Selective scavenging property of the indole moiety for the nitrating species of peroxynitrite

The inhibitory effect on tyrosine nitration and oxidation of peroxynitrite was evaluated for more than 40 reagents including natural and synthetic compounds, and the inhibiting efficiency of each compound for nitration was compared with that for oxidation, to characterize its property as a peroxynitrite scavenger. In the presence of various concentrations of testing compounds, the nitrating and oxidizing activities were measured by monitoring the formation of 3-nitrotyrosine and dityrosine with an HPLC-UV-fluorescence detector. The IC(50) values for nitration and oxidation were determined, and the ratio of these two IC(50) values was calculated for each compound. Although the IC(50) values varied from compound to compound, it was revealed that the ratio of two IC(50) values (IC(50) for oxidation/IC(50) for nitration) was 1 in almost all the compounds tested, except five indole derivatives (L-tryptophan, melatonin, 5-methoxytryptamine, tryptamine, and tetrahydro-beta-carboline) and one synthetic selenium-containing compound ((2R,3R,4S)-2-amino-3,4-dihydroxy-5-phenylselenopentan-1-ol, ADPP). The indole derivatives showed a specific inhibitory effect on tyrosine nitration without affecting the oxidation. ADPP was confirmed to have a preferable inhibitory activity for tyrosine oxidation. It was suggested that compounds showing an IC(50) value ratio of 1 scavenged the common species for nitration and oxidation, while the indole derivatives and ADPP preferably scavenged the nitrating and oxidizing species, respectively. From a stopped flow study, it was also revealed that the nitrotyrosine formation was relatively slow, unlike an OH radical reaction. These results imply that the peroxynirite reaction at least partly proceeds through specific species for nitration.     

Tentative correlation between the electrochemical oxidation of neuroleptics and their pharmacological properties

A number of drugs are largely metabolized after oral administration, especially by redox processes. Among the neuroleptics, loxapine, clotiapine and clozapine, which are seven-membered tricyclic molecules with a piperazine side-chain, are known to be extensively metabolized by oxidation.An electrochemical study of these compounds was initiated in order to determine their in vitro redox properties and to elucidate their oxidation mechanisms. The measurements were carried out in aqueous and non-aqueous media using voltammetric, cyclic voltammetric, coulometric, exhaustive electrolysis and thin-layer spectroelectrochemical techniques.The oxidation mechanisms, which differ essentially depending on the pH of the solution, are suggested. In view of these results, various similarities have been detected between the in vitro oxidation processes and the pharmacological behaviour reported in the literature.For example, the importance of the piperazine side-chain has been pointed out: oxidation no longer occurs if this side-chain is protonated; similarly, binding to the receptor is prevented if the lone electron pair of the tertiary atom is occupied. Nucleophilic additions have also been observed in non-aqueous media and the compounds have been identified using classical spectroscopic techniques. If the oxidation mechanism is identical on the piperazine chain for the three compounds, the process is somewhat different when it occurs on the tricyclic ring. Loxapine and clotiapine exhibit different behaviour from clozapine, in their electrochemical as well as in their pharmacological properties.     

纳米氧化铈在催化氧化木质素制备芳香化合物中的应用研究

木质素是自然界中唯一大规模可再生的含芳环聚合物.通过催化氧化的方法,定向解聚木质素得到芳香类化合物,具有非常重要的价值.近年来,氧化铈作为载体在木质素的多相催化氧化反应中表现较好性能.然而,对于氧化铈直接作为催化剂,并探讨其纳米结构与性能之间的研究未见报道.研究结果表明:纳米氧化铈直接作为催化剂时,对于木质素的催化氧化反应具有较好的性能,顺序为氧化铈纳米八面体纳米四方体纳米球纳米棒.纳米八面体表现出最优的催化性能,以其作为催化剂,对乙醇木质素进行催化氧化,得到了大量芳香酸及其酯类化合物.     

Oxidation number: issues of its determination and range

The paper is aimed at the issues of oxidation state determination and limiting values. The possibility of existence of compounds containing an atom with the oxidation number beyond the current common values, i.e., below −IV and above +VIII are discussed. Three principal modes of preparation of compounds with the oxidation number exceeding VIII, electrochemical anodic oxidation, photoionization, and nuclear β-decay, are evaluated. Failure to prepare compounds containing an atom with the oxidation number below −IV is rationalized. The paper provides an opinion on uncertainties in oxidation state determination in three kinds of compounds: binary compounds, nitrosyl complexes, and compounds containing mutually bonded atoms of the same element. The questions are discussed from the viewpoint of correlation of “man-made” quantities and objective, experimentally obtainable data.     

