Mechanistic and Kinetic Studies on the Homogeneous Gas-Phase Formation of PCTA/DTs from 2,4-Dichlorothiophenol and 2,4,6-Trichlorothiophenol

Polychlorinated thianthrene/dibenzothiophenes (PCTA/DTs) are sulfur analogues compounds to polychlorinated dibenzo-p-dioxin/dibenzofurans (PCDD/Fs). Chlorothiophenols (CTPs) are key precursors to form PCTA/DTs. 2,4-DCTP has the minimum number of Cl atoms to form 2,4,6,8-tetrachlorinated dibenzothiophenes (2,4,6,8-TeCDT), which is the most important and widely detected of the PCDTs. In this paper, quantum chemical calculations were carried out to investigate the homogeneous gas-phase formation of PCTA/DTs from 2,4-DCTP and 2,4,6-TCTP precursors at the MPWB1K/6-311+G(3df,2p)//MPWB1K/6-31+G(d,p) level. Several energetically feasible pathways were revealed to compare the formation potential of PCTA/DT products. The rate constants of the crucial elementary reactions were evaluated by the canonical variational transition-state (CVT) theory with the small curvature tunneling (SCT) correction over a wide temperature range of 600–1200 K. This study shows that pathways that ended with elimination of Cl step were dominant over pathways ended with elimination of the H step. The water molecule has a negative catalytic effect on the H-shift step and hinders the formation of PCDTs from 2,4-DCTP. This study, together with works already published from our group, clearly illustrates an increased propensity for the dioxin formation from CTPs over the analogous CPs.     

Intramolecular 1,2- and 1,3-Hydrogen Transfer Reactions of Thiyl Radicals

This review article summarizes recent experiments on 1,2- and 1,3-hydrogen transfer reactions in thiyl radicals from cysteine and related compounds. Pulse radiolysis in combination with time-resolved UV spectroscopy was applied to monitor the equilibration of initial thiyl radicals with carbon-centered radicals at both the C_α and C_β positions of cysteine. Experiments with thiyl radicals from penicillamine and cysteamine confirmed the formation of carbon-centered radicals at these positions. Complementary evidence for the intermediary formation of carbon-centered radicals was obtained from mass spectrometry and ¹H NMR spectroscopy experiments, both of which indicated covalent H/D exchange at original C H bonds when thiyl radicals were generated in D₂O. The 1,2- and 1,3-hydrogen transfer reactions can have profound consequences for the integrity of proteins when Cys residues are oxidized to Cys thiyl radicals, which subsequently equilibrate with carbon-centered radicals.     

The Role of pH in the Mechanism of .OH Radical Induced Oxidation of Nicotine

The ^.OH radical induced oxidation of nicotine was studied using pulse radiolysis techniques from pH 1 to 13.6. Theoretical calculations were used to help interpret the experimental results. The bond dissociation enthalpies of all of the C H bonds of nicotine were determined using DFT calculations, coupled with the isodesmic reaction. From time-dependent density functional response theory, estimates were obtained of the location of the dominant transient absorption bands (λ_max), their intensities (electronic oscillator strength, f), and the electronic composition of these transitions. OH radicals as well as other potent oxidants reacted with free nicotine through separated, concerted electron proton transfer, leading mostly to the formation of an alpha-aminoalkyl radical located on the C_2′ carbon of the aliphatic ring ( A_2′ ). Protonated nicotine underwent hydrogen atom abstraction at the C_2′ and N_1′ positions, resulting in the formation of the conjugate acid of A_2′ ( A_2′H⁺ ) and the alkylamine radical cation ( N⁺ ), respectively. Doubly protonated nicotine underwent the same reaction pathways, leading to two corresponding conjugate acid species, protonated at the aromatic nitrogen position: PyrH⁺A_2′H⁺ and PyrH⁺N⁺ _. All these radicals interconverted between each other through hydrolytic reactions. The radical A_2′ and its conjugate acid PyrH⁺A_2′ absorbed 10 times stronger than the N⁺ species, based on calculations of f. From the growth of the transient absorption of A_2′ (λ_max=330 nm, ε=8080 M ⁻¹ cm⁻¹), second-order rate constants were determined: k_(OH+Nic)=6.7×10⁹ M ⁻¹ s ⁻¹, k_(OH+NicH)=1.0×10⁹ M ⁻¹ s⁻¹. The alpha-aminoalkyl radicals decayed by disproportionation to form iminium cations 1 – 5 , which contributed to an increase in the specific conductivity of the basic solutions of nicotine following electron pulse irradiation.     

