Kinetic study on hydrolysis and oxidation of formamidine disulfide in acidic solutions

Hydrolysis and oxidation of formamidine disulfide in acidic medium were investigated using high-performance liquid chromatography(HPLC) and mass spectrometry(MS) at 25 °C.By controlling the slow reaction rate and choosing appropriate mobile phase,HPLC provides the unique advantages over other methods(UV-Vis,chemical separation) in species tracking and kinetic study.In addition to thiourea and formamidine sulfinic acid,two unreported products were also detected in the hydrolysis reaction.Mass spectrometry measurement indicates these two products to be formamidine sulfenic acid and thiocyanogen with mass weights of 92.28 and 116.36,respectively.In the oxidation of formamidine disulfide by hydrogen peroxide,besides thiourea,formamidine sulfenic acid,formamidine sulfinic acid,thiocyanogen and urea,formamidine sulfonic acid and sulfate could be detected.The oxidation reaction was found to be first order in both formamidine disulfide and hydrogen peroxide.The rate constants of hydrolysis and oxidation reactions were determined in the pH range of 1.5-3.0.It was found both rate constants are increased with the increasing of pH.Experimental curves of different species can be effectively simulated via a mechanism scheme for formamidine disulfide oxidation,including hydrolysis equilibrium of formamidine disulfide and irreversible hydrolysis of formamidine sulfenic acid.     

Photometric and Gas-Chromatographic Determination of Hydrogen Peroxide and Peroxybutanoic Acid in Oxidized Butanoic Acid

Procedures were developed for determining hydrogen peroxide and peroxy acids mixed with peroxide compounds of other classes in the oxidation products of butanoic acid with atmospheric oxygen and hydrogen peroxide. Conditions were found for the selective decomposition of hydrogen peroxide with catalase in the presence of an excess of the carboxylic acid deactivating the enzyme. The errors introduced by the acylation of hydrogen peroxide with the carboxylic acid in the course of sample treatment with the enzyme were eliminated by adding diphenyl sulfide or dimethyl sulfoxide, which selectively reduced the peroxy acids. The concentrations of hydrogen peroxide and the peroxy acid were found from the difference between the total concentration of the peroxide compounds before and after treating a sample with catalase and a sulfur-containing reagent by the photometric method using a reagent containing Fe²⁺ ions and N, N-dimethyl-p-phenylenediamine. Peroxy acids were determined by GLC from the yields of the oxidation products of diphenyl sulfide with the peroxy acid (diphenyl sulfoxide and diphenyl sulfones).     

Sulfur modification of polyethylene surfaces. III. Frustrated multiple internal reflection spectroscopy of sulfonated polyethylene surfaces

The previous publications of this series show by indirect means that atomic sulfur inserts into the carbon—hydrogen bonds of polyethylene surfaces. In this study, frustrated multiple internal reflection (FMIR) spectroscopy was used to obtain direct evidence of the nature of the surface groups of the modified polyethylene. The FMIR spectra of surfaces consisting of the products of sulfonic acid groups were virtually identical, regardless of whether the original sulfonic acid surface had been prepared by direct sulfonation or by oxidation of surface thiol groups. The latter groups resulted from the insertion of atomic sulfur into the carbon—hydrogen bonds of the surface. These results establish that sulfur is indeed inserted into polyethylene surfaces.     

Determination of carbon-bonded sulfur in soils by hydriodic acid reduction and hydrogen peroxide oxidation

A sequential extraction method has been developed for the determination of carbon-bonded sulfur in soils. The soil sample has been sequentially reduced with HI and oxidized with hydrogen peroxide, and finally the residue has been digested with a mixture of nitric acid and perchloric acid. All inorganic sulfur components and ester sulfur has been reduced to H₂S by HI except the unreducible sulfur including pyritic sulfur, carbon-bonded sulfur and a previously unidentified sulfur fraction. Whereas a part of the carbon-bonded sulfur has been dissolved in the HI reducing solution another part of carbon-bonded sulfur was removed by hydrogen peroxide oxidation. The total carbon-bonded sulfur compose for oxic soils of the HI-dissolved sulfur and the H₂O₂-oxidized sulfur. However, because the pyritic sulfur can be completely decomposed by H₂O₂, this form of sulfur should be subtracted from the sum of the two sulfur fractions in case of anoxic soils. Unidentified sulfur components were also detected in the residue after the sequential extraction.     

