H-atom abstraction from alcohols by alkyl radicals. Studies on the limiting stage

Kinetic data have been obtained for reactions of alkyl radicals with alcohols at low temperatures. The experiments have been made in glassy matrices of H- and D-substituted alcohols and also of their mixtures. The isotopic composition of the reaction products has been studied. Comparison of the data obtained has shown the H tunnelling to be alaways preceded by the stage of mutual fitting of the reagents to their reactive state. In some cases, this stage determines the process rate.     

Rate coefficients of H-atom abstraction from ethers and isomerization of alkoxyalkylperoxy radicals

Group rate expressions for the hydrogen(H)-atom abstraction reactions from ethers by hydrogen atoms and hydroxyl(OH) radicals and the intramolecular hydrogen-transfer isomerization reactions of alkoxyalkylperoxy radicals, which result from the H-abstraction from ethers followed by the addition of O(2), have been evaluated based on the quantum chemical calculations and experimental data. With the relative method proposed in the present study, it was shown that the rate coefficients of the reactions, for which only poor experimental information is available, can be reliably evaluated by calculating and extracting the difference from the well-established reactions of alkane hydrocarbons. The major features on the H-abstraction reactions from O-adjacent sites of ethers compared to those from alkanes were the suppression of the activation energy due to the decrease of the C-H bond dissociation energy and non-next neighbor substituent effect from the alkyl group on the counter side of -O-. For the hydrogen transfer isomerization reactions, similar suppression of the activation energy as well as the change in the ring strain energy was found as a major feature.     

Rate constants and isotope effects for the reaction of H-atom abstraction from RH substrates by PINO radicals

The kinetics of the reactions of hydrogen atom abstraction from the C–H bonds of substrates of different structures by phthalimide-N-oxyl radicals is studied. The rate constants of this reaction are measured and the kinetic isotope effects are determined. It is shown that in addition to the thermodynamic factor, Coulomb forces and donor–acceptor interactions affect the reaction between phthalimide-N-oxyl radicals and substrate molecules, altering the shape of the transition state. This favors the tunneling of hydrogen atoms and leads to a substantial reduction in the activation energy of the process.     

The correlation of rate coefficients for H-atom abstraction by HO radicals with C?H bond dissociation enthalpies

For H-atom abstraction reactions by HO radicals it has been shown that If D_i is taken as the C? H bond dissociation enthalpy at 298 K, then a = 0.323 and D₀is obtained from the empirical formula where D₀ is in kcal/mol and T is in K. Thisrelationship is valid for T between 200 and 400 K. Finally empiricalrelationships are given to help estimate D_i.     

Interplay of intrinsic and environmental effects on the magnetic properties of free radicals issuing from H-atom addition to cytosine.

Possible radical reaction products issuing from H-atom addition to cytosine have been characterized and analyzed by means of a comprehensive quantum mechanical approach including density functional computations (B3LYP), together with simulation of the solvent by the polarizable continuum model (PCM), and averaging of spectroscopic properties over the most important vibrational motions. The hyperfine couplings of the semirigid 5,6-dihydrocytos-6yl radical computed at the optimized geometry are in good agreement with their experimental counterparts. On the other hand, vibrational averaging is mandatory for obtaining an effectively planar structure for the 5,6-dihydrocytos-5yl radical with the consequent equivalence of beta-hydrogens. Finally, only proper consideration of environmental effects restores the agreement between computed and experimental couplings for the base anion protonated at N3.     

Rate constants for abstraction of hydrogen from ethylene by methyl and ethyl radicals relative to abstraction from propane and isobutane

A method is described for the measurement of relative rate constants for abstraction of hydrogen from ethylene at temperatures in the region of 750 K. The method is based on the effect of the addition of small quantities of propane and isobutane on the rates of formation of products in the thermal chain reactions of ethylene. On the assumption that methane and ethane are formed by the following reactions, (1) measurements of the ratio of the rates of formation of methane and ethane in the presence and absence of the additive gave the following results: Values for k₂ and k₃ obtained from these ratios are compared with previous measurements.     

