Structural Analysis of Amylose Tris(3,5-dimethylphenylcarbamate) by NMR Relevant to Its Chiral Recognition Mechanism in HPLC
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- 作者：Chiyo Yamamoto ; Eiji Yashima ; and Yoshio Okamoto
- 刊名：Journal of the American Chemical Society
- 出版年：2002
- 出版时间：October 23, 2002
- 年：2002
- 卷：124
- 期：42
- 页码：12583 - 12589
- 全文大小：860K
- 年卷期：v.124,no.42(October 23, 2002)
- ISSN：1520-5126
文摘
The structural analysis of amylose tris(3,5-dimethylphenylcarbamate) (ADMPC) was performedby NMR spectroscopy using a sample with a lower degree of polymerization in order to understand thechiral recognition mechanism when it was used as a chiral stationary phase (CSP) in high-performanceliquid chromatography (HPLC). ADMPC exhibited chiral discrimination for many enantiomers, including1-(9-anthryl)-2,2,2-trifluoroethanol (1) and 1,1'-bi-2-naphthol (2) in both NMR and HPLC. A good agreementwas observed between the HPLC and NMR results when chloroform was employed as the common solvent.The structure of ADMPC in solution was investigated by NMR using the 2D NOESY technique coupledwith computer modeling, and a left-handed 4/3 helical structure was obtained as the most probable one.The binding geometry between ADMPC and the enantiomers of 1 was also investigated by 1H NMR titration.On the basis of these results combined with molecular modeling, a rational model to explain the chiraldiscrimination mechanism of 1 on ADMPC was proposed.