Contribution of the ligand to the electroreduction of CO2 catalyzed by a cobalt(II) macrocyclic complex

The electrochemical reduction of carbon dioxide using hexa-aza-macrocycles derived from the condensation of 1,10-phenanthroline and its Co(II) complex as an electrocatalyst dissolved in dimethylformamide has been studied by cyclic voltammetry and UV-visible spectroscopy. The ligand does not show catalytic activity and only generates hydrogen when it is reduced under carbon dioxide. The cobalt complex shows electrocatalytic activity toward the reduction of carbon dioxide, generating carbon monoxide and formic acid. Cyclic voltammetry and UV-visible spectroscopy show that the active site for the reduction is the metal center in oxidation state (I), although the reduced cobalt center alone is not enough to promote reduction of the carbon dioxide. Electrolysis at controlled potential shows that only at potentials corresponding to reduction of the ligand (second reduction) does carbon dioxide reduction occur. Cobalt(I) probably reacts with CO₂ forming a non-isolated intermediate which, when reduced, gives CO and formic acid. The second reduction that takes place on the ligand regenerates the catalyst and gives products, thus becoming the rate-determining step of the reaction.     

THE USE OF TETRAZOLIUM SALTS TO DETERMINE SITES OF DAMAGE TO THE MITOCHONDRIAL ELECTRON TRANSPORT CHAIN IN INTACT CELLS FOLLOWING in vitro: PHOTODYNAMIC THERAPY WITH PHOTOFRIN II

Abstract: A method is described utilizing the tetrazolium salts neotetrazolium chloride (NTC), triphenyltetrazolium chloride (TTC), C, N -diphenyl- N' -4,5-dimethylthiazol-2-yrtetrazolium bromide (MTT) and various substrates to elucidate damage to the mitochondrial electron transport chain of intact cells following in vitro photodynamic therapy (PDT). Using this methodology, a portion of the dark toxicity manifested by Photofrin II (PII) was found to occur prior to entry of electrons into the transport chain through Complex I, as evidenced by the fact that the inhibition of MTT reduction was reversible by the addition of malic acid to the culture media. A second site of dark toxicity was found to be Complex IV (cytochrome oxidase). After photoirradiation of the cells, Complex I was found to be affected since malic acid could no longer reverse the inhibition of MTT reduction but it could be reversed by the addition of succinic acid, whose electrons enter the transport chain at Complex II. A second and more sensitive site of photoirradiation damage was found to be Complex IV. A region near cytochrome C was also affected by photoirradiation but appreciably less so than noted for Complexes I and IV. A kinetic analysis of MTT and TTC reduction following photoirradiation indicated that MTT reduction was sustained at a normal rate for 1 h after which it slowed down and eventually plateaued. In contrast, TTC reduction was found to be inhibited almost immediately indicating Complex IV is extremely susceptible to photoirradiation damage. Compared to other assays of mitochondrial function requiring subcellular fractionation, the use of tetrazolium salts is simpler to perform and can be done using physiologically relevant conditions.     

THE USE OF TETRAZOLIUM SALTS TO DETERMINE SITES OF DAMAGE TO THE MITOCHONDRIAL ELECTRON TRANSPORT CHAIN IN INTACT CELLS FOLLOWING in vitro PHOTODYNAMIC THERAPY WITH PHOTOFRIN II

