRC Press. pp 113-154.
Hackenberger CPR, O'Reilly MK, Imperiali B. 2005. Improving glycopep- Harrison RL, Jarvis DL. 2006. Protein N-glycosylation in the baculovirus- tide synthesis: A convenient protocol for the preparation of b- insect cell expression system and engineering of insect cells to produce glycosylamines and the synthesis of glycopeptides. J Org Chem 70: ‘‘mammalianized'' recombinant glycoproteins. Adv Virus Res 68:159– Hada N, Jin Y, Takeda T, Ohtsuka I, Yokoyama S. 2006a. Syntheses of new Hartley G, Taylor R, Prior J, Newstead S, Hitchen PG, Morris HR, Dell A, model compounds related to an antigenic epitope from Bupleurum Titball RW. 2006. Grey variants of the live vaccine strain of Francisella falcatum L. and their distributions in various ganglioside-phospholipid tularensis lack lipopolysaccharide O-antigen, show reduced ability to monolayers. Chem Pharm Bull 54:1281–1284.
survive in macrophages and do not induce protective immunity in mice.
Hada N, Oka J, Nishiyama A, Takeda T. 2006b. Stereoselective synthesis of 1,2-cis-galactosides: Synthesis of a glycolipid containing Gala1-6Gal Hartman J, Albertsson A-C, Sjo¨berg J. 2006. Surface- and bulk-modified component from Zygomycetes species. Tetrahedron Lett 47:6647– galactoglucomannan hemicellulose films and film laminates for versatile oxygen barriers. Biomacromolecules 7:1983–1989.
Hada N, Sato K, Jin Y, Takeda T. 2005. Synthesis of new peptidic Harvey DJ. 1999. Matrix-assisted laser desorption/ionization mass spec- glycoclusters derived from b-alanine. Part 2: Optionally modulated trometry of carbohydrates. Mass Spectrom Rev 18:349–451.
distance between side-chain branched points. Chem Pharm Bull 53: Harvey DJ. 2005a. Fragmentation of negative ions from carbohydrates: Part 2, Fragmentation of high-mannose N-linked glycans. J Am Soc Mass Hada N, Sonoda Y, Takeda T. 2006. Synthesis of a novel glycosphingolipid from the millipede, Parafontaria laminata armigera, and the assembly Harvey DJ. 2005b. Fragmentation of negative ions from carbohydrates: Part of its carbohydrate moiety into multivalent structures. Carbohydr Res 1; Use of nitrate and other anionic adducts for the production of negative ion electrospray spectra from N-linked carbohydrates. J Am Soc Mass Hagihara S, Totani K, Ito Y. 2006. Exploration of oligosaccharide-protein interactions in glycoprotein quality control by synthetic approaches.
Harvey DJ. 2005c. Fragmentation of negative ions from carbohydrates: Part Chem Record 6:290–302.
3, Fragmentation of hybrid and complex N-linked glycans. J Am SocMass Spectrom 16:647–659.
Haginoya E, Hojo H, Nakahara Y, Nakahara Y, Nabeshima K, Toole BP, Watanabe Y. 2006. Synthesis of a glycosylated peptide thioester by the Harvey DJ. 2005d. Proteomic analysis of glycosylation: Structural determi- Boc strategy and its application to segment condensation. Biosci nation of N- and O-linked glycans by mass spectrometry. Expert Rev Biotechnol Biochem 70:1338–1349.
Hainrichson M, Pokrovskaya V, Shallom-Shezifi D, Fridman M, Belakhov V, Harvey DJ. 2005e. Structural determination of N-linked glycans by matrix- Shachar D, Yaron S, Baasov T. 2005. Branched aminoglycosides: assisted laser desorption/ionization and electrospray ionization mass Biochemical studies and antibacterial activity of neomycin B spectrometry. Proteomics 5:1774–1786.
derivatives. Bioorg Med Chem 13:5797–5807.
Harvey DJ. 2006. Analysis of carbohydrates and glycoconjugates by matrix- assisted laser desorption/ionization mass spectrometry: An update Hajjar AM, Harvey MD, Shaffer SA, Goodlett DR, Sjo¨stedt A, Edebro H, covering the period 1999–2000. Mass Spectrom Rev 25:595–662.
Forsman M, Bystro¨m M, Pelletier M, Wilson CB, Miller SI, Skerrett SJ,Ernst RK. 2006. Lack of in vitro and in vivo recognition of Francisella Harvey DJ. 2008a. Analysis of carbohydrates and glycoconjugates by matrix- tularensis subspecies lipopolysaccharide by toll-like receptors. Infect assisted laser desorption/ionization mass spectrometry: An update covering the period 2001–2002. Mass Spectrom Rev 27:125–201.
Halkes KM, Carvalho de Souza A, Maljaars CEP, Gerwig GJ, Kamerling JP.
Harvey DJ. 2009. Analysis of carbohydrates and glycoconjugates by matrix- 2005. A facile method for the preparation of gold glyconanoparticles assisted laser desorption/ionization mass spectrometry: An update from free oligosaccharides and their applicability in carbohydrate- covering the period 2003–2004. Mass Spectrom Rev 28:273–361.
protein interaction studies. Eur J Org Chem:3650–3659.
Harvey DJ, Bousfield GR. 2005. Differentiation between sulphated and Hamcerencu M, Popa M, Riess G, Ritter H, Alupei V. 2005. Unsaturated phosphated carbohydrates in low-resolution matrix-assisted laser esters of cyclodextrin—Synthesis and characterization. Cellulose desorption/ionization mass spectra. Rapid Commun Mass Spectrom Chem Technol 39:389–413.
Hamed AI, Plaza A, Balestrieri ML, Mahalel UA, Springuel IV, Oleszek W, Harvey DJ, Dwek RA, Rudd PM. 2006. Determining the structure of glycan Pizza C, Piacente S. 2006. Cardenolide glycosides from Pergularia moieties by mass spectrometry. In: Coligan JE, Dunn BM, Speicher tomentosa and their proapoptotic activity in Kaposi's sarcoma cells. J DW, Wingfield PT, editors. Current protocols in protein science. New Nat Prod 69:1319–1322.
York: J. Wiley and Sons Inc. p UNIT 12.17.
Hanashima S, Inamori K-I, Manabe S, Taniguchi N, Ito Y. 2006. Systematic Hasegawa T, Umeda M, Numata M, Li C, Bae A-H, Fujisawa T, Haraguchi S, synthesis of bisubstrate-type inhibitors of N-acetylglucosaminyltrans- Sakurai K, Shinkai S. 2006. ‘Click chemistry' on polysaccharides: A ferases. Chem Eur J 12:3449–3462.
convenient, general, and monitorable approach to develop (1-3)-b-D- Mass Spectrometry Reviews DOI 10.1002/mas glucans with various functional appendages. Carbohydr Res 341: Hodoniczky J, Zheng YZ, James DC. 2005. Control of recombinant monoclonal antibody effector functions by Fc N-glycan remodeling Hasegawa Y, Miyauchi M, Takashima Y, Yamaguchi H, Harada A. 2005.
in vitro. Biotechnol Prog 21:1644–1652.
Supramolecular polymers formed from b-cyclodextrins dimer linked by Hoffman M, Jia Z, Pen˜a MJ, Cash M, Harper A, Blackburn ARI, Darvill A, poly(ethylene glycol) and guest dimers. Macromolecules 38:3724– York WS. 2005. Structural analysis of xyloglucans in the primary cell walls of plants in the subclass Asteridae. Carbohydr Res 340:1826– Hashimoto K, Goto S, Kawano S, Aoki-Kinoshita KF, Ueda N, Hamajima M, Kawasaki T, Kanehisa M. 2006. KEGG as a glycome informatics Ho¨ije A, Sandstro¨m C, Roubroeks JP, Andersson R, Gohil S, Gatenholm P.
resource. Glycobiology 16:63R–70R.
2006. Evidence of the presence of 2-O-b-D-xylopyranosyl-a-L- Haslam SM, Khoo KH, Dell A. 2006. Sequencing of oligosaccharides and arabinofuranose side chains in barley husk arabinoxylan. Carbohydr glycoproteins. In: Wong C-H, editor. Carbohydrate-based drug discovery. Hoboken, NJ: Wiley VCH. pp 461–482.
Hojo H, Matsumoto Y, Nakahara Y, Ito E, Suzuki Y, Suzuki M, Suzuki A, Haslam SM, North SJ, Dell A. 2006. Mass spectrometric analysis of N- and O- Nakahara Y. 2005. Chemical synthesis of 23 kDa glycoprotein by glycosylation of tissues and cells. Curr Opin Struct Biol 16:584–591.
repetitive segment condensation: A synthesis of MUC2 basal motifcarrying multiple O-GalNAc moieties. J Am Chem Soc 127:13720– Hattori K, Kenmoku A, Mizuguchi T, Ikeda D, Mizuno M, Inazu T. 2006.
Saccharide-branched cyclodextrins as targeting drug carriers. J InclPhenom Macrocyclic Chem 56:9–15.
Ho¨lemann A, Stocker BL, Seeberger PH. 2006. Synthesis of a core arabinomannan oligosaccharide of Mycobacterium tuberculosis. J Hayase F, Usui T, Watanabe H. 2006. Chemistry and some biological effects Org Chem 71:8071–8088.
of model melanoidins and pigments as Maillard intermediates. MolNutr Food Res 50:1171–1179.
Holmes BJ, Petrucci GA. 2006. Water-soluble oligomer formation from acid- catalyzed reactions of levoglucosan in proxies of atmospheric aqueous Hayashida O, Takaoka Y, Hamachi I. 2005. Synthesis and guest-binding study aerosols. Environ Sci Technol 40:4983–4989.
of polytopic multi(cyclophane) hosts. Tetrahedron Lett 46:6589–6592.
Holtan S, Bruheim P, Skjak-Braek G. 2006. Mode of action and subsite Hederos M, Konradsson P. 2005a. Synthesis of the core tetrasaccharide of studies of the guluronan block-forming mannuronan C-5 epimerases Trypanosoma cruzi glycoinositolphospholipids: Manp(1-6)-Manp(1- AlgE1 and AlgE6. Biochem J 395:319–329.
4)-6-(2-aminoethylphosphonic acid)-GlcNp(1-6)-myo-Ins-1-PO4. JOrg Chem 70:7196–7207.
Hossler P, Goh L-T, Lee MM, Hu W-S. 2006. GlycoVis: Visualizing glycan distribution in the protein N-glycosylation pathway in mammalian cells.
Hederos M, Konradsson P. 2005b. Efficient routes to ethyl-2-deoxy-2- Biotechnol Bioeng 95:946–960.
phthalimido-1-b-D-thio-galactosamine derivatives via epimerization ofthe corresponding glucosamine compounds. J Carbohydr Chem Hotha S, Kashyap S. 2006a. ‘‘Click chemistry'' inspired synthesis of pseudo- oligosaccharides and amino acid glycoconjugates. J Org Chem 71:364–367.
Heiner S, Detert H, Kuhn A, Kunz H. 2006. Hydrophilic photolabelling of glycopeptides from the murine liver-intestine (LI) cadherin recognition Hotha S, Kashyap S. 2006b. ‘‘Click chemistry'' inspired synthesis of pseudo- domain. Bioorg Med Chem 14:6149–6164.
oligosaccharides and amino acid glycoconjugates. J Org Chem 71:852.
Higai K, Aoki Y, Azuma Y, Matsumoto K. 2005. Glycosylation of site- Hsu J, Chang SJ, Franz AH. 2006. MALDI-TOF and ESI-MS analysis of specific glycans of a1-acid glycoprotein and alterations in acute and oligosaccharides labeled with a new multifunctional oligosaccharide chronic inflammation. Biochim Biophys Acta 1725:128–135.
tag. J Am Soc Mass Spectrom 17:194–204.
Huang K-T, Wu B-C, Lin C-C, Luo S-C, Chen C, Wong C-H, Lin C-C. 2006.
Higson AP, Ross AJ, Tsvetkov YE, Routier FH, Sizova OV, Ferguson MAJ, Multi-enzyme one-pot strategy for the synthesis of sialyl Lewis X- Nikolaev AV. 2005. Synthetic fragments of antigenic lipophosphogly- containing PSGL-1 glycopeptide. Carbohydr Res 341:2151–2155.
cans from Leishmania major and Leishmania mexicana and their use forcharacterisation of the Leishmania elongating a- Huang R, Mendis E, Kim S-K. 2005. Improvement of ACE inhibitory activity phosphate transferase. Chem Eur J 11:2019–2030.
of chitooligosaccharides (COS) by carboxyl modification. Bioorg MedChem 13:3649–3655.
Hilz H, de Jong LE, Kabel MA, Schols HA, Voragen AGJ. 2006. A comparison of liquid chromatography, capillary electrophoresis, and Huang Y, Konse T, Mechref Y, Novotny MV. 2002. Matrix-assisted laser mass spectrometry methods to determine xyloglucan structures in black desorption/ionization mass spectrometry compatible b-elimination of currants. J Chromatogr A 1133:275–286.
O-linked oligosaccharides. Rapid Commun Mass Spectrom 16:1199–1204.
Hinckley MB, Reynolds CM, Ribeiro AA, McGrath SC, Cotter RJ, Lauw FN, Huck CW, Bakry R, Huber LA, Bonn GK. 2006. Progress in capillary Golenbock DT, Raetz CRH. 2005. A Leptospira interrogans enzyme electrophoresis coupled to matrix-assisted laser desorption/ionization- with similarity to yeast Ste14p that methylates the 1-phosphate group of time of flight mass spectrometry. Electrophoresis 27:2063–2074.
lipid A. J Biol Chem 280:30214–30224.
Ibey BL, Beier HT, Rounds RM, Cote´ GL, Yadavalli VK, Pishko MV. 2005.
Hinz SWA, Pastink MI, van den Broek LAM, Vincken J-P, Voragen AGJ.
Competitive binding assay for glucose based on glycodendrimer- 2005a. Bifidobacterium longum endogalactanase liberates galactotriose fluorophore conjugates. Anal Chem 77:7039–7046.
from type I galactans. Appl Environ Microbiol 71:5501–5510.
Ibrahem I, Co´rdova A. 2005. Amino acid catalyzed direct enantioselective Hinz SWA, Verhoef R, Schols HA, Vincken J-P, Voragen AGJ. 2005b. Type I formation of carbohydrates: One-step de novo synthesis of ketoses.
arabinogalactan contains b-D-Galp-(1-3)-b-D-Galp structural elements.
Tetrahedron Lett 46:3363–3367.
Carbohydr Res 340:2135–2143.
Iglesias N, Abelenda JA, Rodino M, Sampedro J, Revilla G, Zarra I. 2006.
Hirano K, Sakai S, Ishikawa T, Avci FY, Linhardt RJ, Toida T. 2005.
Apoplastic glycosidases active against xyloglucan oligosaccharides of Preparation of the methyl ester of hyaluronan and its enzymatic Arabidopsis thaliana. Plant Cell Physiol 47:55–63.
degradation. Carbohydr Res 340:2297–2304.
Iijima J, Zhao Y, Isaji T, Kameyama A, Nakaya S, Wang X, Ihara H, Cheng X, Hitchen PG, Dell A. 2005. Bacterial glycoproteomics. Microbiology Nakagawa T, Miyoshi E, Kondo A, Narimatsu H, Taniguchi N, Gu J.
2006. Cell-cell interaction-dependent regulation of N-acetylglucosa- Hocquelet C, Blu J, Jankowski CK, Arseneau S, Buisson D, Mauclaire L.
minyltransferase III and the bisected N-glycans in GE11 epithelial cells: 2006. Synthesis of calixarene-cyclodextrin coupling products. Tetrahe- Involvement of E-cadherin-mediated cell adhesion. J Biol Chem Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES Immerzeel P, Eppink MM, De Vries SC, Schols HA, Voragen AGJ. 2006.
Jang-Lee J, North SJ, Sutton-Smith M, Goldberg D, Panico M, Morris H, Carrot arabinogalactan proteins are interlinked with pectins. Physiol Haslam S, Dell A. 2006. Glycomic profiling of cells and tissues by mass Plant 128:18–28.
spectrometry: Fingerprinting and sequencing methodologies. Methods Imre T, Schlosser G, Pocsfalvi G, Siciliano R, Molna´r-Szo¨llsi E Malorni A, Ve´key K. 2005. Glycosylation site analysis of human alpha- Jankowska M, Mada J. 2005. Glycosylation of allyl 2-acetamido-4,6-O- 1-acid glycoprotein (AGP) by capillary liquid chromatography– benzylidene-2-deoxy-a-D-glucopyranoside with bulky substituted gly- electrospray mass spectrometry. J Mass Spectrom 40:1472–1483.
cosyl donors. Carbohydr Res 340:2048–2051.
Inamori K, Mita S, Gu J, Mizuno-Horikawa Y, Miyoshi E, Dennis JW, Janssen S, Schmidt RR. 2005. Synthesis of ganglioside mimics for binding Taniguchi N. 2006. Demonstration of the expression and the enzymatic studies with myelin-associated glycoprotein (MAG). J Carbohydr activity of N-acetylglucosaminyltransferase IX in the mouse brain.
Chem 24:611–647.
Biochim Biophys Acta 1760:678–684.
Jayachandran R, Radcliffe CM, Royle L, Harvey DJ, Dwek RA, Rudd PM, Inamura S, Fujimoto Y, Kawasaki A, Shiokawa Z, Woelk E, Heine H, Lindner Karande AA. 2006. Oligosaccharides modulate the apoptotic activity of B, Inohara N, Kusumoto S, Fukase K. 2006. Synthesis of peptidoglycan glycodelin. Glycobiology 16:1052–1063.
fragments and evaluation of their biological activity. Org Biomol Chem Jia Z, Cash M, Darvill AG, York WS. 2005. NMR characterization of endogenously O-acetylated oligosaccharides isolated from tomato Inforzato A, Peri G, Doni A, Garlanda C, Mantovani A, Bastone A, (Lycopersicon esculentum) xyloglucan. Carbohydr Res 340:1818– Carpentieri A, Amoresano A, Pucci P, Roos A, Daha MR, Vincenti S, Gallo G, Carminati P, De Santis R, Salvatori G. 2006. Structure and Jin Y, Hada N, Oka J, Kanie O, Daikoku S, Kanie Y, Yamada H, Takeda T.
function of the long pentraxin PTX3 glycosidic moiety: Fine-tuning of 2006. Syntheses of model compounds related to an antigenic epitope in the interaction with C1q and complement activation. Biochemistry pectic polysaccharides from Bupleurum falcatum L. (II). Chem Pharm Bull 54:485–492.
Inoue Y, Miyauchi M, Nakajima H, Takashima Y, Yamaguchi H, Harada A.
Joddar B, Ramamurthi A. 2006. Elastogenic effects of exogenous hyaluronan 2006. Self-threading of a poly(ethylene glycol) chain in a cyclodextrin- oligosaccharides on vascular smooth muscle cells. Biomaterials ring: Control of the exchange dynamics by chain length. J Am Chem Soc Johansson SMC, Arnberg N, Elofsson M, Wadell G, Kihlberg J. 2005.
Ishiwata A, Akao H, Ito Y. 2006. Stereoselective synthesis of a fragment of Multivalent HSA conjugates of 3-sialyllactose are potent inhibitors mycobacterial arabinan. Org Lett 8:5525–5528.
of adenoviral cell attachment and infection. ChemBioChem 6:358– Ishiwata A, Akao H, Ito Y, Sunagawa M, Kusunose N, Kashiwazaki Y. 2006.
Synthesis and TNF-a inducing activities of mycoloyl-arabinan motif of Johnston BD, Jensen HH, Pinto BM. 2006. Synthesis of sulfonium sulfate mycobacterial cell wall components. Bioorg Med Chem 14:3049– analogues of disaccharides and their conversion to chain-extended homologues of salacinol: New glycosidase inhibitors. J Org Chem Ishiwata A, Ohta S, Ito Y. 2006. A stereoselective 1,2-cis glycosylation toward the synthesis of a novel N-linked glycan from the Gram-negative Jonke S, Liu K-G, Schmidt RR. 2006. Solid-phase oligosaccharide synthesis bacterium, Campylobacter jejuni. Carbohydr Res 341:1557–1573.
of a small library of N-glycans. Chem Eur J 12:1274–1290.
Ito H, Kameyama A, Sato T, Kiyohara K, Nakahara Y, Narimatsu H.
Joosten JAF, Tholen NTH, El Maate FA, Brouwer AJ, van Esse GW, Rijkers DTS, Liskamp RMJ, Pieters RJ. 2006. High-yielding microwave- construction and applications. Angew Chem Int Ed Engl 44:4547– assisted synthesis of triazole-linked glycodendrimers by copper- catalyzed [3 þ 2] cycloaddition. Eur J Org Chem:3182–3185.
Ito K, Miyagawa K, Matsumoto M, Yabuno S, Kawakami N, Hamaguchi T, Jørgensen CT, Svendsen A, Brask J. 2005. Enzymatic synthesis of Iizuka M, Minamiura N. 2006. Evidence for the transglycosylation of oligosaccharides from branched cyclodextrins. Carbohydr Res complex type oligosaccharides of glycoproteins by endo-b-N-acetyl- glucosaminidase HS. Arch Biochem Biophys 454:89–99.
Jung H, Kim YH, Kim S. 2005. Structural basis for the presence of a Itoh Y, Wang X, Hinnebusch J, Preston JF III, Romeo T. 2005.
monoglucosylated oligosaccharide in mature glycoproteins. Biochem Depolymerization of b-1,6-N-acetyl-D-glucosamine disrupts the integ- Biophys Res Commun 331:100–106.
rity of diverse bacterial biofilms. J Bacteriol 187:382–387.
