核黄素电化学还原研究

本文采用循环伏安、本体电解、荧光光谱、电子自旋共振波谱等技术对核黄素电化学还原机理进行了研究。结果表明,在DMSO溶液中,核黄素以质子化和非质子化两种形式存在,它们的还原电位分别是-0.78和-1.05(vs.SEC)。两种形式的核黄素都可在汞电极上得到一个电子,生成相应的自由基。自由基的g值分别为2.005和2.002。对质子化式的自由基的ESR超精细谱进行了理论分析,提出了核黄素可能的电化学还原机理。     

肉桂腈电化学还原反应机理

采用循环伏安法研究了肉桂腈在乙腈溶液中的电还原行为,其在-1.46和-2.0V处各存在一个还原峰.第一个峰处恒电位电解得到了线性、环化氢化二聚产物以及苯基戊二腈;第二个峰处电解得到了饱和二氢还原产物苯丙腈.结合循环伏安模拟判定了整个电还原的具体反应机理是肉桂腈通过电化学-电化学-化学-化学(EECC)反应机理生成苯丙腈,同时经历自由基-自由基(RR)过程得到线性和环化二聚产物,肉桂腈还可以与乙腈的共轭碱反应得到苯基戊二腈.最终通过循环伏安模拟求得相应反应的动力学常数,自由基-自由基耦合反应速率常数为104L·mol-.1s-1,第二个电子转移反应速率常数为0.3cm.s-1,其后质子化反应的速率常数为105s-1.     

电极过程自由基中间体的ESR研究(Ⅳ)——脂肪胺的电解氧化

本文用自旋捕捉技术与ESR相结合的方法研究了6种脂肪胺电解氧化过程中产生的瞬态自由基。结果表明,阳极上脂肪胺氧化产生相应的正离子自由基,而后脱去α-C上的质子得到一碳中心自由基,此自由基能被捕捉剂PBN所捕获;阴极上发生H~+还原反应,所得的氢原子也可被PBN捕获。     

邻溴苯甲酸电化学脱溴反应的原位红外光谱研究

采用循环伏安法研究了水溶液中邻溴苯甲酸在不同电极上的电化学还原脱溴反应,与Ti和C电极相比,Cu电极对邻溴苯甲酸有较好的电化学还原活性。同时采用电化学原位红外反射光谱对其反应机理进行了系统分析,结果表明：邻溴苯甲酸在Cu电极上的电还原脱溴反应是一个脱溴加氢的过程,邻溴苯甲酸在电极表面首先得到一个电子变成邻溴苯甲酸自由基负离子;然后脱去溴离子得到苯甲酸自由基,该自由基再得到一个电子变成苯甲酸负离子;最后加成氢质子得到最终产物苯甲酸,这一产物已经通过恒电流电解实验得到了进一步的证实。     

3-硝基苯甲酸在DMSO介质中的电化学还原

本文用循环伏安法、控制电位电解和ESR方法结合, 研究了3-硝基苯甲酸(3-NBA)在DMSO介质中, Pt电极上的电化学还原过程。结果表明, 3-硝基苯甲酸通过三电子还原生成一种亚硝基自由基。观测到了自由基ESR谱的超精细结构。确定了ESR模拟谱的参数: a_1~N=10.91G, a_2~H=1.12G, a_4~H=a_6~H=3.38G, a_5~H=3.96G. 估算了自由基衰变速度常数k=4.814×10~(-2)s~(-1).     

铁-三乙醇胺媒质中靛蓝的间接电化学还原

铁-三乙醇胺(Fe-TEA)可作为媒质用于间接电化学法还原靛蓝.本工作采用循环伏安法研究了靛蓝在Fe-TEA媒质中的电化学行为,比较了石墨、银、镍、不锈钢四种阴极材料的电催化性能,探讨了靛蓝间接电还原的机理.此外,还进行了一组L9(34)正交电解实验,通过正交实验分析了各因素对电流效率的影响.实验结果表明:在Fe(III)-TEA媒质中,以不锈钢网为阴极可实现靛蓝的间接电化学还原,最高电流效率可达44.7%.在实验所设计因素水平范围内,对电流效率影响最大的因素为Fe(III)-TEA媒质浓度.在靛蓝的间接电还原过程中存在一种靛蓝自由基,该自由基能起到靛蓝电还原的媒质作用,在一定实验条件下,该靛蓝自由基的媒质作用可以大于Fe(III)-TEA.     

