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: david.harvey@bioch.ox.ac.uk 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: CHCADHB>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.
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Aly MRE, Schmidt RR. 2005. New diacylamino protecting groups for glucosamine. Eur J Org Chem:4382–4392.
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