Jung Y, Park H, Cho E, Jung S. 2005. Structural analyses of novel Ivleva VB, Sapp LM, O'Connor PB, Costello CE. 2005. Ganglioside analysis glycerophosphorylated a-cyclosophorohexadecaoses isolated from X.
by thin-layer chromatography matrix-assisted laser desorption/ioniza- campestris pv. campestris. Carbohydr Res 340:673–677.
tion orthogonal time-of-flight mass spectrometry. J Am Soc Mass Ju¨rs S, Thiem J. 2005. Alternative approaches towards glycosylated eight- membered ring compounds employing Claisen rearrangement of mono Izumi M, Tsuruta O, Kajihara Y, Yazawa S, Yuasa H, Hashimoto H. 2005.
and disaccharide allyl vinyl ether precursors. Tetrahedron Asym Synthesis and evaluation of 5-thio-L-fucose-containing oligosacchar- ide. Chem Eur J 11:3032–3038.
Kahler CM, Lyons-Schindler S, Choudhury B, Glushka J, Carlson RW, Jacques S, Rich JR, Ling CC, Bundle DR. 2006. Chemoenzymatic synthesis Stephens DS. 2006. O-acetylation of the terminal N-acetylglucosamine of GM3 and GM2 gangliosides containing a truncated ceramide of the lipooligosaccharide inner core in Neisseria meningitidis.
functionalized for glycoconjugate synthesis and solid phase applica- Influence on inner core structure and assembly. J Biol Chem tions. Org Biomol Chem 4:142–154.
Jacquet R, Favetta P, Elfakir C, Lafosse M. 2005. Characterization of a new Kajimura J, Rahman A, Hsu J, Evans MR, Gardner KH, Rick PD. 2006. O- methylated b-cyclodextrin with a low degree of substitution by matrix- acetylation of the enterobacterial common antigen polysaccharide is assisted laser desorption/ionization mass spectrometry and liquid catalyzed by the product of the yiaH gene of Escherichia coli K-12. J chromatography using evaporative light scattering detection. J Chromatogr A 1083:106–112.
Kaltashov IA, Eyles SJ. 2005. Mass spectrometry in biophysics: Conforma- Jain N, Kumar A, Chauhan S, Chauhan SMS. 2005. Chemical and tion and dynamics of biomolecules. Hoboken: John Wiley and Sons.
biochemical transformations in ionic liquids. Tetrahedron 61:1015– Kamekawa N, Hayama K, Nakamura-Tsuruta S, Kuno A, Hirabayashi J.
2006. A combined strategy for glycan profiling: A model study Mass Spectrometry Reviews DOI 10.1002/mas with pyridylaminated oligosaccharides. J Biochem (Tokyo) 140:337– Karginov VA, Yohannes A, Robinson TM, Fahmi NE, Alibek K, Hecht SM.
2006b. b-Cyclodextrin derivatives that inhibit anthrax lethal toxin.
Kameyama A, Kikuchi N, Nakaya S, Ito H, Sato T, Shikanai T, Takahashi Y, Bioorg Med Chem 14:33–40.
Takahashi K, Narimatsu H. 2005. A Strategy for identification of Karnoup AS, Turkelson V, Anderson WHK. 2005. O-linked glycosylation in oligosaccharide structures using observational multistage mass spectral maize-expressed human IgA1. Glycobiology 15:965–981.
library. Anal Chem 77:4719–4725.
Kasijima Y, Yamaguchi M, Hirai N, Ohmachi T, Yoshida T. 2006. In vivo Kameyama A, Nakaya S, Ito H, Kikuchi N, Angata T, Nakamura M, Ishida H- expression of UDP-N-acetylglucosamine: a-3-D-mannoside b-1,2-N- K, Narimatsu H. 2006. Strategy for simulation of CID spectra of N- acetylglucosaminyltransferase I (GnT-1) in Aspergillus oryzae and linked oligosaccharides toward glycomics. J Proteome Res 5:808–814.
effects on the sugar chain of a-amylase. Biosci Biotechnol Biochem Kamitakahara H, Nakatsubo F. 2005. Synthesis of diblock copolymers with cellulose derivatives. 1. Model study with azidoalkyl carboxylic acid Kasuya MCZ, Ikeda M, Hashimoto K, Sato T. 2005a. Effect of anomeric and cellobiosylamine derivative. Cellulose 12:209–219.
linkage on the sialylation of glycosides by cells. J Carbohydr Chem Kamitakahara H, Nakatsubo F, Klemm D. 2006. Block co-oligomers of tri-O- methylated and unmodified cello-oligosaccharides as model com- Kasuya MCZ, Ito A, Cusi R, Sato T, Hatanaka K. 2005b. Cellular uptake and pounds for methylcellulose and its dissolution/gelation behavior.
saccharide chain elongation of ‘‘fluoro-amphiphilic'' glycosides. Chem Lett 34:856–857.
Kamiya Y, Yamaguchi Y, Takahashi N, Arata Y, Kasai K-i, Ihara Y, Matsuo I, Kato K, Jeanneau C, Tarp MA, Benet-Page s A, Lorenz-Depiereux B, Bennett Ito Y, Yamamoto K, Kato K. 2005. Sugar-binding properties of VIP36, EP, Mandel U, Strom TM, Clausen H. 2006. Polypeptide GalNAc- an intracellular animal lectin operating as a cargo receptor. J Biol Chem transferase T3 and familial tumoral calcinosis. Secretion of fibroblast growth factor 23 requires O-glycosylation. J Biol Chem 281:18370– Kamoda S, Ishikawa R, Kakehi K. 2006. Capillary electrophoresis with laser- induced fluorescence detection for detailed studies on N-linked Kato K, Yamaguchi Y, Takahashi N, Nishimura M, Iwamoto S-I, Sekiya S, oligosaccharide profile of therapeutic recombinant monoclonal anti- Tanaka K. 2004. Discrimination of isomeric fragment ions observed in bodies. J Chromatogr A 1133:332–339.
tandem mass spectra of biantennary oligosaccharides by use of selective Kamoda S, Nakano M, Ishikawa R, Suzuki S, Kakehi K. 2005. Rapid and isotope labeling. J Mass Spectrom Soc Jpn 52:284–288.
sensitive screening of N-glycans as 9-fluorenylmethyl derivatives by Kaur D, Berg S, Dinadayala P, Gicquel B, Chatterjee D, McNeil MR, Vissa high-performance liquid chromatography: A method which can recover VD, Crick DC, Jackson M, Brennan PJ. 2006. Biosynthesis of free oligosaccharides after analysis. J Proteome Res 4:146–152.
mycobacterial lipoarabinomannan: Role of a branching mannosyl- Kanazawa A, Okumura S, Suzuki M. 2005. Powder-to-powder polyconden- transferase. Proc Natl Acad Sci USA 103:13664–13669.
sation of natural saccharides. Facile preparation of highly branched Kawar ZS, Haslam SM, Morris HR, Dell A, Cummings RD. 2005. Novel polysaccharides. Org Biomol Chem 3:1746–1750.
poly-GalNAcb1-4GlcNAc (LacdiNAc) and fucosylated poly-Lacdi- Kanda Y, Yamane-Ohnuki N, Sakai N, Yamano K, Nakano R, Inoue M, NAc N-glycans from mammalian cells expressing b1,4-N-acetylgalac- Misaka H, Iida S, Wakitani M, Konno Y, Yano K, Shitara K, Hosoi S, tosaminyltransferase and a1,3-fucosyltransferase. J Biol Chem Satoh M. 2006. Comparison of cell lines for stable production of fucose- negative antibodies with enhanced ADCC. Biotechnol Bioeng 94:680– Kawasaki K, Ernst RK, Miller SI. 2005. Inhibition of Salmonella enterica serovar typhimurium lipopolysaccharide deacylation by aminoarabi- Kandra L, Gye´ma´nt G, Remenyik J, Ragunath C, Ramasubbu N. 2005a.
nose membrane modification. J Bacteriol 187:2448–2457.
Transglycosylations catalysed by Y151M mutant of human salivary a- Kay W, Petersen BO, Duus JØ, Perry MB, Vinogradov E. 2006. Character- amylase (HSA). Biologia, Bratislava 16:57–64.
ization of the lipopolysaccharide and b-glucan of the fish pathogen Kandra L, Remenyik J, Batta G, Somsa´k L, Gye´ma´nt G, Park KH. 2005b.
Francisella victoria. FEBS J 273:3002–3013.
Enzymatic synthesis of a new inhibitor of a-amylases: Acarviosinyl- Ke W, Whitfield DM, Brisson J-R, Enright G, Jarrell HC, Wu W. 2005.
isomaltosyl-spiro-thiohydantoin. Carbohydr Res 340:1311–1317.
Development of specific inhibitors for heparin-binding proteins based Kanekiyo K, Lee J-B, Hayashi K, Takenaka H, Hayakawa Y, Endo S, Hayashi on the cobra cardiotoxin structure: An effective synthetic strategy for T. 2005. Isolation of an antiviral polysaccharide, nostoflan, from a rationally modified heparin-like disaccharides and a trisaccharide.
terrestrial cyanobacterium, Nostoc flagelliforme. J Nat Prod 68:1037– Carbohydr Res 340:355–372.
Keck RG, Briggs JB, Jones AJS. 2005. Oligosaccharide release and MALDI- Kaneko Y, Nimmerjahn F, Ravetch JV. 2006. Anti-inflammatory activity of TOF MS Analysis of N-Linked carbohydrate structures from glyco- immunoglobulin G resulting from Fc sialylation. Science 313:670– proteins. Methods Mol Biol 308:381–396.
Keykhosravani M, Doherty-Kirby A, Zhang C, Brewer D, Goldberg HA, Kang P, Mechref Y, Klouckova I, Novotny MV. 2005. Solid-phase Hunter GK, Lajoie G. 2005. Comprehensive identification of post- permethylation of glycans for mass spectrometric analysis. Rapid translational modifications of rat bone osteopontin by mass spectrom- Commun Mass Spectrom 19:3421–3428.
etry. Biochemistry 44:6990–7003.
Kantchev B, Chang C-C, Chang D-K. 2006. Direct Fmoc/tert-Bu solid phase Kida T, Kikuzawa A, Higashimoto H, Nakatsuji Y, Akashi M. 2005. Synthesis synthesis of octamannosyl polylysine dendrimer-peptide conjugates.
of novel cyclodextrin derivatives by aromatic spacer insertion and their Peptide Sci 84:232–240.
inclusion ability. Tetrahedron 61:5763–5768.
Kantchev EAB, Bader SJ, Parquette JR. 2005. Oligosaccharide synthesis on a Kim J-H, Yang H, Khot V, Whitfield D, Boons G-J. 2006a. Stereoselective soluble, hyperbranched polymer support via thioglycoside activation.
glycosylations using (R)- or (S)-(ethoxycarbonyl)benzyl chiral auxil- iaries at C-2 of glycopyranosyl donors. Eur J Org Chem:5007–5028.
Karginov VA, Nestorovich EM, Yohannes A, Robinson TM, Fahmi NE, Kim JH, Yang H, Park J, Boons GJ. 2005a. A general strategy for Schmidtmann F, Hecht SM, Bezrukov SM. 2006a. Search for cyclo- stereoselective glycosylations. J Am Chem Soc 127:12090–12097.
dextrin-based inhibitors of anthrax toxins: Synthesis, structural Kim S-H, Jia W, Parreira VR, Bishop RE, Gyles CL. 2006b. Phosphoethanol- features, and relative activities. Antimicrob Agents Chemother amine substitution in the lipid A of Escherichia coli O157: H7 and its association with PmrC. Microbiology 152:657–666.
Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES Kim T-K, Zhang R, Feng W, Cai J, Pierce W, Song Z-H. 2005b. Expression novel protein with a role in lipoarabinomannan biosynthesis in and characterization of human CB1 cannabinoid receptor in methyl- mycobacteria. J Biol Chem 281:9011–9017.
otrophic yeast Pichia pastoris. Protein Exp Purif 40:60–70.
Kova´cik V, Bekesova´ S, Pa¨toprsty V, Rehulka P, Chmelı´k J, Kova´c P. 2006.
Kim Y-G, Kim S-Y, Hur Y-M, Joo H-S, Chung J, Lee D-S, Royle L, Rudd PM, Positive-ion fragmentation in matrix-assisted laser desorption/ioniza- Dwek RA, Harvey DJ, Kim B-G. 2006c. The identification and tion tandem time-of-flight mass spectrometry of synthetic analogues of characterization of xenoantigenic nonhuman carbohydrate sequences in the O-specific polysaccharide of Vibrio cholerae O:1. Eur J Mass membrane proteins from porcine kidney. Proteomics 6:1133–1142.
Kislinger T, Humeny A, Peich CC, Becker CM, Pischetsrieder M. 2005.
Kovalchuk SN, Sundukova EV, Kusaykin MI, Guzev KV, Anastiuk SD, Analysis of protein glycation products by MALDI-TOF/MS. Ann NY Likhatskaya GN, Trifonov EV, Nurminski EA, Kozhemyako VB, Acad Sci 1043:249–259.
Zvyagintseva TN, Rasskazov VA. 2006. Purification, cDNA cloning Kitajima T, Chiba Y, Jigami Y. 2006. Saccharomyces cerevisiae a1,6- and homology modeling of endo-1,3-b-D-glucanase from scallop mannosyltransferase has a catalytic potential to transfer a second Mizuhopecten yessoensis. Comp Biochem Physiol B 143:473–485.
mannose molecule. FEBS J 273:5074–5085.
Kozma K, Keusch JJ, Hegemann B, Luther KB, Klein D, Hess D, Haltiwanger Kiyohara M, Hama Y, Yamaguchi K, Ito M. 2006. Structure of b-1,3- RS, Hofsteenge J. 2006. Identification and characterization of a b1,3- xylooligosaccharides generated from Caulerpa racemosa var. laete- glucosyltransferase that synthesizes the Glc-b1,3-Fuc disaccharide on virens b-1,3-xylan by the action of b-1,3-xylanase. J Biochem (Tokyo) thrombospondin type 1 repeats. J Biol Chem 281:36742–36751.
Krief S, Thoison O, Se´venet T, Wrangham RW, Lavaud C. 2005. Triterpenoid Kiyonaka S, Shinkai S, Hamachi I. 2003. Combinatorial library of low saponin anthranilates from Albizia grandibracteata leaves ingested by molecular-weight organo- and hydrogelators based on glycosylated primates in Uganda. J Nat Prod 68:897–903.
amino acid derivatives by solid-phase synthesis. Chem Eur J 9:976– Kro¨ger L, Scudlo A, Thiem J. 2006. Subsequent enzymatic galactosylation and sialylation towards sialylated Thomsen-Friedenreich antigen Knochenmuss R. 2006. Ion formation mechanisms in UV-MALDI. Analyst components. Adv Synth Catal 348:1217–1227.
Kubler-Kielb J, Liu T-Y, Mocca C, Majadly F, Robbins JB, Schneerson R.
Knochenmuss R, McCombie G, Faderl M. 2006. Ion yields of thin MALDI 2006. Additional conjugation methods and immunogenicity of Bacillus samples: Dependence on matrix and metal substrate and implications anthracis poly-g-D-glutamic acid-protein conjugates. Infect Immun for models. J Phys Chem A 110:12728–12733.
Kobayashi A, Kuwata H, Kohri M, Izumi R. 2006a. A bacterial chitinase acts Kubler-Kielb J, Pozsgay V. 2005. A new method for conjugation of as catalyst for synthesis of the N-linked oligosaccharide core carbohydrates to proteins using an aminooxy-thiol heterobifunctional trisaccharide by employing a sugar oxazoline substrate. J Carbohydr linker. J Org Chem 70:6987–6990.
Chem 25:533–541.
Ku¨bler-Kielb J, Vinogradov E, Garcı´a Ferna´ndez JM, Szostko B, Zwiefka A, Kobayashi S, Makino A, Matsumoto H, Kunii S, Ohmae M, Kiyosada T, Gamian A. 2006. Structure and serological analysis of the Hafnia alvei Makiguchi K, Matsumoto A, Horie M, Shoda S-I. 2006b. Enzymatic 481-L O-specific polysaccharide containing phosphate in the backbone polymerization to novel polysaccharides having a glucose-N-acetyl- chain. Carbohydr Res 341:2980–2985.
glucosamine repeating unit, a cellulose-chitin hybrid polysaccharide.
Kuhn J, Schno¨lzer M, Scho¨n S, Mu¨ller S, Prante C, Go¨tting C, Kleesiek K.
2005. Xylosyltransferase I acceptor properties of fibroblast growth Kobayashi S, Makino A, Tachibana N, Ohmae M. 2006c. Chitinase-catalyzed factor and its fragment bFGF (1-24). Biochem Biophys Res Commun synthesis of a chitin-xylan hybrid polymer: A novel water-soluble b(1- 4) polysaccharide having an N-acetylglucosamine xylose repeating Kumar ABV, Varadaraj MC, Gowda LR, Tharanathan RN. 2005. Character- unit. Macromol Mol Commun 27:781–786.
ization of chito-oligosaccharides prepared by chitosanolysis with the Kobayashi S, Ohmae M. 2006. Enzymatic polymerization of polysacchar- aid of papain and pronase, and their bactericidal action against Bacillus ides. Adv Polym Sci 194:159–210.
cereus and Escherichia coli. Biochem J 391:167–175.
Koel M. 2005. Ionic liquids in chemical analysis. Crit Rev Anal Chem Kumar NS, Pinto BM. 2005. Synthesis of D-lyxitol and D-ribitol analogues of the naturally occurring glycosidase inhibitor salacinol. Carbohydr Res340:2612–2619.
Kolarich D, Altmann F, Sunderasan E. 2006. Structural analysis of the glycoprotein allergen Hev b 4 from natural rubber latex by mass Kumar NS, Pinto BM. 2006. Synthesis of thioswainsonine as a potential spectrometry. Biochim Biophys Acta 1760:715–720.
glycosidase inhibitor. Carbohydr Res 341:1685–1691.
Kolarich D, Le´onard R, Hemmer W, Altmann F. 2005. The N-glycans of Kurakake M, Sumida T, Masuda D, Oonishi S, Komaki T. 2006. Production of yellow jacket venom hyaluronidases and the protein sequence of its galacto-manno-oligosaccharides from guar gum by b-mannanase from major isoform in Vespula vulgaris. FEBS J 272:5182–5190.
Penicillium oxalicum SO. J Agric Food Chem 54:7885–7889.
Kolarich D, Weber A, Turecek PL, Schwarz H-P, Altmann F. 2006.
Kurogochi M, Nishimura S-I. 2004. Structural characterization of N- Comprehensive glyco-proteomic analysis of human a1-antitrypsin by matrix-dependent selective and its charge isoforms. Proteomics 6:3369–3380.
MALDI-TOF/TOF tandem mass spectrometry. Anal Chem 76:6097–6101.
Kondo A, Li W, Nakagawa T, Nakano M, Koyama N, Wang X, Gu J, Miyoshi E, Taniguchi N. 2006. From glycomics to functional glycomics of sugar Ku¨ster B, Wheeler SF, Hunter AP, Dwek RA, Harvey DJ. 1997. Sequencing of chains: Identification of target proteins with functional changes using N-linked oligosaccharides directly from protein gels: In-gel deglyco- gene targeting mice and knock down cells of FUT8 as examples.
sylation followed by matrix-assisted laser desorption/ionization mass Biochim Biophys Acta 1764:1881–1889.
spectrometry and normal-phase high performance liquid chromatog- Kotake T, Dina S, Konishi T, Kaneko S, Igarashi K, Samejima M, Watanabe Y, raphy. Anal Biochem 250:82–101.
Kimura K, Tsumuraya Y. 2005. Molecular cloning of a b-galactosidase Kvaerno L, Werder M, Hauser H, Carreira EM. 2005. Carbohydrate sulfonyl from radish that specifically hydrolyzes b-(1-3)- and b-(1-6)-galactosyl chlorides for simple, convenient access to glycoconjugates. Org Lett residues of arabinogalactan protein. Plant Physiol 138:1563–1576.
Kovacevic S, Anderson D, Morita YS, Patterson J, Haites R, McMillan BNI, Kwan EM, Boraston AB, McLean BW, Kilburn DG, Warren RAJ. 2005. N- Coppel R, McConville MJ, Billman-Jacobe H. 2006. Identification of a glycosidase-carbohydrate-binding module fusion proteins as immobi- Mass Spectrometry Reviews DOI 10.1002/mas lized enzymes for protein deglycosylation. Protein Eng Des Sel Lattova´ E, Kapkova´ P, Krokhin O, Perreault H. 2006. Method for investigation of oligosaccharides from glycopeptides: Direct determi- Kwon Y-U, Soucy RL, Snyder DA, Seeberger PH. 2005. Assembly of a series nation of glycosylation sites in proteins. Anal Chem 78:2977–2984.
of malarial glycosylphosphatidylinositol anchor oligosaccharides.
Lattova´ E, Snovida S, Perreault H, Krokhin O. 2005. Influence of the labeling Chem Eur J 11:2493–2504.
group on ionization and fragmentation of carbohydrates in mass Kyogashima M, Tamiya-Koizumi K, Ehara T, Li G, Hu R, Hara A, Aoyama T, spectrometry. J Am Soc Mass Spectrom 16:683–696.
Kannagi R. 2006. Rapid demonstration of diversity of sulfatide Laville I, Pigaglio S, Blais J-C, Doz F, Loock B, Maillard P, Grierson DS, molecular species from biological materials by MALDI-TOF MS.
Blais J. 2006. Photodynamic efficiency of diethylene glycol-linked glycoconjugated porphyrins in human retinoblastoma cells. J Med Lam SN, Gervay-Hague J. 2005a. Glycal scavenging in the synthesis of disaccharides using mannosyl iodide donors. J Org Chem 70:2387– Lazarevic D, Thiem J. 2006. Artificial N-functionalized UDP-glucosamine analogues as modified substrates for N-acetylglucosaminyl trans- Lam SN, Gervay-Hague J. 2005b. Efficient synthesis of Man ferases. Carbohydr Res 341:569–576.
