Studies of the soluble part of oxidised coals

Soluble products obtained from the oxidation of four types of coal, each characterised by different degree of coalification and different degree of sulphur content, are studied. The coals are oxidised with peracetic acid (PAA) and nitric acid. Analyses are performed by Atmospheric Pressure-Temperature Programmed Reduction (AP-TPR) and Fourier Transform Infrared Spectroscopy (FTIR). The soluble products contain much more sulphur than the insoluble products of oxidation. The products obtained from the reaction with HNO₃ contain higher amounts of inorganic sulphur compounds, while those obtained from the reaction with PAA are characterised by an increased content of organic sulphur species.     

Composition of extraction products from alkylated high-sulphur coals

Products of reductive and non-reductive methylation of two high-sulphur coals (Mequinenza and Illinois No. 6) have been extracted by dichloromethane. It has been established that the efficiency of the transformation of coal to the products soluble in CH₂Cl₂ is higher for coals subjected to non-reductive methylation by the Liotta method than for those after reduction in the potassium/liquid ammonia system. The extracts and the extraction residues were subjected to elemental analysis, IR spectroscopy, and AP-TPR (Atmospheric Pressure-Temperature Programmed Reduction) measurements. It has been shown that the main species undergoing extraction by CH₂Cl₂ are aliphatic compounds or aromatic structures of low degree of condensation. The effect of the extraction on the sulphur groups in coal has been discussed.     

Hydrolysis of thiophosphoryl fluoride

The hydrolysis of thiophosphoryl fluoride has been studied both in acid and alkaline medium. The products are phosphate, fluoride and varying amounts of sulphide, sulphite, thiosulphate and elemental sulphur depending on experimental conditions. The probable mode of formation of the different sulphur species has been explained on the basis of sulphur in a higher oxidation state in the thiophosphoryl fluoride molecule.     

An investigation of the sulphur(−II)/sulphur(0) system on bold electrodes

Sulphur deposited on gold by the anodic oxidation of sulphur(−II) species in solution has been studied by X-ray photoelectron spectroscopy. The initial layer behaved as gold sulphide. Multilayers of sulphur had a lower volatility and a smaller electron binding energy than bulk elemental sulphur, indicating that there is interaction with the underlying gold or gold sulphide.The anodic oxidation of sulphur(−II) to sulphur, and the reverse process, has been investigated on gold using the rotating ring disc electrode technique. Polysulphide ions were formed as intermediates in both processes. Polysulphides were also produced by chemical reaction of deposited sulphur with sulphur(−II) species in solution. The polysulphide intermediates were identified as S²⁻₅ at pH 13, a mixture of species with average stoichiometry S²⁻_3.3 at pH 9.2 and S²⁻₂, possibly HS⁻₂, at pH 6.8.     

程序升温还原法研究氧化对煤中硫形态及结构的影响

用程序升温还原法研究了三种不同硫含量的煤被空气和HNO3氧化后含硫气体的逸出规律。结果表明，空气和HNO3氧化后，尽管煤中有机硫总量变化不大，但煤中H2S的释放量有所下降，而COS和SO2的生成量明显增加，这说明氧化作用使得煤中弱的有机硫变成S=O和SO2结构。与以往的研究结果不同的是，发现CS2的生成与FeS密切相关，同时对HNO3氧化后的煤来说，CS2的生成主要以气相中H2S和COS的反应为主。空气氧化后煤中CS2的生成量与原煤的差不多，但HNO3氧化后煤中释放出的CS2有所下降。提出通过（COS+SO2）/H2S的比值来研究煤及其中硫被氧化的程度，并对比了不同煤种及氧化后样品的气相含硫化合物发现：随变质程度的提高和煤中噻吩硫含量的增加，煤被氧化的程度下降。对同一煤种而言，HNO3的氧化程度要高于空气氧化的。     