The reaction of hydroxyl radicals with carbon at 298 K

The reaction of free OH radicals with graphite was studied in a flow system by mass spectrometry, the OH being produced by the reaction H + NO₂ → OH + NO. The OH radicals react rapidly at 298 K to produce approximately equal amounts of CO and CO₂. The collision efficiency (γ) for gasification of the carbon is>5 × 10^?3. OH radicals are much more reactive than free oxygen atoms towards graphite at 298 K. Carbon is an efficient heterogeneous catalyst for the reaction H + OH → H₂O, and when free hydrogen atoms are present, this reaction is several times faster than the gasification of the carbon by OH. Carbon is also an efficient catalyst for the recombination of H atoms: 2H → H₂.     

Radicals generated in autoxidized methyl linoleate by light irradiation

The structure of free radicals generated in the autoxidation of methyl linoleate (ML) was studied by the spin trapping technique using deuterated nitrosodurene, (CD₃)₄C₆HNO, as the spin trap. The secondary alkyl radicals were trapped after irradiation of ML with UV light. The formation rate of secondary alkyl radicals increased upon shortening the wavelength of irradiation light and was closely correlated with the peroxide value of autoxidized ML when a UV light longer than 250 nm was employed. When hydroperoxides separated from autoxidized ML were added to ML, the relationship between the formation rate of secondary alkyl radicals and the amounts of added hydroperoxides was nearly linear. These results suggest that secondary alkyl radicals are generated by proton abstraction of the active radicals, such as RO and HO, which are produced by the photolysis of hydroperoxides with UV light. The spin trapping technique can be applied to the study of lipid oxidation and/or photolysis of autoxidized lipid.     

Reactions of Methylated Naphthalenes with Hydroxyl Radicals Under Simulated Atmospheric Conditions

The gas-phase reactions of OH with 1- and 2-methylnaphthalene, 1,3- and 2,3-dimethylnaphthalene, acenaphthylene and acenaphthene were investigated under simulated atmospheric conditions in a 10m³ smog chamber. The rates of reaction, relative to naphthalene = 1.0, were 1-methylnaphthalene, 1.5; 2-methylnaphthalene, 2.1; 1,3-dimethylnaphthalene, 0.9; 2,3-dimethylnaphthalene, 0.9; acenaphthene, 2.9; and acenaphthylene, 5.8. Solid phase microextraction (SPME) in combination with gas chromatography/mass spectrometry (GC/MS) was used to analyze the organic reaction products, thus avoiding the production of artifacts observed in the previously used cold finger trapping procedure. Reaction products were mainly homologs of those formed in the reaction of naphthalene with OH radicals.     

On the photooxidative behavior of TiO2 and PW12O40: OH radicals versus holes

Parallel experiments under similar conditions, using various substrates (atrazine, fenitrothion, 4-chlorophenol and 2,4-D) and OH radical scavengers (Br⁻, isopropyl alcohol, tertiary butyl alcohol and acetone), have shown that the photooxidizing mode of PW₁₂O₄₀³⁻ and TiO₂, i.e., OH radicals and/or holes (h⁺), depends on the nature of substrate and the mode of investigation. This provides an explanation for the controversial results reported in the literature. Atrazine shows that both PW₁₂O₄₀³⁻ and TiO₂ operate, mainly, via OH radicals and to a lesser extent with holes (h⁺), whereas, fenitrothion suggests that both systems operate almost exclusively, via OH radicals. Differences in the action of the catalysts are encountered in the photodegradation of 4-chlorophenol (4-ClPh) and 2,4-dichlorophenoxyacetic acid (2,4-D). PW₁₂O₄₀³⁻ appears to operate essentially via OH radicals, whereas, h⁺ appear to be the major oxidant with TiO₂. Overall, though, the action of OH radicals relative to h⁺ appears to be more pronounced with PW₁₂O₄₀³⁻ than TiO₂.     

