I. A. Kirilyuk

Production of superoxide in chloroplast thylakoid membranes ESR study with cyclic hydroxylamines of different lipophilicity.

Accumulation of nitroxide radicals, DCP or TMT , under illumination of a thylakoid suspension containing either hydrophilic, DCP‐H, or lipophilic, TMT‐H, cyclic hydroxylamines that have high rate constants of the reaction with superoxide radicals, was measured using ESR. A slower accumulation of TMT in contrast with DCP accumulation was explained by re‐reduction of TMT by the carriers of the photosynthetic electron transport chain within the membrane. Superoxide dismutase suppressed TMT accumulation to a lesser extent than DCP accumulation. The data are interpreted as evidencing the production of intramembrane superoxide in thylakoids.

Inclusion Complexes of Nitroxides of Pyrrolidine and Imidazoline Series with Cucurbit[7]uril

Inclusion of nitroxides into the cavity of molecular nanocontainers may prevent or significantly retard nitroxide reactions with cellular reductans and increase nitroxide lifetime. This paper is aimed at studying possible applications of cucurbit[7]uril (CB7) as a molecular nanocontainer for pH-sensitive nitroxides probes. Inclusion complexes of CB7 with different nitroxides--3-aminomethyl-proxyl (AMP), 3-hydroxymethyl-proxyl (HMP), 4-amino-2,2,5,5-tetramethyl-2,5-dihydroimidazole-1-oxyl (ATI), and 2,2,4,5,5-pentamethyl-2,5-dihydroimidazole-1-oxyl (MTI)--were studied. It was found that reversible formation of inclusion complexes AMP@CB7, AMPH(+)@CB7, HMP@CB7, ATIH(+)@CB7, and MTIH(+)@CB7 is accompanied by a decrease of hyperfine interaction (HFI) constant on nitrogen of the nitroxide group and by a 5-7-fold increase of rotational correlation time monitored by electron paramagnetic resonance (EPR). The binding constants of nitroxide@CB7 complexes were determined, and the influence of alkali metal ions and pH on the equilibrium between free and encapsulated nitroxides was studied. The EPR spectra of CB7 mixtures with protonable nitroxides were found to be more sensitive to pH changes than the spectra of pure nitroxides, and the apparent pK of these mixtures was found to increase with CB7 concentration. The nitroxide@CB7 complexes showed higher resistance to chemical reduction with ascorbic acid compared to free nitroxides. Thus, CB7 can be used for the improvement of functional properties of nitroxides.

Role of the alkyl fragment of initiating alkoxyamine in nitroxide mediated polymerization of styrene

The role of the alkyl fragment of alkoxyamine initiating the homopolymerization of styrene is experimentally and theoretically studied in the case of 2,2,6,6-tetramethylpiperidine-1-oxyl derivatives. The rate constants of homolysis and recombination are measured for the alkoxyamines under study. The characteristics of polymerization initiated by these compounds are experimentally examined. The kinetics of polymerization is theoretically calculated with allowance for the measured kinetic parameters and the experimentally detected side reaction of hydrogen-atom transfer to the nitroxide radical during the thermolysis of alkoxyamine 2-cyano-2-isopropyl-TEMPO.

Interaction of imidazoline- and imidazolidine-based nitroxides with chloroplasts

In this work, we investigated the interaction of a number of novel pH-sensitive spin probes (imidazoline- and imidazolidine-based nitroxides) with isolated chloroplasts. The light-induced changes in the electron paramagnetic resonance signals of these radicals are determined by several factors: ΔpH-driven accumulation of nitroxides inside the thylakoids, consumption (or evolution) of oxygen by chloroplasts, and irreversible loss of spin probe paramagnetism. A comparative study of these radicals characterized by different pKa allowed us to conclude that these spin probes can be used as pH indicators for monitoring the intrathylakoid pH- and light-induced changes in oxygen concentration in chloroplast suspension.

1,3-Dipolar cycloaddition of cyclic α-methoxynitrones, derivatives of 2H-imidazole 1-oxide and 4H-imidazole 3-oxide

The reactions of cyclic aldo- and α-methoxynitrones of the 2H-imidazole-1-oxide and 4H-imidazole 3-oxide series with isocyanates, phenyl isothiocyanate, N-phenylmaleimide, and dimethyl acetylenedicarboxylate were studied. The reactions give the corresponding 1,3-dipolar cycloaddition products. 2,2-Dimethyl-4-phenyl-2H-imidazole 1-oxide does not enter into a similar reaction with isocyanates or phenyl isothiocyanate.

