Electrochemical Behavior of Methanol Influenced by Polyaniline Incorporated with Ferrocenesulfonic-carboxylic Acid

After the synthesis of polyaniline in the presence of ferrocenesulfoniccarboxylic acid, its influence on the electrochemical reaction of methanol was studied. The result indicates that the ferrocenyl in ferrocenesulfoniccarbexylic acid plays an important role in the electrocatalytic oxidation of methanol. CH3OH is adsorbed on PANI-Fc before its electrocatalytic oxidation. When the concentration of methanol is 2 mol/L, it begins to be oxidized. The effect of scan rate on the electrochemical reaction of methanol was also studied and 5 mV/s was favourable. It is another method to insert a metal catalyst in polyaniline without its electrodeposition.     

A COMPARISON OF DENATURATION AND INACTIVATION RATES OF CREATINE KINASE IN GUANIDINE SOLUTIONS

Both the denaturation, as followed by UV absorbance and fluorescence changes, and inac-tivation of creatine kinase in guanidine solutions have been found to be first order reactions.In 3 M guanidine, at 30℃, the inactivation rate constant was found to be 5.9 sec~(-1) and thedenaturation rate constant 1.9 sec~(-1). At lower guanidine concentrations, the inactivation rateconstants were only little affected whereas the denaturation rate constants decreased markedly,being of the order of 0.04 in 1 M and 0.004 in 0.5 M guanidine. The kinetics of the inactiva-tion reaction in 0.5 M guanidine was found to be in agreement with a combination of two firstorder reactions. The enzyme lost activity first by a fast reaction with a rate constant onlyslightly lower than the rate constant in 3 M guanidine followed by a slower reaction with a rateconstant of 0.003 sec~(-1). In 0.3 M guanidine, very little change in either UV absorbance or influorescence was observed, but, in sharp contrast, the enzyme lost considerable activity by a fastreaction and this was followed by a slower reaction of inactivation. Even after prolongeddenaturation in 0.5 and 0.3 M guanidine, residual activities of 3.4% and 30% remained res-pectively. The above results suggest a very fragile active site although dissociation of thedimer and reversible guanidine inhibition may also contribute to the initial rapid inactiva-tion. It is also to be noted that the multiphasic courses of inactivation at lower guanidineconcentrations seem to suggest the presence of partly active intermediates during denaturation.     

Investigation of the oxidation of hydroquinone at the liquid/liquid interface

<正>The oxidation of hydroquinone(QH_2) was investigated for the first time at liquid/liquid(L/L) interface by scanning electrochemical microscopy(SECM).In this study,electron transfer(ET) from QH_2 in aqueous to ferrocene(Fc) in nitrobenzene (NB) was probed.The apparent heterogeneous rate constants for ET reactions were obtained by fitting the experimental approach curves to the theoretical values.The results showed that the rate constants for oxidation reaction of QH_2 were sensitive to the changes of the driving force,which increased as the driving force increased.In addition,factors that would affect ET of QH_2 were studied.Experimental results indicated ion situation around QH_2 molecule could change the magnitude of the rate constants because the capability of oxidation of QH_2 would be affected by them.     

SYNTHESIS OF CONDUCTIVE POLYANILINE VIA OXIDATION BY MnO2

A unique process of chemical oxidation polymerization of aniline using manganese dioxide (MnO2) as the oxidizing agent in an aqueous medium is described. The reaction between aniline and MnO2 follows a mechanism by which the organic monomer is oxidized while the metal oxide undergoes reductive dissolution. The effects of the amount of oxidizing agent and aniline, pH and temperature of the reactive system, type of acid on the yield and conductivity of polyaniline are discussed. The resulting polyaniline was characterized by [R and UV-Vis spectrometry. Polyaniline with a conductivity of 12.5 S/cm was obtained using 0.033 tool of aniline oxidized by 0.023 tool MnO2 in the presence of 100 mL of 2.7 mol/L HCI at 25℃ for 4 h.     

