Photoinduced Processes in Lysine-Tryptophan-Lysine Tripeptide with L and D Tryptophan.

Optical isomers of short peptide Lysine-Tryptophan-Lysine (Lys-{L/D-Trp}-Lys) and Lys-Trp-Lys with an acetate counter-ion were used to study photoinduced intramolecular and intermolecular processes of interest in photobiology. A comparison of L- and D-amino acid reactivity is also the focus of scientists' attention in various specialties because today, the presence of amyloid proteins with D-amino acids in the human brain is considered one of the leading causes of Alzheimer's disease. Since aggregated amyloids, mainly Aß42, are highly disordered peptides that cannot be studied with traditional NMR and X-ray techniques, it is trending to explore the reasons for differences between L- and D-amino acids using short peptides, as in our article. Using NMR, chemically induced dynamic nuclear polarization (CIDNP) and fluorescence techniques allowed us to detect the influence of tryptophan (Trp) optical configuration on the peptides fluorescence quantum yields, bimolecular quenching rates of Trp excited state, and the photocleavage products formation. Thus, compared with the D-analog, the L-isomer shows a greater Trp excited state quenching efficiency with the electron transfer (ET) mechanism. There are experimental confirmations of the hypothesis about photoinduced ET between Trp and the CONH peptide bond, as well as between Trp and another amide group.

New Aspects of the Antioxidant Activity of Glycyrrhizin Revealed by the CIDNP Technique.

Electron transfer plays a crucial role in ROS generation in living systems. Molecular oxygen acts as the terminal electron acceptor in the respiratory chains of aerobic organisms. Two main mechanisms of antioxidant defense by exogenous antioxidants are usually considered. The first is the inhibition of ROS generation, and the second is the trapping of free radicals. In the present study, we have elucidated both these mechanisms of antioxidant activity of glycyrrhizin (GL), the main active component of licorice root, using the chemically induced dynamic nuclear polarization (CIDNP) technique. First, it was shown that GL is capable of capturing a solvated electron, thereby preventing its capture by molecular oxygen. Second, we studied the effect of glycyrrhizin on the behavior of free radicals generated by UV irradiation of xenobiotic, NSAID-naproxen in solution. The structure of the glycyrrhizin paramagnetic intermediates formed after the capture of a solvated electron was established from a photo-CIDNP study of the model system-the dianion of 5-sulfosalicylic acid and DFT calculations.

Highly efficient exciplex formation via radical ion pair recombination in X-irradiated alkane solutions for luminophores with short fluorescence lifetimes.

X-irradiation of alkane solutions of N,N-dimethylaniline with various organic luminophores produces characteristic emission bands ascribed to the corresponding exciplexes. In contrast to optical generation, which requires diffusion-controlled quenching of excited states, an additional channel of exciplex formation via irreversible recombination of radical ion pairs is operative here, which produces exciplexes in solution with high efficiency even for p-terphenyl and diphenylacetylene having fluorescence decay times of 0.95 ns and 8 ps, respectively. The exciplex emission band is sensitive to an external magnetic field and exerts a very large observed magnetic field effect of up to 20%, the maximum possible value under the conditions of the described experiment.

Time-resolved fluorescence study of exciplex formation in diastereomeric naproxen-pyrrolidine dyads.

The influence of chirality on the elementary processes triggered by excitation of the (S,S)- and (R,S)- diastereoisomers of naproxen-pyrrolidine (NPX-Pyr) dyads has been studied by time-resolved fluorescence in acetonitrile-benzene mixtures. In these systems, the quenching of the (1)NPX*-Pyr singlet excited state occurs through electron transfer and exciplex formation. Fluorescence lifetimes and quantum yields revealed a significant difference (around 20%) between the (S,S)- and (R,S)- diastereomers. In addition, the quantum yields of exciplexes differed by a factor of 2 regardless of solvent polarity. This allows us to suggest a similar influence of the chiral centers on the local charge transfer resulting in exciplex and full charge separation that leads to ion-biradicals. A simplified scheme is proposed to estimate a set of rate constant values (k1-k5) for the elementary stages in each solvent system.

Effect of glycyrrhizic acid on lappaconitine phototransformation.

1H NMR and CIDNP methods were used to demonstrate that triterpene glycoside (glycyrrhizic acid, GA) can substantially change the efficiency and direction of phototransformation of alkaloid lappaconitine (LA) due to both its solubilization in GA micelles and protonation of LA amine nitrogen in water-alcohol solutions. The LA solubilization in the GA micelle suppresses the process of deacylation.

Peculiarities of magnetic and spin effects in a biradical/stable radical complex (three-spin system). Theory and comparison with experiment.

The field dependencies of biradical recombination probability in the presence of paramagnetic species with spins S(3) = 1 and S(3) = (1)/(2) have been calculated in the framework of the density matrix formalism. To describe the effect of the "third" spin on the spin evolution in biradical, we have also considered the spin exchange interaction between the added spin and one of the paramagnetic biradical centers. A characteristic feature of the calculated field dependencies is the existence of several extrema with positions and magnitudes depending on the signs and values of the exchange integrals in the system. The method proposed can be used to describe the effect of spin catalysis. It is shown that for the system with the third spin S(3) = 1 spin catalysis manifests itself stronger than in the case of spin S(3) = (1)/(2). The dependence of spin catalysis efficiency on the exchange interaction with the third spin has an extremum with position independent of the value of the spin added.