Targeted borate complex formation as followed with electrospray ionization Fourier transform ion cyclotron mass spectrometry: monomolecular model system and polyborate formation

Gaspar, Andras; Harir, Mourad; Lucio, Marianna; Hertkorn, Norbert; Schmitt‐Kopplin, Philippe

doi:10.1002/rcm.3713

Cited by 10 publications

(19 citation statements)

References 58 publications

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“…Gaspar et al. investigated the formation of polyborate complex ions in a monomolecular model system of caffeic acid using an electrospray source coupled to a Fourier transform ion cyclotron resonance mass spectrometry (FT‐ICR‐MS) 1. Based on the ultrahigh resolution of FT‐ICR‐MS, the formed mono‐ and polyborate complex ions with caffeic acid were confirmed by accurate mass determinations which gave unequivocal elemental formulae.…”

Section: Introductionmentioning

confidence: 99%

Attachment of Chloride Anion to Sugars: Mechanistic Investigation and Discovery of a New Dopant for Efficient Sugar Ionization/Detection in Mass Spectrometers

Boutegrabet

Kanawati

Gebefügi

et al. 2012

Chemistry A European J

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A new method for efficient ionization of sugars in the negative-ion mode of electrospray mass spectrometry is presented. Instead of using strongly hydrophobic dopants such as dichloromethane or chloroform, efficient ionization of sugars has been achieved by using aqueous HCl solution for the first time. This methodology makes it possible to use hydrophilic dopants, which are more appropriate for chromatographic separation techniques with efficient sugar ionization and detection in mass spectrometry. The interaction between chloride anions and monosaccharides (glucose and galactose) was studied by DFT in the gas phase and by implementing the polarizable continuum model (PCM) for calculations in solution at the high B3LYP/6-31+G(d,p)//B3LYP/6-311+G(2d,p) level of theory. In all optimized geometries of identified [M+Cl](-) anions, a non-covalent interaction exists. Differences were revealed between monodentate and bidentate complex anions, with the latter having noticeably higher binding energies. The calculated affinity of glucose and galactose toward the chloride anion in the gas phase and their chloride anion binding energies in solution are in excellent agreement with glucose and galactose [M+Cl](-) experimental intensity profiles that are represented as a function of the chloride ion concentration. Density functional calculations of gas-phase affinities toward chloride anion were also performed for the studied disaccharides sucrose and gentiobiose. All calculations are in excellent agreement with the experimental data. An example is introduced wherein HCl was used to effectively ionize sugars and form chlorinated adduct anions to detect sugars and glycosylated metabolites (anthocyanins) in real biological systems (Vitis vinifera grape extracts and wines), whereas they would not have been easily detectable under standard infusion electrospray mass spectrometry conditions as deprotonated species.

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Section: Introductionmentioning

confidence: 99%

Attachment of Chloride Anion to Sugars: Mechanistic Investigation and Discovery of a New Dopant for Efficient Sugar Ionization/Detection in Mass Spectrometers

Boutegrabet

Kanawati

Gebefügi

et al. 2012

Chemistry A European J

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“…These can be related to various anionic complexes of boric acid. 8 It is interesting to note that despite of the presence of these ions, the signal of an analyte can be enhanced, such as in the case of Fmoc-Cl derivatives (Figure 2). However, additional peaks due to the presence of boric acid complicate the interpretation of mass spectra.…”

Section: Resultsmentioning

confidence: 99%

“…Borates are known to form complexes. 8,10 One may assume that borate ion forms complexes with analyte molecules and those complexes facilitate evaporation of the analytes into the gas phase. This could be the case with all the experiments where ammonium acetate was not present ( Figure 2).…”

Section: Mechanism Of Action Of Boric Acidmentioning

confidence: 99%

Influence of Boric Acid on Electrospray Ionization Efficiency

Rebane

Herodes

2012

Eur J Mass Spectrom (Chichester)

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Liquid chromatography electrospray ionization mass-spectrometry (LC-ESI-MS) was used to analyze 9-fluorenylmethylmethoxycarbonyl chloride (Fmoc-Cl) and diethyl ethoxymethylenemalonate (Deemm) derivatives of three amino acids and five other compounds. Influence of boric acid on their ionization was investigated and dramatic impact on the signal was observed. The strongest signal suppression (6% of signal remains) was observed for the Deemm derivative of beta-Alanine (with ammonium acetate in eluent). With only formic acid as the eluent pH modifier, signal enhancement was observed, being largest for Fmoc-Cl derivative of Phenylalanine, 267%. Investigation of the influence of boric acid shows that it is a possible signal enhancer for LC-ESI-MS analysis.

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“…Such interpretations are possible only because we compared the two systems under the same conditions. Multiplicity of charged ions is highly dependent on the measurement conditions such as pH and concentration 14…”

Section: Resultsmentioning

confidence: 99%

Novel software for data analysis of Fourier transform ion cyclotron resonance mass spectra applied to natural organic matter

Grinhut¹,

Lansky²,

Gaspar³

et al. 2010

Rapid Comm Mass Spectrometry

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Natural organic matter (NOM) occurs as an extremely complex mixture of large, charged molecules that are formed by secondary synthesis reactions. Due to their nature, their full characterization is an important challenge to scientists specializing in NOM as well as analytical chemistry. Ultra-high-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) analysis enables the identification of thousands of masses in a single measurement. A major challenge in the data analysis process of NOM using the FT-ICR MS technique is the need to sort the entire data set and to present it in an accessible mode. Here we present a simple targeted algorithm called the David Mass Sort (DMS) algorithm which facilitates the detection and counting of consecutive series of masses correlated to any selected mass spacing. This program searches for specific mass differences among all of the masses in a single spectrum against all of the masses in the same spectrum. As a representative case, the current study focuses on the analysis of the well-characterized Suwannee River humic and fulvic acid (SRHA and SRFA, respectively). By applying this algorithm, we were able to find and assess the amount of singly and doubly charged molecules. In addition we present the capabilities of the program to detect any series of consecutive masses correlated to specific mass spacing, e.g. COO, H(2), OCH(2) and O(2). Under several limitations, these mass spacings may be correlated to both chemical and biochemical changes which occur simultaneously during the formation and/or degradation of large mixtures of compounds.

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Targeted borate complex formation as followed with electrospray ionization Fourier transform ion cyclotron mass spectrometry: monomolecular model system and polyborate formation

Cited by 10 publications

References 58 publications

Attachment of Chloride Anion to Sugars: Mechanistic Investigation and Discovery of a New Dopant for Efficient Sugar Ionization/Detection in Mass Spectrometers

Attachment of Chloride Anion to Sugars: Mechanistic Investigation and Discovery of a New Dopant for Efficient Sugar Ionization/Detection in Mass Spectrometers

Influence of Boric Acid on Electrospray Ionization Efficiency

Novel software for data analysis of Fourier transform ion cyclotron resonance mass spectra applied to natural organic matter

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