Selective Oxidation of Propane by Lattice Oxygen of Vanadium-Phosphorous Oxide in a Pulse Reactor

Selective oxidation of propane by lattice oxygen of vanadium-phosphorus oxide (VPO) catalysts was investigated with a pulse reactor in which the oxidation of propane and the re-oxidation of catalyst were implemented alternately in the presence of water vapor. The principal products are acrylic acid (AA),acetic acid (HAc), and carbon oxides. In addition, small amounts of C1 and C2 hydrocarbons were also found, molar ratio of AA to HAc is 1.4-2.2. The active oxygen species are those adsorbed on catalyst surface firmly and/or bound to catalyst lattice, i.e. lattice oxygen; the selective oxidation of propane on VPO catalysts can be carried out in a circulating fluidized bed (CFB) riser reactor. For propane oxidation over VPO catalysts, the effects of reaction temperature in a pulse reactor were found almost the same as in a steady-state flow reactor. That is, as the reaction temperature increases, propane conversion and the amount of C1 C2 hydrocarbons in the product increase steadily, while selectivity to acrylic acid and to acetic acid increase prior to 350℃ then begin to drop at temperatures higher than 350℃, and yields of acrylic acid and of acetic acid attained maximum at about 400℃. The maximum yields of acrylic acid and of acetic acid for a single-pass are 7.50% and 4.59% respectively, with 38.2% propane conversion. When theamount of propane pulsed decreases or the amount of catalyst loaded increases, the conversion increases but the selectivity decreases. Increasing the flow rate of carrier gases causes the conversion pass through a minimum but selectivity and yields pass through a maximum. In a fixed bed reactor, it is hard to obtainhigh selectivity at a high reaction conversion due to the further degradation of acrylic acid and acetic acid even though propane was oxidized by the lattice oxygen. The catalytic performance can be improved inthe presence of excess propane. Propylene can be oxidized by lattice oxygen of VPO catalyst at 250℃, nevertheless, selectivity to AA and to HAc are even lower, much more acetic acid was produced (molar ratio of AA to HAc is 0.19:1-0.83:1) though the oxidation products are the same as from propane.     

Highly Chemical and Regio－selective Catalytic Oxidation with a Novel Manganese Catalyst

The chemical selectivity of a novel active manganese compound [Mn2^IVμ-O)3(TMTACN)2] (PF6)2 (1) in catalytic oxidation reactions depended on the structure of substrates and 1 was able to catalyze the oxidation of toluene into benzaldehyde and/or benzoic acid under very mild conditions. The following results were obtained: (1) The selectivity of the oxidation depended on the electronic density of double bonds. Reactivity was absent when strong electron-witherawing groups were conjugated with double bonds. (2) Allylic oxidation reactions mostly take place when double bond is present inside a ring system, whilst epoxiclarion reactions occur when the alkene moiety is part of linear chain. (3) In ring systems, the methylene group was more likely to be oxidized than the methyl group on ailylic position. As expected, the C--H bonds at the bridgeheads were unreactive.The secondary hydroxyl groups are more easily to be oxidized than the primary hydroxyl groups.     