在LiCl熔盐中直接电还原制备钕硅合金

在973 K熔融LiCl盐中,利用恒电压直接电还原Nd_2O_3-SiO_2与Nd_2O_3-Si两种混合氧化物,成功制备出钕硅合金.使用金属孔洞电极,通过循环伏安法结合不同条件下电解产物的X射线衍射(XRD)、扫描电子显微镜(SEM)和能量色散谱仪(EDS)分析研究了其还原机理.结果发现,Nd_2O_3-SiO_2的还原过程分二步进行:首先SiO_2还原为单质硅,然后Nd_2O_3被还原同时形成钕硅合金.此外,还研究了电解电压对电解过程的影响.结果发现,还原速率随着电解电压的增加而增加,氧化物中硅的原子含量为50%左右时,容易还原得到较纯的合金.据了解这是首次运用直接电解还原氧化物的方法得到钕硅合金.     

三价铀的制备和稳定性研究

在盐酸和硫酸介质中,研究了汞阴极电解还原和液态Zn-Hg齐还原制备U(Ⅲ)的实验方法,比较了不同介质、酸度、铀浓度和电解时间对U(Ⅲ)还原率的影响,获得了用电解法定量还原制备U(Ⅲ)的最佳条件。经对U(Ⅲ)在空气和氮气中稳定性的测定,得出U(Ⅲ)在空气中的氧化速率呈一级反应。     

多巴胺在DTNB自组装膜上的电催化研究

在金电极表面制备了DTNB(5,5′ Di thiobis(2 nitrobenzoicacid))自组装单分子层膜(DTNB/AuSAM)。多巴胺在DTNB自组装膜上有一对可逆性良好的氧化还原峰,其氧化峰电流与多巴胺的浓度在5.0×10-6mol/L～1.0×10-4mol/L的范围内呈线性关系,检出限为1.0×10-6mol/L。在pH3.5的缓冲溶液中,在DTNB自组装膜上多巴胺和抗坏血酸的电化学响应可以明显区分,氧化峰电位分离达276mV。可用于抗坏血酸存在下多巴胺的检测。测定了盐酸多巴胺注射液中多巴胺的含量,其平均回收率为104%。     

巯基—二硫键交换在胰岛素与其受体结合中的作用

本文报道DTT还原,DTNB氧化以及NEM修饰对小鼠肝膜巯基含量和与胰岛素受体特异结合的影响。DTT还原导致膜巯基含量和与胰岛素特异结合平行增加,Scatchard分析表明胰岛素结合位点的数目仅有微小变化,但结合常数增高到原来的二倍。用含有DTT的缓冲液洗涤已饱和结合了胰岛素的膜比用不含DTT的缓冲液,导致结合在膜上的胰岛素解离下来的量明显升高,说明有一部分胰岛素与其受体的结合是通过巯基—二硫键交换反应形成共价的二硫键。加入DTT使这种“二硫键联接”的胰岛素也从受体上解离下来。DTNB或NEM对膜与胰岛素的特异结合几乎没有影响,但对已被DTT还原的膜似有逆转DTT还原的效应,推测,鼠肝膜胰岛素受体上可与胰岛素发生共价结合的巯基中,有一部分是不能与DTNB发生反应的,DTT处理膜使胰岛素受体产生更多的巯基而使胰岛素特异性结合,特别是使通过共价二硫键的结合增加。     

INTER AND INTRAMOLECULAR INTERACTIONS OF PORPHYRINS WITH 5,5'-DITHIOBIS(2-NITROBENZOIC ACID)

meso-Tetraphenylporphyrin and its metal [zinc(II) and copper(II)] derivatives form both inter and intramolecular complexes with 5,5′-dithiobis(2-nitrobenzoic acid) (DTNB). The nature of interaction is predominantly charge transfer (CT) in origin, with the porphyrin functioning as a II-donor and DTNB as an acceptor. Among the covalently linked intramolecular systems, the magnitude of CT interaction varies with the position (of one of the aryl groups of the porphyrin) to which DTNB is attached as ortho meta > para. Steady-state and time-resolved fluorescence studies revealed electron transfer to be the dominant pathway for the fluorescence quenching in these systems. Steady-state photolysis experiments probed using EPR and optical absorption studies have shown that electron transfer (from the excited singlet state of the porphyrin) to DTNB results in the formation of thiyl radical and production of free thiolate anion. It is found that the products of electrochemical reduction of covalently linked porphyrin-DTNB systems are different from those observed for the photochemical studies.     

Spectroelectrochemistry study on the electrochemical reduction of ethidium bromide.

The electrochemical reduction mechanism of ethidium bromide was first studied by spectroelectrochemistry. This reduction was proved to be a two-step process by cyclic voltammetry, differential pulse voltammetry and spectroelectrochemistry, in which each step was proved to be a one-electron transfer process by a spectropotentiostatic fluorescence technique. Hydroethidine was confirmed to be the final product by comparing the spectrum of the product of the electrochemical reduction to that of the product of the chemical reduction of ethidium bromide, and a carbon-centered radical was concluded to be a reasonable intermediate product during the electrochemical reduction of ethidium bromide.     

