Laser photolysis study of the triplet states of nitroaromatic amides

The spectrokinetic indices of the triplet states of nitroaromatic amides were established. The quenching of triplet states by tertiary aromatic amines in apolar solvents leads to the formation of triplet exciplexes. A charge transfer state makes the major contribution to the structure of these exciplexes. Hydrogen atom transfer proceeds efficiently in the case of secondary aromatic amines, leading to the formation of the corresponding neutral radicals.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1912–1915, August, 1989.     

Modeling of recombination kinetics of radical pairs in magnetic field. Comparison with experimental dependences on the frequency of encounters in biradicals

The recombination kinetics of spin-correlated radical pairs (RPs) with three nonequivalent magnetic nuclei were calculated under conditions of enforced encounters between radicals at time-independent frequency n_dif. The simplest two-position model of a RP was used, which includes two states (contact state and distance-separated state) of the RP, differing in magnitude of isotropic spin-spin exchange interaction between radicals. The calculated kinetic curves were treated in terms of a three-exponential model. The dependences of corresponding rate constants (k _rec) on n_dif, external magnetic field strength (B ₀), and intensity, A _eff, of isotropic hyperfine coupling (HFC) were obtained. The k _rec-vs.-n_dif or k _rec-vs.-viscosity (n_dif varies simultaneously with the inverse lifetime of the contact state) plots pass through maxima whose positions are shifted from the n_dif region near the A _eff value at B ₀ = 0.5 G toward high n_dif values with an increase in B ₀. At n_dif ≫ A _eff, the k _rec-vs.-B ₀ plots pass through maxima in the region B ₀ = A _eff. The calculated dependences are compared with experimental data on recombination of biradicals. The results of calculations show that the experimentally observed maxima on the k _rec-vs.-B ₀ or k _rec-vs.-n_dif plots can be due to peculiar features of the spin dynamics induced by the hyperfine coupling rather than the exchange interaction effects, as is commonly accepted. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1103–1110, May, 2005.     

DNA Effect on Cis–Trans Equilibrium and Fluorescent Properties of 3,3′-Diethyl-9-thiomethylthiacarbocyanine Iodide in Aqueous Solution

The influence of DNA on the cis–trans equilibrium and fluorescent properties of 3,3-diethyl-9-thiomethylthiacarbocyanine iodide (DTTC) in a phosphate buffer (pH 7) was studied by various photochemical techniques. The interaction of dye molecules with DNA leads to the formation of stable noncovalently bonded complexes. Data obtained from DTTC absorption and fluorescence spectra suggest that complexation proceeds primarily through the cis-form of the dye. Complexation with DNA leads to a substantial increase in the quantum yield of the triplet state of DTTC molecules. The rate constant for quenching the dye triplet state by oxygen turned out to be significantly lower than the diffusion-controlled value.     

Heterogeneous grafting on polymers containing chlorine: Grafting of amide groups in water suspension and the reactivity of the new polymer towards epoxy resins

Heterogeneous grafting on polyvinylchloride suspended in water was carried out using N-butyl-3-mercaptopropionamide as nucleophile. Over 50% graft was obtained by using a small amount of solvent as a swelling agent and tricapryl methyl ammonium chloride as a phase transfer catalyst. Elemental analysis of the grafted polymer shows that the chlorine displaced from the polymers is replaced by the thio-amide group. The above conclusion is supported by NMR and IR analysis. The kinetics of the chlorine displacement from PVC by the thio amide group obeys the Shell progressive mechanism. The rate at which an individual spherical particle reacts depends on the diffusion through the reacted layer. The grafted polymer is soluble in tetrahydrofuran or nitrobenzene. The films obtained from the grafted material are brittle due to excessive internal hydrogen bonding. The electrostatic charge which is a characteristic surface phenomena in PVC is diminished in the grafted polymer which may be due to the existence of the amide group near the surface. The amide groups attached to the side chains on the polymer may participate in various reactions, e.g., with epoxy resins. IR analysis of the cured film indicates the disappearance of the oxiran band at 913 cm^?1 and an increase in the hydroxyl band around 3300 cm^?1. Thus, grafting of amide groups on PVC enables us to further modify PVC by epoxy resins.     

Electrochemical Properties of Poly-o-Phenylenediamine Films in Solutions with Variable Concentration of Hydronium Ions

Electrochemical behavior of poly-o-phenylenediamine (PoPhD) films in lithium perchlorate and perchloric acid solutions of different pH and constant ionic strength is studied using cyclic voltammetry, low-amplitude chronoamperometry, chronopotentiometry, and faradaic-impedance spectroscopy. The experimental results point to the diffusion–migration kinetics of charge transfer processes in redox-active PoPhD films and show that two such processes occur during oxidation–reduction of PoPhD. The processes are separated most fully at low concentrations of hydronium ions. Effect of the electrode potential and electrolyte composition on these processes is examined. Different methods yield similar results and permit their more reliable interpretation.     

Composition of the triacylglycerols of the phloem of Larix sibirica

The annual dynamics of the amount of acylglycerols in the phloem of the Siberian larch has been established. It has been shown that, depending on the phenological state of the wood their amount varies between 0.192 and 1.435%. The triacylglycerols of the phloem form the bulk of the acylglycerols of this tissue over the whole of the annual cycle. The stereovariety composition of the triacylglycerls of the phloem has been studied by the method of stereospecific analysis. It has been established that they have an asymmetric structure. The bulk of them contains acylglycerols in the molecules of which the sn-2 positions are acylated by unsaturated acids.Siberian Technological Institute, Krasnoyarsk. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 154–158, March–April, 1986.     

Flavin-protein interaction in bound glucose oxidase

Glucose oxidase was bound to Sepharose, Sephadex, gelatin, and dextran, yielding immobilized soluble and insoluble derivatives of the enzyme. The soluble preparations possessed higher enzymic activity than the analogous insoluble ones. The reversible dissociation process of the bound enzyme into apoenzyme and flavin adenine dinucleotide (FAD) was studied with the soluble and insoluble glucose oxidase in relation to enzymic activity and conformational changes as measured by circular dichroism and fluorescence methods. Bound apoenzyme was found to be more stable than the apoenzyme obtained from the unmodified glucose oxidase. The binding constant of FAD in bound glucose oxidase (K_diss≈10^-8M) calculated from fluorescent studies was lower than that of FAD in the native enzyme (K_diss10^-10M). The circular dichroism measurements indicated that dextran-bound glucose oxidase has a conformation similar to that of the native enzyme.     

Convexity preserving interpolation by algebraic curves and surfaces

The problem of interpolation by a convex curve to the vertices of a convex polygon is considered. A natural 1-parameter family ofC algebraic curves solving this problem is presented. This is extended to a solution, of a general Hermite-type problem, in, which the curve also interpolates to one or two prescribedtangents at any desired vertices of the polygon. The construction of these curves is a generalization of well known methods for generatingconic sections. Several properties of this family of algebraic curves are discussed. In addition, the method is generalized to convexC interpolation of strictly convex data sets inR ³ by algebraicsurfaces.