Deprotonation of p-Hydroxybenzoic Acid: Does Electrospray Ionization Sample Solution or Gas-Phase Structures?

被引：94

作者：

Schroeder, Detlef ^{[2
]}

Budesinsky, Milos ^{[2
]}

Roithova, Jana ^{[1
]}

机构：

[1] Charles Univ Prague, Dept Organ Chem, Fac Sci, Prague 12843 2, Czech Republic

[2] Acad Sci Czech Republic, Inst Organ Chem & Biochem, CR-16610 Prague 6, Czech Republic

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2012年 / 134卷 / 38期

基金：

欧洲研究理事会;

关键词：

MASS-SPECTROMETRY; 4-HYDROXYBENZOIC ACID; BENZOIC-ACIDS; DISSOCIATION; COMPLEXES; IONS; SPECTROSCOPY; SOLVATION; AIR/WATER; SEPARATION;

D O I：

10.1021/ja3060589

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Despite the simplicity of the molecule, the site of single deprotonation of p-hydroxybenzoic acid upon electrospray ionization (ESI) has recently formed a subject of debate in this journal. By means of NMR experiments in solution and gas-phase studies employing ion-mobility mass spectrometry (IM-MS), the apparent controversy is resolved. It is shown that irrespective of the solvent the carboxylate tautomer is preferred in solution, while the opposite holds true for isolated ions in the gas phase. The tautomer distribution sampled in the gas phase very much depends on the actual solvent used in ESI, the pH value, as well as the total concentration. Moreover, the occurrence of gas-phase reactions in the course of the ESI process influences the tautomer ratio. Implications for correlations between ESI mass spectra and solution-phase chemistry are discussed.

引用

页码：15897 / 15905

页数：9

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