A control of primary structure in the products of macromolecular reactions

Basing on the theory of macromolecular reactions, an influence of various factors on a units' distribution (UD) of the forming macromolecules is considered. In diluted solutions UD is determined by a competition between external reagent and intrachain interaction of reacted and unreacted units, first by neighbor effect. Should accelerating action of remote units is commensurable with that of nearest neighbors, such a conformational effect enlarges the formation of alternating sequences. In a melt, interchain effect shifts UD to a random one. In a polymer blend consisting of reacting and non-reacting but influencing the reactivity components, UD of transforming macromolecules is formed under concerted action of the reaction and interdiffusion. Thus modern achievements of the theory permit to analyze peculiarities of a wide set of reaction systems and facilitate a choice of optimal conditions for the preparation of tailor-made macromolecules.     

Water-catalyzed dehalogenation reactions of isobromoform and its reaction products

A combined experimental and theoretical study of the photochemistry of CHBr(3) in pure water and in acetonitrile/water mixed solvents is reported that elucidates the reactions and mechanisms responsible for the photochemical conversion of the halogen atoms in CHBr(3) into three bromide ions in water solution. Ultraviolet excitation at 240 nm of CHBr(3) (9 x 10(-)(5) M) in water resulted in almost complete conversion into 3HBr leaving groups and CO (major product) and HCOOH (minor product) molecules. Picosecond time-resolved resonance Raman (ps-TR(3)) experiments and ab initio calculations indicate that the water-catalyzed O-H insertion/HBr elimination reaction of isobromoform and subsequent reactions of its products are responsible for the production of the final products observed following ultraviolet excitation of CHBr(3) in water. These results have important implications for the phase-dependent behavior of polyhalomethane photochemistry and chemistry in water-solvated environments as compared to gas-phase reactions. The dissociation reaction of HBr into H(+) and Br(-) ions is the driving force for several O-H insertion and HBr elimination reactions and allows O-H and C-H bonds to be cleaved more easily than in the absence of water molecules. This water-catalysis by solvation of a leaving group and its dissociation into ions (e.g., H(+) and Br(-) in the examples investigated here) may occur for a wide range of chemical reactions taking place in water-solvated environments.     

Isomeric di-tert-butylorthophenylenequinols in redox reactions

Conclusions Oxidation and reduction of orthophenylenequinols gives stable cation- and anion-radicals respectively.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp 2272–2276, October, 1987.     

Rhodium-catalyzed redox allylation reactions of ketones

Ketones react with allyl acetate to generate tertiary homoallylic alcohols in the presence of a rhodium catalyst and bis(pinacolato)diboron. A range of substrates, including aryl, alkyl and cyclic ketones react smoothly under these conditions. Diastereoselective allylation reactions of functionalized ketones such as pregnenolone acetate are also reported.     

Electrochemical investigation of redox reactions of herbal drug-shikonin and its determination in pharmaceutical preparations

The electrochemical behaviour of the anticancer herbal drug shikonin was investigated at glassy carbon electrode in 0.16 M HAc-NaAc (20% ethanol, pH 3.98) buffer solution using cyclic voltammetry, square-wave voltammetry and chronocoulometry. Shikonin gives a pair of quasi-reversible redox peaks at potentials of E _pc = 0.698 V and E _pa =0.632 V by absorption-controlled process at a scan rate of 100 mV/s. The electrode process dynamics parameters (saturated adsorptive amount Γ, charge transfer coefficient α, and apparent rate constant K _s) and reaction mechanism were also investigated with result of two electrons and two hydrogen ions participating in electrode reaction. The experimental conditions were optimized for the determination of shikonin and the square-wave anodic peak currents were linearly related to the shikonin concentrations in the range from 2.08 × 10⁻⁸ to 1.82 × 10⁻⁶ M with correlation coefficient of 0.998 and detection limit of 7.8 × 10⁻⁹ M. Using the established method without pretreatment and pre-separation, shikonin in herbal drug Gromwell Root was determined with satisfactory result.     

