The electrochemistry of ubiquinone-10 in a phospholipid model membrane

The electrochemistry of ubiquinone-10, UQ, incorporated over a phospholipid layer adsorbed on a mercury drop electrode has been investigated over a wide pH range. It is shown that the position of the quinone headgroup in relation to the lipid determines the reversibility of the redox chemistry. For pH <7, the reaction follows a disproportionation route involving the ubiquione radical. There is evidence for the presence of a parallel reaction sequence. The bifurcation point appears to occur for the UQ molecule, which disproportionates after protonation and reduction, in parallel with direct electron transfer to yield the UQ--radical anion. The incorporation of UQ in a lipid monolayer makes its reduction very irreversible for pH > 7.     

The electrochemical reduction of maleimide: The synthesis of succinimide

The electrochemical reduction of maleimide has been investigated in the pH range 0–14 at a variety of electrode materials. The reaction scheme was found to fall into three distinct sections, depending upon the pH at which the reduction was performed. At low pH the reduction product was found to be succinimide, and the mechanism of its formation is described. At higher pH values, the hydrolysis of starting materials complicates the interpretation of the electrochemical measurements, but nevertheless the overalls reduction mechanism could be deduced. Polarographic data complement information obtained from rotating disc experiments, and comparison is made with the electrochemical reduction of phthalimide.     

Oxygen reduction on polycobaltprotoporphyrin film: II. pH effect and the mechanism of oxygen reduction

The oxygen reduction kinetics on polycobaltprotoporphyrin (PCoPP) film has been examined with the rotating disc electrode technique in O₂-saturated solution of various pH. PCoPP film promotes the oxygen reduction process via two electrons to produce peroxide over wide pH range. When pH value of solution decreases, catalytic activity of PCoPP film increases. Possible catalytic mechanisms have been proposed for oxygen reduction.     

The formation of the primary hydrogen peroxide compound (compound I) of Pseudomonas cytochrome c peroxidase as a function of pH

The effect of pH on the stability and overall catalytic activity of half-reduced Pseudomonas cytochrome c peroxidase was studied over the pH range 3.5-8. The stability of the enzyme as deduced from 40 s incubation experiments is virtually unaffected by pH. However, there is a bell-shaped pH dependence for the overall catalytic reaction using H2O2 as oxidizing substrate and cytochrome c-551 as reducing substrate with maximum turnover rate of pH 6. The effects of pH on (1) rate of reduction of the totally ferric enzyme by reduced azurin over the pH range 3.5-8 and (2) the rate of compound I formation from the half-reduced enzyme and hydrogen peroxide over the pH range 4-8 were also investigated. The reduction reaction rate also appears bell-shaped with optimum rate at pH 5.6. The rate of compound I formation is virtually pH independent above pH 5 but drops dramatically as the pH is lowered from 5 to 4. The influence of an ionization with apparent pKa value of 4.4 is implicated in compound I formation. This enzyme acid group must be deprotonated for compound I formation to occur suggesting the importance of base catalysis.     

pH effect on electrocatalytic reduction of CO2 over Pd and Pt nanoparticles

Adsorbed hydrogen participates in electrocatalytic reduction of CO₂ and competitive hydrogen evolution reaction (HER) simultaneously, and its reaction pathway greatly affects the activity and selectivity of CO₂ reduction. In this work, we investigate pH effect on electrocatalytic reduction of CO₂ over Pd and Pt nanoparticles (NPs) with a similar size in a pH range from 1.5 to 4.2. Pt NPs completely contribute to HER in the pH range. Over Pd NPs, Faradaic efficiency for CO production at − 1.19 V (vs. reversible hydrogen electrode) varies from 3.2% at pH of 1.5 to 93.2% at pH of 4.2, and current density for CO production reaches maximum at pH of 2.2. The significant enhancement of Faradaic efficiency and current density for CO production over Pd NPs at high pH values is attributed to decreased kinetics of hydrogen evolution reaction by increasing hydrogen binding energy and lowered adsorption affinity of CO-like intermediate compared to Pt.     

