Negative-ion electrospray mass spectrometric analysis of dicarboxylic acids

Aplin, Robin T.; Moloney, Mark G.; NEWBY, ROBERT; Wright, E. H. M.

doi:10.1002/(sici)1096-9888(199901)34:1<60::aid-jms764>3.0.co;2-q

Cited by 10 publications

(8 citation statements)

References 20 publications

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“…As seen from Table , for all the carboxylate anions under investigation which can assume cyclic confomations, the cyclic confomations are the most energetically favorable, with the exception of oxalate. Such stable intramolecular hydrogen bond formation of dicarboxylate ions in vacuo has previously been reported by Aplin et al Hydrogen bonds that are formed between an acid and its conjugated base, such as the O−H···O - bonds considered here, can be classified as “very strong” hydrogen bonds . Such bonds exhibit bond energies in the range of 15−40 kcal/mol and are quasicovalent in nature.…”

Section: Resultssupporting

confidence: 78%

Electrospray Ionization Ion Mobility Spectrometry of Carboxylate Anions: Ion Mobilities and a Mass−Mobility Correlation

et al. 2005

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A number of carboxylate anions spanning a mass range of 87-253 amu (pyruvate, oxalate, malonate, maleate, succinate, malate, tartarate, glutarate, adipate, phthalate, citrate, gluconate, 1,2,4-benzenetricarboxylate, and 1,2,4,5-benzenetetracarboxylate) were investigated using electrospray ionization ion mobility spectrometry. Measured ion mobilities demonstrated a high correlation between mass and mobility in both N2 and CO2 drift gases. Such a strong mass-mobility correlation among structurally dissimilar ions suggests that the carboxylate functional group that these ions have in common is the source of the correlation. Computational analysis was performed to determine the most stable conformation of the studied carboxylate anions in the gas phase under the current experimental conditions. This analysis indicated that the most stable conformations for multicarboxylate anions included intramolecular hydrogen-bonded ring structures formed between the carboxylate group and the neutral carboxyl group. The carboxylate anions that form ring confirmations generally show higher ion mobility values than those that form extended conformations. This is the first observation of intramolecular hydrogen-bonded ring conformation of carboxylate anions in the gas phase at atmospheric pressure.

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Section: Resultssupporting

confidence: 78%

Electrospray Ionization Ion Mobility Spectrometry of Carboxylate Anions: Ion Mobilities and a Mass−Mobility Correlation

et al. 2005

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“…The existence of multiply charged anions in the gas phase has been the subject of considerable experimental and theoretical investigation for several decades. − Much effort has been devoted to elucidation of the smallest molecular systems capable of forming stable, gas-phase polyanions. Equally interesting are the changes in electronic structure and molecular geometry that ensue when the polyanion X n - ejects an electron to form X ( n -1)- .…”

Section: Introductionmentioning

confidence: 99%

Ab Initio Investigation of Electron Detachment in Dicarboxylate Dianions

Herbert

Ortiz

2000

J. Phys. Chem. A

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Optimized structures for oxalate (C2O4), malonate (O2CCH2CO2), and succinate (O2C(CH2)2CO2) mono- and dianions are computed at the level of second-order Møller−Plesset perturbation theory (MP2). For oxalate, both anions exhibit D 2 d and D 2 h rotamers, and in addition, for the singly charged species, we find an anion−molecule complex of the form CO2 -·CO2. For the malonate and succinate anions we examine both keto and enol isomers; the keto structures are characterized by unhindered rotation of the CO2 moieties about geometries of C 2 symmetry, while the enol isomers are much more rigid as a result of an intramolecular hydrogen bond. In both malonate and succinate, the enol isomer is the more stable form of the monoanion, while the keto isomer is the more stable dianion, although for O2CCH2CO2 2- the estimated isomerization barrier is only about 7 kcal/mol. All of the dianions are adiabatically unbound and the enol dianions are vertically unbound as well. However, vertical detachment energies calculated by electron propagator methods at the partial third-order (P3) quasiparticle level with large, highly polarized basis sets suggest that the more stable keto forms of O2CCH2CO2 2- and O2C(CH2)2CO2 2- are metastable, with vertical detachment barriers of about 0.2 and 0.6 eV, respectively. These results complement recent experimental observations of small dicarboxylate dianions in the gas phase.

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“…The higher [M2H] 2− /[MH] − ratio is observed for longer M, thus formation of [M2H] 2− ions is unfavorable for the shorter chain. Most probably this is because of an intramolecular hydrogen bond formed for the [MH] − ion originated from shorter M, and two identical charges (in our case negative) do not tend to be close to each other 6…”

Section: Resultsmentioning

confidence: 78%

“…Aplin et al . have described the results of their negative ESI mass spectrometric study, performed for different kinds of dicarboxylic acids 6. However, no results of such basic studies as those carried out by the authors have been reported in the literature for dicarboxylated polyethylene glycols (CPEGCs).…”

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confidence: 99%

Formation of [MH]⁻ and [M2H]²⁻ ions in the electrospray ionization mass spectra of dicarboxylated polyethylene glycols

Frańska

Zgoła

Rychłowska

et al. 2004

Rapid Comm Mass Spectrometry

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Negative-ion electrospray mass spectrometric analysis of dicarboxylic acids

Cited by 10 publications

References 20 publications

Electrospray Ionization Ion Mobility Spectrometry of Carboxylate Anions: Ion Mobilities and a Mass−Mobility Correlation

Electrospray Ionization Ion Mobility Spectrometry of Carboxylate Anions: Ion Mobilities and a Mass−Mobility Correlation

Ab Initio Investigation of Electron Detachment in Dicarboxylate Dianions

Formation of [MH]⁻ and [M2H]²⁻ ions in the electrospray ionization mass spectra of dicarboxylated polyethylene glycols

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Negative-ion electrospray mass spectrometric analysis of dicarboxylic acids

Cited by 10 publications

References 20 publications

Electrospray Ionization Ion Mobility Spectrometry of Carboxylate Anions: Ion Mobilities and a Mass−Mobility Correlation

Electrospray Ionization Ion Mobility Spectrometry of Carboxylate Anions: Ion Mobilities and a Mass−Mobility Correlation

Ab Initio Investigation of Electron Detachment in Dicarboxylate Dianions

Formation of [MH]− and [M2H]2− ions in the electrospray ionization mass spectra of dicarboxylated polyethylene glycols

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Formation of [MH]⁻ and [M2H]²⁻ ions in the electrospray ionization mass spectra of dicarboxylated polyethylene glycols