Man5 oligosaccharides, using mannosyl iodide donors. J Org Chem Le Coq J, An H-J, Lebrilla C, Viola RE. 2006. Characterization of human aspartoacylase: The brain enzyme responsible for Canavan disease.
Lamidi M, Ollivier E, Mahiou V, Faure R, Debrauwer L, Ekekang LN, Balansard G. 2005. Gluco-indole alkaloids from the bark of Nauclea Le Que´re´ AJ-L, Deakin WJ, Schmeisser C, Carlson RW, Streit WR, diderrichii. 1H and 13C NMR assignments of 3-5-tetrahydrodeoxycor- Broughton WJ, Forsberg LS. 2006. Structural characterization of a K- difoline lactam and cadambine acid. Magn Reson Chem 43:427–429.
antigen capsular polysaccharide essential for normal symbiotic Lancaster KS, An HJ, Li B, Lebrilla CB. 2006. Interrogation of N-linked infection in Rhizobium sp. Detection of the rkpMNO locus prevents oligosaccharides using infrared multiphoton dissociation in FT-ICR synthesis of 5,7-diacetamido-3,5,7,9-tetradeoxy-non-ulosonic acid. J mass spectrometry. Anal Chem 78:4990–4997.
Biol Chem 281:28981–28992.
Lapadula AJ, Hatcher PJ, Hanneman AJ, Ashline DJ, Zhang H, Reinhold VN.
Lee A, Wu S-W, Scherman MS, Torrelles JB, Chatterjee D, McNeil MR, 2005. Congruent strategies for carbohydrate sequencing. 3. OSCAR: Khoo K-H. 2006a. Sequencing of oligoarabinosyl units released from An algorithm for assigning oligosaccharide topology from MSn data.
mycobacterial arabinogalactan by endogenous arabinanase: Identifica- Anal Chem 77:6271–6279.
tion of distinctive and novel structural motifs. Biochemistry 45:15817–15828.
Lapolla A, Fedele D, Reitano R, Bonfante L, Guizzo M, Seraglia R, Tubaro M, Traldi P. 2005a. Mass spectrometric study of in vivo production of Lee B-S, Krishnanchettiar S, Lateef SS, Gupta S. 2005a. Characterization of advanced glycation end-products/peptides. J Mass Spectrom 40:969– oligosaccharide moieties of glycopeptides by microwave-assisted partial acid hydrolysis and mass spectrometry. Rapid Commun MassSpectrom 19:1545–1550.
Lapolla A, Fedele D, Reitano R, Bonfante L, Pastori G, Seraglia R, Tubaro M, Traldi P. 2005b. Advanced glycation end products/peptides: An in vivo Lee B-S, Krishnanchettiar S, Lateef SS, Lateef NS, Gupta S. 2005b.
investigation. Ann NY Acad Sci 1043:267–275.
Characterization of oligosaccharide moieties of intact glycoproteins bymicrowave-assisted partial acid hydrolysis and mass spectrometry.
Lapolla A, Fedele D, Seraglia R, Traldi P. 2006. The role of mass Rapid Commun Mass Spectrom 19:2629–2635.
spectrometry in the study of non-enzymatic protein glycation indiabetes: An update. Mass Spectrom Rev 25:775–797.
Lee B-S, Krisnanchettiar S, Lateef SS, Lateef NS, Gupta S. 2005c.
Oligosaccharide analyses of glycopeptides of horseradish peroxidase Lapolla A, Fedele D, Traldi P. 2005. Glyco-oxidation in diabetes and related by thermal-assisted partial acid hydrolysis and mass spectrometry.
diseases. Clin Chim Acta 357:236–250.
Carbohydr Res 340:1859–1865.
Lapolla A, Traldi P, Fedele D. 2005. Importance of measuring products of Lee D-W, Baney RH. 2004. Oligochitosan derivatives bearing electron- non-enzymatic glycation of proteins. Clin Biochem 38:103–115.
deficient aromatic rings for adsorption of amitriptyline: Implications for Lapolla A, Tubaro M, Fedele D, Reitano R, Arico NC, Ragazzi E, Seraglia R, drug detoxification. Biomacromolecules 5:1310–1315.
Vogliardi S, Traldi P. 2005c. A matrix-assisted laser desorption/ Lee HJ, Howell SK, Sanford RJ, Beisswenger PJ. 2005d. Methylglyoxal can ionization mass spectrometry study of the non-enzymatic glycation modify GAPDH activity and structure. Ann NY Acad Sci 1043:135– products of human globins in diabetes. Rapid Commun Mass Spectrom Lee H-S, Wolfert MA, Zhang Y, Boons G-J. 2006b. The 2-aminogluconate Laremore TN, Murugesan S, Park T-J, Avci FY, Zagorevski DV, Linhardt RJ.
isomer of Rhizobium sin-1 lipid A can antagonize TNF-production 2006. Matrix-assisted laser desorption/ionization mass spectrometric induced by enteric LPS. ChemBioChem 7:140–148.
analysis of uncomplexed highly sulfated oligosaccharides using ionic Lee JH, Kim Y, Ha MY, Lee EK, Choo J. 2005e. Immobilization of liquid matrices. Anal Chem 78:1774–1779.
aminophenylboronic acid on magnetic beads for the direct determi- Larsen K, Thygesen MB, Guillaumie F, Willats WGT, Jensen KJ. 2006.
nation of glycoproteins by matrix assisted laser desorption ionization Solid-phase chemical tools for glycobiology. Carbohydr Res 341: mass spectrometry. J Am Soc Mass Spectrom 16:1456–1460.
Lee J-H, Shim JS, Lee JS, Kim M-K, Chung M-S, Kim KH. 2006c. Pectin-like Larsen MR, Højrup P, Roepstorff P. 2005. Characterization of gel-separated acidic polysaccharide from Panax ginseng with selective antiadhesive glycoproteins using two-step proteolytic digestion combined with activity against pathogenic bacteria. Carbohydr Res 341:1154–1163.
sequential microcolumns and mass spectrometry. Mol Cell Proteomics Lee JJ, Dissanayake S, Panico M, Morris HR, Dell A, Haslam SM. 2005f.
Mass spectrometric characterisation of Taenia crassiceps metacestode Larsson EA, Sjo¨berg M, Widmalm G. 2005. Synthesis of oligosaccharides N-glycans. Mol Biochem Parasitol 143:245–249.
related to the repeating unit of the capsular polysaccharide from Lee YJ, Lee K, Jung EH, Jeon HB, Kim KS. 2005g. Acceptor-dependent Streptococcus pneumoniae type 37. Carbohydr Res 340:7–13.
stereoselective glycosylation: 20-CB glycoside-mediated direct b-D- Lasˇtovickova´ M, Chmelı´k J. 2006. Simple and fast method for recognition of arabinofuranosylation and efficient synthesis of the octaarabinofurano- reducing and nonreducing neutral carbohydrates by matrix-assisted side in mycobacterial cell wall. Org Lett 7:3263–3266.
laser desorption/ionization time-of-flight mass spectrometry. J Agric Leir S-H, Parry S, Palmai-Pallag T, Evans J, Morris HR, Dell A, Harris A.
Food Chem 54:5092–5097.
2005. Mucin glycosylation and sulphation in airway epithelial cells is Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES not influenced by cystic fibrosis transmembrane conductance regulator Liang H, Tong W-Y, Zhao Y-Y, Cui J-R, Tu G-Z. 2005. An antitumor expression. Am J Respir Cell Mol Biol 32:453–461.
compound julibroside J28 from Albizia julibrissin. Bioorg Med Chem Le´onard R, Lhernould S, Carlue´ M, Fleurat P, Maftah A, Costa G. 2005.
Biochemical characterization of Silene alba a4-fucosyltransferase and Liberek B, Melcer A, Osuch A, Wakiec R, Milewski S, Wisniewsk A. 2005.
Lewis a products. Glycoconj J 22:71–78.
N-alkyl derivatives of 2-amino-2-deoxy-D-glucose. Carbohydr Res Leonard R, Petersen BO, Himly M, Kaar W, Wopfner N, Kolarich D, van-Ree R, Ebner C, Duus JO, Ferreira F, Altmann F. 2005. Two novel types of Lin C-C, Huang KT, Lin C-C. 2005. N-trifluoroacetyl sialyl phosphite donors O-glycans on the mugwort pollen allergen Art v 1 and their role in for the synthesis of a(2-9) oligosialic acids. Org Lett 7:4169–4172.
antibody binding. J Biol Chem 280:7932–7940.
Liou H-L, Dixit SS, Xu S, Tint GS, Stock AM, Lobel P. 2006. NPC2, the Leonard R, Rendic D, Rabouille C, Wilson IB, Preat T, Altmann F. 2006. The protein deficient in Niemann-Pick C2 disease, consists of multiple Drosophila fused lobes gene encodes an N-acetylglucosaminidase glycoforms that bind a variety of sterols. J Biol Chem 281:36710– involved in N-glycan processing. J Biol Chem 281:4867–4875.
Leone S, Molinaro A, Alfieri F, Cafaro V, Lanzetta R, Di Donato A, Parrilli M.
Liparoti V, Molinaro A, Sturiale L, Garozzo D, Nazarenko EL, Gorshkova RP, 2006a. The biofilm matrix of Pseudomonas sp. OX1 grown on phenol is Ivanova EP, Shevcenko LS, Lanzetta R, Parrilli M. 2006. Structural mainly constituted by alginate oligosaccharides. Carbohydr Res analysis of the deep rough lipopolysaccharide from Gram negative bacterium Alteromonas macleodii ATCC 27126T: The first finding of b- Leone S, Molinaro A, Pessione E, Mazzoli R, Giunta C, Sturiale L, Garozzo Kdo in the inner core of lipopolysaccharides. Eur J Org Chem:4710– D, Lanzetta R, Parrilli M. 2006b. Structural elucidation of the core-lipid A backbone from the lipopolysaccharide of Acinetobacter radio- Liu H, Geng M, Xin X, Li F, Zhang Z, Li J, Ding J. 2005. Multiple and resistens S13, an organic solvent tolerant Gram-negative bacterium.
multivalent interactions of novel anti-AIDS drug candidates, sulfated Carbohydr Res 341:582–590.
polymannuronate (SPMG)-derived oligosaccharides, with gp120 and Leppa¨nen A, Stowell SR, Blixt O, Cummings RD. 2005. Dimeric galectin-1 their anti-HIV activities. Glycobiology 15:501–510.
binds with high affinity to a2,3-sialylated and non-sialylated terminal Liu J, Jo¨nsson LA ˚ , Jiang G. 2005. Application of ionic liquids in analytical N-acetyllactosamine units on surface-bound extended glycans. J Biol chemistry. Trends Anal Chem 24:20–27.
Liu S, Ben RN. 2005. C-linked galactosyl serine AFGP analogues as potent Levery SB. 2005. Glycosphingolipid structural analysis and glycosphingo- recrystallization inhibitors. Org Lett 7:2385–2388.
lipidomics. Methods Enzymol 405:300–369.
Liu X, Kwon Y-U, Seeberger PH. 2005. Convergent synthesis of a fully Levina EV, Kalinovsky AI, Levin VS. 2006. New steroid glycosides from the lipidated glycosylphosphatidylinositol anchor of Plasmodium falcipa- starfish Fromia milleporella. Russ J Bioorg Chem 32:84–88.
rum. J Am Chem Soc 127:5004–5005.
Levina EV, Kalinovsky AI, Stonik VA, Dmiternok PS, Andriyashchenko PV.
Liu X, McNally DJ, Nothaft H, Szymanski CM, Brisson J-R, Li J. 2006a.
2005. Steroid compounds from Far Eastern starfishes Henricia aspera Mass spectrometry-based glycomics strategy for exploring N-linked and H. tumida. Russ J Bioorg Chem 31:467–474.
glycosylation in eukaryotes and bacteria. Anal Chem 78:6081–6087.
Lewandrowski U, Resemann A, Sickmann A. 2005. Laser-induced Liu X, Stocker BL, Seeberger PH. 2006. Total synthesis of phosphatidyl- dissociation/high-energy collision-induced dissociation fragmentation inositol mannosides of Mycobacterium tuberculosis. J Am Chem Soc using MALDI-TOF/TOF-MS instrumentation for the analysis of neutral and acidic oligosaccharides. Anal Chem 77:3274–3283.
Liu Y, Ding N, Xiao H, Li Y. 2006b. Efficient syntheses of a series of Li A, Kong F. 2005a. Concise syntheses of arabinogalactans with b-(1-6)- glycosphingolipids with 1,2-trans-glycosidic linkages. J Carbohydr linked galactopyranose backbones and a-(1-3)- and a-(1-2)-linked Chem 25:471–489.
arabinofuranose side chains. Bioorg Med Chem 13:839–853.
Lo´pez O, Maza S, Maya I, Fuentes J, Ferna´ndez-Bolan˜os JG. 2005. New synthetic approaches to sugar ureas. Access to ureido-b-cyclodextrins.
Li A, Kong F. 2005b. Syntheses of b-(1-6)-branched b-(1-3)-linked D- galactans that exist in the rhizomes of Atractylodes lancea DC.
Carbohydr Res 340:1949–1962.
Lo´pez-Prados J, Cuevas F, Reichardt N-C, de Paz J-L, Morales EQ, Martı´n- Lomas M. 2005. Design and synthesis of inositolphosphoglycan Li D, Roh S-A, Shim J-H, Mikami B, Baik M-Y, Park C-S, Park K-H.
putative insulin mediators. Org Biomol Chem 3:764–786.
2005a. Glycosylation of genistin into soluble inclusion complex formof cyclic glucans by enzymatic modification. J Agric Food Chem Lo´pez-Prados J, Martı´n-Lomas M. 2005. Inositolphosphoglycan mediators: An effective synthesis of the conserved linear GPI anchor structure. JCarbohydr Chem 24:393–414.
Li H, Sethuraman N, Stadheim TA, Zha D, Prinz B, Ballew N, Bobrowicz P, Lowe JP, Stuckey DJ, Awan FR, Jeyakumar M, Neville DCA, Platt FM, Choi B-K, Cook WJ, Cukan M, Houston-Cummings NR, Davidson R, Griffin JL, Styles P, Blamire AM, Sibson NR. 2005. MRS reveals Gong B, Hamilton SR, Hoopes JP, Jiang Y, Kim N, Mansfield R, Nett additional hexose N-acetyl resonances in the brain of a mouse model for JH, Rios S, Strawbridge R, Wildt S, Gerngross TU. 2006. Optimization Sandhoff disease. NMR Biomed 18:517–526.
of humanized IgGs in glycoengineered Pichia pastoris. Nat Biotechnol24:210–215.
Lu J, Fraser-Reid B, Gowda C. 2005. A strategy for ready preparation of glycolipids for multivalent presentation. Org Lett 7:3841–3843.
Li J, Du Y, Liang H. 2006. Low molecular weight water-soluble chitosans: Preparation with the aid of cellulase, characterization, and solubility. J Lu W, Leimkuhler C, Gatto GJJ, Kruger RG, Oberthu¨r M, Kahne D, Walsh Appl Polym Sci 102:1098–1105.
CT. 2005. AknT is an activating protein for the glycosyltransferaseAknS in L-aminodeoxysugar transfer to the aglycone of aclacinomycin Li J, Du Y, Yang J, Feng T, Li A, Chen P. 2005b. Preparation and A. Chem Biol 12:527–534.
characterisation of low molecular weight chitosan and chito-oligomers Lucka L, Fernando M, Grunow D, Kannicht C, Horst AK, Nollau P, Wagerer by a commercial enzyme. Polym Degrad Stab 87:441–448.
C. 2005. Identification of Lewis x structures of the cell adhesion Li JS, Li J. 2005. Characterization of N-linked oligosaccharides in molecule CEACAM1 from human granulocytes. Glycobiology 15:87– chorion peroxidase of Aedes aegypti mosquito. Protein Sci 14:2370– Lukasiewicz J, Dzieciatkowska M, Niedziela T, Jachymek W, Augustyniuk Li Y, Wei G, Yu B. 2006. Aryl C-glycosylation of phenols with glycosyl A, Kenne L, Lugowski C. 2006a. Complete lipopolysaccharide of trifluoroacetimidates. Carbohydr Res 341:2717–2722.
Plesiomonas shigelloides O74: H5 (strain CNCTC 144/92). 2. Lipid A, Mass Spectrometry Reviews DOI 10.1002/mas its structural variability, the linkage to the core oligosaccharide, and the application of a sialoglycopolymer with a chitosan backbone as a potent biological activity of the lipopolysaccharide. Biochemistry 45:10434– inhibitor of human influenza virus hemagglutination. Carbohydr Res Lukasiewicz J, Niedziela T, Jachymek W, Kenne L, Lugowski C. 2006b.
Makino A, Kurosaki K, Ohmae M, Kobayashi S. 2006. Chitinase-catalyzed Structure of the lipid A-inner core region and biological activity of synthesis of alternatingly N-deacetylated chitin: A chitin-chitosan Plesiomonas shigelloides O54 (strain CNCTC 113/92) lipopolysac- hybrid polysaccharide. Biomacromolecules 7:950–957.
charide. Glycobiology 16:538–550.
Makino A, Ohmae M, Kobayashi S. 2006. Synthesis of fluorinated chitin Luo Y, Ye S, Kan M, McKeehan WL. 2006a. Structural specificity in a FGF7- derivatives via enzymatic polymerization. Macromol Biosci 6:862– affinity purified heparin octasaccharide required for formation of a complex with FGF7 and FGFR2IIIb. J Cell Biochem 97:1241–1258.
Makishima S, Nozaki K, Mizuno M, Netsu E, Shinji K, Shibayama T, Kanda Luo Y, Ye S, Kan M, McKeehan WL. 2006b. Control of fibroblast growth T, Amano Y. 2006. Recovery of soluble sugars from waste medium for factor (FGF) 7- and FGF1-induced mitogenesis and downstream enokitake (Flammulina velutipes) mushroom cultivation with hydro- signaling by distinct heparin octasaccharide motifs. J Biol Chem thermal reaction and enzyme digestion. J Appl Glycosci 53:261– Lu¨tteke T, Bohne-Lang A, Loss A, Goetz T, Frank M, von der Lieth C-W.
Makita H, Nakahara Y, Fukui H, Miyanori Y, Katahira M, Srki H, Takeda M, 2006. GLYCOSCIENCES.de: An Internet portal to support glycomics Koizumi J-I. 2006. Identification of 2-(cysteinyl)amido-2-deoxy-D- and glycobiology research. Glycobiology 16:71R–81R.
galacturonic acid residue from the sheath of Leptothrix cholodnii.
Lysek R, Schu¨tz C, Voge P. 2005. Total asymmetric synthesis of ()- Biosci Biotechnol Biochem 70:1265–1268.
conduramine B-1 and of its enantiomer. N-Benzyl derivatives of Maljaars CEP, Halkes KM, de Oude WL, Haseley SR, Upton PJ, McDonnell conduramine B-1 are b-glucosidase inhibitors. Bioorg Med Chem Lett MB, Kamerling JP. 2006. Affinity determination of Ricinus communis agglutinin ligands identified from combinatorial O- and S-N-glycopep- Macrae JI, Acosta-Serrano A, Morrice NA, Mehlert A, Ferguson MA. 2005.
tide libraries. J Comb Chem 8:812–819.
Structural characterization of NETNES, a novel glycoconjugate in Maljaars CEP, Halkes KM, de Oude WL, van der Poel S, Pijnenburg NJM, Trypanosoma cruzi epimastigotes. J Biol Chem 280:12201–12211.
Kamerling JP. 2005. Preparation of S- and N-linked glycosylated amino Madsen AS, Hrdlicka PJ, Kumar TS, Wengel J. 2006. Synthesis, nucleic acid acid building blocks for solid-phase glycopeptide library synthesis. J hybridization properties and molecular modelling studies of conforma- Carbohydr Chem 24:353–367.
tionally restricted 30-O,40-C-methylene-linked a-L-ribonucleotides.
Mandal D, Panda N, Kumar S, Banerjee S, Mandal NB, Sahu NP. 2006. A Carbohydr Res 341:1398–1407.
triterpenoid saponin possessing antileishmanial activity from the leaves Maeda K, Mochizuki H, Watanabe M, Yashima E. 2006. Switching of of Careya arborea. Phytochemistry 67:183–190.
macromolecular helicity of optically active poly(phenylacetylene)s Mandato C, Brive L, Miura Y, Davis JA, Di-Cosmo N, Lucariello S, bearing cyclodextrin pendants induced by various external stimuli. J Am Pagliardini S, Seo NS, Parenti G, Vecchione R, Freeze HH, Vajro P.
Chem Soc 128:7639–7650.
2006. Cryptogenic liver disease in four children: A novel congenital Maemura M, Ohgaki A, Nakahara Y, Hojo H, Nakahara Y. 2005. Solid-phase disorder of glycosylation. Pediatr Res 59:293–298.
synthesis of core 8 O-glycan-linked MUC5AC glycopeptide. Biosci Mangold SL, Morgan JR, Strohmeyer GC, Gronenborn AM, Cloninger MJ.
Biotechnol Biochem 69:1575–1583.
2005. Cyanovirin-N binding to Man1-2Man functionalized dendrimers.
Maes E, Gare´naux E, Strecker G, Leroy Y, Wieruszeski J-M, Brassart C, Org Biomol Chem 3:2354–2358.
Gue´rardel Y. 2005. Major O-glycans from the nest of Vespula Manimala JC, Li Z, Jain A, VedBrat S, Gildersleeve JC. 2005. Carbohydrate germanica contain phospho-ethanolamine. Carbohydr Res 340:1852– array analysis of anti-Tn antibodies and lectins reveals unexpected specificities: Implications for diagnostic and vaccine development.