Valence-change in the mass spectra of metal complexes

A review article is presented relating to the concept of valence-change in the mass spectra of metal-containing compounds. It is found that the modes of ion dissociation in these spectra are markedly dependent on the oxidation states normally assumed by the metal concerned and it is postulated that electron-transfer may be possible between the complexed metal atom and its ligands in the ion, such that the odd- or even-electron character of the ion is inter-changeable. Ion reactions such as the consecutive loss of two radicals are normally of low probability in the mass spectra of organic compounds, but are often observed in the mass spectra of metal-containing compounds and can be rationalized in terms of the valence-change concept. Convincing evidence for valence-change in some spectra is provided by the occurrence of reactions leading to the bare metal ion, or to the loss of neutral fragments containing the metal atom in a lower oxidation state than in the precursor molecule. Further applications of the concept may be found in the rationalization of the mass spectra of inorganic and organometallic compounds.     

杂多酸(盐)及单缺位磷钨杂多化合物在醇类氧化反应中的催化活性

在相转移条件下,研究了杂多化合物在苄醇,环己醇氧化反应中的催化活性.六种Keggin结构杂多酸的催化活性按GeMo~12(H~4GeMo~12O~40的简写,其余类推,PW~12,PMo~12,SiMo~12,GeW~12,SiW~12顺序下降,杂多酸中的质子可分别被其它阳离逐渐取代而达到酸性修饰. H~3PW~12O~40随着其质子逐步被Na^+取代,酸性下降,催化活性大大提高;杂多酸(盐)的催化活性随体系pH值的改变将发生奇妙剧烈的变化;单缺位杂多化合物显示出较饱和杂多酸(盐)更高催化活性.溶剂对催化活性有明显影响.     

构建光催化氧化-还原体系的研究进展

光催化氧化-还原体系能够同时驱动光催化氧化反应和还原反应,产生协同效应,从而提高光催化反应的活性。在此,提出了构建光催化氧化-还原体系的原则,并介绍了光催化还原硝基芳烃耦合氧化有机物、光催化还原重金属离子协同氧化有机物、光解水制氢协同氧化有机物三个方面的实例。接着,阐述了光催化氧化-还原体系的反应机理,期望通过构建光催化氧化-还原体系,更有利于太阳能转化并缓解环境和能源问题。     

Effect of metals on melt oxidation of polyethylene

Oxidation of polyethylene (PE) melts in contact with metals (Cu, Pb, Au, Al, Zn, Ag) has been studied by infrared spectroscopy and differential thermal analysis (DTA). These metals may be divided into two groups, depending on their activity for oxidizing PE: namely, high-activity metals (Cu, Pb, Ag, Zn) and low-activity metals (Al, Au). During the oxidation of PE in contact with high-activity metals dissolution of the surface layer of metal is observed with accumulation of metal-containing compounds (salts of carboxylic acids) in the bulk of the polymer. With low-activity metals these phenomena are not observed. The rate of oxidation of PE on low-activity metals approaches the oxidation rate of nonmetals (polytetrafluoroethylene and inorganic glass). With certain high-activity metals (Cu, Pb) the process of oxidation is accelerated only in the early stage of oxidation; then the oxidation rate slows down and the oxidation process ceases. PE films separated from metal after being oxidized on it possess chemical memory, i.e., their oxidation rate depends on the nature of the metal with which they had been in contact, and on the duration of the contact oxidation. The effect of salts of carboxylic acids (metal stearates) on the oxidation of PE melts was also studied. Based on the data obtained, it is concluded that the rate of oxidation of PE melts on high-activity metals is controlled by metal-containing compounds which are the products of contact reactions.     

Voltammetric and impedance studies of inosine-5'-monophosphate and hypoxanthine

The oxidation mechanism and adsorption of inosine 5'-monophosphate and hypoxanthine were investigated in solutions of different pH using voltammetric and impedance methods at glassy carbon electrodes. For both compounds, the pH dependence from differential pulse voltammetry showed that the same number of electrons and protons are involved in the rate-determining step of the electrochemical reaction. In the case of hypoxanthine, it was also possible to study the effect of different concentrations. At high concentrations of hypoxanthine, two oxidation peaks were observed, the first due to hypoxanthine oxidation with formation of oligomers and the second due to hypoxanthine oligomer oxidation, both compounds adsorbing strongly. Impedance measurements corroborated the voltammetric results and enabled the study of the adsorption of hypoxanthine on glassy carbon.     

