Polyferredoxin-based electrode materials

Electrochemical oxidation of the hydrosulfide cluster [Fe4S4(SH)4]2- on gold, platinum or vitreous carbon in a methyl cyanide electrolyte leads to the growth of a conducting film. Spectroscopic and other evidence suggests that the film has cubane centres, predominately in the [4Fe4S]3+ oxidation state, which are linked by disulfide ligands to give an anionic array of [Fe4S4(S approximately)4]n- units. X-ray data suggests some long-range order in the electrode material. The polyferredoxin binds redox active cations consistent with an anionic array.     

1,3,4-oxadiazolin-2-ones from carbo-t-butoxyhydrazones

5-Substituted-1,3,4-oxadiazolin-2-ones 2 were synthesized by the oxidation of carbo-t-butoxyhydrazones 1 of aromatic aldehydes with lead tetraacetate or, preferably, iodosobenzene diacetate. In some instances 5-acetoxy-1,3,4-oxadiazoles 3 were obtained along with 2 . The oxidation of carboethoxyhydrazones 4 gave 2-ethoxy-1,3,4-oxadiazoles 5 .     

添加碱土金属化合物对CeO2甲烷氧化偶联催化性能的影响

天然气中甲烷的利用,特别是氧化偶联(OCM)制乙烯过程近年来成为多相催化研究的热点之一.自从1982年Keller和Bhasin提出该课题以来许多学者已进行了大量催化剂的研制工作.尽管在这方面已取得重要进展,但催化剂的性能距工业化要求还有较大差距.     

Stability of lithium hydride in argon and air

The oxidation behaviors of LiH under a high purity argon atmosphere, an argon atmosphere with some O2 and H2O impurities, and ambient air at both room and high temperatures, are investigated using a variety of analytical instruments including X-ray diffractometry, thermogravimetry, mass spectrometry, scanning electron microscopy, and specific surface area analysis. The oxidation behaviors of the ball-milled LiH under different atmospheres are also studied and compared with those without ball milling. It is shown that no oxidation of LiH occurs under a high-purity argon atmosphere. However, oxidation of LiH takes place when the argon atmosphere contains some H2O and O2 impurities. At temperatures higher than approximately 55 degrees C, oxidation of LiH proceeds via the reaction of LiH + 1/4 O2 = 1/2 Li2O + 1/2 H2, whereas at room temperature oxidation of LiH is likely caused by the simultaneous reactions of LiH + H2O = LiOH + H2 and LiH + 1/2 O2 = LiOH. The oxidation behavior of LiH in ambient air with a 27% relative humidity can be well described by the Johnson-Mehl-Avrami equation. Furthermore, the ball-milled LiH oxidizes faster than the unmilled one, which is due to the finer particle size and larger surface area of the ball-milled powder.     

A facile electrochemical method for the synthesis of new sulfonamide derivatives of potential biological significance

The electrochemical synthesis of some new sulfonamide derivatives was carried out via the electrochemical oxidation of 2,3-dihydrophthalazine-l,4-dione （1） in the presence of arylsulfinic acids （2a and 2b） as nucleophiles. The results show that, the electrogenerated phthalazine-l,4-dione （lox） participates in a Michael type addition reaction with 2a or 2b and via an EC mechanism to produce the corresponding sulfonamide derivatives. This method provides a one-pot procedure for the synthesis of new sulfonamide derivatives of potential biological significance in good yields without using toxic reagents at a carbon electrode in an environmentally friendly manner.     

Synthetic study of optically active 3-azabicyclo[3.3.0]octane-2,6,8-tricarboxylic acid

Synthesis of (1R,2S,5S,6R,8S)-3-azabicyclo[3.3.0]octane-2,6,8-tricarboxylic acid (2) from trans-4-hydroxy-L-proline (5) was attempted. A Diels-Alder reaction of 3,4-dehydroproline derivative 9 and cyclopentadiene afforded a single stereoisomer 11. The Diels-Alder adduct was smoothly converted to the hydrochloride of 2 (24) via RuO(4) oxidation. Although some racemization of the material or product was observed during the synthetic processes, the amino acid 24 proved to be optically pure.     

