Optical Configuration Effect on the Structure and Reactivity of Diastereomers Revealed by Spin Effects and Molecular Dynamics Calculations | Sciact - CRIS-system of Boreskov Institute of Catalysis

Optical Configuration Effect on the Structure and Reactivity of Diastereomers Revealed by Spin Effects and Molecular Dynamics Calculations Full article

Journal

International Journal of Molecular Sciences
ISSN: 1422-0067 , E-ISSN: 1661-6596

Output data

Year: 2022, Volume: 23, Number: 1, Article number : 38, Pages count : 21 DOI: 10.3390/ijms23010038

Tags

chiral linked systems; diastereomers; hyperpolarization; electron transfer; spin selectivity; molecular dynamics; magnetic dipole–dipole interaction of electrons

Authors

Ageeva Aleksandra A. ^1,2 , Doktorov Alexander B. ¹ , Selyutina Olga Yu. ¹ , Magin Ilya M. ^1,2 , Ilyina Margarita G. ³ , Borisevich Sophia S. ^3,4 , Rubtsov Ruslan Yu. ⁴ , Khursan Sergey L. ³ , Stepanov Alexander A. ¹ , Vasilevsky Sergey F. ¹ , Polyakov Nikolay E. ^1,2 , Leshina Tatyana V. ¹

Affiliations

1	Voevodsky Institute of Chemical Kinetics and Combustion, 630090 Novosibirsk, Russia
2	Department of Natural Sciences, Department of Physics, Novosibirsk State University, 630090 Novosibirsk, Russia
3	Ufa Institute of Chemistry, Ufa Federal Research Centre of the Russian Academy of Sciences, 450054 Ufa, Russia
4	The Institute of Problems of Chemical Physics of the Russian Academy of Sciences, 142432 Chernogolovka, Russia

The peculiarities of spin effects in photoinduced electron transfer (ET) in diastereomers of donor-acceptor dyads are considered in order to study the influence of chirality on reactivity. Thus, the spin selectivity—the difference between the enhancement coefficients of chemically induced dynamic nuclear polarization (CIDNP)—of the dyad’s diastereomers reflects the difference in the spin density distribution in its paramagnetic precursors that appears upon UV irradiation. In addition, the CIDNP coefficient itself has demonstrated a high sensitivity to the change of chiral centers: when one center is changed, the hyperpolarization of all polarized nuclei of the molecule is affected. The article analyzes the experimental values of spin selectivity based on CIDNP calculations and molecular dynamic modeling data in order to reveal the effect of optical configuration on the structure and reactivity of diastereomers. In this way, we succeeded in tracing the differences in dyads with L- and D-tryptophan as an electron donor. Since the replacement of L-amino acid with D-analog in specific proteins is believed to be the cause of Alzheimer’s and Parkinson’s diseases, spin effects and molecular dynamic simulation in model dyads can be a useful tool for investigating the nature of this phenomenon.

Ageeva A.A. , Doktorov A.B. , Selyutina O.Y. , Magin I.M. , Ilyina M.G. , Borisevich S.S. , Rubtsov R.Y. , Khursan S.L. , Stepanov A.A. , Vasilevsky S.F. , Polyakov N.E. , Leshina T.V.
Optical Configuration Effect on the Structure and Reactivity of Diastereomers Revealed by Spin Effects and Molecular Dynamics Calculations
International Journal of Molecular Sciences. 2022. V.23. N1. 38 :1-21. DOI: 10.3390/ijms23010038 WOS Scopus РИНЦ OpenAlex

Submitted:	Dec 3, 2021
Accepted:	Dec 20, 2021
Published online:	Dec 21, 2021
Published print:	Jan 1, 2022

Web of science:	WOS:000741199600001
Scopus:	2-s2.0-85121377301
Elibrary:	47542162
OpenAlex:	W4200418378

DB	Citing
OpenAlex	5
Web of science	4
Scopus	5