Determination and fractionation of sulphur in a contaminated dredged sediment

Conversion of sulphur compounds in reduced, contaminated sediments that are brought in upland conditions may largely affect the potential mobility of heavy metal contaminants. We applied selected methods for the determination of total sulphur and sulphur fractions in a contaminated sediment in the reduced state and after gradual drying and oxidation during 1 month. Dry ashing, followed by ion chromatographic detection, was reliable for the determination of total sulphur. Good recoveries were obtained in both reference samples and spiked samples. Total sulphur was 14.5±0.6 g kg⁻¹ relative to dry sediment. Wet chemical methods that involve the determination of acid-volatile, Zn–HCl-reducible, chromium-reducible, acetone-soluble and HI-reducible sulphur were used to estimate specific sulphur forms. Results for acetone-soluble sulphur were to high and not consistent with results for other fractions. Major part of sulphur in the sediment (90%) was inorganic. Sulphides were converted partially to sulphate and to intermediary oxidised sulphur compounds upon oxidation of the sediment. The results suggested that the intermediary oxidised sulphur pool in the reduced sediment (2.5 g kg⁻¹) mainly consisted of pyrite, that was not converted during drying and oxidation. No significant changes in organic sulphur were detected.     

Determination and fractionation of sulphur in a contaminated dredged sediment

Conversion of sulphur compounds in reduced, contaminated sediments that are brought in upland conditions may largely affect the potential mobility of heavy metal contaminants. We applied selected methods for the determination of total sulphur and sulphur fractions in a contaminated sediment in the reduced state and after gradual drying and oxidation during 1 month. Dry ashing, followed by ion chromatographic detection, was reliable for the determination of total sulphur. Good recoveries were obtained in both reference samples and spiked samples. Total sulphur was 14.5±0.6 g kg⁻¹ relative to dry sediment. Wet chemical methods that involve the determination of acid-volatile, Zn–HCl-reducible, chromium-reducible, acetone-soluble and HI-reducible sulphur were used to estimate specific sulphur forms. Results for acetone-soluble sulphur were to high and not consistent with results for other fractions. Major part of sulphur in the sediment (90%) was inorganic. Sulphides were converted partially to sulphate and to intermediary oxidised sulphur compounds upon oxidation of the sediment. The results suggested that the intermediary oxidised sulphur pool in the reduced sediment (2.5 g kg⁻¹) mainly consisted of pyrite, that was not converted during drying and oxidation. No significant changes in organic sulphur were detected.     

NEW ASPECTS IN THE MECHANISM OF INHIBITORY ACTION OF SULPHUR CONTAINING METAL COMPLEX COMPOUNDS IN THE OXIDATION OF HYDROCARBONS

Abstract

The first studies dealing with the antioxidizing action of sulphur containing organic compounds in the stabilization of petroleum products, polymers, rubber etc., suppose an interaction of these inhibitors with hydroperoxides and the decomposition of the latter to molecular inactive products. The absence of reaction of the peroxide radicals, leading the chain of the autoxidation, with the inhibitor is presumed. The initiating properties of the inhibitors-peroxide decomposers were unknown\1, 2,3\. As a result of our and other authors' investigations was shown, that the sulphur containing antioxidants react with the peroxide radicals and they are able to initiate the autoxidation processes, because in the oxidation of hydrocarbons in the simultaneous presence of hydroperoxides and sulphur containing compound, a prooxidizing effect is observed i.e. acceleration of the oxidation in a certain period of the process\4,5,6\. It was observed, that a period of rapid oxidation, followed by autoretardation of the oxygen absorption, appears in the oxidation of tetraline and cumene, respectively in the presence of tetraline and cumene hydroperoxides and metal dialkyldithiophosphates, dithiocarbamates and dithiolates. The oxidation of cumene and tetraline, initiated by AIBN at 60C in the presence of zinc dithiophosphate, zinc dithiocarbamate and nickel dithiolate, proceeds with the appearance of induction periods. In this way, the existence of interaction between RO.₂ and sulphur containing metal complex compounds is verified The Stoichiometric coefficient of inhibition depends on the concentraton of the used inhibitor, which is a proof that in the induction period, the inhibitor is consumed not only by an interaction with the peroxide radicals, but by means of another reaction. This fact explains the existence of different values of the stoichiometric coefficients, measured by different groups of authors, using different initial concentrations of the studied inhibitors. At a definite correlation between AIBN and sulfur containing complexes in the oxidation of cumene, an effect of oscillation is observed i.e. the induction period is followed by a periodical change of the oxygen absorption rate \7,8\. The frequence of oscillation increases with time and the differences between the inflexion become greater. similar effect was observed in the initiated by AIBN oxidation of cumene in presence of Zn-bis(diisopropyl)dithiophosphate-(I), Zn-bis(diethyl)dithiocarbamate-(II),Ni-bis(diphenylethylene)-dithiolate-(III). The existence of oscillating effect obviously is due to the competition of two parallel processes-the absorption and the liberation of gas. With the help of mass spectral I analysis, it was shown that as a result of the reaction of (I), (II), (III) inhibitors and hydroperoxides, oxygen is liberated. The use of acceptors of synglet oxygen (9,10-diphenylantracene) shows that the liberated gas is synglet oxygen\9\.     

