The role of the local environment on the structural heterogeneity of carotenoid $\upbeta$-ionone rings

Pishchalnikov, R.Y.; Yaroshevich, I.A.; Zlenko, D.V.; Tsoraev, G.V.; Osipov, E.M.; Lazarenko, V.A.; Parshina, E.Y.; Chesalin, D.D.; Sluchanko, N.N.; Maksimov, E.G.

Авторы: Pishchalnikov Roman Y., Yaroshevich Igor A., Zlenko Dmitry V., Tsoraev Georgy V., Osipov Evgenii M., Lazarenko Vladimir A., Parshina Evgenia Y., Chesalin Denis D., Sluchanko Nikolai N., Maksimov Eugene G.
Журнал: Photosynthesis Research
Год издания: 2022
Издательство: Springer Nature
Местоположение издательства: Switzerland
DOI: 10.1007/s11120-022-00955-2
Аннотация: Our analysis of the X-ray crystal structure of canthaxanthin (CAN) showed that its ketolated β-ionone rings can adopt two energetically equal, but structurally distinct puckers. Quantum chemistry calculations revealed that the potential energy surface of the β-ionone ring rotation over the plane of the conjugated π-system in carotenoids depends on the pucker state of the β-ring. Considering different pucker states and β-ionone ring rotation, we found six separate local minima on the potential energy surface defining the geometry of the keto-β-ionone ring—two cis and one trans orientation for each of two pucker states. We observed a small difference in energy and no difference in relative orientation for the cis-minima, but a pronounced difference for the position of trans-minimum in alternative pucker configurations. An energetic advantage of β-ionone ring rotation from a specific pucker type can reach up to 8 kJ/mol (669cm−1). In addition, we performed the simulation of linear absorption of CAN in hexane and in a unit cell of the CAN crystal. The electronic energies of S0→S2 transition were estimated both for the CAN monomer and in the CAN crystal. The difference between them reached 690cm−1, which roughly corresponds to the energy gap between A and B pucker states predicted by theoretical estimations. Finally, we have discussed the importance of such effects for biological systems whose local environment determines conformational mobility, and optical/functional characteristics of carotenoid.
Добавил в систему: Максимов Евгений Георгиевич

	ИСТИНА	Войти в систему Регистрация
	ИСТИНА ПсковГУ
	Главная Поиск Статистика О проекте Помощь

ИСТИНА

ИСТИНА ПсковГУ

The role of the local environment on the structural heterogeneity of carotenoid $\upbeta$-ionone ringsстатья

Прикрепленные файлы