Aliphatic peptidyl hydroperoxides as a source of secondary oxidation in hydroxyl radical protein footprinting

Hydroxyl radical footprinting is a technique for studying protein structure and binding that entails oxidizing a protein system of interest with diffusing hydroxyl radicals, and then measuring the amount of oxidation of each amino acid. One important issue in hydroxyl radical footprinting is limiting amino acid oxidation by secondary oxidants to prevent uncontrolled oxidation, which can cause amino acids to appear more solvent accessible than they really are. Previous work suggested that hydrogen peroxide was the major secondary oxidant of concern in hydroxyl radical footprinting experiments; however, even after elimination of all hydrogen peroxide, some secondary oxidation was still detected. Evidence is presented for the formation of peptidyl hydroperoxides as the most abundant product upon oxidation of aliphatic amino acids. Both reverse phase liquid chromatography and catalase treatment were shown to be ineffective at eliminating peptidyl hydroperoxides. The ability of these peptidyl hydroperoxides to directly oxidize methionine is demonstrated, suggesting the value of methionine amide as an in situ protectant. Hydroxyl radical footprinting protocols require the use of an organic sulfide or similar peroxide scavenger in addition to removal of hydrogen peroxide to successfully eradicate all secondary oxidizing species and prevent uncontrolled oxidation of sulfur-containing residues.     

Catalysis by Amberlite IR-120 resin: a rapid and green method for the synthesis of phenols from arylboronic acids under metal, ligand, and base-free conditions

A clean process has been developed for the ipso-hydroxylation of aryl and heteroaryl boronic acids to the corresponding phenols using commercially available and recyclable Amberlite IR-120 resin and aqueous hydrogen peroxide as an oxidizing agent. The ion-exchange sulfonic acid resin catalyst could be readily recycled by filtration and directly reused at least four times without any significant loss of activity.     

Influence of Oxidation Conditions on the Yield of 2-Substituted Imidazole-4,5-dicarboxylic Acids

Conditions were found which allow 2-alkyl-substituted imidazole-4,5-dicarboxylic acids to be synthesized in preparative quantities by the oxidation of 2-alkylbenzimidazoles with hydrogen peroxide. It was shown that optimal results can be obtained at the concentration of 2-alkylimidazole in sulfuric acid of 1 M and the hydrogen peroxide: 2-alkylbenzimidazole molar ratio of 11: 1. Oxidation under these conditions results in higher yields of the target 2-alkylimidazole-4,5-dicarboxylic acids, including those with a branched alkyl group.     

Determination of Sulfur in Trace Amounts

Abstract

An absolute method for the determination of trace amounts of sulfur in water and organic matrices is described. The method involves decomposition of organic samples in an oxygen bomb or oxidation of water samples with hydrogen peroxide. The resultant sulfates are reduced and distilled as hydrogen sulfide by the action of stannous phosphate in anhydrous phosphoric acid. The evolved hydrogen sulfide is absorbed in zinc acetate solution, converted to methylene blue and measured spectrophotometrically at 665 mm. The range is from 2 to 40 μg of sulfur using 1 cm cells.     

Sulfur modification of polyethylene surfaces. II. Modification of polyethylene surfaces with fuming sulfuric acid

Previous work has shown that atomic sulfur irreversibility modifies polyethylene, presumably through an insertion reaction into carbon—hydrogen bonds with formation of surface thiol groups. The thiol groups were then oxidized to sulfonic acid surface groups, which were further reacted chemically as shown by wettability measurements. In this work the thiol group was bypassed and the surface sulfonic acid groups were obtained by exposing the polyethylene surface directly to fuming sulfuric acid. The sulfonic acid groups were reacted further. Critical surface tension values identical with those in the previous work with atomic sulfur were obtained, thus substantiating the previous work.     