Desaturase reactions complicate the use of norcarane as a mechanistic probe. Unraveling the mixture of twenty-plus products formed in enzyme-catalyzed oxidations of norcarane

Norcarane, bicyclo[4.1.0]heptane, has been widely used as a mechanistic probe in studies of oxidations catalyzed by several iron-containing enzymes. We report here that, in addition to oxygenated products, norcarane is also oxidized by iron-containing enzymes in desaturase reactions that give 2-norcarene and 3-norcarene. Furthermore, secondary products from further oxidation reactions of the norcarenes are produced in yields that are comparable to those of the minor products from oxidation of the norcarane. We studied oxidations catalyzed by a representative spectrum of iron-containing enzymes including four cytochrome P450 enzymes, CYP2B1, CYPDelta2B4, CYPDelta2E1, and CYPDelta2E1 T303A, and three diiron enzymes, soluble methane monooxygenase (sMMO) from Methylococcus capsulatus (Bath), toluene monooxygenase (ToMO) from Pseudomonas stutzeri OX1, and phenol hydroxylase (PH) from Pseudomonas stutzeri OX1. 2-Norcarene and 3-norcarene and their oxidation products were found in all reaction mixtures, accounting for up to half of the oxidation products in some cases. In total, more than 20 oxidation products were identified from the enzyme-catalyzed reactions of norcarane. The putative radical-derived product from the oxidation of norcarane, 3-hydroxymethylcyclohexene (21), and the putative cation-derived product from the oxidation of norcarane, cyclohept-3-enol (22), coelute with other oxidation products on low-polarity GC columns. The yields of product 21 found in this study are smaller than those previously reported for the same or similar enzymes in studies where the products from norcarene oxidations were ignored, and therefore, the limiting values for lifetimes of radical intermediates produced in the enzyme-catalyzed oxidation reactions are shorter than those previously reported.     

单分散的还原态和中间氧化态聚苯胺齐聚物的合成与紫外光谱研究

提出了一条合成苯胺齐聚物的新路线:由高氧化态的苯胺四聚体与二苯胺或N-苯基-1,4-对苯二胺反应合成苯基封端的苯胺五聚体和六聚体,用红外、质谱、核磁共振、基底辅助激光解吸质谱(MALDI-MS)进行了表征.提出一条可能的机理,即高氧化态的苯胺四聚体与二苯胺或N-苯基-1,4-对苯二胺在酸性溶液中混合时,四聚体、二苯胺和N-苯基-1,4-对苯二胺的分子中均形成阳离子自由基,四聚体的阳离子自由基与后二者的阳离子自由基耦合形成苯胺五聚体和六聚体.还原态的苯胺齐聚物氧化成中间氧化态的苯胺齐聚物,使用硫酸铵和六水和三氯化铁等氧化剂能打断苯胺五聚体和六聚体的分子链.实验发现,氧化银是将还原态苯胺齐聚物氧化成中间氧化态的齐聚物的最好的氧化剂.用紫外可见光谱对中间氧化态的五聚体和六聚体进行了研究,对其分子中醌环的数目进行了讨论.     

Differential pulse voltammetry in analysis of disinfectants — 2-mercaptobenzothiazole, 4-chloro-3-methylphenol, triclosan, chloramine-T

The aim of this work was to study the possibility of simultaneous voltammetric determination of some disinfectants used as components in cosmetic products. The examined compounds were: triclosan (5-chloro-2-(2,4-dichlorophenoxy)phenol), chloramine-T (N-chloro-p-toluenesulfonamide sodium salt), 4-chloro-3-methylphenol and 2-mercaptobenzothiazole. Measurements were performed using glassy carbon electrode immersed in Britton-Robinson buffers which acted as supporting electrolytes. The dependence of oxidation and reduction potentials on pH was examined using cyclic voltammetry. Britton-Robinson buffer of pH 9.9 was chosen for further studies to ensure the best separation of compounds. The resultant oxidation potentials indicate the possibility to simultaneously determine some of the disinfectants.. Oxidation reactions of mixtures containing two compounds (4-chloro-3-methylphenol and chloramine-T, 2-mercaptobenzothiazole and 4-chloro-3-methylphenol, 2-mercaptobenzothiazole and triclosan) were recorded as differential pulse voltammograms.     