Maillard LT, Gue´rineau V, Badet-Denisot M-A, Badet B, Lapre´vote O, Durand P. 2006. Monitoring enzyme-catalyzed production of glucos- Manzoni L, Castelli R. 2006. Froc: A new fluorous protective group for amine-6P by matrix-assisted laser desorption/ionization time-of-flight peptide and oligosaccharide synthesis. Org Lett 8:955–957.
mass spectrometry: A new enzymatic assay for glucosamine-6P Mares J, Mu¨ller JU, Skirgailiene A, Neumoin A, Bewley CA, Schmidt RR, synthase. Rapid Commun Mass Spectrom 20:666–672.
Zerbe O. 2006. A model for cell-surface-exposed carbohydrate moieties Majcherczyk PA, McKenna T, Moreillon P, Vaudaux P. 2006. The suitable for structural studies by NMR spectroscopy. ChemBioChem discriminatory power of MALDI-TOF mass spectrometry to differ- entiate between isogenic teicoplanin-susceptible and teicoplanin- Mariappan M, Preusser-Kunze A, Balleininger M, Eiselt N, Schmidt B, resistant strains of methicillin-resistant Staphylococcus aureus. FEMS Gande SL, Wenzel D, Dierks T, von Figura K. 2005. Expression, Microbiol Lett 255:233–239.
localization, structural, and functional characterization of pFGE, the Majumdar G, Harrington A, Hungerford J, Martinez-Hernandez A, Gerling paralog of the Ca-formylglycine-generating enzyme. J Biol Chem IC, Raghow R, Solomon S. 2006. Insulin dynamically regulates calmodulin gene expression by sequential O-glycosylation and Marmuse L, Nepogodiev SA, Field RA. 2005a. Exploiting an aromatic phosphorylation of sp1 and its subcellular compartmentalization in aglycone as a reporter of glycosylation stereochemistry in the synthesis liver cells. J Biol Chem 281:3642–3650.
of 1,6-linked maltooligosaccharides. Tetrahedron Asym 16:477–485.
Makarieva TN, Denisenko VA, Dmitrenok PS, Guzii AG, Santalova EA, Marmuse L, Nepogodiev SA, Field RA. 2005b. ‘‘Click'' chemistry en route to Stonik VA, MacMillan JB, Molinski TF. 2005a. Oceanalin A, a hybrid pseudo-starch. Org Biomol Chem 3:2225–2227.
a,o-bifunctionalized sphingoid tetrahydroisoquinoline b-glycoside Masand G, Hanif K, Sen S, Ahsan A, Maiti S, Pasha S. 2006. Synthesis, from the marine sponge Oceanapia sp. Org Lett 7:2897–2900.
conformational and pharmacological studies of glycosylated chimeric Makarieva TN, Guzii AG, Denisenko VA, Dmitrenok PS, Santalova EA, peptides of Met-enkephalin and FMRFa. Brain Res Bull 68:329– Pokanevich EV, Molinski TF, Stonik VA. 2005b. Rhizochalin A, a novel two-headed sphingolipid from the sponge Rhizochalina incrustata. J Maslen S, Sadowski P, Adam A, Lilley K, Stephens E. 2006. Differentiation Nat Prod 68:255–257.
of isomeric N-glycan structures by normal-phase liquid chromatog- Makimura Y, Watanabe S, Suzuki T, Suzuki Y, Ishida H, Kiso M, Katayama T, raphy-MALDI-TOF/TOF tandem mass spectrometry. Anal Chem Kumagai H, Yamamoto K. 2006. Chemoenzymatic synthesis and Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES Matsubara H, Kabuto S, Nakahara N, Ogawa T, Muramoto K, Jimbo M, Mesaros M, Tarzi OI, Erra-Balsells R, Bilmes GM. 2006. The photophysics of Kamiya H. 2005a. Structure and possible function of N-glycans of an some UV-MALDI matrices studied by using spectroscopic, photo- invertebrate C-type lectin from the acorn barnacle Megabalanus rosa.
acoustic and luminescence techniques. Chem Phys Lett 426:334–340.
Fisheries Sci 71:931–940.
Meyer S, van-Liempt E, Imberty A, van-Kooyk Y, Geyer H, Geyer R, van-Die Matsubara N, Oiwa K, Hohsaka T, Sadamoto R, Niikura K, Fukuhara N, I. 2005. DC-SIGN mediates binding of dendritic cells to authentic Takimoto A, Kondo H, Nishimura S-I. 2005b. Molecular design of pseudo-LewisY glycolipids of Schistosoma mansoni cercariae, the first glycoprotein mimetics: Glycoblotting by engineered proteins with an parasite-specific ligand of DC-SIGN. J Biol Chem 280:37349–37359.
oxylamino-functionalized amino acid residue. Chem Eur J 11:6974– Mills K, Eaton S, Ledger V, Young E, Winchester B. 2005. The synthesis of internal standards for the quantitative determination of sphingolipids by Matsuo I, Kashiwagi T, Totani K, Ito Y. 2005. First chemical synthesis of tandem mass spectrometry. Rapid Commun Mass Spectrom 19:1739– triglucosylated tetradecasaccharide (Glc3Man9GlcNAc2), a common precursor of asparagine-linked oligosaccharides. Tetrahedron Lett Mills K, Mills P, Jackson M, Worthington V, Beesley C, Mann A, Clayton P, Grunewald S, Keir G, Young L, Langridge J, Mian N, Winchester B.
Matsuo I, Totani K, Tatami A, Ito Y. 2006. Comprehensive synthesis of ER 2006. Diagnosis of congenital disorders of glycosylation type-I using related high-mannose-type sugar chains by convergent strategy.
protein chip technology. Proteomics 6:2295–2304.
Minamisawa T, Suzuki K, Hirabayashi J. 2006. Systematic identification of Matsuoka K, Terabatake M, Esumi Y, Hatano K, Terunuma D, Kuzuhara H.
N-acetylheparosan oligosaccharides by tandem mass spectrometric 2006. Carbosilane dendrimers bearing globotriaoses: Construction of a fragmentation. Rapid Commun Mass Spectrom 20:267–274.
series of carbosilane dendrimers bearing globotriaoses. Biomacromo- Minamisawa T, Suzuki K, Kajimoto N, Iida M, Maeda H, Hirabayashi J. 2006.
Microscale preparation of even- and odd-numbered N-acetylheparosan Matsushita T, Hinou H, Fumoto M, Kurogochi M, Fujitani N, Shimizu H, oligosaccharides. Carbohydr Res 341:230–237.
Nishimura S-I. 2006. Construction of highly glycosylated mucin-type Miura T, Tsujino S, Satoh A, Goto K, Mizuno M, Noguchi M, Kajimoto T, glycopeptides based on microwave-assisted solid-phase syntheses and Node M, Murakami Y, Imai N, Inazu T. 2005a. Fluorescence enzymatic modifications. J Org Chem 71:3051–3063.
modification of Gb3 oligosaccharide and rapid synthesis of oligosac- Mazumder S, Lerouge P, Loutelier-Bourhis C, Driouich A, Ray B. 2005.
charide moieties using fluorous protective group. Tetrahedron Structural characterisation of hemicellulosic polysaccharides from Benincasa hispida using specific enzyme hydrolysis, ion exchange Miura Y, Tay SKH, Aw MM, Eklund EA, Freeze HH. 2005b. Clinical and chromatography and MALDI-TOF mass spectroscopy. Carbohydr biochemical characterization of a patient with congenital disorder of Polym 59:231-238.
glycosylation (CDG) IIx. J Pediatr 147:851–853.
Mazzaglia A, Forde D, Garozzo D, Malvagna P, Ravoo BJ, Darcy R. 2004.
Miyamoto Y, Mukai T, Nakata N, Maeda Y, Kai M, Naka T, Yano I, Makino Multivalent binding of galactosylated cyclodextrin vesicles to lectin.
M. 2006. Identification and characterization of the genes involved in Org Biomol Chem 2:957–960.
glycosylation pathways of mycobacterial glycopeptidolipid biosyn- Mechref Y, Kang P, Novotny MV. 2006. Differentiating structural isomers of thesis. J Bacteriol 188:86–95.
sialylated glycans by matrix-assisted laser desorption/ionization time- Miyata S, Sato C, Kumita H, Toriyama M, Vacquier VD, Kitajima K. 2006.
of-flight/time-of-flight tandem mass spectrometry. Rapid Commun Flagellasialin: A novel sulfated a2,9-linked polysialic acid glycopro- Mass Spectrom 20:1381–1389.
tein of sea urchin sperm flagella. Glycobiology 16:1229–1241.
Mechref Y, Muzikar J, Novotny MV. 2005. Comprehensive assessment of N- Miyauchi M, Hoshino T, Yamaguchi H, Kamitori S, Harada A. 2005. A glycans derived from a murine monoclonal antibody: A case for [2]rotaxane capped by a cyclodextrin and a guest: Formation of multimethodological approach. Electrophoresis 26:2034–2046.
supramolecular [2]rotaxane polymer. J Am Chem Soc 127:2034–2035.
Mechref Y, Novotny MV. 2006. Miniaturized separation techniques in Miyazawa T, Funazukuri T. 2005. Polysaccharide hydrolysis accelerated by glycomic investigations. J Chromatogr B 841:65–78.
adding carbon dioxide under hydrothermal conditions. Biotechnol Prog Medzihradszky KF. 2005. Characterization of protein N-glycosylation.
Methods Enzymol 405:116–138.
Miyazawa T, Funazukuri T. 2006. Noncatalytic hydrolysis of guar gum under Mehlmann M, Garvin AM, Steinwand M, Gauglitz G. 2005. Reflectometric hydrothermal conditions. Carbohydr Res 341:870–877.
interference spectroscopy combined with MALDI–TOF mass spec- Mizuno M, Goto K, Miura T. 2005. Fluorous glycopeptide synthesis without trometry to determine quantitative and qualitative binding of mixtures protection of sugar hydroxy groups. Chem Lett 34:426–427.
of vancomycin derivatives. Anal Bioanal Chem 382:1942–1948.
Mizuno M, Goto K, Miura T, Inazu T. 2006a. Rapid oligosaccharide and Mehra R, Kelly P. 2006. Milk oligosaccharides: Structural and technological peptide syntheses on a recyclable fluorous support. QSAR Comb Sci aspects. Int Dairy J 16:1334–1340.
Mehta AS, Saile E, Zhong W, Buskas T, Carlson R, Kannenberg E, Reed Y, Mizuno M, Matsumoto H, Goto K, Hamasaki K. 2006b. Synthesis of Quinn CP, Boons G-J. 2006. Synthesis and antigenic analysis of the aminoglycoside derivatives on a Cbz-type heavy fluorous tag.
BclA glycoprotein oligosaccharide from the Bacillus anthracis Tetrahedron Lett 47:8831–8835.
exosporium. Chem Eur J 12:9136–9149.
Moe GR, Dave A, Granoff DM. 2005. Epitopes recognized by a non- Melander C, Adden R, Brinkmalm G, Gorton L, Mischnick P. 2006. New autoreactive murine anti-N-propionyl meningococcal group B poly- approaches to the analysis of enzymatically hydrolyzed methyl saccharide monoclonal antibody. Infect Immun 73:2123–2128.
cellulose. Part 2. Comparison of various enzyme preparations.
Mohamed HE, van de Meene AML, Roberson RW, Vermaas WFJ. 2005.
Myxoxanthophyll is required for normal cell wall structure and Mennella C, Visciano M, Napolitano A, Del-Castillo MD, Fogliano V.
thylakoid organization in the cyanobacterium Synechocystis sp. strain 2006. Glycation of lysine-containing dipeptides. J Peptide Sci 12:291– PCC 6803. J Bacteriol 187:6883–6892.
Mohand FA, Farkasˇ V. 2006. Screening for hetero-transglycosylating Menon KN, Ikeda T, Fujimoto I, Narimatsu H, Nakakita S-I, Hase S, Ikenaka activities in extracts from nasturtium (Tropaeolum majus). Carbohydr K. 2005. Changes in N-linked sugar chain patterns induced by Res 341:577–581.
moderate-to-high expression of the galactosyltransferase I gene in a Momcilovic D, Schagerlo¨f H, Wittgren B, Wahlund K-G, Brinkmalm G.
brain-derived cell line, CG4. J Neurosci Res 80:29–36.
2005a. Improved chemical analysis of cellulose ethers using dialkyl- Mass Spectrometry Reviews DOI 10.1002/mas amine derivatization and mass spectrometry. Biomacromolecules pH changes the profile of nodulation factors produced by Rhizobium tropici CIAT899. Chem Biol 12:1029–1040.
Momcilovic D, Wahlund K-G, Wittgren B, Brinkmalm G. 2005b. Improved Moscatiello R, Mariani P, Sanders D, Maathuis FJM. 2006. Transcriptional matrix-assisted laser desorption/ionisation sample preparation of a analysis of calcium-dependent and calcium-independent signalling partially depolymerised cellulose derivative by continuous spray pathways induced by oligogalacturonides. J Exp Bot 57:2847–2865.
deposition and interfacing with size-exclusion chromatography. Rapid Mouille G, Witucka-Wall H, Bruyant M-P, Loudet O, Pelletier S, Rihouey C, Commun Mass Spectrom 19:947–954.
Lerouxel O, Lerouge P, Ho¨fte H, Pauly M. 2006. Quantitative trait loci Monk CR, Sutton-Smith M, Dell A, Garden OA. 2006. Preparation of CD25þ analysis of primary cell wall composition in Arabidopsis. Plant Physiol and CD25 CD4þ T cells for glycomic analysis—A cautionary tale of serum glycoprotein sequestration. Glycobiology 16:11G–13G.
Mouyna I, Morelle W, Vai M, Monod M, Le´chenne B, Fontaine T, Beauvais A, Montoya-Peleaz PJ, Riley JG, Szarek WA, Valvano MA, Schutzbach JS, Sarfati J, Pre´vost M-C, Henry C, Latge´ J-P. 2005. Deletion of GEL2 Brockhausen I. 2005. Identification of a UDP-Gal: GlcNAc-R encoding for a b(1–3)glucanosyltransferase affects morphogenesis and galactosyltransferase activity in Escherichia coli VW187. Bioorg virulence in Aspergillus fumigatus. Mol Microbiol 56:1675–1688.
Med Chem Lett 15:1205–1211.
Mukherjee R, Gomez M, Jayaraman N, Smith I, Chatterji D. 2005.
Moon Y-H, Kim G, Lee J-H, Jin X-J, Kim D-W, Kim D. 2006. Enzymatic Hyperglycosylation of glycopeptidolipid of Mycobacterium smegmatis synthesis and characterization of novel epigallocatechin gallate gluco- under nutrient starvation: Structural studies. Microbiology 151:2385– sides. J Mol Catal B Enzym 40:1–7.
Moore JP, Nguema-Ona E, Chevalier L, Lindsey GG, Brandt WF, Lerouge P, Mu¨llegger JM, Chen HM, Warren RAJ, Withers SG. 2006. Glycosylation of a Farrant JM, Driouich A. 2006. Response of the leaf cell wall to desiccation in the resurrection plant Myrothamnus flabellifolius. Plant approaches: The generation of a thioglycoprotein. Angew Chem Int Ed Engl 45:2585–2588.
Moraes G, Northcote PT, Silchenko AS, Antonov AS, Kalinovsky AI, Mu¨ller R, Allmaier G. 2006. Molecular weight determination of ultra-high Dmitrenok PS, Avilov SA, Kalinin VI, Stonik VA. 2005. Mollisosides mass compounds on a standard matrix-assisted laser desorption/ A, B1, and B2: Minor triterpene glycosides from the New Zealand and ionization time-of-flight mass spectrometer: PAMAM dendrimer South Australian sea cucumber Australostichopus mollis. J Nat Prod generation 10 and immunoglobulin M. Rapid Commun Mass Spectrom Morales V, Sanz ML, Olano A, Corzo N. 2006. Rapid separation on activated Murayama T, Tanabe T, Ikeda H, Ueno A. 2006. Direct assay for a-amylase charcoal of high oligosaccharides in honey. Chromatographia 64:233– Morelle W, Canis K, Chirat F, Faid V, Michalski J-C. 2006a. The use of mass Murozuka Y, Kasuya MCZ, Kobayashi M, Watanabe Y, Sato T, Hatanaka K.
spectrometry for the proteomic analysis of glycosylation. Proteomics 2005. Efficient sialylation on azidododecyl lactosides by using B16 melanoma cells. Chem Biodiversity 2:1063–1078.
Morelle W, Donadio S, Ronin C, Michalski J-C. 2006b. Characterization of N- Murphy RC, Raetz CRH, Reynolds CM, Barkley RM. 2005. Mass glycans of recombinant human thyrotropin using mass spectrometry.
spectrometry advances in lipidomica: Collision-induced decomposition Rapid Commun Mass Spectrom 20:331–345.
of Kdo2–lipid A. Prostaglandins 77:131–140.
Morelle W, Flahaut C, Michalski J-C, Louvet A, Mathurin P, Klein A. 2006c.
Muthukrishnan S, Jutz G, Andre´ X, Mori H, Mu¨ller AHE. 2005. Synthesis of Mass spectrometric approach for screening modifications of total serum hyperbranched glycopolymers via self-condensing atom transfer N-glycome in human diseases: Application to cirrhosis. Glycobiology radical copolymerization of a sugar-carrying acrylate. Macromolecules Morelle W, Jimenez JC, Cieniewski-Bernard C, Dei-Cas E, Michalski JC.
Muthukrishnan S, Mori H, Mu¨ller AHE. 2005. Synthesis and characterization 2005a. Characterization of the N-linked glycans of Giardia intestinalis.
of methacrylate-type hyperbranched glycopolymers via self-condens- ing atom transfer radical copolymerization. Macromolecules 38:3108– Morelle W, Michalski J-C. 2005. The mass spectrometric analysis of glycoproteins and their glycan structures. Curr Anal Chem 1:29–57.
Muzitano MF, Tinoco LW, Guette C, Kaiser CR, Rossi-Bergmann B, Costa Morelle W, Slomianny M-C, Diemer H, Schaeffer C, van Dorsselaer A, SS. 2006. The antileishmanial activity assessment of unusual flavonoids Michalski J-C. 2005b. Structural characterization of 2-aminobenz- from Kalanchoe pinnata. Phytochemistry 67:2071–2077.
amide-derivatized oligosaccharides using a matrix-assisted laser Nagahori N, Nishimura S-I. 2006. Direct and efficient monitoring of desorption/ionization two-stage time-of-flight tandem mass spectro- glycosyltransferase reactions on gold colloidal nanoparticles by using meter. Rapid Commun Mass Spectrom 19:2075–2084.
mass spectrometry. Chem Eur J 12:6478–6485.
Morgan JR, Cloninger MJ. 2005. Synthesis of carbohydrate-linked poly(- Nagaike F, Onuma Y, Kanazawa C, Hojo H, Ueki A, Nakahara Y, Nakahara Y.
polyoxometalate) poly(amido)amine dendrimers. J Polym Sci A 43: 2006. Efficient microwave-assisted tandem N- to S-acyl transfer and thioester exchange for the preparation of a glycosylated peptide Morinaga O, Tanaka H, Shoyama Y. 2006. Detection and quantification of thioester. Org Lett 8:4465–4468.
ginsenoside Re in ginseng samples by a chromatographic immuno- Naka R, Kamoda S, Ishizuka A, Kinoshita M, Kakehi K. 2006. Analysis of staining method using monoclonal antibody against ginsenoside Re. J total N-glycans in cell membrane fractions of cancer cells using a Chromatogr B 830:100–104.
combination of serotonin affinity chromatography and normal phase Morita YS, Sena CBC, Waller RF, Kurokawa K, Sernee MF, Nakatani F, chromatography. J Proteome Res 5:88–97.
Haites RE, Billman-Jacobe H, McConville MJ, Maeda Y, Kinoshita T.
Nakagawa T, Uozumi N, Nakano M, Mizuno-Horikawa Y, Okuyama N, 2006. PimE is a polyprenol-phosphate-mannose-dependent mannosyl- Taguchi T, Gu J, Kondo A, Taniguchi N, Miyoshi E. 2006. Fucosylation transferase that transfers the fifth mannose of phosphatidylinositol of N-glycans regulates the secretion of hepatic glycoproteins into bile mannoside in mycobacteria. J Biol Chem 281:25143–25155.
ducts. J Biol Chem 281:29797–29806.
Moro´n B, Soria-Dı´az ME, Ault J, Verroios G, Noreen S, Rodrı´guez-Navarro Nakajima K, Kinoshita M, Matsushita N, Urashima T, Suzuki M, Suzuki A, DN, Gil-Serrano A, Thomas-Oates J, Megı´as M, Sousa C. 2005. Low Kakehi K. 2006. Capillary affinity electrophoresis using lectins for the Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES analysis of milk oligosaccharide structure and its application to bovine glycoblotting nanoparticles for high-throughput protein glycomics.
colostrum oligosaccharides. Anal Biochem 348:105–114.
Chem Eur J 11:3825–3834.
Nakamura K, Suzuki Y, Goto-Inoue N, Yoshida-Noro C, Suzuki A. 2006.
Ninonuevo MR, Park Y, Yin H, Zhang J, Ward RE, Clowers BH, German JB, Structural characterization of neutral glycosphingolipids by thin-layer Freeman SL, Killeen K, Grimm R, Lebrilla CB. 2006. A strategy for chromatography coupled to matrix-assisted laser desorption/ionization annotating the human milk glycome. J Agric Food Chem 54:7471– quadrupole ion trap time-of-flight MS/MS. Anal Chem 78:5736–5743.