Oxidative Degradation of Thiaproline Derivatives in Aqueous Solutions Induced by •OH Radicals

The participation of neighboring amino and carboxyl groups in thiazolidyne-4-carboxylic acid (thiaproline) and its two derivatives, thiazolidyne-2-carboxylic acid and thiazolidyne-2,4-dicarboxylic acid, is demonstrated during ^.OH-radical-induced oxidation in aqueous solutions. The reaction of ^.OH radicals with these compounds does not lead to the expected one-electron oxidized sulfur-centered radical cations and subsequently to the intermolecularly (S∴S)-bonded dimeric radical cations (even at very high concentration of thiaprolines (>50 mM )), but rather to the elimination of CO₂ with the parallel formation of αN radicals. The latter radicals formed in thiaproline and thiazolidyne-2,4-dicarboxylic acid subsequently undergo β-fragmentation of the C S bond, leading to the thiyl radicals (RS^.). The αN and RS^. radicals were probed and quantified by one-electron reduction of p-nitroacetophenone (PNAP) and by one-electron oxidation of the monoanion of ascorbic acid (AH⁻), respectively. The calculated stabilization enthalpies of the αN radicals show that the loss of CO₂ is thermodynamically a favorable process. The Gibbs free energies of β-fragmentation processes in thiaproline and thiazolidyne-2,4-dicarboxylic acid are equal to −3.7 and −10.2 kJ mol⁻¹, respectively, showing that at room temperature both are exergonic. A general ^.OH-radical-induced oxidation mechanism of thiaproline derivatives in aqueous solutions is proposed.     

Fragmentation of Fluorinated Model Compounds Exposed to Oxygen Radicals: Spin Trapping ESR Experiments and Implications for the Behaviour of Proton Exchange Membranes Used in Fuel Cells

Low‐molecular weight model compounds (MCs) for Nafion membranes used in fuel cells were exposed at 300 K to ^·OH radicals produced by UV irradiation of aqueous H₂O₂ solutions. The MCs contained fluorinated and partially fluorinated groups terminated by sulphonic or carboxylic acid groups. The fragmentation process in the MCs was studied by spin trapping electron spin resonance (ESR) methods, using 5,5‐dimethylpyrroline‐N‐oxide (DMPO), N‐tert‐butyl‐α‐phenylnitrone (PBN) and 2‐methyl‐2‐nitrosopropane (MNP) as the spin traps. The objective of these experiments was to assess the effect of the type of ionic groups (sulphonic or carboxylic) and of fluorine substitution on the spin adducts detected. DMPO experiments led to the detection of spin adducts of ^·OH and of carbon‐centred radicals (CCRs), and allowed the determination of the ^·OH attack site on the ionic and/or on the protiated or fluorinated groups. CCR adducts were also detected when using PBN as a spin trap; a key point in the interpretation of the PBN results was, however, the realisation that MNP is formed during PBN exposure to UV irradiation and oxygen or other oxidants such as H₂O₂. Experiments with MNP as the spin trap were the most informative in terms of structural details for adducts obtained from each MC. The results allowed the identification of CCRs present as adducts, based on large hyperfine splittings (hfs) from, and the number of, interacting ¹⁹F nuclei; in addition, oxygen‐centred radicals (OCRs) as MNP adducts were also identified, with much lower hfs from ¹⁹F nuclei. Taken together, the results deduced by spin trapping suggest that both sulphonic acid and acetic acid groups can be attacked by ^·OH radicals and confirm two possible degradation mechanisms in Nafion membranes: initiated at the backbone and at the side chain.     

Distribution of OH and CH Radicals in the Boundary Layer with Ethanol Combustion

The influence of free-stream turbulence on the distributions of CH and OH radicals is studied with the use of optical methods of measurements in focused beams. The data on CH concentration are obtained for the minimum level of turbulence, and the OH concentration profiles are obtained for three levels of velocity fluctuations: 1, 8, and 18. It is shown that the regions where the OH and CH radicals are observed in the laminar boundary layer are shifted from the temperature maximum toward the oxidizer zone and toward the fuel zone, respectively. The highest level of the OH concentration is close to values typical of hydrogen combustion. The root-mean-square fluctuations of velocity and the mean values of the OH concentration vary nonmonotonically along the flame.__________Translated from Fizika Goreniya i Vzryva, Vol. 41, No. 4, pp. 22–28, July–August, 2005.     