Abstract A method is described utilizing the tetrazolium salts neotetrazolium chloride (NTC), triphenyltetrazolium chloride (TTC), C,N-diphenyl-N'-4,5-dimethylthiazol-2-yltetrazolium bromide (MTT) and various substrates to elucidate damage to the mitochondrial electron transport chain of intact cells following in vitro photodynamic therapy (PDT). Using this methodology, a portion of the dark toxicity manifested by Photofrin II (PII) was found to occur prior to entry of electrons into the transport chain through Complex I, as evidenced by the fact that the inhibition of MTT reduction was reversible by the addition of malic acid to the culture media. A second site of dark toxicity was found to be Complex IV (cytochrome oxidase). After photoirradiation of the cells, Complex I was found to be affected since malic acid could no longer reverse the inhibition of MTT reduction but it could be reversed by the addition of succinic acid, whose electrons enter the transport chain at Complex II. A second and more sensitive site of photoirradiation damage was found to be Complex IV. A region near cytochrome C was also affected by photoirradiation but appreciably less so than noted for Complexes I and IV. A kinetic analysis of MTT and TTC reduction following photoirradiation indicated that MTT reduction was sustained at a normal rate for 1 h after which it slowed down and eventually plateaued. In contrast, TTC reduction was found to be inhibited almost immediately indicating Complex IV is extremely susceptible to photoirradiation damage. Compared to other assays of mitochondrial function requiring subcellular fractionation, the use of tetrazolium salts is simpler to perform and can be done using physiologically relevant conditions.     

Electrochemical insights into the mechanisms of proton reduction by [Fe2(CO)6{micro-SCH2N(R)CH2S}] complexes related to the [2Fe](H) subsite of [FeFe]hydrogenase

Electrochemical investigations on a structural analogue of the [2Fe](H) subsite of [FeFe]H(2)ases, namely, [Fe(2)(CO)(6){micro-SCH(2)N(CH(2)CH(2)- OCH(3))CH(2)S}] (1), were conducted in MeCN/NBu(4)PF(6) in the presence of HBF(4)/Et(2)O or HOTs. Two different catalytic proton reduction processes operate, depending on the strength and the concentration of the acid used. The first process, which takes place around -1.2 V for both HBF(4)/Et(2)O and HOTs, is limited by the slow release of H(2) from the product of the {2 H(+)/2 e} pathway, 1-2H. The second catalytic process, which occurs at higher acid concentrations, takes place at different potentials depending on the acid present. We propose that this second mechanism is initiated by protonation of 1-2H when HBF(4)/Et(2)O is used, whereas the reduction of 1-2H is the initial step in the presence of the weaker acid HOTs. The potential of the second process, which occurs around -1.4 V (reduction potential of 1-3H(+)) or around -1.6 V (the reduction potential of 1-2H) is thus dependent on the strength of the available proton source.     

Differential pulse polarography in the alternating pulse mode

A polarographic two-drop pulse technique for trace analysis is described. By using a second pulse, in the opposite direction to the first one, on the second drop, a high current sensitivity is obtained, with a very flat background. The theoretical response for a reversible electrode process is presented together with experimental results for the reduction of Pb(2+) in hydrochloric acid medium. It is shown that without enrichment determination of lead at concentrations as low as 71nM is possible with this technique.     

Effect of moisture on copolymer fibers based on 5-amino-2-(p-aminophenyl)-benzimidazole

In recent years, there has been concern in the soft body armor community that copolymer fibers based on 5-amino-2-(p-aminophenyl)-benzimidazole can release hydrochloric acid, which is present in these fibers as a by-product of the manufacturing process. The presence of acids could potentially be detrimental to other fibers that might come in contact with these materials. In an effort to examine this issue, a study was designed to investigate the release of acid in different environments from these fibers. During the first phase of the study, fibers were exposed to water and pH decreases were observed. While immersed in deionized water, two of the fiber samples studied released a sufficient amount of acid to drop the pH of the solution from approximately pH 6.0 to approximately pH 3.0 in less than 10 d at room temperature. Further ion-selective electrode studies of chloride ion released from these fibers indicated that hydrochloric acid may not be the species responsible for this pH reduction. In a second phase of the investigation, fibers were exposed to water vapor in an elevated temperature environment (conditions were 65 °C, 80% RH). While the pH reduction released by the water vapor exposure was substantially less than observed in the submersion phase, a reduction in the yarn tensile strength of some of the fibers was observed during this phase of the study. In a third phase, fibers were exposed in a dry oven (less than 5% RH) at 65 °C. Almost no pH reduction or strength reduction was observed. Molecular spectroscopy was also performed to better understand the effect of elevated temperature and moisture environments on these fibers.     