From group 13-group 13 donor-acceptor bonds to triple-decker cations

Donor-acceptor bonding between group 13 elements seems counter-intuitive because one normally thinks of e.g. boron and aluminium compounds as classical Lewis acids. Indeed, many such compounds have achieved industrial prominence in this regard. Recently, however, it has become possible to stabilize these and other group 13 elements in the +1 oxidation state as opposed to the archetypical +3 oxidation state. Moreover, it turns out that in the +1 oxidation state these species are excellent donors--hence the formation of these unprecedented donor-acceptor bonds. The discovery of such bonds has led, albeit indirectly, to the development of triple-decker main group cations. This aspect is also covered in the review.     

含硝基咔唑类有机电催化剂的合成及其对醇的电催化氧化

有机小分子的电催化氧化是催化领域的一个重要研究内容.通过醇的选择性氧化合成相应醛或酮类化合物在精细化学品和有机化学中间体的合成领域均具有十分重要的意义.有机电催化合成用电子代替强氧化还原剂,可以使反应在比较温和的条件下进行.但在直接电氧化合成反应中,电极表面容易生成有机聚合物膜,使电极钝化,电流效率急剧下降.而在电子转移媒质作用下的有机电催化反应不仅可以避免电极表面钝化,还可以控制目标产物的过度氧化.三芳胺类化合物是一类新型的电氧化还原媒质,由于其具有较宽的电化学氧化还原电位已引起研究者的广泛关注.咔唑类化合物相比于三芳胺类具有更好的平面性,使得取代基效应更为显著.咔唑类化合物被广泛作为荧光材料,但用于电化学方面的研究很少.本文通过在咔唑类化合物中引入具有强吸电子性的硝基以提高该类化合物的氧化电位,并将其作为有机电催化媒质,采用间接电化学氧化的方式,在室温下研究醇的电化学催化氧化反应,合成相应醛类化合物.
　　我们合成了三种含硝基咔唑类有机电催化剂,通过1H NMR对其结构进行了鉴定.采用循环伏安法测试了该类有机电催化剂的电化学氧化还原性能.发现取代基的电子效应对有机电催化剂的氧化还原电位及电化学氧化还原可逆性有很大的影响,供电子基(–OCH3)的引入使氧化电位负移(0.717 V),吸电子基(–Br)的引入使氧化电位明显正移(1.282 V).同时,取代基的引入有效改善了有机电催化剂的电化学可逆性,从而可以作为有效的电氧化还原媒质应用于电化学氧化反应中.而当把化合物中的NO2还原为NH2后,咔唑类化合物的电化学氧化还原可逆性完全消失,表明硝基的引入对咔唑类有机电催化剂的电化学性能有很大的影响.
　　循环伏安结果发现,在咔唑类硝基化合物的作用下,对甲氧基苯甲醇(p-MBzOH)的电化学氧化峰电位从1.350 V降至1.286 V,表明可以在较低电位下进行电解,有效降低了电氧化反应的能耗,同时氧化峰电流明显增加,说明该类有机电催化剂对p-MBzOH具有良好的电催化性能.随着p-MBzOH浓度的增加,氧化峰电流也明显增大,说明在咔唑类有机电催化剂的作用下, p-MBzOH可以在比较高的浓度下进行电化学氧化电解.通过对不同对位取代基的苯甲醇类化合物进行循环伏安研究,发现含硝基咔唑类化合物对具有较高氧化电位的反应底物均表现出良好的电催化氧化性能.
　　在含硝基咔唑类有机电催化剂的氧化电位(1.28 V)和室温下,对不同浓度的p-MBzOH进行恒电位电解6 h,发现当催化剂的用量为底物的2.5 mol%时, p-MBzOH可以完全转化为相应的醛类目标产物.而且恒电位电解后分离回收的含硝基咔唑类有机电催化剂仍具有良好的电化学氧化还原可逆性.     

Investigations on the redox character of dithizone by voltammetric methods: Part II. The elucidation of the deterioration of dithizone solutions

The electrochemical redox behaviour of dithizone and its oxidation products have been examined in detail and the mechanisms of the electrochemical and aerial oxidation of dithizone are considered. All the oxidation products (tetrazolium and disulphide compounds) can be followed by voltammetric methods. The results of the electrochemical investigation of dithizone are useful for practical analytical and electroanalytical applications of dithizone.     

Paradigms and Paradoxes: Common and Maximum Accessible Oxidation States of the Elements

Common and accessible oxidation states of numerous nonmetals and transition metals in compounds with high oxidation state are discussed. These oxidation state concepts are generally, disappointingly and surprisingly elusive.     

Boron-doped diamond electrodes for the mineralization of organic pollutants in the real wastewater

The presence of recalcitrant organic compounds in wastewater poses a serious threat to the ecosystem and human health. Electrochemical advanced oxidation processes constitute a promising way for the mineralization of persistent organic compounds. They are commonly used for the transformation of organic pollutants into more biodegradable compounds or their complete removal from water. In this review, we present the recent advances in the use of boron-doped diamond (BDD) electrodes in the anodic oxidation process for the mineralization of real wastewater. First, the characteristic properties of BDD electrodes are discussed followed by the degradation mechanism. In addition, an overview on the application of BDD electrodes for mineralization of real wastewater is provided.     