Kinetics of FeSe2 oxidation by ferric iron and its reactivity compared with FeS2

The mobility and bioavailability of selenium is a major health and environmental issue and a main concern for geological disposal of high-level radioactive waste. Chemically and/or microbially mediated oxidation of insoluble Se-bearing particulate, such as iron selenides, to dissolved and mobile phases controls the transport and distribution of Se in the environment. The oxidation of ferroselite(FeSe2) by ferric iron was investigated in anoxic conditions. The redox reaction can be represented by: FeSe2 + 2Fe3+ = 2Se0 + 3Fe2+. Kinetic studies indicated that the reaction can be described by second-order rate law, with rate constants of 0.49±0.01, 0.85±0.02, 1.84±0.04, and 3.29±0.13 L mol-1 s-1 at pH 1.62, 1.87, 2.23, and 2.49, respectively. The positive correlation between reaction rate and pH implies that diffusion of Fe3+ oxidant to the mineral surface is the rate-determining step. The strong reactivity of FeSe2 towards Fe3+ suggests that ferric iron may play a significant role in FeSe2 oxidation process(e.g., by Se4+, O2, etc.) and Se0 should be the first reaction product. Also, it was shown that the reduction rate of Fe3+ or Se4+ by pyrite(FeS2) can be significantly increased in the presence of FeSe2, suggesting a stronger reactivity of FeSe2 compared with pyrite. The results obtained extend our knowledge about the subtle interaction between Se, pyrite and iron selenides in the environment, and give insight into the transfer of selenium from iron selenides to bio-available selenium(i.e., selenite and selenate) in the Se-rich environment.     

以方沸石负载Ni(Ⅱ)催化剂修饰的电极电氧化甲醇(英文)

There is a high overvoltage in the oxidation of methanol in fuel cells,and so modified electrodes are used to decrease it.A modified electrode that used Ni(II) loaded analcime zeolite to catalyze the electrooxidation of methanol in alkaline solution was proposed.Analcime zeolite was synthesized by hydrothermal synthesis,and Ni(II) ions were incorporated into the analcime structure,which was then mixed with carbon paste to prepare modified electrode.The electrocatalytic oxidation of methanol on the surface of the modified electrode in alkaline solution was investigated by cyclic voltammetry and chronoamperometry.The effects of the scan rate of the potential,concentration of methanol,and amount of zeolite were investigated.The rate constant for the catalytic reaction of methanol was 6 × 103 cm3 mol-1 s-1 from measurements using chronoamperometry.The proposed electrode significantly improved the electron transfer rate and decreased the overpotential for methanol oxidation.     

RUTHENIUM-TPPTS CATALYZED REDUCTlON OF NITROBENZENE TO ANILINE——A HIGHLY SELECTIVE WATER-SOLUBLE CATALYST SYSTEM

The ruther ium catalvst complex formed from RuCl_3·3H_2O andthe water-soluble ligand tris-(sodium m-sulfophenyl)phosphine, TPPTS, hasbeen examined as a catalyst for the reduction of nitrobenzene to anilineunder water gas shift conditions. The reactions, which were conducted inaqueous methanol. were studied as a function of CO pressure and addedamine base The major product observed over the temperature range of100～150℃ was aniline (>90% yield abovc 130℃ ), with only minor amountsof the corresponding carbamate PhNHCO_2Me(<3%) and formanilide(<4%)being observed. Of the several amine bases examined in this reaction, Et_3Nhas been found to be superior in promoting the fastest rate of nitrobenzenereduction. Replacement of methanol by either THF or xylenes led to a drastic retardation in the amount of aniline produced.     

Chemical oscillations in the metal ion-catalyzed bromate-4-aminophenol reaction

Temporal oscillations of the bromate-4-aminophenol system have been studied in the presence of four different catalysts:tris(1,10-phenanthroline)iron(II) sulfate(ferroin),Ce(III),Mn(II),and Fe(II).Transient temporal oscillations were observed in the four catalyzed systems when the reactions were conducted in a stirred batch reactor.The induction time was prolonged by the presence of ferroin,but it was shortened in the Ce(III)-and Mn(II)-catalyzed systems.On the other hand,the number of peaks was significantly decreased in the presence of ferroin.The development of oscillatory behaviour was found to be more sensitive to the ratio of bromate and 4-aminophenol concentration than to their absolute concentrations.The reaction rates of 4-aminophenol with Ce(IV) and 4-aminophenol with ferritin were measured directly by spectroscopic methods in a sulfuric acid medium.     