Electrochemical reduction of the 4,4′-azobis-benzaldehyde and its bis-methylacetal in methanol at a mercury cathode

The electrochemical behaviour of the 4,4′-azobis-benzaldehyde and its bis-methylacetal in methanol solutions, is studied by d.c. polarography, controlled-potential coulometry, and cyclic voltammetry. The polarographic reduction of the 4,4′-azobis-benzaldehyde involves a two-electron and a four-electron wave, corresponding to the reduction of the azo group and the two aldehydic groups, respectively. The addition of HCl in small concentrations, results in the decrease with time of the second wave due to the acetalization of the two aldehydic groups occurring in bulk. The polarographic curves of the 4,4′-azobis-benzaldehyde-bis-methylacetal in methanol, in excess of any strong acid, show a second reduction wave corresponding to the further reduction of the hydrazo compound formed in the first step. This further reduction proceeds via an intermediate step, consisting in the protonation of the hydrazo group, which exhibits an electrosorption current peak in the corresponding cyclic voltammogram.     

2—氨基—9,10—蒽醌及其衍生物的光谱电化学研究

用循环伏安法研究了２－氨基－９，１０－蒽醌及其衍生物在ＤＭＦ－０．１ｍｏｌ／ＬＴＢＡＰ溶液中的电化学行为，结果表明它们在铂电极上均发生两步连续的单电子还原过程，取代基Ｒ及水和苯甲酸等质子性试剂的加对伏安曲线有很大的影响。     

Stereoselective synthesis of a potent thrombin inhibitor by a novel P2-P3 lactone ring opening

The concise synthesis of a potent thrombin inhibitor was accomplished by a mild lactone aminolysis between an orthogonally protected bis-benzylic amine and a diastereomerically pure lactone. The lactone was synthesized by the condensation of l-proline methyl ester with an enantiomerically pure hydroxy acid, which in turn was synthesized by a highly stereoselective (>500:1 er) and productive (100,000:1, S/C) enzymatic reduction of an alpha-ketoester. In addition, a second route to the enantiomerically pure lactone was accomplished by a diastereoselective ketoamide reduction.     

Electrochemical reduction of pyrethroid insecticides based on esters of α-cyano-3-phenoxybenzyl alcohol at glassy carbon and mercury electrodes in acetonitrile

The electrochemical reduction of eight commercially important pyrethroid insecticides which are esters of either α-cyano-3-phenoxybenzyl alcohol (cycloprothrin, cyphenothrin, cyhalothrin, deltamethrin, esfenvalerate and cypermethrin) or 4-fluro-α-cyano-3-phenoxybenzyl alcohol (cyfluthrin and flumethrin) has been studied under conditions of voltammetry and bulk electrolysis at both glassy carbon and mercury electrodes in acetonitrile. In general, the peak potential of the initial reduction process observed at very negative potentials at both electrode surfaces shifts to a more positive value under conditions of consecutive potential cycling. At the hanging mercury drop electrode the reduction occurs at even more negative potentials than at a glassy carbon electrode because a blocking mechanism appears to be operative. Despite this major difference in the primary reduction step, common voltammetric features are observed at less negative potentials on second and subsequent cycles of the electrode potential at either electrode surface. For example, the initial reduction process always results in the formation of a species which is reversibly reduced at less negative applied potentials. Furthermore, despite the definition of the voltammetric response being highly sensitive to the individual pyrethroid structure, long time-scale bulk electrolysis experiments at glassy carbon or mercury pool electrodes led to the formation of analogous final products. The fact that pyrethroids with a widely varying range of acid moieties exhibit similar voltammetric behaviour suggests that the acid moiety is not directly involved in the initial electron transfer process. Controlled potential electrolysis studies at both electrode surfaces coupled with HPLC and mass spectral identification of products obtained after ethylation with ethyl iodide showed that the reduction mechanism on the longer time-scale involves cleavage of the ester with liberation of free cyanide ion. The major reduction product identified was the anion of either 3-phenoxybenzoic acid or 4-fluoro-3-phenoxybenzoic acid in yields ranging from 31 to 66%.     