Quantification of superoxide radical production in thylakoid membrane using cyclic hydroxylamines

Applicability of two lipophilic cyclic hydroxylamines (CHAs), CM-H and TMT-H, and two hydrophilic CHAs, CAT1-H and DCP-H, for detection of superoxide anion radical (O2(∙-)) produced by the thylakoid photosynthetic electron transfer chain (PETC) of higher plants under illumination has been studied. ESR spectrometry was applied for detection of the nitroxide radical originating due to CHAs oxidation by O2(∙-). CHAs and corresponding nitroxide radicals were shown to be involved in side reactions with PETC which could cause miscalculation of O2(∙-) production rate. Lipophilic CM-H was oxidized by PETC components, reducing the oxidized donor of Photosystem I, P700(+), while at the same concentration another lipophilic CHA, TMT-H, did not reduce P700(+). The nitroxide radical was able to accept electrons from components of the photosynthetic chain. Electrostatic interaction of stable cation CAT1-H with the membrane surface was suggested. Water-soluble superoxide dismutase (SOD) was added in order to suppress the reaction of CHA with O2(∙-) outside the membrane. SOD almost completely inhibited light-induced accumulation of DCP(∙), nitroxide radical derivative of hydrophilic DCP-H, in contrast to TMT(∙) accumulation. Based on the results showing that change in the thylakoid lumen pH and volume had minor effect on TMT(∙) accumulation, the reaction of TMT-H with O2(∙-) in the lumen was excluded. Addition of TMT-H to thylakoid suspension in the presence of SOD resulted in the increase in light-induced O2 uptake rate, that argued in favor of TMT-H ability to detect O2(∙-) produced within the membrane core. Thus, hydrophilic DCP-H and lipophilic TMT-H were shown to be usable for detection of O2(∙-) produced outside and within thylakoid membranes.

Spin probe study of acidity of inorganic materials

Acidic characteristics of various inorganic materials, such as silica gel, aluminum, and titanium(IV) oxides, original and modified with F− and SO42− ions, in the form of hydrogels and nanostructured powders doped by copper(II) ions, are studied. It is shown that pH values inside pores of the studied sorbents (pHintr) differ from the pH of external solutions by 0.5–1.1 units. In the pores of original γ-Al2O3, the pHintr values are higher, while, in pores of γ-Al2O3 samples modified with F− и SO42−, as well as nonmodified α-Al2O3, SiO2 gel, and TiO2 hydrogels, pHintr are lower compared to the pH of the external solution. It is found that pHintr decreases, as the content of Cu2+ ions in the TiO2 phase grows, and, beginning with a certain moment, it coincides with pH of an equilibrium solution. The pKa values of functional group dissociation in some materials are determined. It is shown that, using spin probes, that is, pH-sensitive nitroxyl radicals, the electrostatic potential of the surface of nanostructured TiO2 can be estimated.

Structure and characteristics of chitosan cobalt-containing hybrid systems, the catalysts of olefine oxidation

Cobalt-containing hybrid organo-inorganic materials based on the chitosan-SiO2, chitosan-Al2O3, and chitosan-cellulose systems were obtained. The surface structure and processes that occur during the formation of metal-containing materials, the catalytic properties of which were studied in the oxidation reactions of alkene, were investigated by EPR spectroscopy using a stable pH-sensitive nitroxyl radical, 4-dimethylamino-2-ethyl-5,5-dimethyl-2-(pyridin-4-yl)-2,5-dihydro-1H-imidazole-1-oxyl, as the adsorbed probe molecules.

Medium acidity and catalytic properties of composite materials based on silica and titania and powder cellulose in the presence of Cu2+ ions

Composite materials (CMs) were synthesized from silica and titania xerogels. The influence of the charged state of the CM surface on complexation with Cu2+ ions and the catalytic activity of the obtained samples in model oxidative dehydrogenation of trimethylhydroquinone with air oxygen was analyzed. Using powder cellulose in the synthesis of CMs increased the specific surface of inorganic dioxides and lowered the negative electric potential of the CM surface. This caused a redistribution of the ratio between different types of copper structures formed in the samples during the copper sorption and led to the catalytic activity of the CMs.

Polymerization of Styrene in the Presence of Nitroxide Radicals of the Dihydroimidazole Series

2,2,5,5-Tetramethyl-4-phenyl-2,5-dihydroimidazole-1-oxyl and 2,2,5,5-tetramethyl-4-phenyl-2,5-dihydroimidazole-3-oxide-1-oxyl have been used as regulators of chain growth in the free-radical polymerization of styrene. It has been shown that the compounds of the dihydroimidazole series function as new living polymerization agents and allow the synthesis of polymers with low polydispersity coefficients and desired molecular masses.