Free radicals formation induced by the ozonation of humic substances in aqueous medium

This laboratory study was designed to investigate the mechanism of the formation of the OH radicals during the ozonation of humic substances solutions. The evaluation of the formation of these radical species was performed by using 1,1,2-trichloro ethane (TCA) as a probe. The apparent removal of TCA observed during the ozonation treatment implies the production of secondary species that catalyze the generation of OH radicals from ozone. These species are formed by a reaction between H₂O₂, formed in-situ, and O₂ and by a radical mechanism involving reactive humic substances sites.     

Reaction of SDS with Ozone and OH Radicals in Aqueous Solution

Ozone can be used as an antiseptic in cleaning systems. SDS (Sodium Dodecyl Sulfate) has proved to be a suitable surfactant in such systems. However, kinetic studies have showed that SDS reacts with ozone at high concentrations. In contrast, the natural decomposition of ozone to oxygen is retarded at low SDS concentrations. NMR spectroscopic analyses of SDS solutions being continuously treated with ozone and OH radicals, respectively, have been performed. ¹H-, ¹³C-, COSY-, HMBC- and HSQC-NMR spectra were recorded showing that small carboxyl acids were formed at exposure to ozone. Randomly positioned carbonyl groups were also found along the hydrocarbon chain. However, the largest product was caused by direct reaction of SDS with ozone. The predominant product most likely is a SDS-peroxide. ¹H –NMR spectra of the samples treated with OH radicals also show the formation of small carboxylic and carbonyl groups. However, there is no indication of oxidation of the sulphate group.     

Selectivity in Fast Reactions of Aqueous Oh-Radicals with Amides

Measurement of rates of abstraction of H atoms by aqueous OH radicals from specific sites in aliphatic amides by the technique of pulse radiolysis-kinetic spectroscopy establishes that in this reaction, in which gross rates of reaction fall short of the diffusion-controlled limit by no more than a factor of 10², there is a systematic variation of reactivity with structure. This variation parallels dependence of reactivity upon structure observed in the reactions of several other free radicals in the gas phase.     

Photoreactions in halogen-containing negative-tone novolac resists

The photolysis of halogenophenol novolacs is determined by the substitution of halogens by hydrogen and the formation of quinoid groups and intermolecular crosslinks. This is concluded from elemental analysis, NMR, IR and optical absorption measurements. The rate of halogen release depends on the chemical nature of the halogen. It increases in the order F < Cl < Br < I. Chlorine elimination from 4-position is favored over that from 2- and 3-position. Moreover, dimers release chlorine from 4-position much more readily than trimers and tetramers. ESR measurements at 77 K and flash photolysis studies at 296 K yielded evidence for the intermediate existence of phenoxyl and aryl radicals. Lithographic tests demonstrated the high UV-sensitivity of resist formulations based on halogen-containing novolacs. The increase in sensitivity relative to that of formulations based on nonhalogenated novolacs is 6 to 10fold system: 4-chlorophenol novolac/4,4′-bisazidobiphenyl (5%) and ca. 25fold system: 4-chlorophenol/m-cresol novolac/hexamethoxymethylmelamine (5%). A postulated reactions mechanism concerning the sensitivity increase takes into account that halogen elimination results in the formation of additional radicals that accelerate the rate of crosslinking. Moreover, hydrogen halide generated by hydrogen abstraction of halogen radicals (Hal^˙ + RH → H-Hal + R^˙) provides for the acid required to catalyze the reaction of the melamine compound with the novolac matrix.     

Photocoupling of Methane in Water Vapor to Saturated Hydrocarbons

Methane can be converted into alkanes (from C₂ to C₆) continuously by ultraviolet (185 nm) irradiation in the presence of water vapor. The products from this reaction are alkanes, which is different from the comparable heterogeneous catalytic reactions, where alkene formation is also observed. The mechanism involves the coupling of alkyl radicals formed by hydrogen abstraction with OH radicals produced following the UV irradiation of water.     