Kinetics and mechanism of oxidation of bis(2,4,6-tripyridyl 1,3,5-triazine)iron(II) by vanadium(V), periodate and iodate ions in acetate buffers

The kinetics of oxidation of bis(2,4,6-tripyridyl 1,3,5-s-triazine)iron(II) by vanadium(V), periodate and iodate has been studied in acetate buffers by stopped-flow and spectrophotometric methods. The oxidation reaction of bis(2,4,6-tripyridyl 1,3,5-s-triazine)iron(II) by vanadium(V), periodate and iodate follows first order kinetics for the substrate and oxidant. Hydrogen ion has no significant effect on the rate. A generalized mechanism was proposed for these reactions and these reactions follow the rate law: Rate = k [oxidant] [Fe(tptz)₂ ²⁺].     

Ruthenium(II) tris(bipyridyl) ion as a luminescent probe for oxygen uptake on the catalyzed oxidation of HSO(3)(-)

The present work describes an alternative technique for monitoring the rate of oxygen consumption during the oxidation of HSO(3)(-) catalyzed by manganese and iron ions. The method is based on the spectrofluorimetric monitoring of the quenching effect of molecular oxygen on the emission of the photoexcited [Ru(bipy)(3)](2+) ion, added to the reaction mixtures. The effects of Fe(III), at very low concentrations, and of Mn(II) on the oxidation of HSO(3)(-) by dissolved oxygen, have been investigated. The metal ions in the trivalent oxidation state react with HSO(3)(-) to initiate a radical chain reaction in which HSO(3)(-) is oxidized to sulfate and the metal ion is reduced to the divalent state. The synergistic effect of Mn(II) and Fe(III) was clearly evaluated. Possible parallel reactions with the oxygen indicator, [Ru(bipy)(3)](2+), are considered.     

Theoretical study of the oxidative polymerization of aniline with peroxydisulfate: Tetramer formation

Semi‐empirical quantum chemical study of the oxidative polymerization of aniline with ammonium peroxydisulfate, in aqueous solutions without added acid, has been based on the MNDO‐PM3 computations of thermodynamic, redox, and acid–base properties of reactive species and the intermediates, combined with the MM2 molecular mechanics force‐field method and conductor‐like screening model of solvation. The main reaction routes of aniline tetramerization are proposed. The regioselectivity of the formation of aniline tetramers by redox and electrophilic aromatic substitution reactions is analyzed. It was proved that the linear N? C4 coupled tetra‐aniline is formed as a dominant product by three different pathways: comproportionation redox reaction between N‐phenyl‐1,4‐benzoquinonediimine and 4‐aminodiphenylamine, the one‐electron oxidation of aniline with its half‐oxidized N? C4 coupled trimer, and the electrophilic aromatic substitution reaction of aniline with fully oxidized N? C4 coupled trianiline nitrenium cation. The electrophilic aromatic substitution reaction of the N? C4 coupled aniline trimer with aniline nitrenium cation, as well as the oxidation of aniline with half‐oxidized branched trimer, lead to the branched aniline tetramers. The competing character of different tetramerization routes is highlighted. The oxidative intramolecular cyclization of branched oligoanilines and polyaniline, leading to the generation of substituted phenazine units, has been predicted to accompany the classical routes of the polymerization of aniline. Various molecular (branched vs. linear) oligomeric structures produced at different level of acidity during the course of polymerization and their impact on the formation of supramolecular structures of conducting polyaniline (nanorods and nanotubes vs. granular morphology), are discussed. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008     

Optical Properties of Model Compounds of Polyaniline

The UV and visible spectra of six model compounds were studied. These compounds can be considered as models of polyaniline in the reduced, cation radical, partially oxidized and oxidized forms. After treatment of a mixture of equal molar quantities of the reduced form (DPPD) and the oxidized form (QDIM) with acid, the following reaction was observed: DPPD(I)+QDIM(III)+2H⁺=2DPPD⁺(II) After similar treatment of the partially oxidized form (V) with acid, the radical cation salt formed. The UV and visible spectra of polyaniline in the reduced form, oxidized form and conductive form are similar to the spectra of DPPD, QDIM and DPPD⁺ or radical cation salt of V respectively. We propose that the polyaniline synthesized by chemical oxidation of aniline consists of oxidized and reduced repeat units. Upon protonation a redox reaction (or electron rearrangement) occurs and forms delocalized radical cations (polarons) in the polymer chain which are highly conductive.     