Hydrogen abstraction from trichlorosilane by the trichloromethyl and 1,1-dichlorotrifluoroethyl radicals

The Arrhenius parameters for the reactions and have been measured. Reaction (2a) was generated and studied by the photolysis of tetrachloromethane in the presence of trichlorosilane and reaction(2b) by the photolysis of 1,1,1,-trichlorotrifluoroethane in the presence of trichlorosilane. The measured data are given by the expressions .     

Isotopic effects in H-atom abstraction from matrix molecules by methyl radicals in poly(methyl methacrylate). Determination of the scale of relative reagent motions

The H-abstraction by ?H₃ and ?D₃ radicals from PMMA molecules is investigated at 77 and 120 K. The film samples are prepared from the mixture of normal and deuterated PMMA. The reaction is of the first order with respect to radical concentration. Its rate is retarded in time as compared to the exponential law. An analysis of the molecular product ratio for the reaction allows the primary isotopic effect to be estimated. The initial reaction rate depends nonmonotonously on the proportion of the deuterated polymer in the matrix. Namely, there exists a range of isotopic compositions, with the reaction rate increasing with the portion of a deuteropolymer in the mixture. At 77 K the reaction rate of ?D₃ is lower than that of ?H₃ in PMMA of a mixed isotopic composition. This results from the proximity of ?D₃ with unreactive parental macromolecules, which reduces the local H concentrations around ?D₃ as compared to the mean concentration. At 120 K the radical decay rates do not differ. This fact cannot be explained by unfrozen mobilities of radicals at high temperatures or by their migration from parental macromolecules. The phenomenon is interpreted in terms of thermal fluctuations involving a great area around a radical and ensuring its migration within this area. The electron spin echo method is used to estimate the distance between a radical and its parental macromolecule, a ≥ 9.6 Å. This is the lower limit of the reaction accessibility.     

Hyperthermal reactions of O and O2 with a hydrocarbon surface: direct C-C bond breakage by O and H-atom abstraction by O2

A C-C bond-breaking reaction has been observed when a beam containing hyperthermal oxygen was directed at a continuously refreshed saturated hydrocarbon liquid (squalane) surface. The dynamics of this C-C bond-breaking reaction have been investigated by monitoring time-of-flight and angular distributions of the volatile product, OCH3 or H2CO. The primary product is believed to be the methoxy radical, OCH3, but if this radical is highly internally excited, then it may undergo secondary dissociation to form formaldehyde, H2CO. Either the primary or the secondary product may scatter directly into the gas phase before thermal equilibrium with the surface is reached, or they may become trapped on the surface and desorb in thermal equilibrium with the surface. Direct, single-collision scattering events that produce a C-C bond-breaking product are described with a kinematic picture that allows the determination of the effective surface mass encountered by an incident O atom, the atom-surface collision energy in the center-of-mass frame, and the fraction of the center-of-mass collision energy that goes into translation of the scattered gaseous product and the recoiling surface fragment. The dynamical behavior of the C-C bond-breaking reaction is compared with that of the H-atom abstraction reaction, which was the subject of an earlier study. Another reaction, H-atom abstraction by O2 (which is present in the hyperthermal beam), has also been observed, and the dynamics of this reaction are compared with the inelastic scattering dynamics of O2 and the dynamics of H-atom abstraction by O. The dynamics involving direct inelastic and reactive scattering of O2 are also described in terms of a kinematic picture where the incident O2 molecule is viewed as interacting with a local region of the surface.     

Kinetics and mechanism of hydrogen-atom abstraction from rhodium hydrides by alkyl radicals in aqueous solutions

The kinetics of the reaction of benzyl radicals with [L(1)(H(2)O)RhH{D}](2+) (L(1)=1,4,8,11-tetraazacyclotetradecane) were studied directly by laser-flash photolysis. The rate constants for the two isotopologues, k=(9.3±0.6) × 10(7) M(-1) s(-1) (H) and (6.2±0.3) × 10(7) M(-1) s(-1) (D), lead to a kinetic isotope effect k(H)/k(D)=1.5±0.1. The same value was obtained from the relative yields of PhCH(3) and PhCH(2)D in a reaction of benzyl radicals with a mixture of rhodium hydride and deuteride. Similarly, the reaction of methyl radicals with {[L(1)(H(2)O)RhH](2+) + [L(1)(H(2)O)RhD](2+)} produced a mixture of CH(4) and CH(3)D that yielded k(H)/k(D)=1.42±0.07. The observed small normal isotope effects in both reactions are consistent with reduced sensitivity to isotopic substitution in very fast hydrogen-atom abstraction reactions. These data disprove a literature report claiming much slower kinetics and an inverse kinetic isotope effect for the reaction of methyl radicals with hydrides of L(1)Rh.     

