TY - JOUR

T1 - Optical configuration effect on the structure and reactivity of diastereomers revealed by spin effects and molecular dynamics calculations

AU - Ageeva, Aleksandra A.

AU - Doktorov, Alexander B.

AU - Selyutina, Olga Yu

AU - Magin, Ilya M.

AU - Ilyina, Margarita G.

AU - Borisevich, Sophia S.

AU - Rubtsov, Ruslan Yu

AU - Khursan, Sergey L.

AU - Stepanov, Alexander A.

AU - Vasilevsky, Sergey F.

AU - Polyakov, Nikolay E.

AU - Leshina, Tatyana V.

N1 - Funding Information: Funding: This research was funded by Russian Science Foundation, grant number 18‐13‐00047. Publisher Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland.

PY - 2022/1/1

Y1 - 2022/1/1

N2 - 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 addi-tion, 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.

AB - 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 addi-tion, 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.

KW - Chiral linked systems

KW - Diastereomers

KW - Electron transfer

KW - Hyperpolarization

KW - Magnetic dipole–dipole interaction of electrons

KW - Molecular dynamics

KW - Spin selectivity

KW - Electron Transport

KW - Stereoisomerism

KW - Molecular Dynamics Simulation

KW - Magnetic Resonance Spectroscopy/methods

KW - Proteins/chemistry

KW - Tryptophan/chemistry

KW - Electrons

UR - http://www.scopus.com/inward/record.url?scp=85121377301&partnerID=8YFLogxK

U2 - 10.3390/ijms23010038

DO - 10.3390/ijms23010038

M3 - Article

C2 - 35008460

AN - SCOPUS:85121377301

VL - 23

JO - International Journal of Molecular Sciences

JF - International Journal of Molecular Sciences

SN - 1661-6596

IS - 1

M1 - 38

ER -