Catalytic Oxidation (4th World Congress on Oxidation Catalysis, Potsdam, Germany, September 2001)

This paper presents an overview of the plenary lectures and some of the oral and poster presentations at the 4th International Congress on Oxidation Catalysis in Potsdam (Germany). The main topics were the partial oxidation of alkanes and the oxidation of olefins by H₂O₂. Considerable attention is given to the use of modern physical methods in the mechanistic studies of oxidation catalysis and in the studies of catalyst structures.     

Principal Limitations in Homogeneous Gas Phase Chemistry in Non-Thermal Plasmas

This study highlights the oxidation of H₂, CH₄, and HCl present in the range of some volume percent in a homogeneous O₂ or air phase in a flow through glass barrier discharge reactor. The oxidation of all three compounds is highly exothermic and exergonic at ambient temperature and proceeds at sufficiently high temperatures as radical chain reaction. The conversion of each compound was below 10% in a non-thermal oxygen plasma under various reaction conditions. Increasing concentrations of H₂ and CH₄ above the lower explosion limit did not lead to higher conversion degrees. It is assumed that only initial radical formation by electron impact dissociation and exothermic steps within the chain process run in a sufficiently fast manner at ambient temperature. For endothermic steps within the radical chain, the necessary activation energy is not available and the chain reaction aborts, most likely, after formation of peroxyl (hydro- or methyl-peroxyl) radicals.     

Solid Phase Catalytic Oxidation of Alcohols by Polymer Supported Rare Earth Catalysts

Oxidation of alcohols to the corresponding aldehydes or ketones is one of the most fundamental reactions in organic chemistry [1,2]. Some of the products of the oxidation exhibit an important role in the organic synthesis as well as pharmaceutical synthesis. In most reactions, the lanthanide complexes show satisfied catalytic activities for some compounds. Furthermore, there has been increasing interest in the lanthanide complexes and several reports have appeared in the literature [3, 4]. But the exploitation of these complexes for the oxidation of some organic substrates has been limited. Here we reported a method for the preparation and the catalytic properties as well as the recycling of lanthanide complexes in oxidation of alcohols.The synthetic procedure for the polymer supported lanthanide complexes is shown as following(scheme 1):●-NH2+CICH2COOH(C2Hs)3N→●-NHCH2COOHM=Ce(Ⅲ), Tb(Ⅲ), Sm(Ⅲ)scheme 1The oxidation of benzyl alcohol was carried out in the presence of iodosylbenzene by the polymer supported Ce(Ⅲ), Tb(Ⅲ) and Sm(Ⅲ) catalysts at 80℃ for 4.0h, the yields of benz-aldehyde are as following (table 1):Table 1 Oxidation of benzyl alcohol with the supported catalysts**Reaction condition: benzyl alcohol 0.1 mmol, iodosylbenzene 0.15mmol,catalyst 0.2mg, 80℃ for 4.0h in 1,2-dichloroethane.It can be seen from the table that the Tb(Ⅲ) complex shows higher catalytic activity for the oxidation of benzyl alcohol. Further investigation is now being carded on to optimize the results.     