Simultaneous determination of purine bases, ribonucleosides and ribonucleotides by capillary electrophoresis-electrochemistry with a copper electrode

Simultaneous determination of purine bases, ribonucleosides and ribonucleotides was achieved by coupling capillary electrophoresis (CE) with wall-jet amperometric detection. A 200 μm diameter copper disk electrode was applied at working potential, +0.65 V vs. saturated calomel electrode. The current response of high sensitivity and stability was obtained in strong basic solutions which were suitable for satisfactory CE separations. The calibration curve was linear over 2–3 orders of magnitude and the limits of detection for adenine, guanine, xanthine, uric acid, adenosine, guanosine, adenosine-5′-monophosphate and guanosine-5′-monophosphate were below 9 fmol (S/N=3). The use of this method for the separation and detection of compounds present in human plasma samples was reported.     

Separation of purine and pyrimidine bases by ion chromatography with direct conductivity detection

A simple, rapid and accurate method for the simultaneous determination of four purine and pyrimidine bases (cytosine, 5-methylcytosine, adenine and N6-methyladenine) has been developed. The quantitative determination of these bases was accomplished by ion chromatography (IC) with direct conductivity detection (CD) based on their ionization in acidic medium without chemical suppression. The recovery of cytosine, 5-methylcytosine, and adenine in calf thymus DNA was more than 98% (n=3) and the relative standard deviation (RSD, n=5) less than 2.4%. In a single chromatographic run, the four bases could be separated and determined in less than 10 min. The detection limits were found to be 0.05 microg/mL for cytosine, 0.08 microg/mL for 5-methylcytosine, 0.07 microg/mL for adenine, and 0.07 microg/mL for N6-methyladenine. Linear ranges were 0.2-95.1 microg/mL for cytosine (r2=0.9996), 0.3-196.6 microg/mL for 5-methylcytosine (r2=0.9994), 0.3-105.5 microg/mL for adenine (r2=0.9998), and 0.3-159.1 microg/mL for N6-methyladenine (r2=0.9999). With the proposed method, purine and pyrimidine bases could be successfully detected in calf thymus DNA. We also determined these bases in calf thymus DNA using RP-HPLC. Compared to RP-HPLC, the IC method offers advantages such as high selectivity and simple mobile phase.     

Addition of radicals to quinones—I. ESR study of addition products from chloroquinones and free radicals

The mechanism of addition reactions of radicals formed during thermal decomposition of benzoyl peroxide with various chloro-substituted p-benzoquinones has been studied by the ESR technique in various solvents. The ESR spectra of the intermediate radicals show that addition occurs at the carbonyl oxygen. The important role of charge-transfer complexes in the reaction has been established. For strong CT complexes, the quinone molecule reacts with radicals derived from the solvent.     

Hydrogen abstraction from copolymers of fluorinated olefins and allyl or vinyl ethers by hydroxyl radicals: a computational quantum semi-empirical study

The theoretical study of hydrogen abstraction by hydroxyl radicals on two substrates (copolymers of fluorinated olefins and allyl or vinyl ethers) was carried using the MNDO, AM1 and PM3 quantum semi-empirical methods. This study was performed as a function of the site of hydrogen abstraction and of the computational method. The results of the calculations clearly show that the transition state is early along the reaction coordinate and pinpoint that the reactions are not under enthalpic control. The results provide evidence of the importance of the polar effects due to the fluorine atoms.     

