阴极电泳涂料用树脂－改性聚丁二烯合成工艺研究

液体聚丁二烯（ＬＰＢ）与过氧乙酸反应生成的环氧化聚丁二烯（ＯＰＢ）再与胺化剂反应生成胶化环氧化聚丁二烯（ＤＯＰＢ）是性能优良的电泳涂料用树脂．实验结果表明ＬＰＢ环氧化反应温度只能在１５～６０℃进行，且高温反应时间不能超过５小时；ＬＰＢ的分子量低．则环氧值增大。ＯＰＢ的胶化反应最佳温度为１１０℃，２ｈ内可完成反应．     

钯(II)配合物和氯化锌在DMF中阴极还原的动力学

烯丙基化合物在钯催化下与碳亲核试剂的反应已成为碳一碳键合成的手段.1989年王志勤等研究报导,在DMF溶液中和氯化锌存在下,钯催化醋酸烯丙酯与羰基化合物电化学还原生成高产率的醇.我们对此反应的机理进行了研究,首先用线性电势扫描法确定各电还原反应的还原电势,得出在实验条件下,氯化锌比π-烯丙基钯配合物容易还原,然后     

锂离子电池正极材料研究的新动向和挑战

调研了全球锂离子电池正极材料LiCoO2、LiNiO2、LiMn2O4、LiFePO4 LiNi0.8 Co0.2 O2和Li(CoMnNi)1/3O2的学术研究论文和技术专利申请与授权数按年和语言分布情况。综述了前4种材料作锂离子电池正极材料尚存在的问题和解决对策进展。例如,通过掺杂其他元素、表面包覆、细化材料颗粒及改善正极结构设计来提高正极材料的充放电容量、寿命、功率密度和电池高功率密度使用时的安全性。     

Cathodic synthesis of 2-amino-2-propene-1-ones electrolytical studies on vinylazides,VII

The cathodic preparation of enamino ketones from enazidoketones has been generalised to include heteroaromatic and aliphatic derivatives. Mechanistically the role of different sites of protonation, either on N¹ of the N₃-group or on carbonyl depending on electrolysis potential and acid strength, apparent by product distribution, is clarified. Aldehydic groups are preferentially reduced compared to the vinylazide part. Purely aliphatic azidoketones yield conjugated dienes under reductive acetylation, which might be useful for cycloaddition reactions.Die kathodische Synthese von Enaminoketonen aus ungesättigten Azidoketonen wurde auf heteroaromatisch substituierte und auf rein aliphatische Derivate übertragen. Zum Reduktionsmechanismus wurde der Einfluß verschiedener Stellen der Protonierung (am N¹ der N₃-Gruppe bzw. an der Carbonylgruppe), abhängig von Potential und Säurestärke, untersucht. Aldehydische Gruppen als weitere funktionelle Gruppen im Enazid werden leichter als die Vinylazide reduziert. Die rein aliphatischen Enazidoketone ergeben bei reduktiver Acylierung konjugierte Diene.

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Elektrolytische Untersuchungen an Vinylaziden, 7. Mitt.: Kathodische Synthese von 2-Amino-2-propen-1-onen

     

Cathodic Electrochemical Detection of Nitrophenols at a Bismuth Film Electrode for Use in Flow Analysis

