Synthesis,X-ray analysis,and quantum-chemical DFT study of features in formation of a binuclear phenanthroline complex with a V<Superscript>IV</Superscript>–O–V<Superscript>V</Superscript> core

A new mixed-valence complex [(O)(phen)₂V^IV(μ-O)V^V(O)phen)(mal)]⁺ was synthesized and characterized by the X-ray structural analysis. Its geometric structure was simulated by the DFT M06/6-31G(d,p) method. Comparison of calculated and experimental data made it possible to draw a conclusion on the oxobridging nature of the bond between vanadium fragments and to confirm the value of the target compound charge. The energy characteristics of cation formation reactions in solution were estimated. It was found that the oxidation of V^IV to V^V assists subsequent substitution of ligands. Joining [(O)V^IV(phen)₂]²⁺ and [(O)V^V(O)(phen)(mal)]^– particles proceeds by the donor-acceptor mechanism.     

The formation of a light field with suppressed photon fluctuations by nonlinear optical methods

A quantum theory is developed to describe optical parametric amplification under low-frequency pumping, which is observed in nonlinear photonic crystals in sequential interactions of light waves with multiple frequencies. Spatial variations of the mean number of photons and the Fano factor at signal and additional frequencies are analyzed. It is shown that a field with a sub-Poisson statistics of photons can be formed at a signal frequency which is 1.5 times higher than the frequency of pumping.     

Femtosecond relaxation of photoexcited states in nanosized semiconductor particles of iron oxides

Relaxation of photoexcited states in nanosized semiconductor particles of iron oxides was studied by femtosecond laser photolysis techniques: (1) in an aqueous colloidal solution of -Fe₂O₃; (2) in Fe₂O₃ particles in the Nafion^® cation-exchange polymeric membrane; (3) in an aqueous colloid of -Fe₂O₃; and (4) in nanocrystals of ferrihydrite 5Fe₂O₃·9H₂O, which are contained in the protein shell of ferritine. The photoinduced excited states relax at the femtosecond and picosecond time scale. The spectra of photoinduced absorption of photoexcited states and the relaxation dynamics in the studied iron oxides weakly depend on the structure and surface environment of a nanoparticle.     

Features of the Formation of the [(O)VIV(C2O4)(Phen)(H2O)] Complex in the Malic Acid Oxidation Process

Complex [(O)V^IV(C₂O₄)(Phen)(H₂O)] was obtained on the basis of V₂O₅ and malic acid in the presence of concentrated HNO₃ and phenanthroline. Its structure was determined by the X-ray structural analysis; its magnetic susceptibility was measured. The role of the \(\rm{VO}^+_2\) and VO²⁺ cations in the oxidation and complex-formation processes was considered. A method for the conversion of malic acid to oxalate anions through the formation of oxaloacetic acid and the intermediate products of its decarboxylation reactions was proposed. It was shown by the DFT M06/6-31G(d,p) method that the transition state energy decreases in the way of the HOC(O)C(0)CH₂-COOH bond breakage during decarboxylation compared with the free acid in the intermediate of its anion with VO²⁺.

     

Low-frequency dielectric-barrier discharge in the Townsend mode

An analytic model is proposed of a dielectric-barrier discharge in the Townsend mode, in which the space charge is small compared to the charge accumulated on the dielectric surface. The discharge mode depends substantially on the ratio between the frequency of the external voltage and the ion drift time through the gap. A low-frequency case is investigated, in which the space charge can be ignored. The analytic expressions obtained agree well with experiments and numerical simulations. The physical mechanism for the onset of relaxation oscillations in the Townsend mode is revealed. The time behavior of a dielectric-barrier discharge is qualitatively described, and its basic scaling parameters are determined.     

Photochemical properties of photosystem 1 immobilized in a mesoporous semiconductor matrix

The pigment-protein complex of photosystem 1 (PS1) isolated from cyanobacterium Synechocystis sp. PCC 6803 has been adsorbed on a solid mesoporous film made from TiO₂ nanoparticles. was on The TiO₂ film supported on a glass substrate with a surface area of 1 cm² adsorbs up to 0.045 nmol of PS1. PS1 molecules are distributed in the pores of the mesoporous support. Immobilization has an insignificant effect on the optical and photochemical properties of PS1. A reversible photoinduced EPR signal from the oxidized primary electron donor P700 of immobilized PS1 has been detected. It has been shown by photoelectrochemical methods that the photoexcitation of PS1 results in electron injection from PS1 to the conduction band of TiO₂.     

Enzymatic oxidation of cadmium and lead metals photodeposited on cadmium sulfide

Cadmium and lead metals deposited on CdS particles are shown to act as substrates--electron donors for enzymes, hydrogenase from Thiocapsa roseopersicina (HG), NAD-dependent hydrogenase from Alcaligenes eutrophus (NLH), and ferredoxin:NADP oxidoreductase (FNR) from Chlorella in the formation of hydrogen, NADH and NADPH, respectively. Adsorption of the enzyme on the surface of the metallized CdS particle is required for enzymatic oxidation of metal. The maximum rates for the formation of hydrogen and NADH catalyzed by hydrogenase and NAD-dependent hydrogenase with metals as electron donors are comparable with the rates obtained for these enzymes using soluble substrates. Kinetic analysis of the enzymatic oxidation of cadmium metal has revealed that the rate decreases mainly due to the formation of a solid product, which is supposed to be Cd(OH)2. The deceleration of lead oxidation catalyzed by hydrogenase proceeds at the expense of the inhibitory effect of the formed Pb2+. The enzymatic oxidation of electrochemically prepared cadmium metal is also shown. Based on these results, a new mechanism of action of the enzymes involved in anaerobic biocorrosion is proposed. By this mechanism, the enzyme accelerates the process of metal dissolution through a mediatorless catalysis of the reduction of the enzyme substrate.