Redox chemistry and H-atom abstraction reactivity of a terminal zirconium(iv) oxo compound mediated by an appended cobalt(i) center

The reactivity of the terminal zirconium(iv) oxo complex, O Zr(MesNPⁱPr₂)₃CoCN^tBu (2), is explored, revealing unique redox activity imparted by the pendent redox active cobalt(i) center. Oxo complex 2 can be chemically reduced using Na/Hg or Ph₃C^• to afford the Zr^IV/Co⁰ complexes [(μ-Na)OZr(MesNPⁱPr₂)₃CoCN^tBu]₂ (3) and Ph₃COZr(MesNPⁱPr₂)₃CoCN^tBu (4), respectively. Based on the cyclic voltammogram of 2, Ph₃˙ should not be sufficiently reducing to achieve the chemical reduction of 2, but sufficient driving force for the reaction is provided by the nucleophilicity of the terminal oxo fragment and its affinity to bind Ph₃C⁺. Accordingly, 2 reacts readily with [Ph₃C][BPh₄] and Ph₃CCl to afford [Ph₃COZr(MesNPⁱPr₂)₃CoCN^tBu][BPh₄] ([5][BPh4]) and Ph₃COZr(MesNPⁱPr₂)₃CoCl (6), respectively. The chemical oxidation of 2 is also investigated, revealing that oxidation of 2 is accompanied by immediate hydrogen atom abstraction to afford the hydroxide complex [HOZr(MesNPⁱPr₂)₃CoCN^tBu]⁺ ([9]+). Thus it is posited that the transient [OZr(MesNPⁱPr₂)₃CoCN^tBu]⁺ [2]⁺ cation generated upon oxidation combines the basicity of a nucleophilic early metal oxo fragment with the oxidizing power of the appended cobalt center to facilitate H-atom abstraction.

Bimetallic cooperativity is demonstrated with a Co/Zr complex featuring both nucleophilic Zr(iv) oxo and redox active Co sites.     

Hydrogen abstraction from poly(propylene) and poly(propylene oxide) by hydroxyl radicals: a computational quantum semi-empirical study

The reaction of hydrogen abstraction by hydroxyl radicals on two substrates (poly(propylene) and poly(propylene oxide)) was studied using three quantum semi-empirical methods (MNDO, AM1, PM3). The calculations were performed as a function of the site of abstraction (hydrogen atom on a secondary or tertiary carbon atom), and of the calculation method. In each case, we localised the transition state and showed that this transition state occurs early along the reaction coordinate. The results concerning the activation energies depend on the sites and the calculation methods. The calculated results were compared to experimental ones.     

Determination of purine and pyrimidine bases in DNA by micellar electrokinetic capillary chromatography with electrochemical detection

A method based on micellar electrokinetic capillary chromatography with electrochemical detection was developed for the determination of cytosine, 5-methylcytosine (5-MC), thymine, adenine, and guanine in the hydrolysates of DNA. The working electrode was fabricated in a novel self-positioning carbon disc electrode system that can align the capillary outlet with the working electrode without a three-dimensional micromanipulator. The five analytes could be well separated within 10 min in a 40 cm length capillary at a separation voltage of 9 kV in a 40 mmol/l borate buffer (pH 10.0) containing 100 mmol/l sodium dodecyl sulfate. Good linearity was observed between peak current and concentration of bases over three orders of magnitude with the detection limits (SIN=3) ranging from 1.28 x 10(-6) to 5.02 x 10(-6) mol/l. This proposed method demonstrated long-term stability and reproducibility with relative standard deviations of less than 5% for both migration time and peak current (n=7). It has been successfully applied to determine bases including 5-MC in the hydrolysates of fish sperm DNA, calf thymus DNA, and DNA isolated from spleen cells of female mice.     

Analysis of sugar phosphates in plants by ion chromatography on a titanium dioxide column with pulsed amperometric detection

This paper describes the development of a practical method for the analysis of sugar phosphates from the model higher plant Arabidopsis thaliana by high-performance anion-exchange chromatography with pulsed amperometric detection (HPAEC-PAD). The extraction method of sugar phosphates from higher plants was first optimized for HPAEC-PAD analysis. In order to improve the resolution in HPAEC-PAD, a column packed with titanium dioxide resin was used. The titanium dioxide column was used as a trap-column for sugar phosphates and nucleotides, for the removal of sample matrices. Sample pretreatment was achieved in-line and automatically using a six-port valve placed after the injection valve.