Nakamura S, Yagi F, Totani K, Ito Y, Hirabayashi J. 2005. Comparative Nishimura S-I, Niikura K, Kurogochi M, Matsushita T, Fumoto M, Hinou H, analysis of carbohydrate-binding properties of two tandem repeat-type Kamitani R, Nakagawa H, Deguchi K, Miura N, Monde K, Kondo H.
Jacalin-related lectins, Castanea crenata agglutinin and Cycas revoluta 2005. High-throughput protein glycomics: Combined use of chemo- leaf lectin. FEBS J 272:2784–2799.
selective glycoblotting and MALDI-TOF/TOF mass spectrometry.
Nakano H, Shizuma M, Murakami H, Kiryu T, Kiso T. 2005. One-pot Angew Chem Int Ed Engl 44:91–96.
synthesis of glycosyl poly(arbutin) by enzymatic glycosylation Niwa T. 2006. Mass spectrometry for the study of protein glycation in disease.
followed by polymerization with peroxidase. J Mol Catal B Enzym Mass Spectrom Rev 25:713–723.
Nokami T, Werz DB, Seeberger PH. 2005. Synthesis and reactions of 1,4- Naruchi K, Hamamoto T, Kurogochi M, Hinou H, Shimizu H, Matsushita T, anhydrogalactopyranose and 1,4-anhydroarabinose—Steric and elec- Fujitani N, Kondo H, Nishimura S-I. 2006. Construction and structural tronic limitations. Helv Chim Acta 88:2823–2831.
characterization of versatile lactosaminoglycan-related compound Nolen EG, Kurish AJ, Potter JM, Donahue LA, Orlando MD. 2005.
library for the synthesis of complex glycopeptides and glycosphingo- Stereoselective synthesis of a-C-glucosyl serine and alanine via a cross- lipids. J Org Chem 71:9609–9621.
metathesis/cyclization strategy. Org Lett 7:3383–3386.
Nasi R, Pinto BM. 2006. Synthesis of new analogues of salacinol containing a North SJ, Koles K, Hembd C, Morris HR, Dell A, Panin VM, Haslam SM.
pendant hydroxymethyl group as potential glycosidase inhibitors.
2006. Glycomic studies of Drosophila melanogaster embryos.
Carbohydr Res 341:2305–2311.
Glycoconj J 23:345–354.
Natalello A, Ami D, Brocca S, Lotti M, Doglia SM. 2005. Secondary Novotny MV, Mechref Y. 2005. New hyphenated methodologies in high- structure, conformational stability and glycosylation of a recombinant sensitivity glycoprotein analysis. J Sep Sci 28:1956–1968.
Candida rugosa lipase studied by Fourier-transform infrared spectro- Numata M, Ikeda A, Shinkai S. 2000. Properly assembled dendrons can be scopy. Biochem J 385:511–517.
immobilized into dendrimers by in situ cross-link. Chem Lett 29:370– Nergard CS, Kiyohara H, Reynolds JC, Thomas-Oates JE, Matsumoto T, Yamada H, Michaelsen TE, Diallo D, Paulsen BS. 2005. Structure- O'Connor ET, Piekarowicz A, Swanson KV, Griffiss JM, Stein DC. 2006.
immunomodulating activity relationships of a pectic arabinogalactan Biochemical analysis of Lpt3, a protein responsible for phosphoetha- from Vernonia kotschyana Sch. Bip. ex Walp. Carbohydr Res nolamine addition to lipooligosaccharide of pathogenic Neisseria. J Nergard CS, Kiyohara H, Reynolds JC, Thomas-Oates JE, Matsumoto T, Oguri S, Yoshida A, Minowa MT, Takeuchi M. 2006. Kinetic properties and Yamada H, Patel T, Petersen D, Michaelsen TE, Diallo D, Paulsen BS.
substrate specificities of two recombinant human N-acetylglucosami- 2006. Structures and structure-activity relationships of three mitogenic nyltransferase-IV isozymes. Glycoconj J 23:473–480.
and complement fixing pectic arabinogalactans from the Malianantiulcer plants Cochlospermum tinctorium A. Rich and Vernonia Ohga K, Takashima Y, Takahashi H, Kawaguchi Y, Yamaguchi H, Harada A.
kotschyana Sch. Bip. ex Walp. Biomacromolecules 7:71–79.
2005. Preparation of supramolecular polymers from a cyclodextrindimer and ditopic guest molecules: Control of structure by linker Neubacher B, Schmidt D, Ziegelmu¨ller P, Thiem J. 2005. Preparation of flexibility. Macromolecules 38:5897–5904.
sialylated oligosaccharides employing recombinant trans-sialidasefrom Trypanosoma cruzi. Org Biomol Chem 3:1551–1556.
Ojima N, Masuda K, Tanaka K, Nishimura O. 2005. Analysis of neutral Neuhof T, Schmieder P, Seibold M, Preussel K, von Do¨hren H. 2006.
oligosaccharides for structural characterization by matrix-assisted laser Hassallidin B—Second antifungal member of the Hassallidin family.
desorption/ionization quadrupole ion trap time-of-flight mass spec- Bioorg Med Chem Lett 16:4220–4222.
trometry. J Mass Spectrom 40:380–388.
Ngantung FA, Miller PG, Brushett FR, Tang GL, Wang DI. 2006. RNA Okada H, Fukushi E, Yamamori A, Kawazoe N, Onodera S, Kawabata J, interference of sialidase improves glycoprotein sialic acid content Shiomi N. 2006. Structural analysis of a novel saccharide isolated from consistency. Biotechnol Bioeng 95:106–119.
fermented beverage of plant extract. Carbohydr Res 341:925–929.
Nguema-Ona E, Ande me-Onzighi C, Aboughe-Angone S, Bardor M, Ishii T, Okuyama M, Tanimoto Y, Ito T, Anzai A, Mori H, Kimura A, Matsui H, Chiba Lerouge P, Driouich A. 2006. The reb 1-1 mutation of Arabidopsis.
S. 2005. Purification and characterization of the hyper-glycosylated Effect on the structure and localization of galactose-containing cell wall extracellular a-glucosidase from Schizosaccharomyces pombe. Enzyme polysaccharides. Plant Physiol 140:1406–1417.
Microb Technol 37:472–480.
Niedziela T, Dag S, Lukasiewicz J, Dzieciatkowska M, Jachymek W, Okuyama N, Ide Y, Nakano M, Nakagawa T, Yamanaka K, Moriwaki K, Lugowski C, Kenne L. 2006. Complete lipopolysaccharide of Murata K, Ohigashi H, Yokoyama S, Eguchi H, Ishikawa O, Ito T, Kato Plesiomonas shigelloides O74: H5 (strain CNCTC 144/92). 1.
M, Kasahara A, Kawano S, Gu J, Taniguchi N, Miyoshi E. 2006.
Structural analysis of the highly hydrophobic lipopolysaccharide, Fucosylated haptoglobin is a novel marker for pancreatic cancer: A including the O-antigen, its biological repeating unit, the core detailed analysis of the oligosaccharide structure and a possible oligosaccharide, and the linkage between them. Biochemistry mechanism for fucosylation. Int J Cancer 118:2803–2808.
Omaetxebarria MJ, Ha¨gglund P, Elortza F, Hooper NM, Arizmendi JM, Niedziela T, Letowska I, Lukasiewicz J, Kaszowska M, Czarnecka A, Kenne Jensen ON. 2006. Isolation and characterization of glycosylphospha- L, Lugowski C. 2005. Epitope of the vaccine-type Bordetella pertussis tidylinositol-anchored peptides by hydrophilic interaction chromatog- strain 186 lipooligosaccharide and antiendotoxin activity of antibodies raphy and MALDI tandem mass spectrometry. Anal Chem 78:3335– directed against the terminal pentasaccharide-tetanus toxoid conjugate.
Infect Immun 73:7381–7389.
Omtvedt LA, Royle L, Husby G, Sletten K, Radcliffe CM, Harvey DJ, Dwek Niikura K, Kamitani R, Kurogochi M, Uematsu R, Shinohara Y, Nakagawa H, Deguchi K, Monde K, Kondo H, Nishimura S. 2005. Versatile antibodies secreted in deposition disorders indicates that subsets of Mass Spectrometry Reviews DOI 10.1002/mas plasma cells differentially process IgG glycans. Arthritis Rheum Paschinger K, Staudacher E, Stemmer U, Fabini G, Wilson IBH. 2005.
Fucosyltransferase substrate specificity and the order of fucosylation in Onodera K-i, Hanashiro K, Yasumoto T. 2006. Camellianoside, a novel invertebrates. Glycobiology 15:463–474.
antioxidant glycoside from the leaves of Camellia japonica. Biosci Patel A, Lindhorst TK. 2006. Multivalent glycomimetics: Synthesis of Biotechnol Biochem 70:1995–1998.
nonavalent mannoside clusters with variation of spacer properties.
O'Reilly MK, Zhang G, Imperiali B. 2006. In vitro evidence for the dual Carbohydr Res 341:1657–1668.
function of Alg2 and Alg11: Essential mannosyltransferases in N- Pedersen NR, Kristensen JB, Bauw G, Ravoo BJ, Darcy R, Larsen KL, linked glycoprotein biosynthesis. Biochemistry 45:9593–9603.
Pedersen LH. 2005. Thermolysin catalyses the synthesis of cyclodextrin Ortega-Caballero F, Bjerre J, Laustsen LS, Bols M. 2005. Four orders of esters in DMSO. Tetrahedron Asym 16:615–622.
magnitude rate increase in artificial enzyme-catalyzed aryl glycoside Pe´rez S, Mulloy B. 2005. Prospects for glycoinformatics. Curr Opin Struct hydrolysis. J Org Chem 70:7217–7226.
Biol 15:517–524.
Oscarson S, Sehgelmeble FW. 2005. A stereoselective approach to Pe´rez-Balderas F, Herna´ndez-Mateo F, Santoyo-Gonza´lez F. 2005. Synthesis phosphodiester-linked oligomers of the repeating unit of Escherichia of multivalent neoglycoconjugates by 1,3 dipolar cycloaddition of coli K52 capsular polysaccharide containing b-D-fructofuranosyl nitrile oxides and alkynes and evaluation of their lectin-binding moieties. Tetrahedron Asym 16:121–125.
affinities. Tetrahedron 61:9338–9348.
Ostendorp T, Weibel M, Leclerc E, Kleinert P, Kroneck PMH, Heizmann CW, Peri F, Marinzi C, Barath M, Granucci F, Urbano M, Nicotra F. 2006.
Fritz G. 2006. Expression and purification of the soluble isoform of Synthesis and biological evaluation of novel lipid A antagonists. Bioorg human receptor for advanced glycation end products (sRAGE) from Med Chem 14:190–199.
Pichia pastoris. Biochem Biophys Res Commun 347:4–11.
Peri F, Nicotra F, Leslie CP, Micheli F, Seneci P, Marchioro C. 2003. D- Otto VI, Damoc E, Cueni LN, Schu¨rpf T, Frei R, Ali S, Callewaert N, Moise glucose as a regioselectively addressable scaffold for combinatorial A, Leary JA, Folkers G, Przybylski M. 2006. N-glycan structures and N- chemistry on solid phase. J Carbohydr Chem 22:57–71.
glycosylation sites of mouse soluble intercellular adhesion molecule-1 Pe´roche S, Degobert G, Putaux J-L, Blanchin M-G, Fessi H, Parrot-Lopez H.
revealed by MALDI-TOF and FTICR mass spectrometry. Glycobiology 2005. Synthesis and characterisation of novel nanospheres made from amphiphilic perfluoroalkylthio-b-cyclodextrins. Eur J Pharm Biopharm Pabba J, Mohal N, Vasella A. 2006. Synthesis of glucuronic, mannuronic, and galacturonic acid-derived imidazoles as inhibitors of bovine liver b- Perrone A, Plaza A, Bloise E, Nigro P, Hamed AI, Belisario MA, Pizza glucuronidase. Helv Chim Acta 89:1373–1386.
C, Piacente S. 2005. Cytotoxic furostanol saponins and a megasti- Palm AK, Novotny MV. 2005. A monolithic PNGase F enzyme microreactor gmane glucoside from Tribulus parvispinus. J Nat Prod 68:1549– enabling glycan mass mapping of glycoproteins by mass spectrometry.
Rapid Commun Mass Spectrom 19:1730–1738.
Peter-Katalinic J. 2005. O-glycosylation of proteins. Methods Enzymol Palm M, Zacchi G. 2003. Extraction of hemicellulosic oligosaccharides from spruce using microwave oven or steam treatment. Biomacromolecules4:617–623.
Petruccelli S, Otegui MS, Lareu F, Dinh OT, Fitchette A-C, Circosta A, Rumbo M, Bardor M, Carcamo R, Gomord V, Beachy RN. 2006. A Pan C, Xu S, Hu L, Su X, Ou J, Zou H, Guo Z, Zhang Y, Guo B. 2005. Using KDEL-tagged monoclonal antibody is efficiently retained in the oxidized carbon nanotubes as matrix for analysis of small molecules by endoplasmic reticulum in leaves, but is both partially secreted and MALDI-TOF MS. J Am Soc Mass Spectrom 16:883–892.
sorted to protein storage vacuoles in seeds. Plant Biotechnol J 4:511– Paramonov N, Rangarajan M, Hashim A, Gallagher A, Aduse-Opoku J, Slaney JM, Hounsell E, Curtis MA. 2005. Structural analysis of a novelanionic polysaccharide from Porphyromonas gingivalis strain W50 Pinto MR, Gorin PAJ, Wait R, Mulloy B, Barreto-Bergter E. 2005. Structures related to Arg-gingipain glycans. Mol Microbiol 58:847–863.
of the O-linked oligosaccharides of a complex glycoconjugate fromPseudallescheria boydii. Glycobiology 15:895–904.
Park H, Choi Y, Kang S, Lee S, Kwon C, Jung S. 2006. pH-dependent inclusion complexation of carboxymethylated cyclosophoraoses to N- Plaza A, Perrone A, Balestrieri C, Balestrieri ML, Bifulco G, Carbone V, acetylphenylalanine. Carbohydr Polym 64:85–91.
Hamed A, Pizza C, Piacente S. 2005a. New antiproliferative 14,15-secopregnane glycosides from Solenostemma argel. Tetrahedron 61: Park JK, Khan T, Jung JY. 2006. Structural studies of the glucuronic acid oligomers produced by Gluconacetobacter hansenii strain. CarbohydrPolym 63:482–486.
Plaza A, Perrone A, Balestrieri ML, Felice F, Balestrieri C, Hamed AI, Pizza Park N-Y, Baek N-I, Cha J, Lee S-B, Auh J-H, Park C-S. 2005a. Production of C, Piacente S. 2005b. New unusual pregnane glycosides with a new sucrose derivative by transglycosylation of recombinant antiproliferative activity from Solenostemma argel. Steroids 70:594– Sulfolobus shibatae b-glycosidase. Carbohydr Res 340:1089–1096.
Park T-H, Choi K-W, Park C-S, Lee S-B, Kang H-Y, Shon K-J, Park J-S, Cha J.
Pochec E, Litynska A, Bubka M, Amoresano A, Casbarra A. 2006.
2005b. Substrate specificity and transglycosylation catalyzed by a Characterization of the oligosaccharide component of a3b1 integrin thermostable b-glucosidase from marine hyperthermophile Thermo- from human bladder carcinoma cell line T24 and its role in adhesion and toga neapolitana. Appl Microbiol Biotechnol 69:411–422.
migration. Eur J Cell Biol 85:47–57.
Parry S, Hadaschik D, Blancher C, Kumaran MK, Bochkina N, Morris HR, Pojasek K, Raman R, Sasisekharan R. 2005. Structural characterization of Richardson S, Aitman TJ, Gauguier D, Siddle K, Scott J, Dell A. 2006a.
glycosaminoglycans. In: Yarema KJ, editor. Handbook of Carbohydrate Glycomics investigation into insulin action. Biochim Biophys Acta Engineering. Boca Raton, FL: Taylor and Francis. pp 177–210.
Powell AK, Harvey DJ. 1996. Stabilisation of sialic acids in N-linked Parry S, Hanisch FG, Leir S-H, Sutton-Smith M, Morris HR, Dell A, Harris A.
oligosaccharides and gangliosides for analysis by positive ion matrix- 2006b. N-glycosylation of the MUC1 mucin in epithelial cells assisted laser desorption-ionization mass spectrometry. Rapid Commun and secretions. Glycobiology 16:623–634.
Mass Spectrom 10:1027–1032.
Paschinger K, Hackl M, Gutternigg M, Kretschmer-Lubich D, Stemmer U, Preusser-Kunze A, Mariappan M, Schmidt B, Gande SL, Mutenda K, Wenzel Jantsch V, Lochnit G, Wilson IB. 2006. A deletion in the golgi alpha- D, von-Figura K, Dierks T. 2005. Molecular characterization of the mannosidase II gene of Caenorhabditis elegans results in unexpected human Ca-formylglycine-generating enzyme. J Biol Chem 280: non-wild-type N-glycan structures. J Biol Chem 281:28265–28277.
Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES Price NPJ. 2006. Oligosaccharide structures studied by hydrogen-deuterium polyketide sugars from racemic b-hydroxy aldehydes. Tetrahedron Lett exchange and MALDI-TOF mass spectrometry. Anal Chem 78:5302– Reynolds CM, Kalb SR, Cotter RJ, Raetz CRH. 2005. A phosphoethanol- Prior JL, Prior RG, Hitchen PG, Diaper H, Griffin KF, Morris HR, Dell A, amine transferase specific for the outer 3-deoxy-D-manno-octulosonic Titball RW. 2003. Characterization of the O antigen gene cluster and acid residue of Escherichia coli lipopolysaccharide. Identification of the structural analysis of the O antigen of Francisella tularensis subsp.
eptB gene and Ca2þ hypersensitivity of an eptB deletion mutant. J Biol tularensis. J Med Microbiol 52:845–851.
Psylinakis E, Boneca IG, Mavromatis K, Deli A, Hayhurst E, Foster SJ, Reynolds CM, Ribeiro AA, McGrath SC, Cotter RJ, Raetz CRH, Trent MS.
Va˚rum KM, Bouriotis V. 2005. Peptidoglycan N-acetylglucosamine 2006. An outer membrane enzyme encoded by Salmonella typhimurium deacetylases from Bacillus cereus, highly conserved proteins in lpxR that removes the 3'-acyloxyacyl moiety of lipid A. J Biol Chem Bacillus anthracis. J Biol Chem 280:30856–30863.
Pudelko M, Lindgren A, Tengel T, Reis CA, Elofsson M, Kihlberg J. 2006.
Ribeiro AO, Tome´ JPC, Neves MGPMS, Tome´ AC, Cavaleiro JAS, Iamamoto Formation of lactones from sialylated MUC1 glycopeptides. Org Y, Torres T. 2006. [1,2,3,4-Tetrakis(a/b-D-galactopyranos-6-yl)phtha- Biomol Chem 4:713–720.
locyaninato]zinc(II): A water-soluble phthalocyanine. Tetrahedron Lett Raju TS, Scallon BJ. 2006. Glycosylation in the Fc domain of IgG increases resistance to proteolytic cleavage by papain. Biochem Biophys Res Robinson S, Routledge A, Thomas-Oates J. 2005. Characterisation and proposed origin of mass spectrometric ions observed 30 Th above the Raman R, Raguram S, Venkataraman G, Paulson JC, Sasisekharan R. 2005.
ionised molecules of per-O-methylated carbohydrates. Rapid Commun Glycomics: An integrated systems approach to structure-function Mass Spectrom 19:3681–3688.
relationships of glycans. Nat Methods 2:817–824.
Ro¨hrig CH, Retz OA, Hareng L, Hartung T, Schmidt RR. 2005. A new Raman R, Venkataraman M, Ramakrishnan S, Lang W, Raguram S, strategy for the synthesis of dinucleotides loaded with glycosylated Sasisekharan R. 2006. Advancing glycomics: Implementation strat- amino acids—Investigations on in vitro non-natural amino acid egies at the Consortium for Functional Glycomics. Glycobiology mutagenesis for glycoprotein synthesis. ChemBioChem 6:1805–1816.
Roper JR, Guther ML, Macrae JI, Prescott AR, Hallyburton I, Acosta-Serrano Ra¨tto¨ M, Verhoef R, Suihko M-L, Blanco A, Schols HA, Voragen AGJ, A, Ferguson MA. 2005. The suppression of galactose metabolism in Wilting R, Siika-aho M, Buchert J. 2006. Colanic acid is an procylic form Trypanosoma brucei causes cessation of cell growth and exopolysaccharide common to many enterobacteria isolated from alters procyclin glycoprotein structure and copy number. J Biol Chem paper-machine slimes. J Ind Microbiol Biotechnol 33:359–367.
Ray B. 2006. Polysaccharides from Enteromorpha compressa: Isolation, Ro¨sch A, Kunz H. 2006. Highly regioselective synthesis of a 3-O-sulfonated purification and structural features. Carbohydr Polym 66:408– arabino Lewis asparagine building block suitable for glycopeptide synthesis. Carbohydr Res 341:1597–1608.
Rebber BL, Halfacre JA, Beran KA, Beller NR, Gomez M, Bashir S, Rose NL, Completo GC, Lin S-J, McNeil M, Palcic MM, Lowary TL. 2006.
Giannakopulos AE, Derrick PJ. 2006. Theoretical investigation of the Expression, purification, and characterization of a galactofuranosyl- proton affinity and gas-phase basicity of neutral x,y-dihydroxybenzoic transferase involved in Mycobacterium tuberculosis arabinogalactan acid and its derivatives. Eur J Mass Spectrom 12:385–396.
biosynthesis. J Am Chem Soc 128:6721–6729.
