Spectral study on inclusion interaction and enantiorecognition of 2‐aryl carboxylic acids with hydroxypropyl‐β‐cyclodextrin

• Published in: Chirality (New York, N.Y.) Vol. 32; no. 10; pp. 1257 - 1263
• Main Authors: Jin, Yang, Sun, Wenyu, Lv, Huawei, Tong, Shengqiang
• Format: Journal Article
• Language: English
• Published: Chichester Wiley Subscription Services, Inc 01.10.2020
• Subjects: 2‐aryl carboxylic acids; Acids; Aromatic compounds; Carboxylic acids; Chromophores; Conformation; Cyclodextrins; Doppler effect; Electron clouds; Enantiomers; enantiorecognition; hydroxypropyl‐β‐cyclodextrin; Inclusion complexes; inclusion constant; Liquid chromatography; Molecular interactions; Molecular orbitals; Naproxen; Red shift; Spectra; ultraviolet spectrophotometer; β-Cyclodextrin
• ISSN: 0899-0042; 1520-636X; 1520-636X
• DOI: 10.1002/chir.23276

The inclusion interaction between hydroxypropyl‐β‐cyclodextrin (HP‐β‐CD) and 21 2‐aryl carboxylic acids was investigated by UV (ultraviolet) spectrophotometer. The inclusion constant of each 2‐aryl carboxylic acids with HP‐β‐CD was determined by Benesi–Hildebrand's equation. According to our previous work, it was found that a high inclusion constant for inclusion complex formed by a racemate and cyclodextrin was always observed with the fact that a high enantioseparation factor was achieved for the racemate in enantioseparation by liquid–liquid chromatography, which suggested that high binding combination between racemate and cyclodextrin is very important for a successful enantioseparation in enantioselective liquid–liquid extraction. Among all the studied subjects, mandelic acid enantiomer, 2,3‐diphenylpropionic acid enantiomer, and naproxen enantiomer were selected for the further study. The inclusion constants of enantiomers of these three subjects were determined by UV spectra, which indicated that a necessary difference in inclusion constants between enantiomer and cyclodextrin was also essential. It was found in UV spectra that the absorbance of the analytes with the addition of cyclodextrin would increase or decrease, which was determined by the type of electron excitation. The conformation changes of small molecules can lead to the changes of chromophore valence electron clouds distribution, causing the HOMO‐LUMO energy difference decreased. Thus, a red shift of the wavelength of the maximum absorption was produced indicating that the possibility of the molecular interaction of enantiomers with HP‐β‐CD exists. The relationship between inclusion constants and separation factors of chiral drugs was investigated for the first time.