Some aspects of the winkler determination of oxygen in water

The reactions in the Winkler determination of oxygen have been examined with a rotating platinum electrode and a recording polarograph. In this manner the extent of the reaction has been determined over the pH range 7-10; at a pH of 7 only about 5% of the dissolved oxygen reacts; at a pH of 9 or above the reaction is essentially quantitative. The reaction of dissolved oxygen with manganese(II) is quite rapid. The sluggish response of the polarograph recorder prevented an accurate determination of the rate, but the reaction half-times were about 2 sec or less over the pH range used.     

Catalytic Oxidation of Furan and Hydrofuran Compounds. 8. Conversions of 2(5H)-Furanone by Hydrogen Peroxide in Media of Various pH

The reaction of 2(5H)-furanone with aqueous hydrogen peroxide in media of pH within the range 1-8 have been studied in the absence of catalysts for the first time. It was discovered that at pH 3 to 8 2(5H)-furanone was almost quantitatively converted into succinic acid and reduction of the acidity of the medium facilitates the reaction. A possible scheme is considered for the conversions of 2(5H)-furanone under the reaction conditions.     

Polarographic investigation of syn-phenyl 2-pyridyl ketone oxime

The polarographic reduction of syn-phenyl 2-pyridyl ketone oxime to -(2-pyridyl)benzylamine over the pH range 0.78–12.88 is reported. Two waves are observed, both of which are pH-dependent. The complex electrode reaction is discussed and a mechanism advanced to describe the reduction of the oxime group over the pH range considered.     

Electrochemical and kinetic study of the coupling reaction between 4-nitroso and 4-hydroxylaminopyridine-1-oxide

The study of the reduction process of nitrosopyridine-1-oxide at platinum electrodes in aqueous solution by controlled potential coulometry is reported. The results obtained are consistent with the hypothesis that a pH dependent reaction takes place between the depolarizer and the reduction product. Such results have been confirmed by conventional kinetic experiments. The pH dependence of the rate constant can be accounted for in terms of a base catalyzed mechanism.     

Kinetics and mechanism of oxygen electroreduction on Vulcan XC72R carbon black modified by pyrolysis products of cobalt 5,10,15,20-tetrakis(4-methoxyphenyl)porphyrine in a broad pH interval

The kinetic parameters of oxygen reduction reaction on Vulcan XC72R carbon black, carbon black modified by pyrolysis products of cobalt 5,10,15,20-tetrakis(4-methoxyphenyl)porphyrine named by MXC72R, and commercial Pt/C platinum catalyst have been considered. Comparison of their electrochemical properties including pH influence in a broad interval from 0.3 to 14.6 has shown platinum-similar behavior of MXC72R in the reaction under study. An increasing order of electrochemical activity for oxygen reduction reaction is obtained, namely XC72R?<?MXC72R?<?Pt/C. The mechanism of oxygen reduction reaction is discussed emphasizing the important accelerating role of protonation of adsorbed oxygen molecule and inhibiting role of oxygen-containing species (formed due to water molecule discharge) and strongly adsorbed foreign species. The importance of the research on oxygen reduction reaction in a broad pH interval to evaluate the efficiency of various precious metal-free catalytic systems in comparison to platinum is emphasized.     

桑色素极谱行为的研究

研究了桑色素在pH=1～14的水溶液中的极谱行为. 于不同pH范翻内得列了四个还原波. 研究证实在pH<4条件下获得的P_1波为表面催化氢波. 其余三个波为不同形态桑色素的单电子吸附还原波, 并伴有随后化学反应过程. 测得在单分子层饱和吸附条件下, 每一个桑色素分子所占汞电极面积为1.36 nm.     

