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Kinetic Manifestation of Bimolecular Multistage Physicochemical Processes in Solutions

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A special issue of International Journal of Molecular Sciences (ISSN 1422-0067). This special issue belongs to the section "Physical Chemistry and Chemical Physics".

Deadline for manuscript submissions: closed (31 October 2020) | Viewed by 10057

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Prof. Dr. Alexander B. Doktorov

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Voevodsky Institute of Chemical Kinetics and Combustion Siberian Branch of the Russian Academy of Sciences, Novosibirsk, Russia
Interests: physicochemical processes in solutions; diffusion-influenced reactions; multistage chemical reactions; electron and energy transfer reactions; luminescence quenching; multisite reactions; kinetic equations; magneto-spin effects in chemical reactions

Special Issue Information

Dear Colleagues,

Physicochemical processes in condensed matters (in liquid and solid solutions) are widely spread in nature, and their theoretical and experimental investigation is important for biological and technological applications. Among these are, for example, electron excitation energy transfer (that determines, in particular, concentration quenching of luminescence), electron (or proton) migrations in photosynthetic systems, transfer of nuclear spin polarization, electron spin exchange (leading to EPR lines broadening), chemical reactions occurring in colloid or polymer solutions, in nano- and biosystems, or trapping and detrapping problems semiconductor and many others. An important specific feature of such processes is an essential dependence of their kinetic manifestations on molecular mobility of reactants (that ensures the encounter of reactants in solution), the character of which is significantly affected by a chemically inert solvent. This determines the so-called “cage effect” that results, along with bulk reactions, in the existence of a new kind of geminate reactions. The presence of such an effect makes it necessary to take into consideration the nonstationary stage of the kinetics; and this leads to the necessity of deriving kinetic equations, developing adequate molecular models of reacting systems, analytically or numerically calculating their kinetics or reaction yields, as well as experimentally establishing the mechanism of multistage physicochemical processes under study. This Special Issue on “Kinetic Manifestation of Bimolecular Multistage Physicochemical Processes in Solutions” will include a selection of research papers and reviewers about all kinetic aspects of any multistage physicochemical process in solutions.

Prof. Dr. Alexander B. Doktorov
Guest Editor

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Keywords

Physicochemical processes in solutions
Diffusion-influenced reactions
Multistage chemical reactions
Electron and energy transfer reactions
Luminescence quenching
Multisite reactions
Kinetic equations
Magneto-spin effects in chemical reactions
Kinetics and quantum or reaction yield

Published Papers (4 papers)

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Research

21 pages, 7203 KiB

Open AccessArticle

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

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

Int. J. Mol. Sci. 2022, 23(1), 38; https://doi.org/10.3390/ijms23010038 - 21 Dec 2021

Cited by 3 | Viewed by 2147

Abstract

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. Full article

(This article belongs to the Special Issue Kinetic Manifestation of Bimolecular Multistage Physicochemical Processes in Solutions)

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11 pages, 1594 KiB

Open AccessArticle

Role of Chiral Configuration in the Photoinduced Interaction of D- and L-Tryptophan with Optical Isomers of Ketoprofen in Linked Systems

by Aleksandra A. Ageeva, Ilya M. Magin, Alexander B. Doktorov, Victor F. Plyusnin, Polina S. Kuznetsova, Alexander A. Stepanov, Alexander A. Alekseev, Nikolay E. Polyakov and Tatyana V. Leshina

Int. J. Mol. Sci. 2021, 22(12), 6198; https://doi.org/10.3390/ijms22126198 - 08 Jun 2021

Cited by 5 | Viewed by 1922

Abstract

The study of the L- and D-amino acid properties in proteins and peptides has attracted considerable attention in recent years, as the replacement of even one L-amino acid by its D-analogue due to aging of the body is resulted in a number of pathological conditions, including Alzheimer’s and Parkinson’s diseases. A recent trend is using short model systems to study the peculiarities of proteins with D-amino acids. In this report, the comparison of the excited states quenching of L- and D-tryptophan (Trp) in a model donor–acceptor dyad with (R)- and (S)-ketoprofen (KP-Trp) was carried out by photochemically induced dynamic nuclear polarization (CIDNP) and fluorescence spectroscopy. Quenching of the Trp excited states, which occurs via two mechanisms: prevailing resonance energy transfer (RET) and electron transfer (ET), indeed demonstrates some peculiarities for all three studied configurations of the dyad: (R,S)-, (S,R)-, and (S,S)-. Thus, the ET efficiency is identical for (S,R)- and (R,S)-enantiomers, while RET differs by 1.6 times. For (S,S)-, the CIDNP coefficient is almost an order of magnitude greater than for (R,S)- and (S,R)-. To understand the source of this difference, hyperpolarization of (S,S)-and (R,S)- has been calculated using theory involving the electron dipole–dipole interaction in the secular equation. Full article

