| Autor: |
Magin IM; Voevodsky Institute of Chemical Kinetics and Combustion, 630090 Novosibirsk, Russia., Pushkin IA; Voevodsky Institute of Chemical Kinetics and Combustion, 630090 Novosibirsk, Russia.; Department of Natural Sciences, Novosibirsk State University, 630090 Novosibirsk, Russia., Ageeva AA; Voevodsky Institute of Chemical Kinetics and Combustion, 630090 Novosibirsk, Russia.; Department of Natural Sciences, Novosibirsk State University, 630090 Novosibirsk, Russia., Martianova SO; Voevodsky Institute of Chemical Kinetics and Combustion, 630090 Novosibirsk, Russia.; Department of Natural Sciences, Novosibirsk State University, 630090 Novosibirsk, Russia., Polyakov NE; Voevodsky Institute of Chemical Kinetics and Combustion, 630090 Novosibirsk, Russia., Doktorov AB; Voevodsky Institute of Chemical Kinetics and Combustion, 630090 Novosibirsk, Russia., Leshina TV; Voevodsky Institute of Chemical Kinetics and Combustion, 630090 Novosibirsk, Russia. |
| Abstrakt: |
It is well-known that non-covalent interactions play an essential role in the functioning of biomolecules in living organisms. The significant attention of researchers is focused on the mechanisms of associates formation and the role of the chiral configuration of proteins, peptides, and amino acids in the association. We have recently demonstrated the unique sensitivity of chemically induced dynamic nuclear polarization (CIDNP) formed in photoinduced electron transfer (PET) in chiral donor-acceptor dyads to non-covalent interactions of its diastereomers in solutions. The present study further develops the approach for quantitatively analyzing the factors that determine the association by examples of dimerization of the diastereomers with the RS, SR, and SS optical configurations. It has been shown that, under the UV irradiation of dyads, CIDNP is formed in associates, namely, homodimers (SS-SS), (SR-SR), and heterodimers (SS-SR) of diastereomers. In particular, the efficiency of PET in homo-, heterodimers, and monomers of dyads completely determines the forms of dependences of the CIDNP enhancement coefficient ratio of SS and RS, SR configurations on the ratio of diastereomer concentrations. We expect that the use of such a correlation can be useful in identifying small-sized associates in peptides, which is still a problem. |