Specific features of formyl- and acetylferrocene oxidation with peroxides in water and organic solvents

Specific features of formyl- and acetylferrocene oxidation with peroxides ROOR (R = H, tert-C₄H₉) in different solvents are studied. It is shown that despite of the presence in complexes of strong electronacceptor substituents they can be oxidized with hydrogen peroxide in the absence of strong Brønsted acids. Dilution of water with organic solvent leads to deceleration and complete standstill of the reaction. In the absence of acids the second order of the process with respect to peroxide and first one with respect to the metal complex was evaluated. In the presence of perchloric or trifluoroacetic acid the order with respect to peroxide decreases to the first one. The dependence of the reaction rate on the concentration of acid has an extremum point. The activity of other peroxides in the reaction with the above-mentioned compounds is significantly lower than the activity of hydrogen peroxide. Probable alternative mechanisms of oxidation of the abovementioned ferrocenes with hydrogen peroxide in the presence and in the absence of acids differing in the way of coordination of reagents with one another and considering direct participation of substituent in the oxidation is suggested.     

Exposure of self-assembly interiors to external elements. A kinetic approach

Five cationic surfactants, each bearing a single sulfur at various locations along their chains, were adsorbed into sodium dodecyl sulfate micelles. An oxidant, periodate, was added to the system, and the subsequent rate of thioether oxidation to sulfoxide, determined by NMR, was found to be diminished (more or less equally for all sulfur loci) by 2 orders of magnitude. In contrast, rates of hydrogen peroxide oxidation were hardly perturbed by micellization. Once again, however, there was no rate dependence on sulfur location within the chains. These results are interpreted in terms of a disordered micelle in which all chain positions have roughly equivalent access to the micelle surface. The kinetic method for assessing exposure to the external medium is applicable to self-assemblies and polymer systems wherever the NMR resolution so permits.     

Ascorbic acid reaction with disulphide compounds: effects and applications

A method was developed for estimation of concentrations of cystine based on the reaction of this oxidised amino acid with ascorbic acid and copper ion. The standard curve which was constructed was used as the basis for investigation of the effects which both cystine and glutathione disulphide, and some disulphide proteins, exerted on the amount of hydrogen peroxide formed in the reaction of ascorbic acid. The hydrogen peroxide product was lowered in the presence of the disulphide compounds. The disulphide compounds also lowered the amount of deoxyribose reacting material formed during the ascorbic acid oxidation. The reaction between ascorbic acid and copper and cystine was used to estimate the amount of the disulphide amino acid in acid digests of proteins.     

The antioxidant profile of 2,3-dihydrobenzo[b]furan-5-ol and its 1-thio, 1-seleno, and 1-telluro analogues

A novel synthesis of 2,3-dihydrobenzo[b]thiophene-5-ol based on intramolecular homolytic substitution on sulfur was reported. The "antioxidant profile" of the series of 2,3-dihydrobenzo[b]furan-5-ol (2a) its 1-thio (2b), 1-seleno (2c) and 1-telluro (2d) analogues was determined by studies of redox properties, the capacity to inhibit stimulated lipid peroxidation, the reactivity toward tert-butoxyl radicals, the ability to catalyze decomposition of hydrogen peroxide in the presence of glutathione, and the inhibiting effect on stimulated peroxidation in liver microsomes. The one-electron reduction potentials of the aroxyl radicals corresponding to compounds 2a-2d, E degrees (ArO(*)/ArO(-)) were 0.49, 0.49, 0.49, and 0.52 V vs NHE, respectively, as determined by pulse radiolysis. With increasing chalcogen substitution the compounds become slightly more acidic (pK(a) = 10.6, 10.0, 9.9, and 9.5, respectively, for compounds 2a-2d). By using Hess' law, the homolytic O-H bond dissociation enthalpies of compounds 2a-2d (340, 337, 336, and 337 kJ mol(-)(1), respectively) were calculated. The reduction potentials for the proton coupled oxidation of compounds 2a-2d (ArOH --> ArO(*) + H(+)) as determined by cyclic voltammetry in acetonitrile were 1.35 (irreversible), 1.35 (quasireversible) 1.13 (reversible), and 0.74 (reversible) V vs NHE, respectively. As judged by the inhibited rates of peroxidation, R(inh), in a water/chlorobenzene two-phase lipid peroxidation system containing N-acetylcysteine as a thiol-reducing agent in the aqueous phase, the antioxidant capacity increases (2d > 2c = 2b > 2a) as one traverses the group of chalcogens. Whereas the times of inhibition, T(inh), were slightly reduced for the oxygen (2a) and sulfur (2b) derivatives in the absence of the thiol-reducing agent, they were drastically reduced for the selenium (2c) and tellurium (2d) derivatives. This seems to indicate that the organochalcogen compounds are continuously regenerated at the lipid aqueous interphase and that regeneration is much more efficient for the selenium and tellurium compounds. The absolute rate constants for the oxidation of compounds 2a-2b by the tert-butoxyl radical in acetonitrile/di-tert-butyl peroxide (10/1) were the same-2 x 10(8) M(-)(1) s(-)(1). Whereas the oxygen, sulfur, and selenium derivatives 2a-2c were essentially void of any glutathione peroxidase-like activity, the organotellurium compound 2d accelerated the initial reduction of hydrogen peroxide, tert-butyl hydroperoxide, and cumene hydroperoxide in the presence of glutathione 100, 333, and 213 times, respectively, as compared to the spontaneous reaction. Compounds 2a-2d were assessed for their capacity to inhibit lipid peroxidation in liver microsomes stimulated by Fe(II)/ADP/ascorbate. Whereas the oxygen, sulfur, and selenium compounds showed weak inhibiting activity (IC(50) values of approximately 250, 25, and 13 microM, respectively), the organotellurium compound 2d was a potent inhibitor with an IC(50) value of 0.13 microM.     