Assay of sulphur compounds with 1-chlorobenzotriazole

A simple but accurate potentiometric method for the estimation of certain sulphur containing organic compounds has been developed, based on their oxidation with 1-chlorobenzotriazole. A back-titration procedure can also be used. The nature of oxidation in different media is discussed and the oxidation products have been identified.     

Time resolved sulphur and nutrient distribution in Norway spruce drill cores using ICP-OES

Methods were developed for detailed dendrochemical studies of low sulphur contents in Norway spruce (Picea abies L. Karst.). This tree species is the dominant conifer species in Northern and Central Europe and therefore predestined for a possible use as an environmental archive. Two independent digestion procedures were investigated with respect to their suitability for element determination and optimised for analysis of the low sulphur content in wood. A modified oxygen bomb combustion procedure and a microwave acid digestion procedure were evaluated with the goal to obtain sufficient detection limits in order to access low concentrated non-metals with an appropriate time resolution. Method development included evaluation of strategies preventing losses of volatile sulphur species. Digestion efficiency was demonstrated by recovery rates for various certified plant standard reference materials (NIST 1572, NIST 1547, RM 8436, BCR 101, NIST 1515, RM 8436, NIST 1573, NIST 1575) as well as self prepared standards with defined low sulphur content of 20 to 200 mg kg^?1, which are typical for Norway spruce wood samples. Ultra sonic nebulisation (USN) was evaluated with respect to signal enhancement for sample introduction to inductively coupled plasma optical emission spectrometry (ICP-OES). The optimised procedure was applied to Norway spruce drill cores from locations with different environmental conditions in Switzerland, in order to investigate the anthropogenic impact of sulphur and the suitability of Norway spruce as an environmental archive for sulphur.     

Thiol signalling network with an eye to diabetes

Redox regulatory system controls normal cellular functions. Controlled changes in redox couples potential serve as components for signal transduction, similarly to the phosphorylation cascade. Cellular redox biology requires both compartimentalisation and communication of redox systems: the thermodynamic disequilibrium of the major redox switches allows rapid and sensitive responses to perturbations in redox environments. The many oxidation states of sulphur are found in numerous sulphur species with distinct functional groups (thiols, disulphides, polysulphides, sulphenic, sulphinic and sulphonic acids, etc.), which participate in a complicated network of sulphur-based redox events. Human diseases such as diabetes mellitus and its cardiovascular complications have been associated with increased production of reactive oxygen species and perturbations of thiol redox homeostasis. The review surveys literature related to some etiopathogenic aspects and therapeutic perspectives. The dual toxic-protective property of sulphydryl-donor molecules in experimental settings proposes the general problem of designing antioxidants for therapeutic use.     

Identification des allotropes S6 et S7 du soufre dans le trophosome du vestimentifère Riftia pachyptila

The two sulphur allotropes S₆ and S₇ were characterised by gas chromatography/mass spectrometry coupling experiments in trophosomes of Riftia pachyptila (Vestimentifera), which inhabit hydrothermal vents. Both allotropes (approximately 3% for both) are associated with the usual form S₈ that represents about 97% of the total sulphur fraction. These new natural varieties of sulphur could be due to bacterial oxidation of hydrogen sulphide in extreme conditions (about 300 kg cm^–2). However, the occurrence of the same allotropes in mineral sulphur from different origin, terrestrial and extraterrestrial as well, could indicate that natural sulphur is a mixture of these three allotropes, with proportions depending on its geographical origin.     

Mechanisms of antioxidant action: The photo-antioxidant mechanisms of the 4-alkyl-2-mercapto thiazolines in polypropylene

An explanation is given for the favourable effect of oxidative processing on the behaviour of the 4-alkyl-2-mercapto thiazoles (RMTs) as photo-antioxidants in polypropylene (PP). The thiols are shown to be oxidised to the corresponding disulphides, followed by further oxidation through radical intermediates to products which have undergone sulphur loss. The chemistry of the oxidative transformations is believed to involve radical species during the early stages of photo-oxidation.     