Regue´ M, Izquierdo L, Fresno S, Jimenez N, Pique´ N, Corsaro MM, Parrilli Rousseau C, Ortega-Caballero F, Nordstrøm LU, Christensen B, Petersen TE, M, Naldi T, Merino S, Toma´s JM. 2005a. The incorporation of Bols M. 2005. Artificial glycosyl phosphorylases. Chem Eur J 11: glucosamine into enterobacterial core lipopolysaccharide. Two enzy- matic steps are required. J Biol Chem 280:36648–36656.
Roychowdhury A, Wolfert MA, Boons G-J. 2005. Synthesis and proin- Regue´ M, Izquierdo L, Fresno S, Pique´ N, Corsaro MM, Naldi T, De Castro C, flammatory properties of muramyl tripeptides containing lysine and Waidelich D, Merino S, Toma´s JM. 2005b. A second outer-core region diaminopimelic acid moieties. ChemBioChem 6:2088–2097.
in Klebsiella pneumoniae lipopolysaccharide. J Bacteriol 187:4198– Rustam T, McClean S, Newcombe J, McFadden J, Eales-Reynolds L-J. 2006.
Reduced toxicity of lipo-oligosaccharide from a phoP mutant of Reife RA, Coats SR, Al-Qutub M, Dixon DM, Braham PA, Billharz RJ, Neisseria meningitidis: An in vitro demonstration. J Endotox Res Howald WN, Darveau RP. 2006. Porphyromonas gingivalis lip- opolysaccharide lipid A heterogeneity: Differential activities of tetra- Sagi D, Kienz P, Denecke J, Marquardt T, Peter-Katalinic J. 2005.
and penta-acylated lipid A structures on E-selectin expression and Glycoproteomics of N-glycosylation by in-gel deglycosylation and TLR4 recognition. Cell Microbiol 8:857–868.
matrix-assisted laser desorption/ionisation-time of flight mass spec- Rele SM, Cui W, Wang L, Hou S, Barr-Zarse G, Tatton D, Gnanou Y, Esko JD, trometry mapping: Application to congenital disorders of glycosyla- Chaikof EL. 2005. Dendrimer-like PEO glycopolymers exhibit anti- tion. Proteomics 5:2689–2701.
inflammatory properties. J Am Chem Soc 127:10132–10133.
Saito R, Yamaguchi K. 2005. Effect of guest compounds on template Ren S-F, Zhang L, Cheng Z-H, Guo YL. 2005. Immobilized carbon nanotubes polymerization of multivinyl monomer of cyclodextrins. Macro- as matrix for MALDI-TOF-MS analysis: Applications to neutral small carbohydrates. J Am Soc Mass Spectrom 16:333–339.
Saksena R, Adamo R, Kova´c P. 2005. Studies toward a conjugate vaccine for Rendic D, Linder A, Paschinger K, Borth N, Wilson IB, Fabini G. 2006.
anthrax. Synthesis and characterization of anthrose [4,6-dideoxy-4-(3- Modulation of neural carbohydrate epitope expression in Drosophila melanogaster cells. J Biol Chem 281:3343–3353.
methyl glycosides. Carbohydr Res 340:1591–1600.
Restelli V, Wang MD, Huzel N, Ethier M, Perreault H, Butler M. 2006. The Saksena R, Zhang J, Kova´c P. 2005. Immunogens from a synthetic effect of dissolved oxygen on the production and the glycosylation hexasaccharide fragment of the O-SP of Vibrio cholerae O:1, serotype profile of recombinant human erythropoietin produced from CHO cells.
Ogawa. Tetrahedron Asym 16:187–197.
Biotechnol Bioeng 94:481–489.
Sandler JS, Forsburg SL, Faulkner DJ. 2005. Bioactive steroidal glycosides Reyes E, Co´rdova A. 2005. Amino acid-catalyzed dynamic kinetic from the marine sponge Erylus lendenfeldi. Tetrahedron 61:1199– asymmetric transformations (DYKAT): One-step de novo synthesis of Mass Spectrometry Reviews DOI 10.1002/mas Sanz ML, Coˆte´ GL, Gibson GR, Rastall RA. 2005. Prebiotic properties of Sekiya S, Yamaguchi Y, Kato K, Tanaka K. 2005. Mechanistic elucidation of alternansucrase maltose-acceptor oligosaccharides. J Agric Food Chem the formation of reduced 2-aminopyridine-derivatized oligosaccharides and their application in matrix-assisted laser desorption/ionization mass Sanz ML, Coˆte´ GL, Gibson GR, Rastall RA. 2006. Selective fermentation of spectrometry. Rapid Commun Mass Spectrom 19:3607–3611.
gentiobiose-derived oligosaccharides by human gut bacteria and Seo E-S, Lee J-H, Park J-Y, Kim D, Han H-J, Robyt JF. 2005. Enzymatic influence of molecular weight. FEMS Microbiol Ecol 56:383–388.
synthesis and anti-coagulant effect of salicin analogs by using the Sanz-Nebot V, Benavente F, Gime´nez E, Barbosa J. 2005. Capillary Leuconostoc mesenteroides glucansucrase acceptor reaction. J Bio- electrophoresis and matrix-assisted laser desorption/ionization-time of flight-mass spectrometry for analysis of the novel erythropoiesis- Seppala U, Hagglund P, Wurtzen PA, Ipsen H, Thorsted P, Lenhard T, stimulating protein (NESP). Electrophoresis 26:1451–1456.
Roepstorff P, Spangfort MD. 2005. Molecular characterization of major Sarkar M, Leventis PA, Silvescu CI, Reinhold VN, Schachter H, Boulianne cat allergen Fel d 1: Expression of heterodimer by use of a baculovirus GL. 2006. Null mutations in drosophila N-acetylglucosaminyltransfer- expression system. J Biol Chem 280:3208–3216.
ase I produce defects in locomotion and a reduced life span. J Biol Chem Seyfried NT, Blundell CD, Day AJ, Almond A. 2005. Preparation and application of biologically active fluorescent hyaluronan oligosacchar- Sasaki A, Ishimizu T, Geyer R, Hase S. 2005. Synthesis of b-mannosides ides. Glycobiology 15:303–312.
using the transglycosylation activity of endo-b-mannosidase from Shao N, Guo Z. 2005. Solution-phase synthesis with solid-state workup of an Lilium longiflorum. FEBS J 272:1660–1668.
O-glycopeptide with a cluster of cancer-related T antigens. Org Lett Sasaki S, Shirahashi Y, Nishiyama K, Watanabe H, Hayase F. 2006.
Identification of a novel blue pigment as a melanoidin intermediate in Sherlock O, Dobrindt U, Jensen JP, Vejborg RM, Klemm P. 2006.
the D-xylose-glycine reaction system. Biosci Biotechnol Biochem Glycosylation of the self-recognizing Escherichia coli Ag43 auto- transporter protein. J Bacteriol 188:1798–1807.
Sasisekharan R, Shriver Z, Sundaram M, Venkataraman G. 2006. Analytical Shimizu M, Igasaki T, Yamada M, Yuasa K, Hasegawa J, Kato T, Tsukagoshi techniques for the characterization and sequencing of glycosylamino- H, Nakamura K, Fukuda H, Matsuoka K. 2005. Experimental glycans. In: Wong C-H, editor. Carbohydrate-based drug discovery.
determination of proline hydroxylation and hydroxyproline arabinoga- Hoboken, NJ: Wiley VCH. pp 517–540.
lactosylation motifs in secretory proteins. Plant J 42:877–889.
Sato H, Seino T, Yamamoto A, Torimura M, Tao H. 2005. Soft laser Shimma Y-I, Saito F, Oosawa F, Jigami Y. 2006. Construction of a library of desorption/ionization mass spectrometry using a pyroelectric ceramic human glycosyltransferases immobilized in the cell wall of Saccha- plate. Chem Lett 34:1178–1179.
romyces cerevisiae. Appl Environ Microbiol 72:7003–7012.
Sato K, Hada N, Takeda T. 2006. Syntheses of new peptidic glycoclusters Shinya T, Me´nard R, Kozone I, Matsuoka H, Shibuya N, Kauffmann S, derived from b-alanine: Di- and trimerized glycoclusters and Matsuoka K, Saito M. 2006. Novel b-1,3-, 1,6-oligoglucan elicitor from glycocluster-clusters. Carbohydr Res 341:836–845.
Alternaria alternata 102 for defense responses in tobacco. FEBS J Satterfield MB, Welch MJ. 2005. Comparison by LC-MS and MALDI-MS of prostate-specific antigen from five commercial sources with certified Shoda S-I, Misawa Y, Nishijima Y, Tawata Y, Kotake T, Noguchi M, reference material 613. Clin Biochem 38:166–174.
Kobayashi A, Watanabe T. 2006. Chemo-enzymatic synthesis of novel Schagerlo¨f H, Richardson S, Momcilovic D, Brinkmalm G, Wittgren B, oligo-N-acetyllactosamine derivatives having a b(1-4)-b(1-6) repeating Tjerneld F. 2006. Characterization of chemical substitution of unit by using transition state analogue substrate. Cellulose 13:477–484.
hydroxypropyl cellulose using enzymatic degradation. Biomacromo- Sicherl F, Wittmann V. 2005. Orthogonally protected sugar diamino acids as lecules 7:80–85.
building blocks for linear and branched oligosaccharide mimetics.
Schimmel J, Eleute´rio MIP, Ritter G, Schmidt RR. 2006. Synthesis of Angew Chem Int Ed Engl 44:2096–2099.
saponins with cholestanol, cholesterol, and friedelanol as aglycones.
Siemiatkoski J, Lyubarskaya Y, Houde D, Tep S, Mhatre R. 2006. A Eur J Org Chem:1701–1721.
comparison of three techniques for quantitative carbohydrate analysis Schmitt A, Bigl K, Meiners I, Schmitt J. 2006. Induction of reactive oxygen used in characterization of therapeutic antibodies. Carbohydr Res species and cell survival in the presence of advanced glycation end products and similar structures. Biochim Biophys Acta 1763:927–936.
Silchenko AS, Avilov SA, Antonov AS, Kalinovsky AI, Dmitrenok PS, Schmitt A, Gasic-Milenkovic J, Schmitt J. 2005. Characterization of Kalinin VI, Stonik VA, Woodward C, Collin PD. 2005. Glycosides from advanced glycation end products: Mass changes in correlation to side the sea cucumber Cucumaria frondosa. III. Structure of frondosides A2- chain modifications. Anal Biochem 346:101–106.
1, A2-2, A2-3, and A2-6, four new minor monosulfated triterpene Schulz E, Karas M, Rosu F, Gabelica V. 2006. Influence of the matrix on glycosides. Can J Chem 83:21–27.
analyte fragmentation in atmospheric pressure MALDI. J Am Soc Mass Silipo A, Lanzetta R, Parrilli M, Sturiale L, Garozzo D, Nazarenko EL, Gorshkova RP, Ivanova EP, Molinaro A. 2005a. The complete structure Schuster M, Umana P, Ferrara C, Bru¨nker P, Gerdes C, Waxenecker G, of the core carbohydrate backbone from the LPS of marine halophilic Wiederkum S, Schwager C, Loibner H, Himmler G, Mudde GC. 2005.
bacterium Pseudoalteromonas carrageenovora type strain IAM Improved effector functions of a therapeutic monoclonal Lewis Y- 12662T. Carbohydr Res 340:1475–1482.
specific antibody by glycoform engineering. Cancer Res 65:7934– Silipo A, Leone S, Molinaro A, Sturiale L, Garozzo D, Nazarenko EL, Gorshkova RP, Ivanova EP, Lanzetta R, Parrilli M. 2005b. Complete Schweizer F, Hindsgaul O. 2006. Synthesis of a galacto-configured C- structural elucidation of a novel lipooligosaccharide from the outer ketoside-based g-sugar-amino acid and its use in peptide coupling membrane of the marine bacterium Shewanella pacifica. Eur J Org reactions. Carbohydr Res 341:1730–1736.
Sˇebela M, Sˇtosova´ T, Havli J, Wielsch N, Thomas H, Zdra´hal Z, Shevchenko Silipo A, Molinaro A, Cescutti P, Bedini E, Rizzo R, Parrilli M, Lanzetta R.
A. 2006. Thermostable trypsin conjugates for high-throughput 2005c. Complete structural characterization of the lipid A fraction of a proteomics: Synthesis and performance evaluation. Proteomics 6: clinical strain of B. cepacia genomovar I lipopolysaccharide.
Sekiya S, Wada Y, Tanaka K. 2005. Derivatization for stabilizing sialic acids Silipo A, Molinaro A, Comegna D, Struiale L, Cescutti P, Garozzo D, in MALDI-MS. Anal Chem 77:4962–4968.
Lanzetta R, Parrilli M. 2006. Full structural characterisation of the Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES lipooligosaccharide of a Burkholderia pyrrocinia clinical isolate. Eur J St. John FJ, Rice JD, Preston JF. 2006. Characterization of XynC from Bacillus subtilis subsp. subtilis strain 168 and analysis of its role in Silipo A, Molinaro A, Nazarenko EL, Sturiale L, Garozzo D, Gorshkova RP, depolymerization of glucuronoxylan. J Bacteriol 188:8617–8626.
Nedashkovskaya OI, Lanzetta R, Parrilli M. 2005d. Structural Stadthagen G, Jackson M, Charles P, Boudou F, Barilone N, Huerre M, characterization of the carbohydrate backbone of the lipooligosacchar- Constant P, Liav A, Bottova I, Nigou J, Brando T, Puzo G, Daffe´ M, ide of the marine bacterium Arenibacter certesii strain KMM 3941T.
Benjamin P, Coade S, Buxton RS, Tascon RE, Rae A, Robertson BD, Carbohydr Res 340:2540–2549.
Lowrie DB, Young DB, Gicquel B, Griffin R. 2006. Comparative Silipo A, Molinaro A, Sturiale L, Dow JM, Erbs G, Lanzetta R, Newman M- investigation of the pathogenicity of three Mycobacterium tuberculosis A, Parrilli M. 2005e. The elicitation of plant innate immunity by mutants defective in the synthesis of p-hydroxybenzoic acid derivatives.
lipooligosaccharide of Xanthomonas campestris. J Biol Chem 280: Microbes Infect 8:2245–2253.
Stadthagen G, Kordulakova J, Griffin R, Constant P, Bottova I, Barilone N, Silva´n JM, van de Lagemaat J, Olano A, del Castillo MD. 2006. Analysis and Gicquel B, Daffe M, Jackson M. 2005. p-Hydroxybenzoic acid biological properties of amino acid derivates formed by Maillard synthesis in Mycobacterium tuberculosis. J Biol Chem 280:40699– reaction in foods. J Pharm Biomed Anal 41:1543–1551.
Skhirtladze A, Plaza A, Montoro P, Benidze M, Kemertelidze E, Pizza C, Staehelin C, Forsberg LS, D'Haeze W, Gao M-Y, Carlson RW, Xie Z-P, Piacente S. 2006. Furostanol saponins from Yucca gloriosa L. rhizomes.
Pellock BJ, Jones KM, Walker GC, Streit WR, Broughton WJ. 2006.
Biochem Syst Ecol 34:809–814.
Exo-oligosaccharides of Rhizobium sp. strain NGR234 are required forsymbiosis with various legumes. J Bacteriol 188:6168–6178.
Skov LK, Seppala U, Coen JJ, Crickmore N, King TP, Monsalve R, Kastrup JS, Spangfort MD, Gajhede M. 2006. Structure of recombinant Ves v 2 Staniszewska M, Jarosz S, Jon M, Gamian A. 2005. Advanced glycation end- at 2.0 Angstrom resolution: Structural analysis of an allergenic products prepared in solution under high pressure contain epitopes hyaluronidase from wasp venom. Acta Cryst 62:595–604.
distinct from those formed in the dry reaction at high temperature. ArchImmunol Exp Ther 53:71–78.
Smith DK, Hirst AR, Love CS, Hardy JG, Brignell SV, Huang B. 2005. Self- assembly using dendritic building blocks—Towards controllable Stanley P, Sundaram S, Tang J, Shi S. 2005. Molecular analysis of three gain- nanomaterials. Prog Polym Sci 30:220–293.
of-function CHO mutants that add the bisecting GlcNAc to N-glycans.
Glycobiology 15:43–53.
Snovida SI, Chen VC, Krokhin O, Perreault H. 2006. Isolation and identification of sialylated glycopeptides from bovine a Stead C, Tran A, Ferguson DJ, McGrath S, Cotter R, Trent S. 2005. A novel 3- protein by off-line capillary electrophoresis MALDI-TOF mass deoxy-D-manno-octulosonic acid (Kdo) hydrolase that removes the spectrometry. Anal Chem 78:6556–6563.
outer Kdo sugar of Helicobacter pylori lipopolysaccharide. J Bacteriol187:3374–3383.
Snovida SI, Chen VC, Perreault H. 2006. Use of a 2,5-dihydroxybenzoic acid/aniline MALDI matrix for improved detection and on-target Steiner K, Pohlentz G, Dreisewerd K, Berkenkamp S, Messner P, Peter- derivatization of glycans: A preliminary report. Anal Chem 78:8561– Katalinic J, Scha¨ffer C. 2006. New Insights into the glycosylation of the surface layer protein SgsE from Geobacillus stearothermophilus NRS2004/3a. J Bacteriol 188:7914–7921.
Sol A, Charmot A, Krausz P, Trombotto S, Queneau Y. 2005. Synthesis of new glucosylated porphyrins bearing an a- Strasser R, Schoberer J, Jin C, Glo¨ssl J, Mach L, Steinkellner H. 2006.
D-linkage. J Carbohydr Chem Molecular cloning and characterization of Arabidopsis thaliana Golgia-mannosidase II, a key enzyme in the formation of complex N-glycans Sol V, Chaleix V, Champavier Y, Granet R, Huang Y-M, Krausz P. 2006.
in plants. Plant J 45:789–803.
Glycosyl bis-porphyrin conjugates: Synthesis and potential applicationin PDT. Bioorg Med Chem 14:7745–7760.
Strasser R, Stadlmann J, Svoboda B, Altmann F, Glo¨ssl J, Mach L. 2005.
Molecular basis of N-acetylglucosaminyltransferase I deficiency in Solte´s L, Stankovskya´ M, Brezova´ V, Schiller J, Arnhold J, Mendichi R, Arabidopsis thaliana plants lacking complex N-glycans. Biochem J Kogan G, Gemeiner P. 2006. Hyaluronan degradation by copper(II) chloride and ascorbate: Rotational viscometric, EPR spin-trapping andMALDI-TOF mass spectrometric investigations. Carbohydr Res Stu¨biger G, Marchetti M, Nagano M, Grimm R, Gmeiner G, Reichel C, Allmaier G. 2005a. Characterization of N- and O-glycopeptides ofrecombinant human erythropoietins as potential biomarkers for doping Sørensen AL, Reis CA, Tarp MA, Mandel U, Ramachandran K, Sankaranar- analysis by means of microscale sample purification combined with ayanan V, Schwientek T, Graham R, Taylor-Papadimitriou J, Hollings- MALDI-TOF and quadrupole IT/RTOF mass spectrometry. J Sep Sci worth MA, Burchell J, Clausen H. 2006. Chemoenzymatically synthesized multimeric Tn/STn MUC1 glycopeptides elicit cancer-specific anti-MUC1 antibody responses and override tolerance.
Stu¨biger G, Marchetti M, Nagano M, Reichel C, Gmeiner G, Allmaier G.
2005b. Characterisation of intact recombinant human erythropoietins Soria-Dı´az ME, Rodrı´guez-Carvajal MA, Tejero-Mateo P, Espartero JL, applied in doping by means of planar gel electrophoretic techniques and Moro´n B, Sousa C, Megı´as M, Thomas-Oates J, Gil-Serrano AM. 2006.
matrix-assisted laser desorption/ionisation linear time-of-flight mass Structural determination of the Nod factors produced by Rhizobium spectrometry. Rapid Commun Mass Spectrom 19:728–742.
gallicum bv. gallicum R602. FEMS Microbiol Lett 255:164–173.
Sturiale L, Barone R, Fiumara A, Perez M, Zaffanello M, Sorge G, Pavone L, Sparbier K, Koch S, Kessler I, Wenzel T, Kostrzewa M. 2005. Selective Tortorelli S, O'Brien JF, Jaeken J, Garozzo D. 2005a. Hypoglycosy- isolation of glycoproteins and glycopeptides for MALDI-TOF MS lation with increased fucosylation and branching of serum transferrin N- detection supported by magnetic particles. J Biomol Tech 16:405–411.
glycans in untreated galactosemia. Glycobiology 15:1268–1276.
Sparbier K, Wenzel T, Kostrzewa M. 2006. Exploring the binding profiles of Sturiale L, Garozzo D, Silipo A, Lanzetta R, Parrilli M, Molinaro A. 2005b.
ConA, boronic acid and WGA by MALDI-TOF/TOF MS and magnetic New conditions for matrix-assisted laser desorption/ionization mass particles. J Chromatogr B 840:29–36.
spectrometry of native bacterial R-type lipopolysaccharides. Rapid Srinivas O, Mitra N, Surolia A, Jayaraman N. 2005. Photoswitchable cluster Commun Mass Spectrom 19:1829–1834.
glycosides as tools to probe carbohydrate-protein interactions: Syn- Subramaniam V, Gurcha SS, Besra GS, Lowary TL. 2005. Modified mannose thesis and lectin-binding studies of azobenzene containing multivalent disaccharides as substrates and inhibitors of a polyprenol mono- sugar ligands. Glycobiology 15:861–873.
phosphomannose-dependent a-(1-6)-mannosyltransferase involved in Mass Spectrometry Reviews DOI 10.1002/mas mycobacterial lipoarabinomannan biosynthesis. Bioorg Med Chem Taguchi F, Takeuchi K, Katoh E, Murata K, Suzuki T, Marutani M, Kawasaki T, Eguchi M, Katoh S, Kaku H, Yasuda C, Inagaki Y, Toyoda K, Sun Y, Hayakawa S, Ogawa M, Izumori K. 2005. Evaluation of the site Shiraishi T, Ichinose Y. 2006. Identification of glycosylation genes and specific protein glycation and antioxidant capacity of rare sugar- glycosylated amino acids of flagellin in Pseudomonas syringae pv.
protein/peptide conjugates. J Agric Food Chem 53:10205–10212.
tabaci. Cell Microbiol 8:923–938.