The bismuth film electrode (BiFE) is presented for use in both batch voltammetric and flow injection (FI) amperometric detection of some nitrophenols (2‐nitrophenol, 2‐NP; 4‐nitrophenol, 4‐NP; 2,4‐dinitrophenol, 2,4‐DNP). The bismuth film was deposited ex situ (batch measurements) and in‐line (FI) onto a glassy carbon substrate electrode. Batch analysis of the nitrophenols was carried out in 0.04 M Britton Robinson (BR) buffer pH 4, while for FI measurements, a carrier/electrolyte solution composed of 0.1 M BR buffer pH 4 mixed with methanol (20+80, v/v%) was employed to resemble media used in preconcentration/clean‐up and flow separation sample pretreatment procedures. Under batch conditions, the voltammetric behavior of the nitrophenols was examined for dependence on medium pH in the range of 2 to 10. Employing the square‐wave voltammetry mode, the limits of detection were 0.4 μg L^?1, 1.4 μg L^?1, and 3.3 μg L^?1 for 2‐NP, 4‐NP, and 2,4‐DNP, respectively. Under flow conditions, a simple in‐line electrochemical bismuth film renewal procedure was tested and shown to provide very good inter‐ and intra‐electrode reproducibility of the current signals at low μg L^?1 analyte concentrations. The limits of detection for 2‐NP, 4‐NP and 2,4‐DNP obtained using FI and amperometric detection at ?1.0 V (vs. Ag/AgCl) were 0.3 μg L^?1, 0.6 μg L^?1 and 0.7 μg L^?1, respectively, with linear ranges extending up to 20 μg L^?1. The attractive performance of the BiFE under flow analysis conditions offers great promise with respect to its detection capability and to its use for a prolonged period of time with no need for inconvenient removal of the electrode from the system for mechanical surface treatment.     

Cathodic and Adsorptive Stripping Votammetry of Naftazone

Abstract

Naftazone (1,2-naphthoquinone-2-semicarbazone) undergoes a reversible two-electron transfer in both acidic and alkaline solutions and also gives rise at pH > 7 to an anodic wave attributed to the formation of a mercury derivative. Cathodic stripping voltammetry is proposed to determine the compound down to 5 × 10^?9 M after accumulation of its mercury salt formed at -0.05V in a 0.05M sodium hydroxide solution. These results have been compared with those obtained by performing an adsorptive collection of the drug in a pH 3 sodium perchlorate solution. Concentrations ranging from 1 × 10^?7 to 2 × 10^?7M can be easily investigated, the detection limit being 7 × 10^?11M. The influence of several operational parameters has also been considered.     

Cathodic protection of ships in brackish water

The operation of ice-going vessels depends on the condition of the hull surface. Corrosion increases the roughness of ship hull, which increases drag and fuel consumption. The hull surface smoothness is maintained by using coatings and cathodic protection. The cold brackish water is different from ocean water as it has lower salt content, lower conductivity, and higher concentration of dissolved oxygen. These factors mean that the design of the cathodic protection system for ship hulls requires different design values, such as protection current density and protected length, than those given in cathodic protection standards. In this paper, we have estimated the protection current density with polarization curves and the protected length by using Wagner number and dimension and conductivity scaling. In brackish water the protection current density was two times that in ocean water. The protected length in brackish water varied between 10 and 15% of that in ocean water. In poorly conducting brackish water, the current capacity of a cathodic protection system is used mostly for overcoming the solution resistance, not for delivering protection current.     

Cathodic Stripping Voltammetric Study Of DL-N-Acetylhomocysteine Thiolactone (Citiolone)

Abstract

The behaviour of DL-N-acetylhomocysteine thiolactone (citiolone) at a hanging mercury drop electrode is studied by cathodic stripping voltammetry (c.s.v.) as an example for determination of thiolactones. Voltammetric response is only obtained at pH> 9.3, when the cyclic structure of thiolactone is open. A spectrometric study is made in order to ascertain this behaviour. Under the recommended conditions and at pH> 9.3, the sulfur containing group can form mercury complexes and citiolone can be determined from the stripping peak that appears at about -0.470 V within the concentration range 3.5 10^?7- 1 10^?9 mol l^?1. Calibration functions are reported and detection limits calculated. The interference of several organic compounds is reported.     

旋转环-盘电极研究MnO2还原机理

目前大多数人认为二氧化锰的阴极还原是按电子-质子机理进行的．但也有人认为氧化氢氧化锰（MnOOH）并不是电子-质子机理的初级产物，而初级产物是二价锰离子，MnOOH是Mn2＋与MnO2作用的结果．早在五十年代以Cahoon为代表的人们就提出这种观点[1]；后来由于Vosburgh[2][3]问和K     

Determination of Ytterbium Traces by Cathodic Stripping Voltammetry

The method of ytterbium(III) trace concentration in the presence of 2‐thenoyltrifluoroacetone (TTA) and polyethyleneglycol (PEG) in ammonium chloride is described. The adsorption was performed at the HMDE at ?1.0 V using linear scan voltammetry and square‐wave voltammetry. The relationship between properties of the SW response of the mixed ligand complex and parameters of a charge transfer were analyzed using theoretical data of SW redox processes.     