Direct oxidimetric determination of thiocarbonate sulphur with ferricyanide, using iron(II)-dimethylglyoxime or sodium nitroprusside as indicator

Direct determination of 15-50 mg of thiocarbonate sulphur can be achieved by a one-step titration with potassium ferricyanide, using iron(II)-dimethylglyoxime or sodium nitroprusside as indicator. Only one sulphur atom of the thiocarbonate ion undergoes oxidation to elemental sulphur, the other two separating as carbon disulphide.     

The regulation of biothiol-responsive performance and bioimaging application of benzo[c][1,2,5]oxadiazole dyes

The different oxidation states of sulphur atom play a significant role on functional materials. In this work, a aryl-thioether and its sulphone substituted benzo[c][1,2,5]oxadiazole dyes were synthesized and utilized to determine thiol-containing amino acids. The result of selectivity experiments showed they detected the cysteine and homocysteine under physiological condition with negligible interference from other amino acids. In comparison to the thioether dye, the sulphone-based dye exhibited much faster response time for Cys and Hcy. However, the sulphone restricted its thiol-reactivity and bioimaging performance in living cells. By reducing the oxidation state of sulphur atom, we amazedly found that the sulfoxide-based dye still maintained high selectivity ultrafast response time for Cys/Hcy under physiological condition. It was worth mentioning that it also had high reactivity and good bioimaging performance that sulfone compounds did not have.     

The regulation of biothiol-responsive performance and bioimaging application of benzo[c][1,2,5]oxadiazole dyes

The different oxidation states of sulphur atom play a significant role on functional materials. In this work, a aryl-thioether and its sulphone substituted benzo[c][1,2,5]oxadiazole dyes were synthesized and utilized to determine thiol-containing amino acids. The result of selectivity experiments showed they detected the cysteine and homocysteine under physiological condition with negligible interference from other amino acids. In comparison to the thioether dye, the sulphone-based dye exhibited much faster response time for Cys and Hcy. However, the sulphone restricted its thiol-reactivity and bioimaging performance in living cells. By reducing the oxidation state of sulphur atom, we amazedly found that the sulfoxide-based dye still maintained high selectivity ultrafast response time for Cys/Hcy under physiological condition. It was worth mentioning that it also had high reactivity and good bioimaging performance that sulfone compounds did not have.     

2-Trifluoromethylimidazole, 2,4,5-tris (trifluoromethyl)imidazole and related compounds

2-Trifluoromethylimidazole, prepared by the reaction of imidazole-2-carboxylic acid with sulphur tetrafluoride, afforded a silver salt which reacted with organohalides (bromomethane, ethyl bromoacetate, N,N-dimethyl-2-chloroethylamine, and chloroacetonitrile) to give the corresponding N-alkylated derivatives. 2-Trifluoromethylimidazole-4,5-dicarboxylic acid was obtained by oxidation of 2-trifluoromethylbenzimidazole, and on decarboxylation gave only traces of 2-trifluoromethylimidazole; the major product was 2-trifluoromethylimidazole- 4-carboxylic acid. The di-acid and sulphur tetrafluoride gave 2,4,5-tris (trifluoromethyl) imidazole.     

Mechanisms of antioxidant action: Sulphur compounds as inhibitors of mechanochemical degradation of rubber

It is shown that the stability of sulphur vulcanised natural rubber to mechanodegradation (fatigue) is associated with the formation of labile oxidation products. The addition of sulphides and their oxidation products to a non-sulphur vulcanisate has a similar effect. Stress relaxation shows that the initial rate of chain scission under stress is directly related to the fatigue resistance of the vulcanisate. However, the oxidation process also produces peroxidolytic antioxidants (PD-C). It is concluded that the fatigue resistance of sulphur vulcanisates is due to a combination of facile restructurisation and an oxidation chain-breaking mechanism.     

X-ray photoelectron spectrometric and x-ray fluorometric studies of sulphur compounds on the surface of copper plates exposed to the atmosphere

X-Ray photoelectron spectroscopy (XPS) and XRF as techniques for monitoring air pollution are compared. Sulphide and oxides of sulphur (SO(2), SO(3) and SO(2-)(4)) have been determined on copper plates exposed for different lengths of time to an atmosphere containing hydrogen sulphide. The total amount of sulphur increases with the time of exposure but the sulphide reaches a constant value after 59 days. An interpretation of the mechanism of oxidation of hydrogen sulphide is offered.