抗癌新药染料木素的电化学行为及其应用研究

研究了新型抗癌药物染料木素在pH=1～12水溶液中的极谱行为。在不同pH范围内得到了染料木素的四个还原波。研究证实在ph＜5的条件下所获得的P1波及5＜pH＜10介质中获得的P2波为染料木素中性分子的两电子,单质子及其电离形成一价阴离子的两电子,单质子不可逆吸附还原波。在pH＜6的条件下所获得的P3波属于染料木素解离形成阴离子的不可逆强吸附前波,而P4波则属于染料木素在碱性介质中解离形成高价阴离子的不可逆吸附还原波。此外通过邻苯三酚自氧化产生活性氧自由基的再还原,对染料木素清除活性氧自由基的能力进行了研究,从电化学的角度对其药理机制进行了阐述。     

甲酸存在下硝酸根在二氧化钛表面光催化还原成氨

用甲酸作空穴清除剂,研究了ＴｉＯ２水悬浮体系中硝酸根光催化还原氨的反应。与草酸作空穴清除剂相比,甲酸加速硝酸根的还原更显著。研究了硝酸根和甲酸根的浓度效应及ｐＨ效应。实验结果表明,硝酸根在ＴｉＯ２表面的吸附是加附是加速该光催化还原反应的重要因素。     

Interference in the kinetic determination of ascorbic acid by sulphide and sulphite

The reduction of 2,6-dichlorophenolindophenol (DCPI) by sulphides and sulphites has been studied kinetically by the stopped-flow technique. The reaction is first-order with respect to each of the reactants. From the distribution diagrams for the species DH(+)(2), DH and D(-) for DCPI and H(2)Q, HQ(-) and Q(2-) for sulphides or sulphites, a mechanism is proposed which suggests partial reactions of all possible combinations of the reacting species at any pH. An equation for calculation of the second-order reaction rate constants k at any pH is derived, which gives k as a function of [H(+)], the partial reaction rate constants and the dissociation constants of DCPI and H(2)S or H(2)SO(3). Values of the overall reaction rate constants over a wide pH-range have been determined, together with values of k for all possible partial reactions. For particular pH-values the second-order reaction rate constant was determined by four different methods. Mean values of k = 251 +/- 1 and 240 +/- 1 l.mole(-1).sec(-1) were obtained for pH 3.15 and 4.17, respectively, for the DCPI-Na(2)S reaction and k = 137 +/- 1, 127 +/- 1 and 136 +/- 1 l.mole(-1).sec(-1) for pH 2.02, 4.25 and 5.10, respectively, for the DCPI-Na(2)SO(3) reaction. From the slopes of the linear Arrhenius plots activation energies of 6.6 +/- 0.2 and 4.0 +/- 0.1 kcal/mole for the DCPI-Na(2)S and DCPI-Na(2)SO(3) reactions, respectively were calculated. The effect of ionic strength on the reactions supports the proposed mechanism.     

Photochemical reduction of cytochrome c by a 1,4,5,8-naphthalenediimide radical anion

Steady-state UV irradiation of aqueous solutions containing cytochrome c (cyt c) and N,N'-bis(2-phosphonoethyl)-1,4,5,8-naphthalenediimide (BPNDI), a water-soluble aromatic imide, resulted in the reduction of the heme iron from the Fe(III) to the Fe(II) oxidation state. The reaction kinetics were followed by the increase of the ferrocytochrome c absorbance band at 549 nm. The rate of the photochemical reaction was pH dependent, reaching its maximum values over the pH range 4-7. Addition of electrolyte (NaCl) at pH 5 resulted in a decrease in the reaction rate, as expected for reactions between oppositely charged species. Flash photolysis studies revealed that the actual reductant in the reaction was a photogenerated BPNDI radical anion, which transferred an electron to the cyt c heme iron. The participation of imide radicals in the process was confirmed by the ready reduction of cyt c by BPNDI radicals chemically generated with sodium dithionite.     

Aqueous Electrochemistry of Anthraquinone and Its Correlation with the Dissolved States of a Cationic Surfactant

Cyclic voltammetry was employed to study the electrochemical behavior of anthraquinone (AQ) in aqueous solution at a glassy carbon electrode using the sodium salt of anthraquinone-2-sulphonic acid (AQS). The cyclic voltammograms show a reduction wave and a corresponding oxidation wave. The electrochemical reaction of AQ in aqueous solution involves a two electron transfer process followed by a coupled chemical reaction and exhibits strong pH dependence at low pH (<4). A satellite peak is also observed at the cathodic side of the reduction wave for the reduction of the sulfonate group of AQS. The electrochemical investigation was also carried out in the presence of a cationic surfactant, cetyltrimethylammonium bromide (CTAB). Similar redox behavior can be observed for the electrochemical reaction of AQS in the presence of CTAB solutions similar to the aqueous media. The electrochemical responses have been found to depend on the dissolved states of the surfactant. The current-potential behavior of AQS depends on the concentration of CTAB and micellization has a profound effect on the electrochemical behavior of AQ.     

