Minimizing cationization effects in the analysis of complex mixtures of oligosaccharides

North, Simon J.; Okafo, George; Birrell, Helen; Haskins, N. J.; Camilleri, Patrick

doi:10.1002/(sici)1097-0231(19971015)11:15<1635::aid-rcm66>3.0.co;2-2

Cited by 29 publications

(22 citation statements)

References 18 publications

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“…Intrigued by the possibility of driving the adduct pattern toward formation of one particular adduct, 40 we added lithium chloride to samples to produce concentrations of 2, 4, and 6 mM. The effect on MC-LR was limited (Tables 2 and 3); a small [MCLRþLi] þ signal appeared, and the [MCLRþH] þ signal decreased.…”

Section: Alkali Metalsmentioning

confidence: 99%

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Adduct simplification in the analysis of cyanobacterial toxins by matrix‐assisted laser desorption/ionization mass spectrometry

Howard

Boyer

2007

Rapid Comm Mass Spectrometry

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A novel method for simplifying adduct patterns to improve the detection and identification of peptide toxins using matrix-assisted laser desorption/ionization (MALDI) time-of-flight (TOF) mass spectrometry is presented. Addition of 200 microM zinc sulfate heptahydrate (ZnSO(4) . 7H(2)O) to samples prior to spotting on the target enhances detection of the protonated molecule while suppressing competing adducts. This produces a highly simplified spectrum with the potential to enhance quantitative analysis, particularly for complex samples. The resulting improvement in total signal strength and reduction in the coefficient of variation (from 31.1% to 5.2% for microcystin-LR) further enhance the potential for sensitive and accurate quantitation. Other potential additives tested, including 18-crown-6 ether, alkali metal salts (lithium chloride, sodium chloride, potassium chloride), and other transition metal salts (silver chloride, silver nitrate, copper(II) nitrate, copper(II) sulfate, zinc acetate), were unable to achieve comparable results. Application of this technique to the analysis of several microcystins, potent peptide hepatotoxins from cyanobacteria, is illustrated.

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Section: Alkali Metalsmentioning

confidence: 99%

“…This is particularly common in the MALDI analysis of neutral compounds such as polymers,39 which are otherwise not efficiently ionized. A related approach40 added lithium chloride to the matrix for the analysis of oligosaccharides, resulting in the suppression of proton, sodium and potassium adducts and enhancement of a single [M+Li] + signal.…”

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confidence: 99%

Adduct simplification in the analysis of cyanobacterial toxins by matrix‐assisted laser desorption/ionization mass spectrometry

Howard

Boyer

2007

Rapid Comm Mass Spectrometry

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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%

“…In contrast, cationization assists ionization of analytes that are difficult to ionize by other ionization pathways. Therefore, salts of metal cations such as Li + , Cu 2+ , and Ag + are often added to MALDI samples to enhance signal or suppress cationization by Na + and K + [31,34,35]. Several other mechanical methods, including a postcrystallization wash [36] layered deposition of matrix and analyte [37], and the use of liquid matrices (ionic liquids containing matrix anions) [38], have also been proposed and tested to minimize cationization 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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“…On the other hand, it offers the advantage that clean‐up of samples is facilitated by, for example, the use of C18 ZipTips. Other groups, notably that of Camilleri et al ,9–13 have investigated the use of 2‐aminoacridone derivatives for structural determination of carbohydrates by electrospray‐MS/MS and shown them to provide valuable structural information on these compounds. We,14 and others,15–20 have been investigating the use of similar derivatives for increasing sensitivity.…”

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confidence: 99%

N-(2-Diethylamino)ethyl-4-aminobenzamide derivative for high sensitivity mass spectrometric detection and structure determination of N-linked carbohydrates

Harvey¹

2000

Rapid Commun. Mass Spectrom.

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N-Linked glycans were derivatised by reductive amination using N-(2-diethylamino)ethyl-4-aminobenzamide (DEAEAB, procainamide) and examined by electrospray mass spectrometry. This derivative ionised primarily by protonation of the tertiary amine group and attachment of an alkali metal to give [M + H + X](2+) ions which were much more abundant that doubly charged ions from glycans derivatised with other aromatic amines. Fragmentation of these ions depended on the nature of the alkali metal (X). Lithium and sodium adducts fragmented to give prominent ions produced by cleavages within the DEAEAB derivative whereas the other adducts produced more abundant ions from fragmentation of the carbohydrate. Elimination of a sugar fragment, usually by cleavage adjacent to GlcNAc or sialic acid, together with a hydrogen atom, produced the most abundant singly charged fragment ions. These ions then formally fragmented by glycosidic cleavages. Potassium, rubidium and caesium adducts produced abundant losses of the alkali metal, but the resulting ions appeared not to undergo extensive fragmentation. Most fragment ions from all of the adducts were singly charged, the remainder being doubly charged. Although the spectra of the [M + X + H](2+) ions were not as informative as those from the singly charged ions from other derivatives, they, nevertheless, provided much valuable information on the structure of these glycans.

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Minimizing cationization effects in the analysis of complex mixtures of oligosaccharides

Cited by 29 publications

References 18 publications

Adduct simplification in the analysis of cyanobacterial toxins by matrix‐assisted laser desorption/ionization mass spectrometry

Adduct simplification in the analysis of cyanobacterial toxins by matrix‐assisted laser desorption/ionization mass spectrometry

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

N-(2-Diethylamino)ethyl-4-aminobenzamide derivative for high sensitivity mass spectrometric detection and structure determination of N-linked carbohydrates

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