Brewer Bobby N, Zu Chengli, Koscho Michael E
Department of Chemistry, Mississippi State University, Mississippi 39762, USA.
Chirality. 2005 Oct;17(8):456-63. doi: 10.1002/chir.20188.
The ability to use mixtures of deprotonated N-(3,5-dinitrobenzoyl)amino acids as chiral selectors for the determination of enantiomeric composition by electrospray ionization-mass spectrometry is demonstrated. For each experiment, two N-(3,5-dinitrobenzoyl)amino acids were chosen such that each would have opposite selectivity for the enantiomers of the analyte. Electrospray ionization-mass spectrometry, monitored in the negative ion mode, of solutions containing the two N-(3,5-dinitrobenzoyl)amino acids, sodium hydroxide, and the analyte, in a one-to-one mixture of methanol and water, afford peaks in the mass spectrum that correspond to the deprotonated 1:1 analyte-selector complexes. The ratio of the intensities of the complexes in the mass spectrum can be related to the enantiomeric composition of the analyte. Additionally, the sense and extent of chiral recognition is consistent with chromatographic observations, using chiral stationary phases derived from N-(3,5-dinitrobenzoyl)amino acids. Each analysis of enantiomeric composition requires less than 10 s to complete, indicating that this method has great potential for the development of fast-/high-throughput chiral analyses.
已证明能够使用去质子化的N-(3,5-二硝基苯甲酰基)氨基酸混合物作为手性选择剂，通过电喷雾电离质谱法测定对映体组成。对于每个实验，选择两种N-(3,5-二硝基苯甲酰基)氨基酸，使得每种氨基酸对分析物的对映体具有相反的选择性。在负离子模式下监测含有两种N-(3,5-二硝基苯甲酰基)氨基酸、氢氧化钠和分析物的溶液的电喷雾电离质谱，该溶液为甲醇和水的一对一混合物，在质谱中产生对应于去质子化的1:1分析物-选择剂复合物的峰。质谱中复合物强度的比率可与分析物的对映体组成相关。此外，使用源自N-(3,5-二硝基苯甲酰基)氨基酸的手性固定相，手性识别的方向和程度与色谱观察结果一致。每次对映体组成分析完成时间不到10秒，表明该方法在快速/高通量手性分析的发展方面具有巨大潜力。