Use of the dichromate solution as a dosimeter for high dose and high dose rate

The radiolytic reduction of Cr(VI) in N₂O-saturated aqueous solutions has been investigated over a large range of pH by steady state radiolysis. At pH 3 in the presence of formate as scavenger for ·OH, G(−Cr(VI)) is higher than the expected yield and a strong dose rate effect is observed. The solution cannot be used for dosimetry at this pH. The proposed mechanism to explain the enhanced response and the dose rate dependence involves the reduction of the unstable radiolytically produced Cr(IV) by HCO₂⁻. At pH 9.2 the reaction between Cr(IV) and formate is absent and no dose rate effect was observed up to 70 kGy min⁻¹, which makes this system particularly attractive as a dosimeter in the 0.1–10 kGy dose range. Radiation chemical aspects relating to the use of this system as a high-dose and high-dose rate chemical dosimeter are discussed.     

Reduction of Methylene Green by EDTA:Kinetic and Thermodynamic Aspects

The reduction of methylene green (MG) into protonated leuco dye with ethylenediamine tetraacetic acid (EDTA) in aqueous alkaline medium was studied spectrophotometrically at λ_max 660 nm. EDTA behaved as an effective electron donor during the reduction of MG in an aerobic condition. Consumption of EDTA in the reduction of MG means that it is oxidized. This is an unexpected result since EDTA does not normally function as a reducing agent. The nitrogen-containing chelating agents with secondary or tertiary nitrogen behaved as an electron donor in photochemical reaction of dye. The rate of reduction depends upon pH in the same way as the base titration of EDTA. Effects of salt and temperature have been investigated for the reduction process. The salting agent KNO₃ has been found to uniquely enhance the rate of reduction of MG by EDTA in the aerobic condition. Detailed kinetic and thermodynamic aspects have been discussed to realize the interaction between MG and EDTA. Kinetic studies revealed that reaction was sensitive and regeneration of oxidized form of the dye was observed. Reversible first order reaction kinetics with respect to EDTA, MG and NaOH was found.     

Green Synthesis of Silver Nanoparticles Using Ionic Liquid and Application for the Detection of Dissolved Oxygen

The electrochemical synthesis of silver nanoparticles (nano‐Ag) has been successfully carried out on glassy carbon electrode (GCE) and indium tin oxide electrode (ITO) using 1‐butyl‐3‐methylimidazolium tetrafluoroborate (BMT) as green electrolytes. Further the electrodeposited nano‐Ag modified ITO electrode has been examined using atomic force microscopy (AFM), and X‐ray diffraction studies (XRD). The electrodeposited Ag nanoparticles on ITO were found in the size range of 5 to 35 nm. The nano‐Ag film modified GCE was further coated with nafion (Nf) and BMT (1 : 1 ratio) mixture and found to be stable in BMT and in pH 7 phosphate buffer solution (PBS). The nano‐Ag/BMT‐Nf film modified GCE successfully applied for the oxygen reduction reaction in neutral pH (pH 7.0 PBS). The proposed film modified GCE successfully reduces the over potential and show well defined reduction peaks for the detection of dissolved oxygen using cyclic voltammetry (CV) and rotating disc voltammetry (RDE). The film also applied for the detection of dissolved oxygen using electrochemical impedance spectroscopic studies (EIS).     

Reduction of dicarbonyl compounds on the dme: Part VII. Electrochemical behaviour of glyoxal

Polagraphic and kinetic studies of both the first and the second reduction waves of glyoxal have been carried out in aqueous solutions in the pH range 0 – 11.Tafel slopes and reaction orders with respect to glyoxal, H⁺ ion and proton donors present in solutions have been obtained at potentials corresponding to the foot of the waves. Reactions mechanisms are proposed for this potential zone.The proposed mechanism accounts both for our experimental data and for those previously reported in the literature.