Redox transformations in desorption electrospray ionization

被引:48
作者
Benassi, Mario [1 ]
Wu, Chunping [1 ]
Nefliu, Marcela [1 ]
Ifa, Demian R. [1 ]
Volny, Michael [1 ]
Cooks, R. Graham [1 ]
机构
[1] Purdue Univ, Dept Chem, W Lafayette, IN 47907 USA
基金
美国国家科学基金会;
关键词
Mass spectrometry; Desorption electrospray ionization; Gas-phase ion reactions; Oxidation of biomolecules; Radical ions; CURRENT ELECTROLYTIC CELL; MASS-SPECTROMETRY; ION-SOURCE; GAS-PHASE; ELECTROCHEMICAL PROCESSES; POTENTIAL GRADIENTS; EMITTER; MECHANISMS; SIMULATION; PROTEINS;
D O I
10.1016/j.ijms.2008.10.012
中图分类号
O64 [物理化学(理论化学)、化学物理学]; O56 [分子物理学、原子物理学];
学科分类号
070203 ; 070304 ; 081704 ; 1406 ;
摘要
Redox changes occur in some circumstances when organic compounds are analyzed by desorption electrospray ionization mass spectrometry (DESI-MS). However, these processes are limited in scope and the data presented here suggest that there are only limited analogies between the redox behavior in DESI and the well-known solution-phase electrochemical processes in standard electrospray ionization (ESI). Positive and negative ion modes were both investigated and there is a striking asymmetry between the incidence of oxidation and of reduction. Although in negative ion mode DESI experiments, some aromatic Compounds were ionized as odd-electron anion radicals, examples of full reduction were not found. By contrast, oxidation in the form of oxygen atom addition (or multiple oxygen atom additions) was observed for several different analytes. These oxidation reactions point to chemically rather than electrochemically controlled processes. Data is presented which suggests that oxidation is predominantly caused by reaction with discharge-created gas-phase radicals. The fact that common reducing agents and known antioxidants such as ascorbic acid are not modified, while a saturated organic acid like stearic acid is oxidized in DESI, indicates that the usual electrochemical redox reactions are not significant but that redox chemistry can be induced under special experimental conditions. (C) 2008 Elsevier B.V. All rights reserved.
引用
收藏
页码:235 / 240
页数:6
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