Kinetics and mechanism of the oxidation of dibenzothiophene in hydrocarbon solution Oxidation by aqueous hydrogen peroxide-acetic acid mixtures

The oxidation of white oil solutions of dibenzothiophene (DBT) by aqueous hydrogen peroxide-acetic acid solutions was studied kinetically at 50–100°. Under these conditions, the rate of DBT oxidation was found to be first order in acetic acid, second order in hydrogen peroxide, and inversely proportional to the water concentration. The activation energy between 50–100° in 64·5% acetic acid was 14 kcal/mole. We have also found that the monoxide is oxidized about 1·4 times faster than DBT. A mechanism consistent with the kinetic data has been postulated. The rate-determining step appears to be attack of a peracetic acid-hydrogen peroxide dimer on the sulfur atom of DBT.     

固体磺酸促进亚硝酸异戊酯催化氧化苯甲醇反应

 以亚硝酸异戊酯为催化剂, 通过固体磺酸的促进作用原位产生亚硝酰正离子, 实现了催化氧气氧化苯甲醇制备苯甲醛. 300 oC 处理的 Amberlyst 15 表现出较高的促进效果, 在 0.5 MPa O2, 80 oC 反应 2 h, 苯甲醇转化率和苯甲醛选择性可分别达到 90% 和 97%. 通过红外、热分析及酸碱滴定研究了不同方法制得的固体酸的差别及其对反应促进效果的影响, 并利用紫外-可见光谱和衍生化方法检测了亚硝酰正离子.     

Analysis of formaldehyde formation in wastewater using on-fiber derivatization-solid-phase microextraction-gas chromatography-mass spectrometry

A method has been developed for the quantification of the formation of formaldehyde during the advanced oxidation treatment (AOT) of wastewater destined for reuse. This method uses solid-phase microextraction (SPME) with on-fiber derivatization followed by gas chromatography-mass spectrometry (GC-MS) analysis. Based on calculated method detection limits (MDL) and ambient background levels, the method reporting (MRL) limit for formaldehyde was set at 10 microg/L. Precision for formaldehyde using this technique resulted in 23% relative standard deviation (RSD), while the internal standard, acetone-d(6), was only 6%. This method was used to evaluate the formation of formaldehyde in bench scale UV-AOT experiments using natural organic matter (NOM) fortified reagent water and tertiary treated wastewater effluent. Results suggest that the formation of formaldehyde increases in both the reagent water and wastewater matrices with increasing UV exposure and hydrogen peroxide concentrations, with overall higher concentrations of formaldehyde in the wastewater samples. No appreciable amount of formaldehyde formation was observed when UV was applied in the absence of hydrogen peroxide in both matrices tested.     