Kinetics and Mechanism of Cetyltrimethylammonium Bromide Catalyzed N-Bromosuccinimide Oxidation of D-Mannose in Acidic Medium

The kinetics and mechanism of N-bromosuccinimide (NBS) oxidation of D-mannose in the absence and presence of cetyltrimethylammonium bromide (CTAB) in acidic media have been studied under the condition [D-mannose]_T ? [NBS]_T at 40°C. Under the kinetic conditions, both the slower uncatalyzed and faster catalyzed paths go on. Both the paths show the fractional and first order dependence on [D-mannose] and [NBS]_T, respectively. The rate decreased with increase in acidity. Neither succinimide (NHS) nor Hg(II) influenced the reaction rate. Activation parameters of the reactions were determined by studying the reaction at different temperatures (30–50°C). The influence of salts on the reaction rate was also studied. CTAB accelerates the reactions and the observed effects have been explained by considering the hydrophobic and electrostatic interaction between the surfactants and reactants. In the reaction, approximately 1 mole of NBS oxidized one mole of D-mannose. A reaction scheme of the oxidation of D-mannose by NBS was found to be in consistent with the rate law and the reaction stoichiometry.     

Ozonocatalytic decomposition of glyoxal and glyoxylic and formic acids in the presence of iron(III) ions

Rate constants of reactions of ozone with glyoxal, glyoxylic and formic acid in aqueous solutions at pH 1.5 were determined. It was shown that iron(III) in the form of ions accelerates oxidation of glyoxal and glyoxylic acid, but does not influence reaction between ozone and formic acid. It was established that the catalyst acts effectively if its concentration is comparable to the concentration of the oxidized substrate, the optimal stoichiometric ratio (Fe³⁺/substrate) being close to 1/3. The catalytic reaction mechanism was studied using a competitive chelate ligand, oxalic acid. We concluded that the catalytic activity of iron(III) in the investigated reaction was due to its ability to form chelate complexes in which the substrate was more easily oxidized by molecular ozone.     

Pulse radiolysis studies of the reactions of CO3*- and NO2* with nitrosyl(II)myoglobin and nitrosyl(II)hemoglobin

The reactions of carbonate radical anion [CO3*-, systematic name: trioxidocarbonate*1-] with nitrosyl(II)hemoglobin (HbFe(II)NO) and nitrosyl(II)myoglobin (MbFe(II)NO) were studied by pulse radiolysis in N2O-saturated 0.25 M sodium bicarbonate solutions at pH 10.0 and room temperature. The reactions proceed in two steps: outer-sphere oxidation of the nitrosyliron(II) proteins to their corresponding nitrosyliron(III) forms and subsequent dissociation of NO*. The second-order rate constants measured for the first reaction steps were (4.3 +/- 0.2) x 10(8) and (1.5 +/- 0.3) x 10(8) M(-1) s(-1), for MbFe(II)NO and HbFe(II)NO, respectively. The reactions between nitrogen dioxide and MbFe(II)NO or HbFe(II)NO were studied by pulse radiolysis in N2O-saturated 0.1 M phosphate buffer pH 7.4 containing 5 mM nitrite. Also for the reactions of this oxidant with the nitrosyliron(II) forms of Mb and Hb a two-step reaction was observed: oxidation of the iron was followed by dissociation of NO*. The second-order rate constants measured for the first reaction steps were (2.9 +/- 0.3) x 10(7) and (1.8 +/- 0.3) x 10(7) M(-1) s(-1), for MbFe(II)NO and HbFe(II)NO, respectively. Both radicals appear to be able to oxidize the iron(II) centers of the proteins directly. Only for the reactions with HbFe(II)NO it cannot be excluded that, in a parallel reaction, CO3*- and NO2* first react with amino acid(s) of the globin, which then oxidize the nitrosyliron(II) center.     

