Kölliker S, Oehme M, Dye C
Organic Analytical Chemistry, University of Basle, Neuhausstrasse 31, CH-4057 Basle, Switzerland.
Anal Chem. 1998 May 1;70(9):1979-85. doi: 10.1021/ac9709458.
Ion trap multiple fragmentation mass spectrometry (MS(n)()) combined with high-performance liquid chromatography (HPLC) has been used for the structure elucidation and identification of 2,4-dinitrophenylhydrazone derivatives of carbonyl compounds in ambient air samples. Atmospheric pressure chemical ionization in the negative ion mode was the most suitable detection method. Different measures are described to decrease the MS background originating from the HPLC system. Low-picogram quantities were detectable in extracted mass chromatograms generated from full-scan records. Fragment ions produced by MS/MS allowed identification of substructures of the carbonyls. Detailed fragmentation paths were studied by MS(3) to MS(4) using reference compounds. A fragmentation scheme was established which enabled a structure confirmation and identification with 1-10 ng by HPLC/MS/MS. The identification of a compound coeluting with n-pentanal-DNPH and of a dimerization byproduct are given as examples.
离子阱多级碎裂质谱法（MS(n)()）与高效液相色谱法（HPLC）联用，已用于环境空气样品中羰基化合物2,4-二硝基苯腙衍生物的结构解析和鉴定。负离子模式下的大气压化学电离是最合适的检测方法。描述了不同措施以降低源自HPLC系统的质谱背景。在全扫描记录生成的提取质量色谱图中可检测到低皮克量。MS/MS产生的碎片离子可用于鉴定羰基的子结构。使用参考化合物通过MS(3)至MS(4)研究了详细的碎裂途径。建立了一种碎裂方案，可通过HPLC/MS/MS对1-10 ng的化合物进行结构确认和鉴定。给出了与正戊醛-DNPH共洗脱的化合物以及二聚化副产物的鉴定示例。