Enabling Aromatic Hydroxylation in a Cytochrome P450 Monooxygenase Enzyme through Protein Engineering

The cytochrome P450 (CYP) family of heme monooxygenases catalyse the selective oxidation of C−H bonds under ambient conditions. The CYP199A4 enzyme from Rhodopseudomonas palustris catalyses aliphatic oxidation of 4-cyclohexylbenzoic acid but not the aromatic oxidation of 4-phenylbenzoic acid, due to the distinct mechanisms of aliphatic and aromatic oxidation. The aromatic substrates 4-benzyl-, 4-phenoxy- and 4-benzoyl-benzoic acid and methoxy-substituted phenylbenzoic acids were assessed to see if they could achieve an orientation more amenable to aromatic oxidation. CYP199A4 could catalyse the efficient benzylic oxidation of 4-benzylbenzoic acid. The methoxy-substituted phenylbenzoic acids were oxidatively demethylated with low activity. However, no aromatic oxidation was observed with any of these substrates. Crystal structures of CYP199A4 with 4-(3′-methoxyphenyl)benzoic acid demonstrated that the substrate binding mode was like that of 4-phenylbenzoic acid. 4-Phenoxy- and 4-benzoyl-benzoic acid bound with the ether or ketone oxygen atom hydrogen-bonded to the heme aqua ligand. We also investigated whether the substitution of phenylalanine residues in the active site could permit aromatic hydroxylation. Mutagenesis of the F298 residue to a valine did not significantly alter the substrate binding position or enable the aromatic oxidation of 4-phenylbenzoic acid; however the F182L mutant was able to catalyse 4-phenylbenzoic acid oxidation generating 2′-hydroxy-, 3′-hydroxy- and 4′-hydroxy metabolites in a 83 : 9 : 8 ratio, respectively. Molecular dynamics simulations, in which the distance and angle of attack were considered, demonstrated that in the F182L variant, in contrast to the wild-type enzyme, the phenyl ring of 4-phenylbenzoic acid attained a productive geometry for aromatic oxidation to occur.     

Theoretical and electrochemical studies on organometallic symmetrical schiff base complexes of Zn(II), Cu(II), Ni(II) and Co(II)

The electronic communication between two redox centres through a Schiff base complex has been investigated in a series of ethylenediimine-bis(1-ferrocenyl-1,3-butanedionate) complexes of Zn(II) 1, Cu(II) 2, Ni(II) 3 and Co(II) 4. Cyclic voltammetry experiments of 1 and 2 exhibit a unique two-electron reversible oxidation wave, whereas in the case of 3 and 4 two and three one-electron oxidation processes are, respectively, observed. These results suggest some electronic interaction between the iron atoms of the ferrocenyl groups. DFT calculations carried out on model complexes show that for all the studied compounds the removal of the first two electrons corresponds to the oxidation processes of the iron centres in the weakly coupled ferrocenyl termini. The electronic communication between the two iron centres increases on going from 1 to 4. Finally, a re-indexation of the bands observed in the UV-Visible spectra has been carried out using TDDFT calculations.     

XPS spectroscopic study of potentiostatic and galvanostatic oxidation of Pt electrodes in H2SO4 and HClO4

The surface oxides produced from potentiostatic and galvanostatic oxidation of Pt electrodes in HClO₄ and H₂SO₄ are examined using X-ray photoelectron spectroscopy. The oxide I species produced as the initial oxidation product by successively more anodic potentiostatic oxidation in 0.2 M HClO₄ is found to have a Pt²⁺ oxidation state, a binding energy characteristic of neither PtO, Pt(OH)₂ or PtO₂, and a limiting thickness of 8 Å. Galvanostatic oxidation in HClO₄ and H₂SO₄ is found to produce PtO₂·H₂O as an unlimiting growth oxide or a limiting growth oxide layer depending on the concentration of the acid electrolyte. The incorporation of the acid electrolyte anion in the surface layer is shown to have an effect on which type of oxide layer is produced. X-ray decomposition and chemical modification by Ar⁺ stripping are shown to produce chemical artifacts complicating any interpretation of a Pt oxide surface layer.     

