Attachment of alkali cations on β‐D‐glucopyranose: matrix‐assisted laser desorption/ionization time‐of‐flight studies and <i>ab initio</i> calculations

Botek, Edith; Debrun, J.L.; Hakim, B.; Morin‐Allory, Luc

doi:10.1002/rcm.222

Cited by 20 publications

(18 citation statements)

References 16 publications

(17 reference statements)

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“…The formation of the [2Carb ϩ Cs] ϩ complex was maximal at 10 -15 M Cs ϩ and efficiently suppressed by increasing Cs ϩ concentration (data not shown). In contrast, smaller cations such as°Li ϩ°a nd°Na ϩ°b ind°tightly°to°carbohydrates° [25][26][27]. Due to their high coordination affinity they decompose to the respective cation coordinated carbohydrate fragments° [26].°In°contrast,°large°cations,°such°as°Cs ϩ°a nd Rb ϩ ,°form°lower°affinity°carbohydrate°complexes° [26,27].°As°a°result,°they°preferentially°undergo°cation elimination°without°carbohydrate°decomposition° [26].…”

Section: Lc/ms Methods Developmentmentioning

confidence: 99%

Sensitive LC MS quantitative analysis of carbohydrates by Cs⁺ attachment

Rogatsky

Jayatillake

Goswami

et al. 2005

J. Am. Soc. Mass Spectrom.

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The development of a sensitive assay for the quantitative analysis of carbohydrates from human plasma using LC/MS/MS is described in this paper. After sample preparation, carbohydrates were cationized by Cs ϩ after their separation by normal phase liquid chromatography on an amino based column. Cesium is capable of forming a quasi-molecular ion [M ϩ Cs] ϩ with neutral carbohydrate molecules in the positive ion mode of electrospray ionization mass spectrometry. The mass spectrometer was operated in multiple reaction monitoring mode, and transitions [M ϩ 133] ¡ 133 were monitored (M, carbohydrate molecular weight). The new method is robust, highly sensitive, rapid, and does not require postcolumn addition or derivatization. It is useful in clinical research for measurement of carbohydrate molecules by isotope dilution assay. (J Am Soc Mass Spectrom 2005, 16, 1805-1811

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Section: Lc/ms Methods Developmentmentioning

confidence: 99%

Sensitive LC MS quantitative analysis of carbohydrates by Cs⁺ attachment

Rogatsky

Jayatillake

Goswami

et al. 2005

J. Am. Soc. Mass Spectrom.

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“…Cationization by alkali metal cations such as Na + and K + is one of the secondary ionization processes that occur in MALDI [25][26][27][28][29][30][31][32][33]. Cationization is also believed to influence protonation, deprotonation, and electron transfer ionization processes that occur in MALDI.…”

Section: Introductionmentioning

confidence: 99%

Sodium Cation Affinities of Commonly Used MALDI Matrices Determined by Guided Ion Beam Tandem Mass Spectrometry

Chinthaka¹,

Rodgers²

2012

J. Am. Soc. Mass Spectrom.

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The sodium cation affinities of six commonly used MALDI matrices are determined here using guided ion beam tandem mass spectrometry techniques. The collision-induced dissociation behavior of six sodium cationized MALDI matrices, Na + (MALDI), with Xe is studied as a function of kinetic energy. The MALDI matrices examined here include: nicotinic acid, quinoline, 3-aminoquinoline, 4-nitroaniline, picolinic acid, and 3-hydroxypicolinic acid. In all cases, the primary dissociation pathway corresponds to endothermic loss of the intact MALDI matrix. The cross section thresholds are interpreted to yield zero and 298 K Na + −MALDI bond dissociation energies (BDEs), or sodium cation affinities, after accounting for the effects of multiple ionneutral collisions, the kinetic and internal energy distributions of the reactants, and dissociation lifetimes. Density functional theory calculations at the B3LYP/6-311+G(2d,2p)//B3LYP/6-31G* and MP2(full)/6-311+G(2d,2p)//B3LYP/6-31G* levels of theory are used to characterized the structures and energetics for these systems. The calculated BDEs exhibit very good agreement with the measured values for most systems. The experimental and theoretical Na + −MALDI BDEs determined here are compared with those previously measured by cation transfer equilibrium methods.

