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

Autor: Ageeva AA; Voevodsky Institute of Chemical Kinetics and Combustion, 630090 Novosibirsk, Russia.; Department of Natural Sciences, Department of Physics, Novosibirsk State University, 630090 Novosibirsk, Russia., Doktorov AB; Voevodsky Institute of Chemical Kinetics and Combustion, 630090 Novosibirsk, Russia., Selyutina OY; Voevodsky Institute of Chemical Kinetics and Combustion, 630090 Novosibirsk, Russia., Magin IM; Voevodsky Institute of Chemical Kinetics and Combustion, 630090 Novosibirsk, Russia.; Department of Natural Sciences, Department of Physics, Novosibirsk State University, 630090 Novosibirsk, Russia., Ilyina MG; Ufa Institute of Chemistry, Ufa Federal Research Centre of the Russian Academy of Sciences, 450054 Ufa, Russia., Borisevich SS; Ufa Institute of Chemistry, Ufa Federal Research Centre of the Russian Academy of Sciences, 450054 Ufa, Russia.; The Institute of Problems of Chemical Physics of the Russian Academy of Sciences, 142432 Chernogolovka, Russia., Rubtsov RY; The Institute of Problems of Chemical Physics of the Russian Academy of Sciences, 142432 Chernogolovka, Russia., Khursan SL; Ufa Institute of Chemistry, Ufa Federal Research Centre of the Russian Academy of Sciences, 450054 Ufa, Russia., Stepanov AA; Voevodsky Institute of Chemical Kinetics and Combustion, 630090 Novosibirsk, Russia., Vasilevsky SF; Voevodsky Institute of Chemical Kinetics and Combustion, 630090 Novosibirsk, Russia., Polyakov NE; Voevodsky Institute of Chemical Kinetics and Combustion, 630090 Novosibirsk, Russia.; Department of Natural Sciences, Department of Physics, Novosibirsk State University, 630090 Novosibirsk, Russia., Leshina TV; Voevodsky Institute of Chemical Kinetics and Combustion, 630090 Novosibirsk, Russia.
Jazyk: angličtina
Zdroj: International journal of molecular sciences [Int J Mol Sci] 2021 Dec 21; Vol. 23 (1). Date of Electronic Publication: 2021 Dec 21.
DOI: 10.3390/ijms23010038
Abstrakt: 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.
Databáze: MEDLINE
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