- Online Investigation of Aqueous-Phase Electrochemical Reactions by Desorption Electrospray Ionization Mass Spectrometry
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Electrochemistry (EC) combined with mass spectrometry (MS) is a powerful tool for elucidation of electrochemical reaction mechanisms. However, direct online analysis of electrochemical reaction in aqueous phase was rarely explored. This paper presents the online investigation of several electrochemical reactions with biological relevance in the aqueous phase, such as nitrosothiol reduction, carbohydrate oxidation, and carbamazepine oxidation using desorption electrospray ionization mass spectrometry (DESI-MS). It was found that electroreduction of nitrosothiols [e.g.; nitrosylated insulin B (13-23)] leads to free thiols by loss of NO, as confirmed by online MS analysis for the first time. The characteristic mass shift of 29 Da and the reduced intensity provide a quick way to identify nitrosylated species. Equally importantly, upon collision-induced dissociation (CID), the reduced peptide ion produces more fragment ions than its nitrosylated precursor ion (presumably the backbone fragmentation cannot compete with the facile NO loss for the precursor ion), thus facilitating peptide sequencing. In the case of saccharide oxidation, it was found that glucose undergoes electro-oxidation to produce gluconic acid at alkaline pH, but not at neutral and acidic pHs. Such a pH-dependent electrochemical behavior was also observed for disaccharides such as maltose and cellobiose. Upon electrochemical oxidation, carbamazepine was found to undergo ring contraction and amide bond cleavage, which parallels the oxidative metabolism observed for this drug in leucocytes. The mechanistic information of these redox reactions revealed by EC/DESI-MS would be of value in nitroso-proteome research and carbohydrate/drug metabolic studies.
- Lu, Mei,Liu, Yong,Helmy, Roy,Martin, Gary E.,Dewald, Howard D.,Chen, Hao
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p. 1676 - 1685
(2015/09/22)
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- Chemiluminescence Involving Acidic and Ambident Ion Light Emitters. The Chemiluminescence of the 9-Acridinepercarboxylate Anion
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The reaction of phenyl 9-acridinecarboxylate (1) with an excess of peroxide ion in THF/water (67/33 mol percent) leads to the emission of either bright yellow-green light or bright blue light, depending on the reaction conditions.The blue emission is favored by high concentrations of hydrogen peroxide and water, for example. 9-Acridinepercarboxylic acid is a common intermediate in the reactions.The light emitter responsible for the blue chemiluminescence is acridone, whereas that responsible for the yellow-green chemiluminescence is the anion of acridone.The effects of base concentration and solvent composition on the relative proportions of these two emitters have produced evidence that, contrary to the expectation of simple theory, a dioxetanone is not an intermediate in the reaction.Other cases where chemiluminescence may involve percarboxylate and peroxide ions are discussed.
- White, Emil H.,Roswell, David F.,Dupont, Andrea C.,Wilson, Alan A.
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p. 5189 - 5196
(2007/10/02)
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