Chintalapudi Kavyasree, Badu-Tawiah Abraham K
Department of Chemistry and Biochemistry, The Ohio State University Columbus OH 43210 USA
Chem Sci. 2020 Aug 25;11(36):9891-9897. doi: 10.1039/d0sc03403g.
Positional isomers of alkenes are frequently transparent to the mass spectrometer and it is difficult to provide convincing data to support their presence. This work focuses on the development of a new reactive nano-electrospray ionization (nESI) platform that utilizes non-inert metal electrodes (, Ir and Ru) for rapid detection of fatty acids by mass spectrometry (MS), with concomitant localization of the C[double bond, length as m-dash]C bond to differentiate fatty acid isomers. During the electrospray process, the electrical energy (direct current voltage) is harnessed for oxide formation on the electrode surface electro-oxidation. The as-formed surface oxides are found to facilitate epoxide formation at the C[double bond, length as m-dash]C bond position and the products are analyzed by MS in real-time. This phenomenon has been applied to analyze isomers of unsaturated fatty acids from complex serum samples, without pre-treatment.
烯烃的位置异构体通常对质谱仪是透明的,很难提供令人信服的数据来支持它们的存在。这项工作重点在于开发一种新的反应性纳米电喷雾电离(nESI)平台,该平台利用非惰性金属电极(铱和钌)通过质谱(MS)快速检测脂肪酸,同时定位碳 - 碳双键以区分脂肪酸异构体。在电喷雾过程中,电能(直流电压)被用于在电极表面形成氧化物——电氧化过程。发现所形成的表面氧化物有助于在碳 - 碳双键位置形成环氧化物,并且产物通过质谱实时分析。这种现象已被应用于分析来自复杂血清样品的不饱和脂肪酸异构体,无需预处理。