Effect of phenolic compounds and quinones on radiation-induced oxidation processes of hexane and ethanol

The radiation-chemical yields were determined for the products of γ-radiation induced oxidation of hexane and ethanol in the presence of natural and synthetic phenolic compounds and quinones. It was found that the commercial antioxidants ionol and bisphenol 2246 more effectively inhibit the hexane oxidation process while α-tocopherol and quinones are superior to other test compounds in the suppression of ethanol oxidation. The results indicate that the antioxidant properties of phenolic compounds and quinones depend not only on their structure but also on the nature of the oxidation substrate. The cause of this phenomenon is discussed.     

Spectrophotometric investigation of the kinetics of the oxidation of model compounds and lignin by a peroxidase-H2O2 complex

It has been established that in relation to the increase in the maximum initial rate of oxidation of model compounds and of lignin by a peroxidase-H₂O₂ complex, the substances studied form the following sequence: guaiacol,α-guaiacylpropanol, ferulic acid,α-guaiacylpropanone, andα-lignin. On the basis of the results of the investigation it is suggested that the oxidation of lignin is carried out by a peroxidase-O₂ complex. With a rise in the concentration of hydrogen peroxide the oxidation of model compounds is inhibited.     

Nanosecond redox equilibrium method for determining oxidation potentials in organic media

A general, nanosecond equilibrium method is described for determining thermodynamically meaningful oxidation potentials in organic media for compounds that form highly reactive cation radicals upon one-electron oxidation. The method provides oxidation potentials with unusually high precision and accuracy. Redox ladders have been constructed of appropriate reference compounds in dichloromethane and in acetonitrile that can be used to set up electron-transfer equilibria with compounds with unknown oxidation potentials. The method has been successfully applied to determining equilibrium oxidation potentials for a series of aryl-alkylcyclopropanes, whose oxidation potentials were imprecisely known previously. Structure-property trends for oxidation potentials of the cyclopropanes are discussed.     

Catalytic Systems Based on Magnesium and Zinc Compounds in the Oxidation Reactions of Alkylarenes and the Decomposition Reactions of the Corresponding Hydroperoxides

The oxidation of aromatic hydrocarbons in the presence of magnesium and zinc 2-ethylhexanoates and a mixed catalyst based on these compounds is studied. It is shown that magnesium and zinc carboxylates are active catalytic systems which catalyze the decomposition of hydroperoxides representing the primary alkylarene oxidation products alongside with activation of oxygen.     

Enzymatic oxidation of lignin and compounds modeling it. II. A study of the peroxidase oxidation of model compounds of the structural unit of lignin by the chemiluminescence method

An investigation of the radical mechanism of the peroxidase oxidation of monomeric phenols (vanillin, vanillyl alcohol, isoeugenol, and α-quaiacylpropanone) has been made by the chemiluminescence method. It has been established that chemiluminescence is observed in those compounds that contain hydroxy or carbonyl groups on a carbon atom in the α position or have a C=C bond in the β position conjugated with the aromatic ring. The hypothesis has been put forward that peroxide compounds are inhibitors of autocatalytic processes in the oxidation of lignin in the presence of peroxidase.     

A new electrocatalytic mechanism for the oxidation of phenols at platinum electrodes

Electrochemical oxidation of phenolic compounds generally produces unstable phenoxy radicals that readily polymerize to passivate the surface of solid electrodes. In this study, the electrocatalytic oxidation of phenol in the presence and absence of methanol was investigated by cyclic voltammetry on a platinum electrode. The cyclic voltammogram of phenol in a mixture of phosphate buffer/methanol solution showed well-defined peaks at ∼600 mV vs. Ag/AgCl reference electrode, which surprising, gradually increased with repetitive scanning, stabilizing after 50 cycles. This unexpected behavior is in contrast to previous studies involving phenolic compounds, which always show a decrease in intensity during continuous potential scanning. Scanning electrochemical spectroscopy (SEM) was further used to investigate the changes in the surface morphology of the Pt electrode after electrodeposition. A new electrocatalytic mechanism for phenol oxidation on the surface of a Pt electrode is suggested in the presence of methanol. The proposed mechanism is based on the formation of a film of Pt oxide/hydroxides onto which the phenol and the products of its electrochemical oxidation are further deposited. The mechanism was also studied using more complex phenolic compounds including resveratrol, quercetin and bisphenol A. The results emphasized the effect of aryl substituents on the electrochemistry of this particular class of compounds.