Sun Y, Hayakawa S, Puangmanee S, Izumori K. 2006. Chemical properties Taira H, Nagase H, Endo T, Ueda H. 2006. Isolation, purification and and antioxidative activity of glycated a-lactalbumin with a rare sugar, characterization of large-ring cyclodextrins (CD36-CD39). J Incl allose, by Maillard reaction. Food Chem 95:509–517.
Phenom Macrocyclic Chem 56:23–28.
Sundgren A, Lahmann M, Oscarson S. 2005. Block synthesis of Tajiri M, Yoshida S, Wada Y. 2005. Differential analysis of site-specific Streptococcus pneumoniae type 14 capsular polysaccharide structures.
glycans on plasma and cellular fibronectins: Application of a hydro- J Carbohydr Chem 24:379–391.
philic affinity method for glycopeptide enrichment. Glycobiology15:1332–1340.
Suzuki H, Yamagaki T, Tachibana K. 2005. Optimization of matrix and amount of ammonium chloride additive for effective ionization of Takahashi H, Takashima Y, Yamaguchi H, Harada A. 2006. Selection between neutral oligosaccharides as chloride ion adducts in negative-mode pinching-type and supramolecular polymer-type complexes by a- MALDI-TOF mass spectrometry. J Mass Spectrom Soc Jpn 53:227– cyclodextrin-b-cyclodextrin hetero-dimer and hetero-cinnamamide guest dimers. J Org Chem 71:4878–4883.
Suzuki H, Yamagaki T, Tachibana K. 2006. Optimization for effective Takahashi N, Okada H, Fukushi E, Onodera S, Nishimoto T, Kawabata J, ionization of neutral oligosaccharides in negative-ion MALDI-MS.
Shiomi N. 2005. Structural analysis of six novel oligosaccharides Nippon Kagakkai Koen Yokoshu 86:503.
synthesized by glucosyl transfer from b-D-glucose 1-phosphate toraffinose and stachyose using Thermoanaerobacter brockii kojibiose Suzuki S, Fujimori T, Yodoshi M. 2006. Recovery of free oligosaccharides phosphorylase. Tetrahedron Asym 16:57–63.
from derivatives labeled by reductive amination. Anal Biochem 354:94–103.
Takashiba M, Chiba Y, Jigami Y. 2006. Identification of phosphorylation sites in N-linked glycans by matrix-assisted laser desorption/ionization time- Suzuki T, Hara I, Nakano M, Shigeta M, Nakagawa T, Kondo A, Funakoshi Y, of-flight mass spectrometry. Anal Chem 78:5208–5213.
Taniguchi N. 2006a. Man2C1, an a-mannosidase, is involved inthe trimming of free oligosaccharides in the cytosol. Biochem J 400: Takeda M, Makita H, Ohno K, Nakahara Y, Koizumi J. 2005. Structural analysis of the sheath of a sheathed bacterium, Leptothrix cholodnii. IntJ Biol Macromol 37:92–98.
Suzuki T, Hara I, Nakano M, Zhao G, Lennarz WJ, Schindelin H, Taniguchi N, Totani K, Matsuo I, Ito Y. 2006b. Site-specific labeling of Takemori N, Komori N, Matsumoto H. 2006. Highly sensitive multistage cytoplasmic peptide: N-glycanase by N,N'-diacetylchitobiose-related mass spectrometry enables small-scale analysis of protein glycosylation compounds. J Biol Chem 281:22152–22160.
from two-dimensional polyacrylamide gels. Electrophoresis 27:1394–1406.
Suzuki Y, Suzuki M, Ito E, Goto-Inoue N, Miseki K, Iida J, Yamazaki Y, Yamada M, Suzuki A. 2006c. Convenient structural analysis of Talabnin K, Yagi H, Takahashi N, Suzuki T, Kato K, Uemura H, Saichua P, glycosphingolipids using MALDI-QIT-TOF mass spectrometry with Kaewkes S, Wongkham S, Suzuki Y, Sripa B. 2006. Glycobiological increased laser power and cooling gas flow. J Biochem (Tokyo) 139: study of adult Opisthorchis viverrini: Characterization of N-linked oligosaccharides. Mol Biochem Parasitol 147:230–233.
Suzuki Y, Suzuki M, Ito E, Ishii H, Miseki K, Suzuki A. 2005. Convenient and Tamayo R, Choudhury B, Septer A, Merighi M, Carlson R, Gunn JS. 2005.
rapid analysis of linkage isomers of fucose-containing oligosaccharides Identification of cptA, a PmrA-regulated locus required for phospho- by matrix-assisted laser desorption/ionization quadrupole ion trap time- ethanolamine modification of the Salmonella enterica serovar typhi- of-flight mass spectrometry. Glycoconj J 22:427–431.
murium lipopolysaccharide core. J Bacteriol 187:3391–3399.
Suzuki Y, Suzuki M, Nakahara Y, Ito Y, Ito E, Goto N, Miseki K, Iida J, Suzuki Tanabe K, Ikenaka K. 2006. In-column removal of hydrazine and N- A. 2006d. Structural characterization of glycopeptides by N-terminal acetylation of oligosaccharides released by hydrazionolysis. Anal protein ladder sequencing. Anal Chem 78:2239–2243.
Svarovsky SA, Szekely Z, Barchi JJ. 2005. Synthesis of gold nanoparticles Tanaka E, Nakahara Y, Kuroda Y, Takano Y, Kojima N, Hojo H, Nakahara Y.
bearing the Thomsen-Friedenreich disaccharide: A new multivalent 2006. Chemoenzymatic synthesis of a MUC1 glycopeptide carrying presentation of an important tumor antigen. Tetrahedron Asym 16:587– non-natural sialyl TF-b O-glycan. Biosci Biotechnol Biochem 70: Swanson KV, Griffiss JM. 2006. Separation and identification of neisserial Tang H, Mechref Y, Novotny MV. 2005. Automated interpretation of MS/MS lipooligosaccharide oligosaccharides using high-performance anion- spectra of oligosaccharides. Bioinformatics 21:i431–i439.
exchange chromatography with pulsed amperometric detection.
Tang S-Y, Yang S-J, Cha H, Woo E-J, Park C, Park K-H. 2006. Contribution of Carbohydr Res 341:388–396.
W229 to the transglycosylation activity of 4-a-glucanotransferase from Swanwick RS, Daines AM, Flitsch SL, Allemann RK. 2005. Synthesis of Pyrococcus furiosus. Biochim Biophys Acta 1764:1633–1638.
homogenous site-selectively glycosylated proteins. Org Biomol Chem Taylor AM, Holst O, Thomas-Oates J. 2006. Mass spectrometric profiling of O-linked glycans released directly from glycoproteins in gels using in- Szafranek J, Kumirska J, Czerwicka M, Kunikowska D, Dziadziuszko H, gel reductive b-elimination. Proteomics 6:2936–2946.
Glosnicka R. 2006. Structure and heterogeneity of the O-antigen chain ten Cate MGJ, Omerovi M, Oshovsky GV, Crego-Calama M, Reinhoudt DN.
of Salmonella agona lipopolysaccharide. FEMS Immunol Med Micro- 2005. Self-assembly and stability of double rosette nanostructures with biol 48:223–236.
biological functionalities. Org Biomol Chem 3:3727–3733.
Szolcsa´nyi P, Gracza T. 2006. PdCl2/CuCl2-catalysed chlorocyclisation of Terada M, Khoo KH, Inoue R, Chen CI, Yamada K, Sakaguchi H, Kadowaki sugar-derived aminoalkenitols in the synthesis of new iminohexitols.
N, Ma BY, Oka S, Kawasaki T, Kawasaki N. 2005. Characterization of oligosaccharide ligands expressed on SW1116 cells recognized by Sztaricskai F, Sum A, Roth E, Pelyva´s IF, Sa´ndor S, Batta G, Herczegh P, mannan-binding protein. A highly fucosylated polylactosamine type N- Reme´nyi J, Mikla´n Z, Hudecz F. 2005. A new class of semisynthetic glycan. J Biol Chem 280:10897–10913.
anthracycline glycoside antibiotics incorporating a squaric acid moiety.
Teramoto N, Abe Y, Enomoto A, Watanabe D, Shibata M. 2005. Novel J Antibiot 58:704–714.
synthetic route of a trehalose-based linear polymer by ring opening of Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES two epoxy groups with aliphatic diamine. Carbohydr Polym 59:217– ide structures containing dideoxy sugars and a cyclic phosphate. Org Biomol Chem 4:1236–1241.
Terinek M, Vasella A. 2005. Synthesis and evaluation of two mannosamine- Ueki M, Yamaguchi M. 2005. Analysis of acidic carbohydrates as their derived lactone-type inhibitors of snail b-mannosidase. Tetrahedron quaternary ammonium or phosphonium salts by matrix-assisted laser Asym 16:449–469.
desorption/ionization mass spectrometry. Carbohydr Res 340:1722– Thaysen-Andersen M, Højrup P. 2006. Enrichment and characterization of glycopeptides from gel-separated glycoproteins. Am Biotechnol Lab Uematsu R, Furukawa J-I, Nakagawa H, Shinohara Y, Deguch K, Monde K, Nishimura S-I. 2005. High throughput quantitative glycomics and Tholey A, Heinzle E. 2006. Ionic (liquid) matrices for matrix-assisted laser glycoform-focused proteomics of murine dermis and epidermis. Mol desorption/ionization mass spectrometry-applications and perspec- Cell Proteomics 4:1977–1989.
tives. Anal Bioanal Chem 386:24–37.
Uemura Y, Asakuma S, Nakamura T, Arai I, Taki M, Urashima T. 2005.
Thoma G, Streiff MB, Katopodis AG, Duthaler RO, Voelcker NH, Ehrhardt C, Occurrence of a unique sialyl tetrasaccharide in colostrum of a Masson C. 2006. Non-covalent polyvalent ligands by self-assembly of bottlenose dolphin (Tursiops truncatus). Biochim Biophys Acta small glycodendrimers: A novel concept for the inhibition of polyvalent carbohydrate-protein interactions in vitro and in vivo. Chem Eur J Ullmer R, Plematl A, Rizzi A. 2006. Derivatization by 6-aminoquinolyl-N- hydroxysuccinimidyl carbamate for enhancing the ionization yield of Tie J-K, Zheng M-Y, Pope RM, Straight DL, Stafford DW. 2006.
small peptides and glycopeptides in matrix-assisted laser desorption/ Identification of the N-linked glycosylation sites of vitamin K- ionization and electrospray ionization mass spectrometry. Rapid dependent carboxylase and effect of glycosylation on carboxylase Commun Mass Spectrom 20:1469–1479.
function. Biochemistry 45:14755–14763.
Usuki S, Thompson SA, Rivner MH, Taguchi K, Shibata K, Ariga T, Yu RK.
Tolbert TJ, Franke D, Wong C-H. 2005. A new strategy for glycoprotein 2006. Molecular mimicry: Sensitization of Lewis rats with Campylo- synthesis: Ligation of synthetic glycopeptides with truncated proteins bacter jejuni lipopolysaccharides induces formation of antibody toward expressed in E. coli as TEV protease cleavable fusion protein. Bioorg GD3 ganglioside. J Neurosci Res 83:274–284.
Med Chem 13:909–915.
Utz S, Roditi I, Renggli CK, Almeida IC, Acosta-Serrano A, Bu¨tikofer P.
Totani K, Ihara Y, Matsuo I, Koshino H, Ito Y. 2005. Synthetic substrates for 2006. Trypanosoma congolense procyclins: Unmasking cryptic major an endoplasmic reticulum protein-folding sensor, UDP-glucose: surface glycoproteins in procyclic forms. Eukaryot Cell 5:1430–1440.
Glycoprotein glucosyltransferase. Angew Chem Int Ed Engl 44: Vaidyanathan G, Affleck DJ, Schottelius M, Wester H, Friedman HS, Zalutsky MR. 2006. Synthesis and evaluation of glycosylated octreotate Totani K, Matsuo I, Ihara Y, Ito Y. 2006. High-mannose-type glycan analogues labeled with radioiodine and 211At via a tin precursor.
modifications of dihydrofolate reductase using glycan-methotrexate Bioconjug Chem 17:195–203.
conjugates. Bioorg Med Chem 14:5220–5229.
Van Riet E, Wuhrer M, Wahyuni S, Retra K, Deelder AM, Tielens AGM, Van Touboul D, Roy S, Germain DP, Baillet A, Brion F, Prognon P, Chaminade P, Der Kleij D, Yazdanbakhsh M. 2006. Antibody responses to Ascaris- Lapre´vote O. 2005. Fast fingerprinting by MALDI-TOF mass derived proteins and glycolipids: The role of phosphorylcholine.
spectrometry of urinary sediment glycosphingolipids in Fabry disease.
Parasite Immunol 28:363–371.
Anal Bioanal Chem 382:1209–1216.
van Roon A-MM, Aguilera B, Cuenca F, van Remoortere A, van der Marel Tran AX, Lester ME, Stead CM, Raetz CRH, Maskell DJ, McGrath SC, GA, Deelder AM, Overkleeft HS, Hokke CH. 2005. Synthesis and Cotter RJ, Trent MS. 2005. Resistance to the antimicrobial peptide antibody-binding studies of a series of parasite fuco-oligosaccharides.
polymyxin requires myristoylation of Escherichia coli and Salmonella Bioorg Med Chem 13:3553–3564.
typhimurium lipid A. J Biol Chem 280:28186–28194.
Vedam V, Kannenberg E, Datta A, Brown D, Haynes-Gann JG, Sherrier DJ, Tran AX, Whittimore JD, Wyrick PB, McGrath SC, Cotter RJ, Trent MS.
Carlson RW. 2006. The pea nodule environment restores the ability of a 2006. The lipid A 1-phosphatase of Helicobacter pylori is required for Rhizobium leguminosarum lipopolysaccharide acpXL mutant to add resistance to the antimicrobial peptide polymyxin. J Bacteriol 188: 27-hydroxyoctacosanoic acid to its lipid A. J Bacteriol 188:2126– Tranchepain F, Deschrevel B, Courel M-N, Levasseur N, Le Cerf D, Verhagen C, Bryld T, Raunkjær M, Vogel S, Buchalova´ K, Wengel J. 2006. A Loutelier-Bourhis C, Vincent J-C. 2006. A complete set of hyaluronan conformationally locked aminomethyl C-glycoside and studies on its N- fragments obtained from hydrolysis catalyzed by hyaluronidase: pyren-1-ylcarbonyl derivative inserted into oligodeoxynucleotides. Eur Application to studies of hyaluronan mass distribution by simple HPLC J Org Chem:2538–2548.
devices. Anal Biochem 348:232–242.
Verhoef R, Beldman G, Schols HA, Siika-aho M, Ra¨tto¨ M, Buchert J, Voragen Triguero A, Cabrera G, Cremata JA, Yuen C-T, Wheeler J, Ramirez NI. 2006.
AGJ. 2005. Characterisation of a 1,4-b-fucoside hydrolase degrading Plant-derived mouse IgG monoclonal antibody fused to KDEL colanic acid. Carbohydr Res 340:1780–1788.
endoplasmic reticulum-retention signal is N-glycosylated homogene- Vialle S, Sepulcri P, Dubayle J, Talaga P. 2005. The teichoic acid (C- ously throughout the plant with mostly high-mannose-type N-glycans.
polysaccharide) synthesized by Streptococcus pneumoniae serotype 5 Plant Biotechnol J 3:449–457.
has a specific structure. Carbohydr Res 340:91–96.
Trimpin S, Ra¨der HJ, Mu¨llen K. 2006. Investigations of theoretical principles Vila-Perello´ M, Gallego R, Andreu D. 2005. A simple approach to well- for MALDI-MS derived from solvent-free sample preparation: Part I.
defined sugar-coated surfaces for interaction studies. ChemBioChem Preorganization. Int J Mass Spectrom 253:13–21.
Tropis M, Meniche X, Wolf A, Gebhardt H, Strelkov S, Chami M, Schomburg Vinogradov E, Caroff M. 2005. Structure of the Bordetella trematum LPS O- D, Kramer R, Morbach S, Daffe M. 2005. The crucial role of trehalose chain subunit. FEBS Lett 579:18–24.
and structurally related oligosaccharides in the biosynthesis and transfer von der Lieth C-W, Lu¨tteke T, Frank M. 2006. The role of informatics in of mycolic acids in Corynebacterineae. J Biol Chem 280:26573– glycobiology research with special emphasis on automatic interpreta- tion of MS spectra. Biochim Biophys Acta 1760:568–577.
Turek D, Sundgren A, Lahmann M, Oscarson S. 2006. Synthesis of von Witzendorff D, Ekhlasi-Hundrieser M, Dostalova Z, Resch M, Rath D, oligosaccharides corresponding to Vibrio cholerae O139 polysacchar- Michelmann HW, Topfer-Petersen E. 2005. Analysis of N-linked Mass Spectrometry Reviews DOI 10.1002/mas glycans of porcine zona pellucida glycoprotein ZPA by MALDI-TOF Webber D, Radcliffe CM, Royle L, Tobiasen G, Merry AH, Rodgers AL, MS: A contribution to understanding zona pellucida structure.
Sturrock ED, Wormald MR, Harvey DJ, Dwek RA, Rudd PM. 2006.
Sialylation of urinary prothrombin fragment 1 is implicated as a Vosseller K, Trinidad JC, Chalkley RJ, Specht CG, Thalhammer A, Lynn AJ, contributory factor in the risk of calcium oxalate kidney stone Snedecor JO, Guan S, Medzihradszky KF, Maltby DA, Schoepfer R, formation. FASEB J 273:3024–3037.
Burlingame AL. 2006. O-linked N-acetylglucosamine proteomics of Weerapana E, Glover KJ, Chen MM, Imperiali B. 2005. Investigating postsynaptic density preparations using lectin weak affinity chromatog- bacterial N-linked glycosylation: Synthesis and glycosyl acceptor raphy and mass spectrometry. Mol Cell Proteomics 5:923–934.
activity of the undecaprenyl pyrophosphate-linked bacillosamine. J Am Voutquenne L, Guinot P, Froissard C, Thoison O, Litaudon M, Lavaud C.
Chem Soc 127:13766–13767.
2005. Haemolytic acylated triterpenoid saponins from Harpullia Wei L, Wei G, Zhang H, Wang PG, Du Y. 2005a. Synthesis of new, potent avermectin-like insecticidal agents. Carbohydr Res 340:1583– Wa C, Cerny R, Hage DS. 2006. Obtaining high sequence coverage in matrix- assisted laser desorption time-of-flight mass spectrometry for studies of Wei Y, Yen TY, Cai J, Trent JO, Pierce WM, Young WW. 2005b. Structural protein modification: Analysis of human serum albumin as a model.
features of the lysosomal hydrolase mannose 6-phosphate uncovering Anal Biochem 349:229–241.
enzyme. Glycoconj J 22:13–19.
Wacker M, Feldman MF, Callewaert N, Kowarik M, Clarke BR, Pohl NL, Weimer PJ, Price NPJ, Kroukamp O, Joubert L-M, Wolfaardt GM, Van Zyl Hernandez M, Vines ED, Valvano MA, Whitfield C, Aebi M. 2006.
WH. 2006. Studies of the extracellular glycocalyx of the anaerobic Substrate specificity of bacterial oligosaccharyltransferase suggests a cellulolytic bacterium Ruminococcus albus 7. Appl Environ Microbiol common transfer mechanism for the bacterial and eukaryotic systems.
Proc Natl Acad Sci USA 103:7088–7093.
Westerlind U, Norberg T. 2006. Chemical synthesis of analogs of the Wacker R, Stoeva S, Betzel C, Voelter W. 2005. Complete structure glycopeptide contulakin-G, an analgetically active conopeptide from determination of N-acetyl-D-galactosamine-binding mistletoe lectin-3 Conus geographus. Carbohydr Res 341:9–18.
from Viscum album L. album. J Peptide Sci 11:289–302.
Wilson JC, Hitchen PG, Frank M, Peak IR, Collins PM, Morris HR, Dell A, Wada Y. 2006. Mass spectrometry for congenital disorders of glycosylation, Grice ID. 2005. Identification of a capsular polysaccharide from CDG. J Chromatogr B 838:3–8.
Moraxella bovis. Carbohydr Res 340:765–769.
Wahrenbrock MG, Varki A. 2006. Multiple hepatic receptors cooperate to Wolfenden ML, Cloninger MJ. 2005. Mannose/glucose-functionalized eliminate secretory mucins aberrantly entering the bloodstream: Are dendrimers to investigate the predictable tunability of multivalent circulating cancer mucins the ‘‘tip of the iceberg''? Cancer Res interactions. J Am Chem Soc 127:12168–12169.
Wolfenden ML, Cloninger MJ. 2006. Carbohydrate-functionalized den- Walter M, Wiegand M, Lindhorst TK. 2006. Synthesis of cluster mannosides drimers to investigate the predictable tunability of multivalent carrying a photolabile diazirine group. Eur J Org Chem:719–728.
interactions. Bioconjug Chem 17:958–966.
Wang H-W, Liu Y-Q, Feng C-G. 2006. Isolation and identification of a novel Wong C-H. 2005. Protein glycosylation: New challenges and opportunities. J flavonoid from Penthorum chinense P. J Asian Nat Prod Res 8:757–761.
Org Chem 70:4219–4225.