Is the protein surrounding the active site critical for hydrogen peroxide reduction by selenoprotein glutathione peroxidase? An ONIOM study

In this ONIOM(QM:MM) study, we evaluate the role of the protein surroundings in the mechanism of H2O2 reduction catalyzed by the glutathione peroxidase enzyme, using the whole monomer (3113 atoms in 196 amino acid residues) as a model. A new optimization scheme that allows the full optimization of transition states for large systems has been utilized. It was found that in the presence of the surrounding protein the optimized active site structure bears a closer resemblance to the one in the X-ray structure than that without the surrounding protein. H2O2 reduction occurs through a two-step mechanism. In the first step, the selenolate anion (E-Se(-)) formation occurs with a barrier of 16.4 kcal/mol and is endothermic by 12.0 kcal/mol. The Gln83 residue plays the key role of the proton abstractor, which is in line with the experimental suggestion. In the second step, the O-O bond is cleaved, and selenenic acid (R-Se-OH) and a water molecule are formed. The calculated barrier for this process is 6.0 kcal/mol, and it is exothermic by 80.9 kcal/mol. The overall barrier of 18.0 kcal/mol for H2O2 reduction is in reasonable agreement with the experimentally measured barrier of 14.9 kcal/mol. The protein surroundings has been calculated to exert a net effect of only 0.70 kcal/mol (in comparison to the "active site only" model including solvent effects) on the overall barrier, which is most likely due to the active site being located at the enzyme surface.     

Ion Implantation in Semiconductors: Science and Technology,S. Namba (Ed.), Plenum Press,New York (1975)

A study has been made of the polarographic behaviour of 4-thiouracil and its N-methylated derivatives, and of 4-thiouridine. Similar electrochemical properties are exhibited by all the compounds with a 2-keto-4-thione structure. In acid medium they give a typical catalytic hydrogen discharge wave, which disappears completely at pH values above 6. At pH values above 4.2 a second catalytic wave appears. Maximal catalytic activity is exhibited at pH 7.1, and decreases with increasing pH. Both catalytic waves possess pronounced surface characteristics, most likely due to adsorption of the molecules with differing orientations on the electrode surface. The second catalytic wave overlaps the reduction wave, which is placed in evidence under conditions where the catalytic effect is absent. The reduction wave is a 4e^?/4H⁺ process involving reduction of the 4-thiouracil ring to 5,6-dihydropyrimidone-2. The same product is formed by a 2e^?/2H⁺ reduction of 5,6-dihydro-4-thiouracil. The potential applications of the electrochemical properties of 4-thiouracil to studies on tRNA structure are discussed.     

A STUDY OF THE SAFRANINE-ASCORBIC ACID PHOTOCHEMICAL REDOX REACTION

Abstract— Flash-photolysis of safranine in deoxygenated 5 per cent aqueous pyridine produces a transient bleaching, which disappears by a second order process. Very probably this transient species consists of a pair of radicals or radical ions and not of the safranine in the triplet state. These radicals are also produced in chlorophyll sensitized reactions. Present results combined with previous work by us[I] indicate that the chlorophyll sensitization of safranine bleaching involves the formation of these radicals.
The direct photochemical reduction of safranine to its leuco form occurs through the intermediate formation of the radicals. The appearance and disappearance of these radicals is fast compared to the role of photochemical formation and thermal disappearance of leuco safranine. Ascorbic acid influences but is not essential to the photo-bleaching of safranine in 5 per cent aqueous pyridine. An increase in ascorbic acid concentration increases the steady-state yield of the radicals but decreases the steady-state yield of the leuco safranine. In the absence of ascorbic acid or other added substance, safranine photobleaches irreversibly in deoxygenated 5 per cent aqueous pyridine. A plausible mechanism is proposed in explanation of the direct photochemical reduction of safranine.     