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“…As described below, methylation also contributes to RDA degradation, and this feature may be entwined with the specificity and avidity of metal ion binding. 31 We have assumed these factors to be fundamental for the detection of configurationally diagnostic fragment ions and have provided supporting data below.CID of the methylated disaccharides Gal-α(1-4)-Gal and Glc-α(1-4)-Glc (m/z 477) provided nearly identical spectra with major B-and C-type fragments at m/z 241 and m/z 259, along with an ion at m/z 445, produced by loss of methanol ( Figure 1A and B, respectively). Certainly, as methyl glycosides, these small oligomers appear relatively stable to ring fracture, and as a consequence, no linkage or monomer characterization is evident.…”

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confidence: 97%

Congruent Strategies for Carbohydrate Sequencing. 1. Mining Structural Details by MSⁿ

et al. 2005

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This report is the first in a series of three focused on establishing congruent strategies for carbohydrate sequencing. The reports are divided into (i) analytical considerations that account for all aspects of small oligomer structure by MS n disassembly, (ii) database support using an ion fragment library and associated tools for highthroughput analysis, and (iii) a concluding algorithm for defining oligosaccharide topology from MS n disassembly pathways. The analytical contribution of this first report explores the limits of structural detail exposed by ion trap mass spectrometry with samples prepared as methyl derivatives and analyzed as metal ion adducts. This data mining effort focuses on correlating the fragments of small oligomers to stereospecific glycan structures, an outcome attributed to a combination of metal ion adduction and analyte conformation. Facile glycosidic cleavage introduces a point of lability (pyranosyl-1-ene) that upon collisional activation initiates subsequent ring fragmentation. Product masses and ion intensities vary with interresidue linkage, branching position, and monomer stereochemistry. Excessive fragmentation is the property of small oligomers where collisional energy within a smaller number of oscillators dissipates through extensive fragmentation. The procedures discussed in this report are unified into a singular strategy using an ion trap mass spectrometer with the sensitivity expected for electron multiplier detection. Although a small set of structures have been discussed, the basic principles considered are fully congruent, with ample opportunities for expansion.The proliferation of reports attributing biological function to oligosaccaharide epitopes continues unabated. To fully appreciate their specific biological roles, an improved accounting of carbohydrate structural details needs greater scrutiny and more judicious reporting. Unfortunately, a comprehensive strategy for carbohydrate sequencing is lacking. Over the past decades, the absence of an integrated strategy to fully define a carbohydrate sequence has been given little attention due to overwhelming and direct functional lineage of nucleic acid and protein polymers. Even selective strategies to assign components of structure show little focus toward congruency. The reporting of partial sequences, assumed motifs, sequence arrays devoid of linkage and branching definition, and multiple structures enclosed in brackets are currently acceptable conclusions in published reports. The general acceptance of such reports diminishes the driving force for the development of improved and comprehensive methodologies.A sequence definition should provide all the components of structure necessary for reporting or synthesis. Structural components should include monomer identification, positions of interresidue linkage, and array topology, where a linkage definition includes anomericity, and array topologies describe linear and branching sequence information. When considering molecular glycosylation, sites of conjugatio...

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Attachment of alkali cations on β‐D‐glucopyranose: matrix‐assisted laser desorption/ionization time‐of‐flight studies and ab initio calculations

Cited by 20 publications

References 16 publications

Sensitive LC MS quantitative analysis of carbohydrates by Cs⁺ attachment

Sensitive LC MS quantitative analysis of carbohydrates by Cs⁺ attachment

Sodium Cation Affinities of Commonly Used MALDI Matrices Determined by Guided Ion Beam Tandem Mass Spectrometry

Congruent Strategies for Carbohydrate Sequencing. 1. Mining Structural Details by MSⁿ

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Attachment of alkali cations on β‐D‐glucopyranose: matrix‐assisted laser desorption/ionization time‐of‐flight studies and ab initio calculations

Cited by 20 publications

References 16 publications

Sensitive LC MS quantitative analysis of carbohydrates by Cs+ attachment

Sensitive LC MS quantitative analysis of carbohydrates by Cs+ attachment

Sodium Cation Affinities of Commonly Used MALDI Matrices Determined by Guided Ion Beam Tandem Mass Spectrometry

Congruent Strategies for Carbohydrate Sequencing. 1. Mining Structural Details by MSn

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Sensitive LC MS quantitative analysis of carbohydrates by Cs⁺ attachment

Sensitive LC MS quantitative analysis of carbohydrates by Cs⁺ attachment

Congruent Strategies for Carbohydrate Sequencing. 1. Mining Structural Details by MSⁿ