Density functional theory analysis of the reaction pathway for methane oxidation to acetic acid catalyzed by Pd2+ in sulfuric acid

Density functional theory has been used to investigate the thermodynamics and activation barriers associated with the direct oxidation of methane to acetic acid catalyzed by Pd2+ cation in concentrated sulfuric acid. Pd2+ cations in such solutions are ligated by two bisulfate anions and by one or two molecules of sulfuric acid. Methane oxidation is initiated by the addition of CH4 across one of the Pd-O bonds of a bisulfate ligand to form Pd(HSO4)(CH3)(H2SO4)2. The latter species will react with CO to produce Pd(HSO4)(CH3CO)(H2SO4)2. The most likely path to the final products is found to be via oxidation of Pd(HSO4)(CH3)(H2SO4)2 and Pd(HSO4)(CH3CO)(H2SO4)2 to form Pd(eta2-HSO4)(HSO4)2(CH3)(H2SO4) and Pd(eta2-HSO4)(HSO4)2(CH3CO)(H2SO4), respectively. CH3HSO4 or CH3COHSO4 is then produced by reductive elimination from the latter two species, and CH(3)COOH is then formed by hydrolysis of CH3COHSO4. The loss of Pd2+ from solution to form Pd(0) or Pd-black is predicted to occur via reduction with CO. This process is offset, though, by reoxidation of palladium by either H2SO4 or O2.     

Prosthetic heme modification during halide ion oxidation. Demonstration of chloride oxidation by horseradish peroxidase

Myeloperoxidase (MPO), eosinophil peroxidase (EPO), and chloroperoxidase can oxidize iodide, bromide, and chloride, but most peroxidases, including the prototypical horseradish peroxidase (HRP), reportedly only oxidize iodide and, in some cases, bromide. We report here that incubation of HRP with Br(-) and H(2)O(2) at acidic pH results in both bromination of monochlorodimedone and modification of the heme group. Mass spectrometry indicates that the heme 2- and 4-vinyl groups are modified by either replacement of a vinyl hydrogen by a bromide or addition of HOBr to give a bromohydrin. These reactions do not occur if protein-free heme and Br(-) are co-incubated with H(2)O(2) or if the HRP reaction is carried out at pH 7. Surprisingly, similar prosthetic heme modifications occur in incubations of HRP with H(2)O(2) and Cl(-). A mechanism is proposed involving oxidation of Br(-) or Cl(-) to give HOBr or HOCl, respectively, followed by addition to a vinyl group. In the reaction with Cl(-), a meso-chloro heme adduct is also formed. This first demonstration of Cl(-) oxidation by HRP, and the finding that prosthetic heme modification occurs when Br(-) or Cl(-) is oxidized in the absence of a cosubstrate, show that only modest tuning is required to achieve the unique chloride oxidation activity of MPO and EPO. The results raise the question of how the prosthetic hemes of MPO and EPO, whose function is to produce oxidized halide species, escape modification.     

A green approach for the electroorganic synthesis of 2-[(4-methyl-2-pyridyl)amino]-1,4-benzenediol derivatives in aqueous solution

The electrochemical synthesis of some new 2-[(4-methyl-2-pyridyl)amino)-1,4-benzenediol derivatives was performed via the electrochemical oxidation of hydroquinones in the presence of 2-amino-4-methylpyridine in an aqueous solution. The results demonstrate that electrogenerated p-benzoquinone participated in the Michael-type addition reaction via an electrochemical–chemical (EC) reaction mechanism pathway and converted to the corresponding 2-[(4-methyl-2-pyridyl)amino)-1,4-benzenediol derivatives. These new compounds have been synthesized in high yields and purity without using any toxic reagents or catalyst at the surface of carbon electrode.     

Oxidative diphosphonylation of 1,4-dihydropyridines and pyridinium salts

An oxidative double phosphonylation of dihydropyridines 1 and pyridinium salts 2 is achieved through the use of dialkyl phosphites, DDQ, and triethylamine. Acceptable to good yields of 2, 6-diphosphonylated-1,2-dihydropyridines 3 are obtained in a one-pot reaction involving tandem nucleophilic addition/oxidation processes. Isomerization of 3 to the more stable 2,4-diphosphonylated-1, 4-dihydropyridine 4 was observed in some cases.