Wang J, Li J, Chen H-N, Chang H, Tanifum CT, Liu H-H, Czyryca PG, Chang Wong NSC, Yap MGS, Wang DIC. 2006. Enhancing recombinant C-WT. 2005a. Glycodiversification for the optimization of the glycoprotein sialylation through CMP-sialic acid transporter over kanamycin class aminoglycosides. J Med Chem 48:6271–6285.
expression in Chinese hamster ovary cells. Biotechnol Bioeng 93: Wang J, Mou H, Jiang X, Guan H. 2006a. Characterization of a novel beta- agarase from marine Alteromonas sp. SY37-12 and its degrading Woosley B, Xie M, Wells L, Orlando R, Garrison D, King D, products. Appl Microbiol Biotechnol 71:833–839.
Bergmann C. 2006a. Comprehensive glycan analysis of recombinant Wang X, McGrath SC, Cotter RJ, Raetz CRH. 2006b. Expression cloning and Aspergillus niger endo-polygalacturonase C. Anal Biochem 354:43– periplasmic orientation of the Francisella novicida Lipid A 40- phosphatase LpxF. J Biol Chem 281:9321–9330.
Woosley BD, Kim YH, Kolli VSK, Wells L, King D, Poe R, Orlando R, Wang X, Ribeiro AA, Guan Z, McGrath SC, Cotter RJ, Raetz CRH. 2006c.
Bergmann C. 2006b. Glycan analysis of recombinant Aspergillus niger Structure and biosynthesis of free lipid A molecules that replace endo-polygalacturonase A. Carbohydr Res 341:2370–2378.
lipopolysaccharide in Francisella tularensis subsp. novicida. Bio- Wopereis S, Morava E, Gru¨newald S, Mills PB, Winchester BG, Clayton P, Coucke P, Huijben KMLC, Wevers RA. 2005. A combined defect in the Wang Y, Han F, Hu B, Li J, Yu W. 2006d. In vivo prebiotic properties of biosynthesis of N- and O-glycans in patients with cutis laxa and alginate oligosaccharides prepared through enzymatic hydrolysis of neurological involvement: The biochemical characteristics. Biochim alginate. Nutr Res 26:597–603.
Biophys Acta 1741:156–164.
Wang Y, Yan Q, Wu J, Zhang L-H, Ye X-S. 2005b. A new one-pot synthesis of Wu P, Malkoch M, Hunt JN, Vestberg R, Kaltgrad E, Finn MG, Fokin VV, a-Gal epitope derivatives involved in the hyperacute rejection response Sharpless BS, Hawker CJ. 2005. Multivalent, bifunctional dendrimers in xenotransplantation. Tetrahedron 61:4313–4321.
prepared by click chemistry. Chem Commun:5775–5777.
Warabi K, Hamada T, Nakao Y, Matsunaga S, Hirota H, van Soest RWM, Wu X, Bundle DR. 2005. Synthesis of glycoconjugate vaccines for Candida Fusetani N. 2005. Axinelloside A, an unprecedented highly sulfated albicans using novel linker methodology. J Org Chem 70:7381– lipopolysaccharide inhibiting telomerase, from the marine sponge, Axinella infundibula. J Am Chem Soc 127:13262–13270.
Wuhrer M, Balog CIA, Catalina MI, Jones FM, Schramm G, Haas H, Ward RE, Ninonuevo M, Mills DA, Lebrilla CB, German JB. 2006. In vitro Doenhoff MJ, Dunne DW, Deelder AM, Hokke CH. 2006a. IPSE/alpha- fermentation of breast milk oligosaccharides by Bifidobacterium 1, a major secretory glycoprotein antigen from schistosome eggs, infantis and Lactobacillus gasseri. Appl Environ Microbiol 72:4497– expresses the Lewis X motif on core-difucosylated N-glycans. FEBS J Warnock D, Bai X, Autote K, Gonzales J, Kinealy K, Yan B, Qian J, Wuhrer M, Balog CIA, Koeleman CAM, Deelder AM, Hokke CH. 2005. New Stevenson T, Zopf D, Bayer RJ. 2005. In vitro galactosylation of human features of site-specific horseradish peroxidase (HRP) glycosylation IgG at 1 kg scale using recombinant galactosyltransferase. Biotechnol uncovered by nano-LC-MS with repeated ion-isolation/fragmentation cycles. Biochim Biophys Acta 1723:229–239.
Mass Spectrometry Reviews DOI 10.1002/mas ANALYSIS OF CARBOHYDRATES AND GLYCOCONJUGATES Wuhrer M, Deelder AM. 2005. Negative-mode MALDI-TOF/TOF-MS of Yamagaki T, Suzuki H, Tachibana K. 2006b. Semiquantitative analysis of oligosaccharides labeled with 2-aminobenzamide. Anal Chem isomeric oligosaccharides by negative-ion mode UV-MALDI TOF postsource decay mass spectrometry and their fragmentation mecha- Wuhrer M, Deelder AM. 2006. Matrix-assisted laser desorption/ionization in- nism study at N-acetyl hexosamine moiety. J Mass Spectrom 41:454– source decay combined with tandem time-of-flight mass spectrometry of permethylated oligosaccharides: Targeted characterization of Yamagaki T, Suzuki H, Tachibana K. 2006c. Study of negative-ion MALDI- specific parts of the glycan structure. Rapid Commun Mass Spectrom MS of neutral oligosaccharides I: Linkage isomers' analyses by postsource and in-source decay measurements. J Mass Spectrom Soc Wuhrer M, Koeleman CA, Deelder AM, Hokke CH. 2006b. Repeats of Jpn 54:141–149.
LacdiNAc and fucosylated LacdiNAc on N-glycans of the human Yamaguchi M, Kojima K, Hayashi N, Kakizaki I, Kon A, Takagaki K. 2006.
parasite Schistosoma mansoni. FEBS J 273:347–361.
Efficient and widely applicable method of constructing neo-proteogly- Wuhrer M, Koeleman CA, Hokke CH, Deelder AM. 2006c. Mass can utilizing copper(I) catalyzed 1,3-dipolar cycloaddition. Tetrahe- spectrometry of proton adducts of fucosylated N-glycans: Fucose dron Lett 47:7455–7458.
transfer between antennae gives rise to misleading fragments. Rapid Yamamoto N, Takayanagi A, Sakakibara T, Dawson PE, Kajihara Y.
Commun Mass Spectrom 20:1747–1754.
2006. Highly efficient synthesis of sialylglycopeptides overcoming Wuhrer M, Koeleman CAM, Fitzpatrick JM, Hoffmann KF, Deelder AD, unexpected aspartimide formation during activation of Fmoc- Hokke CH. 2006d. Gender-specific expression of complex-type N- Asn(undecadisialyloligosaccharide)-OH. Tetrahedron Lett 47:1341– glycans in schistosomes. Glycobiology 16:991–1006.
Wyatt MF, Stein BK, Brenton AG. 2006. Characterization of various analytes Yamamoto S, Muramatsu H, Muramatsu T. 2005. Mutational studies on endo- using matrix-assisted laser desorption/ionization time-of-flight mass b-N-acetylglucosaminidase D which hydrolyzes core portion of asparagine-linked complex type oligosaccharides. Glycoconj J 22: lidene]malononitrile matrix. Anal Chem 78:199–206.
Xia B, Kawar ZS, Ju T, Alvarez RA, Sachdev GP, Cummings RD. 2005a.
Yamanoi T, Yoshida N, Oda Y, Akaike E, Tsutsumida M, Kobayashi N, Osumi Versatile fluorescent derivatization of glycans for glycomic analysis.
K, Yamamoto K, Fujita K, Takahashi K, Hattori K. 2005. Synthesis of Nat Methods 2:845–850.
mono-glucose-branched cyclodextrins with a high inclusion ability fordoxorubicin and their efficient glycosylation using Mucor hiemalis Xia B, Royall JA, Damera G, Sachdev GP, Cummings RD. 2005b. Altered O- endo-b-N-acetylglucosaminidase. Bioorg Med Chem Lett 15:1009– glycosylation and sulfation of airway mucins associated with cystic fibrosis. Glycobiology 15:747–775.
Yang Y-L, Yang F-L, Jao S-C, Chen M-Y, Tsay S-S, Zou W, Wu S-H. 2006.
Xiao Z, Prieto D, Conrads TP, Veenstra TD, Issaq HJ. 2005. Proteomic Structural elucidation of phosphoglycolipids from strains of the patterns: Their potential for disease diagnosis. Mol Cell Endocrinol bacterial thermophiles Thermus and Meiothermus. J Lipid Res 47: Xie B, Zhou G, Chan S-Y, Shapiro E, Kong X-P, Wu X-R, Sun T-T, Costello Yang Z, Wong EL-M, Shum TY-T, Che C-M, Hui Y. 2005. Fluorophore- CE. 2006. Distinct glycan structures of uroplakins Ia and Ib: Structural appended steroidal saponin (dioscin and polyphyllin D) derivatives. Org basis for the selective binding of FimH adhesin to uroplakin Ia. J Biol Lett 7:669–672.
Yaoi K, Kondo H, Noro N, Suzuki M, Tsuda S, Mitsuishi Y. 2005a. Functions Xing G-W, Wu D, Poles MA, Horowitz A, Tsuji M, Ho DD, Wong C-H. 2005.
and structures of xyloglucan hydrolyases belonging to glycoside Synthesis and human NKT cell stimulating properties of 3-O-sulfo-a/b- hydrolyse family 74. J Appl Glycosci 52:169–176.
galactosylceramides. Bioorg Med Chem 13:2907–2916.
Yaoi K, Nakai T, Kameda Y, Hiyoshi A, Mitsuishi Y. 2005b. Cloning and Xu S, Li Y, Zou H, Qiu J, Guo Z, Guo B. 2003. Carbon nanotubes as assisted characterization of two xyloglucanases from Paenibacillus sp. strain matrix for laser desorption/ionization time-of-flight mass spectrometry.
KM21. Appl Environ Microbiol 71:7670–7678.
Anal Chem 75:6191–6195.
Yashunsky DV, Borodkin VS, Ferguson MAJ, Nikolaev AV. 2006. The Xue J, Zhu J, Marchant RE, Guo Z. 2005. Pentaerythritol as the core of chemical synthesis of bioactive glycosylphosphatidylinositols from multivalent glycolipids: Synthesis of a glycolipid with three SO3Lea Trypanosoma cruzi containing an unsaturated fatty acid in the lipid.
ligands. Org Lett 7:3753–3756.
Angew Chem Int Ed Engl 45:468–474.
Yagi H, Takahashi N, Yamaguchi Y, Kimura N, Uchimura K, Kannagi R, Kato Yasuda J, Eguchi H, Fujiwara N, Ookawara T, Kojima S, Yamaguchi Y, K. 2005. Development of structural analysis of sulfated N-glycans by Nishimura M, Fujimoto J, Suzuki K. 2006. Reactive oxygen species multidimensional high performance liquid chromatography mapping modify oligosaccharides of glycoproteins in vivo: A study of a methods. Glycobiology 15:1051–1060.
spontaneous acute hepatitis model rat (LEC rat). Biochem Biophys Yamagaki T. 2005. Development of structure analysis method of isomeric Res Commun 342:127–134.
oligosaccharides by MALDI-TOF mass spectrometry. Bunseki Kagaku Ye X-S, Sun F, Liu M, Li Q, Wang Y, Zhang G, Zhang L-H, Zhang X-L. 2005.
Synthetic iminosugar derivatives as new potential immunosuppressive Yamagaki T, Fukui K, Tachibana K. 2006. Analysis of glycosyl bond cleavage agents. J Med Chem 48:3688–3691.
and related isotope effects in collision-induced dissociation quadru-pole-time-of-flight mass spectrometry of isomeric trehaloses. Anal Yeager AR, Finney NS. 2005. Synthesis of fluorescently labeled UDP- GlcNAc analogues and their evaluation as chitin synthase substrates. JOrg Chem 70:1269–1275.
Yamagaki T, Suzuki H, Tachibana K. 2005. In-source and postsource decay in negative-ion matrix-assisted laser desorption/ionization time-of-flight Ying L, Liu R, Zhang J, Lam K, Lebrilla CB, Gervay-Hague J. 2005. A mass spectrometry of neutral oligosaccharides. Anal Chem 77:1701– topologically segregated one-bead-one-compound combinatorial gly- copeptide library for identification of lectin ligands. J Comb Chem7:372–384.
Yamagaki T, Suzuki H, Tachibana K. 2006a. A comparative study of the fragmentation of neutral lactooligosaccharides in negative-ion mode by Yonezawa N, Kudo K, Terauchi H, Kanai S, Yoda N, Tanokura M, UV-MALDI-TOF and UV-MALDI ion-trap/TOF mass spectrometry. J Ito K, Miura K, Katsumata T, Nakano M. 2005. Recombinant Am Soc Mass Spectrom 17:67–74.
porcine zona pellucida glycoproteins expressed in Sf9 cells bind to Mass Spectrometry Reviews DOI 10.1002/mas bovine sperm but not to porcine sperm. J Biol Chem 280:20189– Zhang J, Schubothe K, Li B, Russell S, Lebrilla CB. 2005d. Infrared multiphoton dissociation of O-linked mucin-type oligosaccharides.
Yoon SJ, Nakayama K-I, Takahashi N, Yagi H, Utkina N, Wang HY, Kato K, Anal Chem 77:208–214.
Sadilek M, Hakomori S-I. 2006. Interaction of N-linked glycans, having Zhang M, Shi Z, Bai Y, Gao Y, Hu R, Zhao F. 2006. Using molecular multivalent GlcNAc termini, with GM3 ganglioside. Glycoconj J recognition of b-cyclodextrin to determine molecular weights of low- molecular-weight explosives by MALDI-TOF mass spectrometry. J Am Yoshida N, Takatsuka K, Katsuragi T, Tani Y. 2005. Occurrence of fructosyl- Soc Mass Spectrom 17:189–193.
amino acid oxidase-reactive compounds in fungal cells. Biosci Zhao J, Simeone DM, Heidt D, Anderson MA, Lubman DM. 2006.
Biotechnol Biochem 69:258–260.
Comparative serum glycoproteomics using lectin selected sialic acid Yu B, Cong H, Liu H, Li Y, Liu F. 2005a. Ionene-dynamically coated capillary glycoproteins with mass spectrometric analysis: Application to for analysis of urinary and recombinant human erythropoietin by pancreatic cancer serum. J Proteome Res 5:1792–1802.
capillary electrophoresis and online electrospray ionization mass Zhao W, Kong F. 2005. Facile synthesis of the heptasaccharide repeating unit spectrometry. J Sep Sci 28:2390–2400.
of O-deacetylated GXM of C. neoformans serotype B. Bioorg Med Yu F, Prestegard JH. 2006. Structural monitoring of oligosaccharides through Chem 13:121–130.
13C enrichment and NMR observation of acetyl groups. Biophys J Zheng W, Kollmeyer J, Symolon H, Momin A, Munter E, Wang E, Kelly S, Allegood JC, Liu Y, Peng Q, Ramaraju H, Sullards MC, Cabot M, Yu H, Teramoto A, Fukudome M, Xie R-G, Yuan D-Q, Fujita K. 2006. A Merrill AHJ. 2006. Ceramides and other bioactive sphingolipid facile sulfonylation method enabling direct syntheses of per(2-O- backbones in health and disease: Lipidomic analysis, metabolism and sulfonyl)-b-cyclodextrins. Tetrahedron Lett 47:8837–8840.
roles in membrane structure, dynamics, signaling and autophagy.
Biochim Biophys Acta 1758:1864–1884.
Yu SY, Wu SW, Khoo KH. 2006. Distinctive characteristics of MALDI-Q/ TOF and TOF/TOF tandem mass spectrometry for sequencing of Zheng X, Wu S-L, Hancock WS. 2006. Glycation of interferon-beta-1b and permethylated complex type N-glycans. Glycoconj J 23:355–369.
human serum albumin in a lyophilized glucose formulation: Part III:Application of proteomic analysis to the manufacture of biological Yu YG, Gilar M, Kaska J, Gebler JC. 2005b. Deglycosylation and sample drugs. Int J Pharm 322:136–145.
cleanup method for mass spectrometry analysis of N-linked glycans. LCGC North America:23–25.
Zhong R, Pen˜a MJ, Zhou G-K, Nairn CJ, Wood-Jones A, Richardson EA, Morrison WH III, Darvill AG, York WS, Ye Z-H. 2005. Arabidopsis Yu YQ, Gilar M, Kaska J, Gebler JC. 2005c. A rapid sample preparation Fragile Fiber8, which encodes a putative glucuronyltransferase, is method for mass spectrometric characterization of N-linked glycans.
essential for normal secondary wall synthesis. Plant Cell 17:3390–3408.
Rapid Commun Mass Spectrom 19:2331–2336.
Zhou Q, Kyazike J, Echelard Y, Meade HM, Higgins E, Cole ES, Edmunds T.
Yurkova I, Kisel M, Arnhold J, Shadyro O. 2005. Free-radical fragmentation 2005. Effect of genetic background on glycosylation heterogeneity in of galactocerebrosides: A MALDI-TOF mass spectrometry study.
human antithrombin produced in the mammary gland of transgenic Chem Phys Lipids 134:41–49.
goats. J Biotechnol 117:57–72.
Zaliz CLR, Erra-Balsells R, Nonami H, Sato Y, Varela O. 2005. Synthesis and Zhu J, Marchant RE. 2006. Dendritic saccharide surfactant polymers as polymerization of conveniently substituted 6-amino-6-deoxy-D-galac- antifouling interface materials to reduce platelet adhesion. Biomacro- tonic acid derivatives. Arkivoc:76–87.
Zaliz CLR, Varela O. 2006. Facile synthesis of a D-galactono-1,6-lactone Zhu J, Yan F, Guo Z, Marchant RE. 2005a. Surface modification of liposomes derivative, a precursor of a copolyester. Carbohydr Res 341:2973– by saccharides: Vesicle size and stability of lactosyl liposomes studied by photon correlation spectroscopy. J Colloid Interface Sci 289:542–550.
Zandleven J, Beldman G, Bosveld M, Benen J, Voragen A. 2006a. Mode of Zhu L, van de Lavoir M-C, Albanese J, Beenhouwer DO, Cardarelli PM, action of xylogalacturonan hydrolase towards xylogalacturonan and Cuison S, Deng DF, Deshpande S, Diamond JH, Green L, Halk EL, xylogalacturonan oligosaccharides. Biochem J 387:719–725.
Heyer BS, Kay RM, Kerchner A, Leighton PA, Mather CM, Morrison Zandleven J, Beldman G, Bosveld M, Schols HA, Voragen AGJ. 2006b.
SL, Nikolov ZL, Passmore DB, Pradas-Monne A, Preston BT, Rangan Enzymatic degradation studies of xylogalacturonans from apple and VS, Shi M, Srinivasan M, White SG, Winters-Digiacinto P, Wong S, potato, using xylogalacturonan hydrolase. Carbohydr Polym 65:495–503.
Zhou W, Etches RJ. 2005b. Production of human monoclonal antibody Zehl M, Pittenauer E, Rizzi A, Allmaier G. 2006. Characterization of in eggs of chimeric chickens. Nat Biotechnol 23:1159–1169.
moenomycin antibiotic complex by multistage MALDI-IT/RTOF-MS Zhu P, Boykins RA, Tsai C-M. 2006. Genetic and functional analyses of the and ESI-IT-MS. J Am Soc Mass Spectrom 17:1081–1090.
IgtH gene, a member of the b-1,4-galactosyltransferase gene family in Zeleny R, Leonard R, Dorfner G, Dalik T, Kolarich D, Altmann F. 2006.
the genus Neisseria. Microbiology 152:123–134.
Molecular cloning and characterization of a plant a,3/4-fucosidase Zhu S, Shimokawa S, Shoyama Y, Tanaka H. 2006a. A novel analytical based on sequence tags from almond fucosidase I. Phytochemistry ELISA-based methodology for pharmacologically active saikosapo- nins. Fitoterapia 77:100–108.
Zhang G, Fu M, Ning J. 2005a. First synthesis of 5,6-branched galacto- Zhu S, Zhang Y, Li M, Yu J, Zhang L, Li Y, Yu B. 2006b. Synthesis and hexasaccharide, the dimer of the trisaccharide repeating unit of the cell- cytotoxicities of dioscin derivatives with decorated chacotriosyl wall galactans of Bifidobacterium catenulatum YIT 4016. Tetrahedron residues. Bioorg Med Chem Lett 16:5629–5632.
Asym 16:733–738.
Zhu X, Kawatkar S, Rao Y, Geert-Jan Boons G-J. 2006c. Practical approach Zhang G, Fu M, Ning J. 2005b. Synthesis of galactose-containing analogues for the stereoselective introduction of b-arabinofuranosides. J Am of (1-6)-branched (1-3)-glucohexaose and its lauryl glycoside.
Chem Soc 128:11948–11957.
Carbohydr Res 340:597–602.
Ziegler T, Schips C. 2006. An efficient Mitsunobu protocol for the one-pot Zhang H, Singh S, Reinhold VN. 2005. Congruent strategies for carbohydrate synthesis of S-glycosyl amino-acid building blocks and their use in sequencing. 2. FragLib: An MSn spectral library. Anal Chem 77:6263– combinatorial spot synthesis of glycopeptide libraries. Nat Protoc Zhang J, LaMotte L, Dodds ED, Lebrilla CB. 2005c. Atmospheric pressure Zou K, Tong W-Y, Liang H, Cui J-R, Tu G-Z, Zhao Y-Y, Zhang R-Y. 2005.
MALDI Fourier transform mass spectrometry of labile oligosacchar- Diastereoisomeric saponins from Albizia julibrissin. Carbohydr Res ides. Anal Chem 77:4429–4438.
Mass Spectrometry Reviews DOI 10.1002/mas

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