Biochemical reaction engineering for redox reactions

Redox reactions are still a challenge for biochemical engineers. A personal view for the development of this field is given. Cofactor regeneration was an obstacle for quite some time. The first technical breakthrough was achieved with the system formate/formate dehydrogenase for the regeneration of NADH2. In cases where the same enzyme could be used for chiral reduction as well as for cofactor regeneration, isopropanol as a hydrogen source proved to be beneficial. The coproduct (acetone) can be removed by pervaporation. Whole-cell reductions (often yeast reductions) can also be used. By proper biochemical reaction engineering, it is possible to apply these systems in a continuous way. By cloning a formate dehydrogenase and an oxidoreductase "designer bug" can be obtained where formate is used instead of glucose as the hydrogen source. Complex sequences of redox reactions can be established by pathway engineering with a focus on gene overexpression or with a focus on establishing non-natural pathways. The success of pathway engineering can be controlled by measuring cytosolic metabolite concentrations. The optimal exploitation of such systems calls for the integrated cooperation of classical and molecular biochemical engineering.     

Strong correlations in actinide redox reactions

Reduction-oxidation (redox) reactions of the redox couples An(VI)/An(V), An(V)/An(IV), and An(IV)/An(III), where An is an element in the family of early actinides (U, Np, and Pu), as well as Am(VI)/Am(V) and Am(V)/Am(III), are modeled by combining density functional theory with a generalized Anderson impurity model that accounts for the strong correlations between the 5f electrons. Diagonalization of the Anderson impurity model yields improved estimates for the redox potentials and the propensity of the actinide complexes to disproportionate.     

Electrochemical simulation of redox reactions of glutathione

The effect of glutathione on the active oxygen reduction products at copper and platinum electrodes was studied by chronovoltammetry and pulse voltammetry. Electrochemical reduction of glutathione at the same electrodes was also examined. A mechanism was proposed for the reaction of glutathione with oxygen and its active forms, and attempts were made to simulate redox reactions initiating oxidative stress in vitro and glutathione effect thereon by electrochemical methods.     

Optimum acidity and masking of redox reactions

Theoretical relationships for the estimation of optimum acidity and masking of redox reactions are developed on the basis of the coefficients of side reactions. The concentrations of reacting components are calculated from optimum conditions and the values of standard redox potentials. A good agreement of the theory and experiment is shown on several illustrative examples.     

Chemical polarisation of electrons in redox reactions

In the system Ti(III)? H₂O₂? RH (RH is isobutyric acid or isopropanol) the concentration and polarisation of the β-radical decreases during the reaction, while the polarisation of the α-radical increases with the decrease of the α-radical concentration. The second fact is not in accordance with Adrian's model of inducing the polarisation in redox systems during the radical recombination process.     

Homogeneous redox catalysis of electrochemical reactions: Part I. Introduction

In redox homogeneous catalysis the catalyst couple merely plays the role of an electron carrier by contrast with chemical catalysis which involves the transitory formation of catalyst-substrate adduct. A detailed kinetic analysis of redox catalysis in the case of an EC-type electrode reaction is given involving the following reaction sequence

$\begin{array}{l}B\stackrel{k}{\to }C\\ \begin{array}{c}A+1e?B\\ B\to C\end{array}\}directelectrodereductionofthesubstrate\end{array}$ The Hush-Marcus relationship between heterogeneous and homogeneous electron transfer rate constants is used to select the range of the parameter variations and to predict the magnitude of the catalytic efficiency as a function of the potential separation between the catalyst reduction and the direct substrate reduction, the ratio of the catalyst over the substrate concentration and the electrochemical standard rate constant of the substrate. Two situations are of particular interest for the kinetic analysis of the experimental data: (a) kinetic control of the direct substrate reduction by the follow-up chemical reaction with diffusion by charge transfer with activation or diffusion control of the solution electron exchange, the rate determining step of the catalytic sequence being A+Q→P+B. In these conditions, kinetic information on the substrate reduction process is obtainable which could not have been derived from a direct electrochemical analysis.     

