食品工业科技2026，Vol.47Issue(5)：92-100,9.DOI:10.13386/j.issn1002-0306.2025020096
虾青素光异构化机理:实验与量子化学相结合研究
Mechanism of Photoisomerization of Astaxanthin:Experimental and Quantum Chemistry Study
摘要
Abstract
To investigate the photoisomerization mechanism of astaxanthin(AST),the types and contents of Z-configuration in photocatalytic conversion of AST were analyzed by HPLC and Q value method.Additionally,the AST configuration was optimized and frequency analysis was performed using density functional theory(DFT).Thermodynamic,kinetic,and energetic parameters of all-E-and Z-AST isomers were further calculated.The results demonstrated that 9-Z-and 13-Z-isomers were predominantly generated under photocatalysis,with the 13-Z content(17.72%)being significantly higher than 9-Z(13.57%)(P<0.05).Upon illumination,neutral AST molecules generated diradicals,facilitating bond twisting.All-E AST exhibited the smallest frontier orbital energy gap,promoting its transition from the ground state to the excited state,and subsequent isomerization into other configurations.Gibbs free energy analysis revealed the following stability order of AST isomers:all-E>9-Z>13-Z>15-Z,basically consistent with experimental observations.Moreover,the activation energy for all-E→9-Z conversion was higher than for all-E→15-Z/13-Z,while single-Z→double-Z isomerization required significantly higher energy than all-E→mono-Z conversion.Notably,the 13-Z-isomer formation rate was about 4-fold and 100-fold higher than that of 15-Z>and 9-Z,respectively.The negligible tunneling effect during mutual transformation explained the scarcity of multi-Z-isomers in experiments and the predominance of 13-Z over 9-Z AST.Collectively,these findings elucidate the controlled generation mechanism of AST isomers and establish a theoretical framework for carotenoid isomerization.关键词
虾青素/异构化/量子化学/全反式异构体/顺式异构体Key words
astaxanthin/isomerization/quantum chemistry/all-E-isomer/Z-isomer分类
轻工纺织引用本文复制引用
周乐松,邹晓君,陈佳玲,肖杰,曹庸,刘晓娟..虾青素光异构化机理:实验与量子化学相结合研究[J].食品工业科技,2026,47(5):92-100,9.基金项目
广州市重点研发计划项目(SL2022B03J00806) （SL2022B03J00806）
国家自然科学基金(32172195). （32172195）