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%.     

A DFT study of CO<Subscript>2</Subscript> electrochemical reduction on Pb(211) and Sn(112)

Electrochemical reduction of CO2 has the benefit of turning greenhouse gas emissions into useful resources. We performed a comparative study of the electrochemical reduction of CO2 on stepped Pb(211) and Sn(112) surfaces based on the results of density functional theory slab calculations. We mapped out the potential energy profiles for electrochemical reduction of CO2 to formate and other possible products on both surfaces. Our results show that the first step is the formation of the adsorbed formate(HCOO*) species through an Eley-Rideal mechanism. The formate species can be reduced to HCOO- through a oneelectron reduction in basic solution, which produces formic acid as the predominant product. The respective potentials of forming HCOO* are predicted to be -0.72 and -0.58 V on Pb and Sn. Higher overpotentials make other reaction pathways accessible, leading to different products. On Sn(112), CO and CH4 can be generated at -0.65 V following formate formation. In contrast, the limiting potential to access alternative reaction channels on Pb(211) is -1.33 V, significantly higher than that of Sn.     

A Study on the Electrochemical and Electrochemiluminescent Behavior of Homogentisic Acid at Carbon Electrodes

The electrochemical oxidation and electrochemiluminescent behavior of homogentisic acid (HGA) has been studied in aqueous solutions over a wide pH range by linear sweep voltammetry, cyclic voltammetry, chronocoulometry at a glassy carbon electrode, by controlled potential electrolysis at a large area spectroscopic graphite electrode, and by spectroelectrochemistry at an optically transparent drilled holes graphite (DHG) electrode in a thin‐layer cell. The studies reveal that the electrochemical oxidation of HGA at carbon electrodes is a reversible process involving two‐electron, two‐proton transfer. In addition to the electrochemical oxidation, the chemical oxidation of HGA by dissolved oxygen was investigated by spectroscopic method combined with voltammetry. It was revealed that HGA is fairly stable in strongly acidic media but readily oxidized by dissolved oxygen in alkaline media giving rise to 1,4‐benzoquinone‐2‐acetic acid, the same product as that of electrooxidation of HGA. This oxidation product is stable in acidic, neutral and weakly alkaline media, but can further degrade in strongly alkaline media yielding oxalate as the final product. The electrochemiluminescent mechanism of HGA in the presence of Ru(bpy)₃²⁺ at a glassy carbon electrode was also investigated in detail, based on which a sensitive ECL method for determination of HGA was developed, and the detection limit was 3.0×10^?8 mol L^?1.     

Electrochemical reduction of 5,5′-dichlorohydurilic acid. mechanism and analytical applications

The electrochemical reduction of 5,5′-dichlorohydurilic acid has been studied at the dropping mercury electrode (DME) and the pyrolytic graphite electrode (PGE). At the DME the single polarographic reduction wave observed at pH 6–11 involves a direct 4e—2H⁺ reduction of the carbon-halogen bond to give hydurilic acid and chloride. The state of hydration or ionization of the 5,5′-dichlorohydurilic acid has no effect on the electrochemical reaction. At the PGE, 5,5′-dichlorohydurilic acid shows two voltammetric peaks. Peak I_c, observed between pH 5 and 7, arises from an overall 4e—2H⁺ reduction of 5,5′-dichlorohydurilic acid via a mechanism that involves initial electron attack at a carbonyl group alpha to a carbon-halogen bond with simultaneous elimination of chloride ion. The peak II_c process involves an initial 2e—1H⁺ reduction of a partially hydrated form of 5,5′-dichlorohydurilic acid with only one unhydrated halocarbonyl moiety available for reaction. Attack is again via the carbonyl group with simultaneous elimination of chloride and formation of 5-chlorohydurilic acid. A chemical dehydration step then occurs with a rate constant of ca. 0.24 s^?1 at pH 8.2, with formation of a further reducible halocarbonyl group. This is again reduced in an overall 2e—2H⁺ reaction to give hydurilic acid and chloride ion. The peak II_c process hence proceeds via an ECE mechanism. The different mechanisms observed for reduction of 5,5′-dichlorohydurilic acid at mercury and pyrolytic graphite electrodes are unusual. Analytical methods have been developed for the polarographic determination of 5,5′-dichlorohydurilic acid via its reduction wave at the DME, and for the voltammetric determination of hydurilic acid via its first oxidation peak at the PGE.     

