期刊
ANALYTICAL CHEMISTRY
卷 90, 期 6, 页码 4089-4097出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.analchem.7b05407
关键词
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资金
- Collaborative Research Fund of Hong Kong Research Grants Council [C5031-14E]
- State Key Laboratory of Chirosciences
- University Research Facility in Chemical and Environmental Analysis (UCEA) of The Hong Kong Polytechnic University
- Research Grants Council [CityU 11300917]
- City University of Hong Kong (CityU) [7004401]
- Chow Yei Ching School of Graduate Studies, CityU
- Department of Chemistry, CityU
Naproxen is one of the most consumed nonsteroidal anti-inflammatory drugs and marketed as S-naproxen since R-naproxen is hepatotoxic. In this study, chiral recognition of naproxen has been investigated by tandem mass spectrometry (MS/MS). Among all diastereomeric complexes formed between naproxen and the examined chiral selectors, including cyclodextrins (alpha/beta/gamma-CD), modified phenylalanines (N-acetyl-phenylalanine, N-t-butoxycarbonyl-phenylalanine, N-9-fluorenylmethyloxycarbonyl-phenylalanine), amino acids (Trp, Phe, Tyr, His), glucose, tartaric acid, and vancomycin, a novel binuclear metal bound diastereomeric complexes RM(II))(2)(S/R-naproxen)(L-His)(2)-3H](+) (M = Cu, Ni, or Co with Cu being the best) could allow effective identification of the absolute configuration of naproxen and determination of its enantiomeric excess (ee) through MS/MS analysis. The key candidate structure of [(Cu(II))(2)(S/R-naproxen)(L-His)(2)-3H](+) has been revealed by means of collision-induced dissociation, ion mobility mass spectrometry and density functional theory calculations, indicating an interesting and unusual self-assembled compact geometry with the two Cu(II) ions bridged closely together (Cu-Cu distance is 3.04 angstrom) by the carboxylate groups of the two histidines. It was shown that the difference in dissociation efficiency between the two diastereomers was attributed to the interaction between the NH2 bond of the amino group of one histidine and the naphthyl ring of naproxen. The present report is the first to observe and characterize the complex of (Cu(II))(2)(His)(2) with aromatic acid, which could contribute to the chiral recognition of other chiral aromatic acids, design of catalysts based on binuclear copper bound complex, as well as the better understanding of metal ion complexation by His or His-containing ligands.
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