Stepwise Oxidation of Thiophene and Its Derivatives by Hydrogen Peroxide Catalyzed by Methyltrioxorhenium(VII)

The oxidation of thiophene derivatives by hydrogen peroxide is catalyzed by methyltrioxorhenium(VII) (CH(3)ReO(3)). This compound reacts with hydrogen peroxide to form 1:1 and 1:2 rhenium peroxides, each of which transfers an oxygen atom to the sulfur atom of thiophene and its derivatives. Complete oxidation to the sulfone occurs readily by way of its sulfoxide intermediate. The rates for each oxidation step of dibenzothiophenes, benzothiophenes, and substituted thiophenes were determined. The rate constants for the oxidation of the thiophenes are 2-4 orders of magnitude smaller than those for the oxidation of aliphatic sulfides, whereas the rate constants are generally the same for the oxidation of the thiophene oxides and aliphatic sulfoxides. The rate constant for conversion of a sulfide to a sulfoxide (thiophene oxide) increases when a more electron-donating substituent is introduced into the molecule, whereas the opposite trend was found for the reaction that converts a sulfoxide to a sulfone (thiophene dioxide). Mechanisms consistent with this are proposed. The first trend reflects the attack of the nucleophilic sulfur atom of a thiophene center on a peroxide that has been electrophilically activated by coordination to rhenium. The second, more subtle, trend arises when both sulfoxide and peroxide are coordinated to rhenium; the inherently greater nucleophilicity of peroxide then takes control.     

The removal of chlorinated organic herbicide in water by gamma-irradiation

In this study, the radiation-induced degradation of 2,4-dichlorophenoxyacetic acid (2,4-D) herbicide in aqueous solution was studied under various conditions as a function of irradiation dose in the absence and presence of hydrogen peroxide. The obtained data confirmed that largest yield of radiolytic degradation is obtained in oxidation processes/ionizing radiation, where oxidation is carried out with hydroxyl radicals. For complete degradation of 50?ppm 2,4-D, a required dose was lower in the presence of hydrogen peroxide. The formed major toxic phenolic intermediates were 2,4-dichlorophenol (2,4-DCP) and 4-chlorophenol (4-CP). The chemical analysis of the 2,4-D and the intermediates resulted from the radiolytic degradation were performed using a gas chromatography associated to mass spectrometry (GC?CMS) with ion trap dedector (ITD) and ion chromatography (IC). The formation of chlorophenols in addition to chloride, formaldehyde and carboxylic acids was studied as a function of absorbed dose.     

闭系中硫(-II)氧化的非线性动力学一般特征

硫元素可出现有一2‘0‘＋2‘＋4、＋6等多个价态．－2价的硫化合物在氧化过程中涉及价态变化较多,反应机理十分复杂,有些中间体难于分离和检定．但在硫化学非线性动力学研究中使用不同的氧化剂（H20。、C10。一、Bio。一和104一等）发现了一些基本的共同特怔,应与S（－11）化合物氧化反应中许多复杂现象［‘］（振荡、双节律、混饨和反应扩散波等）有密切关系,本文就封闭体系中硫化学非线性机理特征进行探讨和研究．1封闭体系中反应动力学特征根据实验和文献,在硫化合物的氧化动力学曲线中Pt电位、pH及其一些氧化剂中间物的浓度（…     

闭系中硫(-Ⅱ)氧化的非线性动力学一般特征

The general dynamic features of the batch oxidation of Sulfur(-Ⅱ) compounds (S2- , thiosulfate,thiocynate and thiourea et al.) were discussed. The changes of Ph with reaction time consist of a rise and two separate drops. Dynamic model was proposed, further experimental studies on the batch oxidation of thiourea and thiocyanate by ClO2- were also carried out. Simulation curve was well consistent with experiment in a batch reactor. Non-catalytic oscillation of peroxide (hydrogen peroxide, persulfate et al.)- S(-Ⅱ) compound system resulted from the nonlinear dynamic of sulfur oxidation. In the oxidation of S(-Ⅱ) compounds by oxyhalogen compounds(ClO2- et al.), nonlinear dynamics of both oxyhalogen compound and sulfur compound should be considered simultaneously. So complex phenomena such as birhythmicity and chaos may be discovered.