The Rise of Radicals in Bioinorganic Chemistry

Prior to 1950, the consensus was that biological transformations occurred in two-electron steps, thereby avoiding the generation of free radicals. Dramatic advances in spectroscopy, biochemistry, and molecular biology have led to the realization that protein-based radicals participate in a vast array of vital biological mechanisms. Redox processes involving high-potential intermediates formed in reactions with O₂ are particularly susceptible to radical formation. Clusters of tyrosine (Tyr) and tryptophan (Trp) residues have been found in many O₂-reactive enzymes, raising the possibility that they play an antioxidant protective role. In blue copper proteins with plastocyanin-like domains, Tyr/Trp clusters are uncommon in the low-potential single-domain electron-transfer proteins and in the two-domain copper nitrite reductases. The two-domain muticopper oxidases, however, exhibit clusters of Tyr and Trp residues near the trinuclear copper active site where O₂ is reduced. These clusters may play a protective role to ensure that reactive oxygen species are not liberated during O₂ reduction.     

Kinetics and mechanism of nitrobenzene degradation by hydroxyl radicals-based ozonation process enhanced by high gravity technology

This study investigated the indirect oxidation of nitrobenzene (NB) by hydroxyl radicals (·OH) in a rotating packed bed (RPB) using competitive kinetics method with p-nitrochlorobenzene as a reference compound. The rate constants of NB with ·OH are calculated to be between (1.465±0.113) × 10⁹ L/(mol·s) and (2.497±0.192) × 10⁹ L/(mol·s). The experimental data are fitted by the modified Arrhenius equation, where the activation energy is 4877.74 J/mol, the order of NB concentration, rotation speed, and initial pH is 0.2425, 0.1400 and 0.0167, respectively. The ozonation process of NB could be enhanced by RPB, which is especially effective for highly concentrated NB-containing wastewater under alkaline conditions. The high gravity technology can accelerate ozone mass transfer and self-decomposition of ozone to produce more ·OH, resulting in an increase in the indirect oxidation rate of NB by ·OH and consequently effective degradation of NB in wastewater.     

Intermolecular Hydrogen Abstraction Reaction between Nitrogen Radicals in Purine Rings and Alkyl Ethers: A Highly Selective Method for the Synthesis of N‐9 Alkylated Purine Nucleoside Derivatives

A highly selective method for the synthesis of N‐9 alkylated purine nucleoside derivatives via an intermolecular hydrogen abstraction reaction between nitrogen radicals in purine rings and alkyl ethers was developed. Novel purine nucleoside derivatives were obtained with good to high yields in the presence of (diacetoxyiodo)benzene (DIB) and iodine in one‐step reaction.     

Calculated energies of adsorption of non-hydrocarbon species on diamond H/C(1 1 1) surface and the abstraction energies of these species abstracted by hydrogen atoms using ab initio calculation

The energetics of adsorption of non-hydrocarbon radical species on H/C(1 1 1) diamond surface and the abstraction energies of these species abstracted by hydrogen atoms, which are in excess in gas phase in the diamond thin film growth using the chemical vapor deposition (CVD) method, were examined using ab initio calculation method. Based on the calculated results for the examined species, which include H, F, OH, NH₂, Cl, CH_mX_n (X=F or Cl) radicals, the tendency of incorporation of F, O, N, H and Cl atoms in the diamond thin film is discussed. The high adsorption energy and the high abstraction energy abstracted by excess gas-phase H atoms for F radicals suggest that F atom has the highest tendency to stay in the diamond thin film among the examined non-carbon atoms. In contrast, the comparable adsorption energy of Cl atom with other examined radicals except F radical, and its low abstraction energy, indicate that Cl atom possesses the least tendency to be incorporated in the diamond thin film. For O, N and H atoms, their calculated abstraction energy values suggest that the overall order of tendency of incorporation in diamond thin film is F>O>N>H>Cl. In addition, the energetically comparable adsorption energy for the CH₂Cl radical, compared with the other examined CH_mX_n species, and the low abstraction energy of Cl atom support that CH₂Cl is a good growth species in diamond CVD thin film growth.     

Study of radical products of mechanically destructed poly(N-vinylene carbazole)

Free radicals generated by mechanical destruction of poly(N-vinylene carbazole) have been studied. Two types of chain-end radicals have been found in the system at 100K in accord with the polymer fracture theory. At 273K these radicals started to decay and new, more stable main-chain radicals have been observed. When O₂ was introduced into the system, the chain-end radicals disappeared rapidly giving rise to ROO· radicals, which decayed at 200K generating nitrogen centred cation radicals.