Synthesis of Piperidine Derivatives by Reduction of Pyridinium Salts

Piperidine derivatives 1a–e and 2a–f have been prepared by the reduction of 3‐and 4‐substituted pyridinium salts with NaBH₄ in moderate to excellent yields. The reactions regioselectively give 1,2,5,6‐tetrahydropyridines, and the yields depend greatly upon the nature of substituents on the phenyl ring and on the nitrogen atom, the nature and the position of the substituents on the pyridyl ring, and the chain length between the aryloxy and the pyridyl groups.     

加油站地下储运设备阴极防蚀之研究

加油站的地下金属结构物除地下储运设备外 (油管与油槽 ) ,地表尚有钢筋混凝土结构 ,且混凝土中的钢筋常与地下储运设备相搭接而造成彼此间的电通性 ;由于地下储运设备的包覆阻抗多大于混凝土阻抗 ,以致在进行阴极保护时 ,保护电流较易由钢筋流过 ,造成储运设备的保护电位不足 .本研究使用外加电流式阴极保护法进行加油站的阴极防蚀 ,讨论钢筋与地下储运设备搭接或未搭接时的防蚀效果 .结果显示 ,在加油站内进行阴极保护电位评估时 ,若只采用 - 85 0mV作为保护评估标准 ,可能会产生误判结果 ,应当使用电流断电器量测结构物在阴极保护下的极化量 ,方能正确判断保护效果     

生物样品中砷的阴极溶出伏安法测定

提出了用阴极溶出伏安法测定生物样品中痕量砷 ;砷 (Ⅲ )在HCl-CuCl介质中产生一灵敏的溶出峰 ,峰电位位于 -0.804V ,砷含量在10×10 -9～500×10 -9(w)范围内与峰电流成正比 ;研究了酸度、CuCl浓度和起始电位对峰电流的影响 ;该法用于奶牛饲料和猪肾中砷的测定 ,分析结果令人满意     

Spectral Studies on Some Pyrimidine Derivatives in Different Solvents

The electronic absorption spectra of 2-aminopyrimidine (compound I), 2-amino-4-methylpyrimidine (compound II), 2-amino-4,6-dimethylpyrimidine (compound III), 2-amino-4,6-dimethoxypyrimidine (compound IV), 4-amino-2,6-dimethylpyrimidine (compound V), and 4,5-diamopyrimidine (compound VI) have been measured in water and in a series of different organic solvents. The solvent effects on the spectra are discussed and the solvent induced spectral shifts are analyzed in terms of different solute–solvent interaction mechanisms, using the multiple linear regression technique.     

靛红在碳糊电极上的阴极吸附伏安法研究

利用极谱分析仪,在0.40 mol/L的HAc-NaAc(pH 6.0)缓冲液中,发现靛红在碳糊电极(CPE)上有一灵敏的吸附伏安还原峰,峰电位为-0.44 V(vs.SCE)。该还原峰的二阶导数峰电流与靛红的浓度在4.0×10-8~1.0×10-7mol/L(富集90 s)范围内成良好的线性关系,相关系数为0.9954,检出限为8.0×10-9mol/L(S/N=3,富集110 s)。探讨了靛红在碳糊电极上的伏安性质和电极反应机理,并且成功应用于中草药青黛中靛红含量的测定。     

Nafion修饰电极阴极溶出伏安法测定痕量钛

本文采用Ｎａｆｉｏｎ修饰玻碳电极阴极溶出伏安法测定痕量钛。研究了Ｎａｆｉｏｎ膜的有关特性和测定的佳化条件。当富集时间为１ｍｉｎ时，Ｔｉ（Ⅳ）浓度与峰电流在１．０～５０ｎｇ／ｍｌ范围内呈线性关系。本法应用于铝合金和白泥标样中钛的测定，结果满意。     