Polarographic Studies of Dithiodiacetic Acid and the Uranyl-Dithiodiacetic Acid Complex

The polarographic behaviour of dithiodiacetic acid and that of U(VI) in a solution containing dithiodiacetic acid as complexing agent have been investigated. For the dithiodiacetic acid system, two waves appear over the pH range studied. The prewave is kinetic in nature and the mainwave is diffusion-controlled. However, as U(VI) is added into the dithiodiacetic acid system, the polarogram changes due to the existence of a complex. The current-potential curve of the first wave is not the normal S shape. This is due to the superposition of the first wave of the ligand and the wave due to the reduction of the U(VI) in the complex to U(V). The second wave is due to the reduction of the complex The first wave is an adsorption-controlled current and the second wave is partly diffusion-controlled and partly adsorption-controlled. We propose an electrode reaction mechanism for both systems and the complex species. The dissociation constant of the complex HASSAUO⁺₂ is found to be of the order of 10^?4.     

Study of the electrochemical reduction of dioxygen in acetonitrile in the presence of weak acids

The electrochemical reduction of dioxygen has been studied in acetonitrile at glassy-carbon electrodes. The initial step is the reversible one-electron reduction to form superoxide. In the presence of hydrogen-bond donors (water, methanol, 2-propanol), the superoxide forms a complex with the donor resulting in a positive shift in the potential that can be analyzed to obtain formation constants for these complexes. Stronger acids result in protonation of the superoxide followed by reduction to produce HO2-. In the absence of hydrogen-bond donors, the reduction of superoxide occurs at very negative potentials, and this second reduction peak is very much drawn-out along the potential axis, indicating a small value of the transfer coefficient, alpha. The addition of hydrogen-bond donors, HA, brings about a positive shift in this peak, without a noticeable change in shape. The reaction occurring at the second peak is a concerted proton and electron transfer (CPET) in which the electron is transferred to superoxide and a proton is transferred from HA to the superoxide, forming HO2- and A- in a concerted process. An estimation of the standard potential for this reaction shows that the second reduction always occurs at a high driving force, which explains the small value of alpha that is observed. Consistent with a CPET, a kinetic isotope effect, HA versus DA, was detected for the three hydrogen-bond donors. The increasing positive shift of the second peak with increasing water concentration has been interpreted as being a consequence of the change in the formal potential, as water is both a reactant in the process and a participant through the hydrogen-bond stabilization of the anions.     

Improved Synthesis of 3-Nitrophenylacetic Acid

In the development of certain work in our laboratory, we needed large quantities of 3-nitrophenylacetic acid. This material is very expensive commercially. It therefore became necessary to find a convenient and efficient process since none of the reported procedures is suitable for a large scale preparation of 3-nitrophenylacetic acid. In the first synthesis reported by Frederick et al.¹, 3-nitrobenzyl chloride was converted to 3-nitrophenylaceto-nitrile which was hydrolyzed to 3-nitrophenylacetic acid in 38% yield. The utility of this method for making large quantities of 3-nitrophenylacetic acid is restricted by the high cost of 3-nitrobenzyl halides. The second 2 method published by Jennings² is a multistep process starting with 3-nitrobenzaldehyde and the reported overall yield is 31%. This method also is not suitable for a large scale preparation due to the hazardous nature of the acid azide which is formed as one of the intermediates in this five step sequence. The third method describes the conversion of 3-nitroacetophenone to 3-nitrophenyl-acetic acid by willgerodt reaction.³ Although the starting material 3-nitroacetophenone is inexpensive but the reported yield of 3-nitrophenylacetic acid is only 7%. The high temperature required in the willgerodt reaction causes the reduction of nitro group by sulfur resulting in a bad mixture thus lowering the yield of nitrothio-morpholide (3) and making its isolation difficult.     