Stabilization of high-performance oxygen reduction reaction pt electrocatalyst supported on reduced graphene oxide/carbon black composite

Oxygen reduction reaction (ORR) catalyst supported by hybrid composite materials is prepared by well-mixing carbon black (CB) with Pt-loaded reduced graphene oxide (RGO). With the insertion of CB particles between RGO sheets, stacking of RGO can be effectively prevented, promoting diffusion of oxygen molecules through the RGO sheets and enhancing the ORR electrocatalytic activity. The accelerated durability test (ADT) demonstrates that the hybrid supporting material can dramatically enhance the durability of the catalyst and retain the electrochemical surface area (ECSA) of Pt: the final ECSA of the Pt nanocrystal on the hybrid support after 20?000 ADT cycles is retained at >95%, much higher than the commercially available catalyst. We suggest that the unique 2D profile of the RGO functions as a barrier, preventing leaching of Pt into the electrolyte, and the CB in the vicinity acts as active sites to recapture/renucleate the dissolved Pt species. We furthermore demonstrate that the working mechanism can be applied to the commercial Pt/C product to greatly enhance its durability.     

Investigation of Electrochemical Behavior of Some Dithiophosphonates in Acetonitrile on the Platinum and Gold Electrodes

Some dithiophosphonate derivatives were synthesized and the electrochemical reduction mechanism was investigated by cyclic voltammetry (CV), square wave voltammetry (SWV) and chronoamperometry (CA) in 0.1 M tetrabutylammoniumtetrafluoroborate (TBATFB) in acetonitrile at platinum (Pt) and gold (Au) electrodes. Dithiophosphonates showed a cyclic voltammetric reduction peak at about ?1.1 V at Pt and ?1.3 V at Au electrode (vs. Ag/Ag⁺) in this media. It was also shown that dithiophosphonates can be determined quantitatively in acetonitrile using a calibration graph. The number of electrons transferred were calculated as 2 using ferrocene as a reference compound at the UME electrode. Mechanism of dithiophosphonates was also examined on Pt and Au electrodes and electrochemical reduction of dithiophosphonates seems to follow an EC mechanism with an irreversible electron transfer step. The reaction product in the bulk electrolysis experiment was isolated and identified using proton‐coupled P‐31 NMR, ¹³C‐NMR and IR spectroscopy. The adsorption tests for dithiophosphonates were revealed that no strong or weak adsorption phenomena exist on both Pt and Au electrodes. Simulation curves were acquired by DigiSim 3.03 version to investigate the reduction mechanism and to estimate the kinetic parameters for electrochemical and chemical steps.     

Disposable Amperometric Sensors for Thiols with Special Reference to Glutathione

The antioxidant ‘reduced glutathione’ tripeptide is conventionally called glutathione (GSH). The oxidized form is a sulfur‐sulfur linked compound, known as glutathione disulfide (GSSG). Glutathione is an essential cofactor for antioxidant enzymes; it provides protection also for the mitochondria against endogenous oxygen radicals. The ratio of these two forms can act as a marker for oxidative stress. The majority of the methods available for estimation of both the forms of glutathione are based on colorimetric and electrochemical assays. In this study, electrochemical sensors were developed for the estimation of both GSH and GSSG. Two different types of transducers were used: i) screen‐printed three‐electrode disposable sensor (SPE) containing carbon working electrode, carbon counter electrode and silver/silver chloride reference electrode; ii) three‐electrode disposable system (CDE) consisting of three copper electrodes. 5,5′‐dithiobis(2‐nitrobenzoic acid) (DTNB) was used as detector element for estimation of total reduced thiol content. The enzyme glutathione reductase along with a co‐enzyme reduced nicotinamide adenine dinucleotide phosphate was used to estimate GSSG. By combining the two methods GSH can also be estimated. The detector elements were immobilized on the working electrodes of the sensors by bulk polymerization of acrylamide. The responses were observed amperometrically. The detection limit for thiol (GSH) was less than 0.6 ppm when DTNB was used, whereas for GSSG it was less than 0.1 ppm.     

Elektrochemische untersuchung von bis(diphenyldithiophosphin) disulfid

The electrochemical behaviour of bis(diphenyldithiophosphine)disulphide (RSSR) and mercuric diphenyldithiophosphinate [(RS)₂Hg] in ethanol-lithium perchlorate and ethanol-sulphuric acid media was studied by the methods of classical polarography, and electrolysis at controlled-potential and at a rotating disc platinum electrode. The data obtained show that RSSR is not reduced directly on the dropping mercury electrode but is adsorbed. It then undergoes a rapid chemical reaction causing the formation of (RS)₂Hg, which is electroactive. The electrolysis at controlled potential proves that (RS)₂Hg undergoes a two-electron reduction, giving diphenyldithiophosphinic acid (RSH) as a main product, whereas the oxidation of RSH leads to the production of (RS)₂Hg. Regardless of the fact that the chemical and adsorption equilibria during reduction of RSSR and (RS)₂Hg are complex, the coulometric generation of RSH is not difficult to achieve, and permits the use of RSSR as a coulometric reagent.