Observation of electrochemically generated nitrenium ions by desorption electrospray ionization mass spectrometry

被引：50
作者：
Brown, Timothy A. [1 ]
Hosseini-Nassab, Niloufar [1 ]
Chen, Hao [2 ,3 ]
Zare, Richard N. [1 ]
机构：
[1] Stanford Univ, Dept Chem, Stanford, CA 94305 USA
[2] Ohio Univ, Ctr Intelligent Chem Instrumentat, Dept Chem & Biochem, Athens, OH 45701 USA
[3] Ohio Univ, Ctr Intelligent Chem Instrumentat, Edison Biotechnol Inst, Athens, OH 45701 USA
来源：
CHEMICAL SCIENCE | 2016年 / 7卷 / 01期
基金：
美国国家科学基金会;
关键词：
ELECTROCHEMISTRY/LIQUID CHROMATOGRAPHY/MASS SPECTROMETRY; DIARYLNITRENIUM IONS; ARYLNITRENIUM IONS; CLOZAPINE; CHEMISTRY; DESORPTION/IONIZATION; AGRANULOCYTOSIS; INSTRUMENTATION; INTERMEDIATE; REDUCTION;
D O I：
10.1039/c5sc02939b
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
We report the observation of the electrochemically generated nitrenium ions of 4,4'-dimethyoxydiphenylamine and di-p-tolylamine in solution by mass spectrometry. This setup takes inspiration from desorption electrospray ionization mass spectrometry to sample directly from the surface of a rotating waterwheel working electrode for mass spectrometric analysis. Detection of the 4,4'-dimethyoxydiphenylamine nitrenium ion was expected based upon para- methoxy resonance stabilization, whereas observation of the di-p-tolylamine nitrenium ion might be unexpected because resonance stabilization from the para-substituted position is unavailable. However, the short timescale analysis of the setup allows for the isolation of the di-p-tolylamine nitrenium ion, which is electrogenerated in solution and detected mass spectrometrically.
引用
收藏
页码：329 / 332
页数：4
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