A Novel Cathode Material for Cathodic Dehalogenation of 1,1‐Dibromo Cyclopropane Derivatives

Leaded bronze turned out to be an excellent cathode material for the dehalogenation reaction of cyclopropanes without affecting the strained molecular entity. With this particular alloy, beneficial properties of lead cathodes are conserved, whereas the corrosion of cathode is efficiently suppressed. The solvent in the electrolyte determines whether a complete debromination reaction is achieved or if the process can be selectively stopped at the monobromo cyclopropane intermediate. The electroorganic conversion tolerates a variety of functional groups and can be conducted at rather complex substrates like cyclosporine A. This approach allows the sustainable preparation of cyclopropane derivatives.     

Cathodic stripping voltammetric analysis of arsenic species in environmental water samples

A simple, fast and sensitive arsenic speciation method has been developed for environmental water analysis by using differential pulse cathodic stripping voltammetry (CSV) performed on a hanging mercury drop electrode (HMDE). Electroactive As(III) is determined by direct CSV analysis. As(V) is converted to As(III) species first and is subsequently quantified by the concentration difference between total inorganic arsenic and As(III). A new batch-mode As(V) reduction procedure by l-cysteine was developed in this study. The optimized parameters for quantitative As(V) reduction include treatment with 20 mM l-cysteine and 0.03 M HCl for 6 min at 70 °C. Organic arsenic, including monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA), can be decomposed to As(V) through UV photooxidation with peroxydisulfate and quantified through subtracting total inorganic arsenic from the total arsenic. At optimum condition, the detection limits for As(III), As(V), and organic arsenic (MMA and DMA) were all 0.3 μg/L and with the linear range from 2.5 to 190 μg/L. Interference from ions common in natural water (Mn, Fe, Cr, Cd, Ca, Zn, Mg, and phosphate) is minimal. The method was validated by analyzing the NIST 1640 natural water standard reference material and by recovery tests on spiked tap water and groundwater. When applied to on-site analysis of sediment pore water and stream water, the CSV results agree well with those obtained by inductively coupled plasma–mass spectrometry (ICP–MS) and graphite furnace atomic absorption spectrometry (GFAAS) methods.     

Influence of Cathodic Pretreatment in the Electrocatalytic Properties PANI Modified Electrodes

Herein, we reported the detection of dopamine (DA) based on use of a cathodically pretreated polyaniline (PANI) modified electrode. The PANI electrode presents a remarkable change in their electrocatalytic properties after a simple cathodic pretreatment, which consisted in applying a potential of ?0.7 V for 3 s. While the as‐prepared PANI shows no electrochemical response for DA, the cathodically pretreated PANI presented reversible electrochemical responses with well‐defined anodic and cathodic peaks. The electrochemical behavior of DA at the PANI electrode was investigated by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Under the optimized experimental conditions, the anodic peak currents increased proportionally to the DA concentration, displaying a linear relationship in the concentration range of 0.11 to 1.75×10^?4 M with a detection limit of 13.7 μM (3 σ/slope). Recovery studies in pharmaceutical formulations presented values between 98 % and 104 %. The cathodically pretreated PANI electrode was successfully applied for DA detection in real samples of pharmaceutical formulation showing good agreement with spectrometric comparative method. The unexpected easily capability of modulate the electrocatalytic properties of the electropolymerized PANI film using a simple pretreatement was successfully demonstrated. The cathodically pretreatment PANI electrode showed electrochemical responses for DA with excellent selectivity, sensitivity, and high stability.     

新型有机二硫化物电池正极材料的研究进展

综述了有机二硫化物正极材料的发展过程。有机二硫化物可以用作锂二次电池的正极活性材料，在充电过程中，－ＳＨ氧化而生成Ｓ－Ｓ作为储能官能团；在放电过程中，Ｓ－Ｓ断裂还原成－ＳＨ，完成化学能向电能的转化。