Substitution and redox reactions involving vanadium oxotrifluorine

VOF₃ is soluble in acetonitrile but is slowly reduced to give a vanadyl (IV) species as one product. It reacts rapidly with Me₃SiNet₂ in MeCN below ambient temperature; fluorine is replaced by -NEt₂ ligands but the spectroscopic and magnetic properties of the products indicate that, in addition, reduction to V^IV occurs not some extent. The products are formulated as VOF_3-n(NEt₂)_n containing small quantities of VOF_2-m(NEt₂)_m(NEt₂H) (n = 1-3, m = 0-2). A similar reaction occurs between VOF₃ and Me₃SiOMe but with Me₃SiOSiMe₃ only VO₂F is formed.     

One-electron redox reactions of troxerutin in aqueous solutions

The oxidation of flavonoids is of great interest because of their action as antioxidants with the ability to scavenge radicals by means of electron-transfer processes. The redox reactions of the flavonoid derivative troxerutin, (2-[3,4-bis-(2-hydroxyethoxy) phenyl]-3[[6-deoxy-α-L-manno-pyranosyl)-β-(D-glucopyranosyl]-oxy]-5-hydroxy-7-(2-hydroxyethoxy)-4H-1-benzo-pyran-4-one), were investigated over a wide range of conditions, using pulse radiolysis and cyclic voltammetry. The oxidation mechanism proceeds in sequential steps. One-electron redox potentials for troxerutin were found to be +1.196, +0.846 and −0.634 V vs. NHE.     

Thermodynamics of redox reactions involving nicotinamide adenine dinucleotide

Literature data on the thermodynamics of redox nicotinamide adenine dinucleotide (NAD) dependent reactions have been analyzed. It has been established that for the redox reaction of NAD

where all substances except H₂ are in the aqueous buffer with the ionization enthalpy equal to zero, the most reliable thermodynamic parameters should be considered as: ΔH(298.15 K; pH 7)=?27.4±1.7 kJ mole^?1; ΔG (298.15K; pH 7)=±17.8 kJ mole^?1. From the above thermodynamic parameters of the reaction ΔH, ΔG and ΔS for reactions of NAD with natural substrates, synthetic mediators and some inorganic compounds have been calculated.     

One-electron redox reactions of trifluoperazine in aqueous solutions

Absolute rate constants have been measured for the reactions of the primary and specific one-electron oxidant radicals with the protonated form of trifluoperazine (TFP). The primary radicals, e^- _aq and OH·, react with TFP at diffusion controlled rates. The transients thus produced have been characterized. Halogenated aliphatic peroxyl radicals oxidize TFP with rate constants between 10⁷ and 10⁸ dm³ mol^-1 s^-1, depending on the structure of the peroxyl radical. The reactivity of peroxyl radicals has been found to vary with Taft's inductive parameter. Oxidation of TFP at acidic pH has been studied using stopped-flow technique. The reaction between TFP radical cation and ascorbic acid has also been examined using pulse radiolysis technique. The results indicate that TFP radical cation is repaired by ascorbate. One-electron reduction potential of TFP · + /TFP at pH 3.5 has been calculated to be 0.964 V vs. NHE.     

Kinetics of two redox reactions in 2-butoxyethanol and water near its critical point of solution

The rate constants of two redox reactions and in the critical solution of 2-butoxyethanol and water have been measured by using the UV spectrophotometry at the initial reaction stage. It was found that the rate constants at various temperatures for two reactions were well described by the Arrhenius equation in the noncritical region. The critical slowing down effect was detected in the critical region. The critical slowing down exponents were determined to be 0.044 ± 0.004 and 0.046 ± 0.005 for reactions and , respectively. The values of the critical slowing down exponents showed that only dynamic critical slowing down effect, and no thermodynamic singularity could be observed for the two reactions.     

Physicochemical aspects of the redox reactions of free radicals

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2338–2354, October, 1990.