(This article belongs to the Special Issue Kinetic Manifestation of Bimolecular Multistage Physicochemical Processes in Solutions)

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13 pages, 3857 KiB

Open AccessArticle

Effect of Mechanical Shaking on the Physicochemical Properties of Aqueous Solutions

by Sergey V. Gudkov, Nikita V. Penkov, Ilya V. Baimler, Gennady A. Lyakhov, Vladimir I. Pustovoy, Alexander V. Simakin, Ruslan M. Sarimov and Ivan A. Scherbakov

Int. J. Mol. Sci. 2020, 21(21), 8033; https://doi.org/10.3390/ijms21218033 - 28 Oct 2020

Cited by 62 | Viewed by 3411

Abstract

Long-lived luminescence in the blue region was found to occur in deionized water saturated with atmospheric gases following mechanical shaking. Luminescence intensity decreased exponentially after the cessation of stress. During vigorous mechanical shaking, we observed gas bubbles in solution, and the liquid–gas interface area increased noticeably. At the same time, the concentration of molecular oxygen decreased, which could not be attributed to the water warming up with exposure to mechanical stress. However, deaerated water rapidly became saturated with gases following mechanical stress. The recommendation that cell culture media should be mixed after they are removed from the fridge in order to allow saturation with oxygen is probably misleading. It was shown that gases existed in water both in the form of individual molecules and nanobubbles. Mechanical stress did not influence the number or size of nanobubbles. While gas nanobubbles were absent in freshly prepared deaerated water, they appeared following exposure to mechanical stress. In addition, in mechanically treated gas-saturated water, there was seemingly an equilibrium shift towards the decomposition of carbonic acid to water and carbon dioxide. At the same time, the pH of water tended to increase immediately after mechanical stress. It was demonstrated that reactive oxygen species (ROS) form in gas-saturated water under mechanical stress (30 Hz, amplitude of 5 mm). The relative generation rate of hydrogen peroxide and of the hydroxyl radical was 1 nM/min and 0.5 nM/min, respectively. It was found that with an increase in the frequency of mechanical action (f), the rate of ROS generation increased in proportion to f ². The major pathways for hydrogen peroxide generation are probably associated with the formation of singlet oxygen and its further reduction, and the alternative pathway is the formation of hydrogen peroxide as a result of hydroxyl radical recombination. Full article

(This article belongs to the Special Issue Kinetic Manifestation of Bimolecular Multistage Physicochemical Processes in Solutions)

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15 pages, 3892 KiB

Open AccessArticle

Stereoselectivity of Electron and Energy Transfer in the Quenching of (S/R)-Ketoprofen-(S)-Tryptophan Dyad Excited State

by Aleksandra A. Ageeva, Simon V. Babenko, Ilya M. Magin, Victor F. Plyusnin, Polina S. Kuznetsova, Alexander A. Stepanov, Sergey F. Vasilevsky, Nikolay E. Polyakov, Alexander B. Doktorov and Tatyana V. Leshina

Int. J. Mol. Sci. 2020, 21(15), 5370; https://doi.org/10.3390/ijms21155370 - 28 Jul 2020

Cited by 9 | Viewed by 2101

Abstract

Photoinduced elementary processes in chiral linked systems, consisting of drugs and tryptophan (Trp) residues, attract considerable attention due to several aspects. First of all, these are models that allow one to trace the full and partial charge transfer underlying the binding of drugs to enzymes and receptors. On the other hand, Trp fluorescence is widely used to establish the structure and conformational mobility of proteins due to its high sensitivity to the microenvironment. Therefore, the study of mechanisms of Trp fluorescence quenching in various systems has both fundamental and practical interest. An analysis of the photo-chemically induced dynamic nuclear polarization (CIDNP) and Trp fluorescence quenching in (R/S)-ketoprofen-(S)-tryptophan ((S/R)-KP-(S)-Trp) dyad carried out in this work allowed us to trace the intramolecular reversible electron transfer (ET) and obtain evidence in favor of the resonance energy transfer (RET). The fraction of dyad’s singlet excited state, quenched via ET, was shown to be 7.5 times greater for the (S,S)-diastereomer than for the (R,S) analog. At the same time, the ratio of the fluorescence quantum yields shows that quenching effectiveness of (S,S)-diastereomer to be 5.4 times lower than for the (R,S) analog. It means that the main mechanism of Trp fluorescence quenching in (S/R)-KP-(S)-Trp dyad is RET. Full article

(This article belongs to the Special Issue Kinetic Manifestation of Bimolecular Multistage Physicochemical Processes in Solutions)

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