Electrochemical Hydrogenation of α-Arylvinylphosphonic Acids on Platinum and Palladium Modified with Adatoms

A general characteristic of cathodic reduction of -phenylvinylphosphonic acid and its methyl- and chloro-parasubstituted derivatives on Pt/Pt, Pd/Pt, and Pd/Pt modified with Cd and Cu adatoms, is given. At effective pressures of about 10³–10⁴ Pa the processes occur at high rates and at some potentials are limited by the reactant diffusion from the bulk solution. In the presence of Cd and Cu adatoms two reduction waves (presumably, single-electron) may be isolated, i.e. the hampering by adatoms is more pronounced for a second successive stage of the process. At low effective hydrogen pressures the hydrogenation rate is higher on Pd electrodes, which possess a larger sorption capacity. Potential intervals where the reduction of substituted reactants may be complicated by destruction, are found. It is shown that -phenylvinylphosphonic acid undergoes a complete reduction with a current efficiency of 100% in both hydrochloric- and sulfuric-acid solutions. Conditions where the reduction of -(4-chlorophenyl)vinylphosphonic acid proceeds largely without destruction are found. Prospects for use of electrochemical reduction as a preparative method of a selective production of -arylethylphosphonic acids are considered.     

The effect of thermal pretreatment on the electrochemical response for palladium in aqueous media

Previous work on the electrochemistry of palladium in aqueous acid solution demonstrated the existence of two multilayer hydrous oxide reduction peaks, one at ca. 0.24 V and another at ca. 0.55 V vs. RHE, plus the presence of a reversible active surface state transition at ca. 0.24 V. In the present work with thermally activated palladium it was observed that, in agreement with the hydrous oxide reduction behaviour of the system, there is a second active state transition at E≥ca. 0.45 V. In most of its reactions in aqueous acid solution, apart from its unusual capacity to absorb hydrogen, palladium exhibits properties very similar to those of platinum; however, palladium seems to be more prone to dissolution and subsurface oxygen formation. Also the premonolayer oxidation responses of these two metals are often different as the more active state of the palladium surface is not as readily generated as that of platinum. The electrocatalytic properties of palladium, as reported earlier, correlate quite well with the hydrous oxide and premonolayer oxidation behaviour of this electrode system. Electronic Publication     

A note to the article “polarographic reduction of germanium” by A.K. Dasgupta and C.K.N. Nair

The nature of the two reduction waves of tetravalent germanium in ammonia-ammonium chloride buffer is described. Contrary to the statement of dasgup'ta and NAIR1 only the height of the first diffusion current should be used for analytical purposes. The second wave corresponds to a catalytic hydrogen evolution. The use of cthylenediaminetetra-acetic acid of pH 6–8 for the analysis of germanium is preferable².     

Electrochemical reduction of camphorquinone in DMF in the presence of a proton donor

The electroreduction of camphorquinone in DMF, at mercury electrodes, was investigated by a variety of techniques. In DMF, in the absence of proton donor, camphorquinone exhibits two one-electron waves: the first, a one-electron reversible wave to be due to a reversible charge transfer without a coupled chemical reaction. After the first charge transfer, the semidione anion radical is reduced to the dianion. The irreversibility of the second wave derives from a fast irreversible protonation of the dianion. A wide variety of changes in behaviour is observed in the reduction of camphorquinone as increasing amounts of benzoic acid are added: a new two-electron irreversible wave appears at a potential less negative than the original wave. A proton donor to substrate ratio of 2 is required to completely suppress the two original waves. A mechanism for the electroreduction of camphorquinone is proposed and discussed on the basis that the prewave current is controlled by the diffusion of the undissociated acid species and that the undissociated acid, rather than the solvated proton, takes part in the protonation, prior to the charge transfer.