Kinetics and mechanism of oxidation reactions of porphyrin-iron(IV)-oxo intermediates

The kinetics of the reactions of three porphyrin-iron(IV)-oxo derivatives with alkenes and benzylic alcohols were measured. The iron-oxo systems studied were 5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin-iron(IV)-oxo (2a), 5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrin-iron(IV)-oxo (2b), and 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin-iron(IV)-oxo (2c). Species 2 were stable for hours at room temperature as dilute solutions in acetonitrile and reacted hundreds to thousands of times faster in the presence of high concentrations of substrates. Typical second-order rate constants determined from pseudo-first-order kinetic studies are 1-2 x 10(-2) M(-1) s(-1) for reactions with styrene and 3 x 10(-2) M(-1) s(-1) for reactions with benzyl alcohol. The reactivity order for the iron-oxo species was 2a > 2b > 2c, which is inverted from that expected on the basis of the electron demand of the porphyrin macrocycles, and the oxidation reaction was suppressed when excess porphyrin-iron(III) complex was added to reaction mixtures. These observations indicate that the reactions involve disproportionation of the iron(IV)-oxo species 2 to give an iron(III) species and a more highly oxidized iron species, presumed to be an iron(IV)-oxo porphyrin radical cation, that is the true oxidant in the reactions. Analyses of the kinetics of oxidations of a series of para-substituted benzylic alcohols with Hammett sigma+ -substituent constants and with a dual-parameter method developed by Jiang (Jiang, X. K. Acc. Chem. Res. 1997, 30, 283) indicated that considerable positive charge developed on the benzylic carbons in the oxidation reactions, as expected for electrophilic oxidants, and also that substantial radical character developed on the benzyl carbon in the transition states.     

Spectrophotometric determination of trace iron by using its catalytic effect on the N-phenylanthranilic acid-potassium periodate reaction.

The analytical features of the reaction between N-phenylanthranilic acid (PAA) and potassium periodate in acidic medium are explored with the aim of improving the catalytic kinetic determination of iron in water samples. In the presence of Fe(II, III), PAA is oxidized by potassium periodate in a formic acid medium to form a violet-colored compound. The reaction is followed spectrophotometrically by measuring the increase in the absorbance of the oxidation product at 525 nm. The variables that affected the reaction rate were investigated and the reaction conditions were established. Calibration graphs are linear in the range of concentrations 2 - 500 ng mL(-1). As low as 10(-8) mol L(-1) Fe(II, III) can be easily determined by the fixed time method. The established catalytic method was successfully applied to the determination of iron in tap water and in pharmaceutical samples.     

Redox-Initiated Grafting of Acrylic Monomers onto Poly(vinyl Alcohol)

Loss of capacity of magnetic micro ion-exchange resins has been suggested to be caused by cleavage of unstable linkages formed during the graft polymerization reaction. The nature of the grafting process was investigated by using a series of model compounds having the same structural features as the glutaraldehyde-crosslinked poly(vinyl alcohol) core matrix. These compounds were then subjected to hydrogen peroxide oxidation, followed by the addition of monomer in the presence of iron(II). The identity and extent of peroxidation of the intermediate compounds was determined. In each of the peroxidation reactions the tertiary acetal hydrogen was oxidized to a hydroperoxy derivative. Some of these derivatives were able to dimerize to form peroxy compounds. The reactions occurred rapidly at room temperature when an acetal compound was shaken with hydrogen peroxide. Good yields could be obtained by precipitation of the sodium salts of the hydroperoxides. The hydroperoxy derivatives were shown to initiate polymerization of methyl acrylate, acrylic acid, and acrylamide when in the presence of iron(II).