硫代氨基脲对铜阳极溶出和阴极沉积过程影响的CV和EQCM研究

Cu的阳极溶出和阴极沉积是镀铜、铜电解和有机电合成等领域中一个重要的过程.本文运用电化学循环伏安(CV)和石英晶体微天平(EQCM)方法研究了酸性介质中硫代氨基脲(HT)对铜阳极溶出和阴极沉积过程的影响.结果表明:在含HT的溶液中,铜阳极溶出和阴极沉积过程的M/n分别为33.0和31.6g/mol,是一个2-电子过程.实验条件下,HT能吸附在铜电极表面,阻化了铜的电极过程,但并不改变铜电极阳极溶出和阴极沉积的历程.本文从电极表面质量定量变化的角度提供了Cu阳极溶出和阴极沉积过程的新数据.     

Simultaneous Fluorescence Detection of Mercury(Ⅱ) and Silver Ions Based on Rhodamine B Isothiocyanate and 5-Carboxyfluorescein-ss DNA Modified Probe

A new fluorescence sensor is developed for simultaneous detection of Hg~(2+) and Ag~+. During the detection process,Hg~(2+) forms complexes with the fluorescent dye rhodamine B isothiocyanate(RBITC) modified onto the surface of gold nanoparticles(Au NPs),resulting in RBITC's displacement from the surface of Au NPs and the recovery of fluorescence. Meanwhile,Ag~+ forms “C-Ag~+-C” complex with C-rich 5-carboxyfluorescein(FAM)-ss DNA modified onto the surface of Au NPs,which keeps the fluorescent dye FAM close to the Au NPs and results in quench of fluorescence. The experimental results show a wide linear range and a good sensitivity. The limit of detection is 1.06 nmol/L for Ag~+ and 0.48 nmol/L for Hg~(2+). This detection method is not only easy to operate but also efficient.     

多壁碳纳米管-离子液体修饰电极测定Cu~（2＋）

采用涂覆法制备多壁碳纳米管（MWCNT）-离子液体（[BMIM]PF6）修饰电极,研究Cu2＋在该修饰电极上的阳极溶出伏安行为。考察了实验条件对Cu2＋电化学行为的影响。研究表明,Cu2＋在修饰电极上可得到灵敏的溶出峰。在优化的实验条件下,Cu2＋在1.0×10-6～1.0×10-5mol/L浓度范围内与其氧化峰电流呈...     

高温高浓度溴化锂溶液中磷脱氧铜耐蚀性研究

利用电化学测试技术和化学业浸泡法对磷脱氧铜在高温65%LiBr溶液中的耐蚀性进行了研究。结果表明,LiOH对腐蚀行为起双重作用,低浓度有利于形成Cu2O、CuO氧化膜,而高浓度则形成HCu2O2^-和CuO2^2-型化合物,促进氧化膜溶解;最佳LiOH浓度为0.10mol/L,65%LiBr 0.10mol/L LiOH溶液中添加200mg/L Na2MoO4时缓蚀效果较好,这是由于吸附在阳极表面的MoO4^2-参与电极反应过程,还原生成的MoO2掺杂在Cu2O和CuO氧化膜中阻碍侵蚀性Br^-吸附,有效地抑制铜的活性溶解。     

分级纳米多孔铋电化学传感器用于镉离子的检测

采用电化学方法实现对水溶液中重金属离子的超灵敏检测是分子生物学、环境学和医学等领域长期研究的课题，而如何制备具有高比表面积和快速响应特性的电极则是电化学痕量检测的关键。以双相合金Mg₇₉Bi₂₁条带为前驱体，通过一步脱合金法制备了分级纳米多孔铋（hierarchical nanoporous bismuth, HNBi）电极，结合方波阳极溶出伏安法，实现了对水溶液中Cd²⁺的快速检测，检测极限低于10⁻⁹ mol/L，线性动态响应范围介于10⁻⁸ mol/L和10⁻⁶ mol/L之间。HNBi电极绿色环保，在电化学检测领域显示出巨大的应用潜力。     

Voltammetric Response of Epinephrine at Carbon Nanotube Modified Glassy Carbon Electrode and Activated Glassy Carbon Electrode

0Introduction Epinephrine(EP)isanimportantcate cholamineneurotransmitterinthemammaliancentralnervoussystem,whichissecretedbythesu prarenalglandalongwithnorepinephrine.Itisgen erallyusedtotreathypertension,bronchialasthma,organicheartdisease,andincardiacsurgeryand myocardialinfarction[1].VariousmethodshavebeendevelopedforEPstudy,suchascapillaryelectro phoresis(CE)[2],highperformanceliquidchroma tography(HPLC)andflowinjectionanalysis(FIA)[3].Numerousobservationsontheelectro chemicalbehavio…     

Electrocatalytic oxidation of H<Subscript>2</Subscript>O<Subscript>2</Subscript> at a carbon paste electrode modified with a nickel (II)-5, 11, 17, 23-tetra-tert-butyl-25, 27-bis(Diethylcarbamoylmethoxy) calix[4] arene complex and its application

Electrochemical behavior of a carbon paste electrode (CPE) modified with nickel(II)-5, 11, 17, 23-tetra-tert-butyl-25, 27-bis(diethylcarbamoylmethoxy) calix[4]arene (Ni (II)-L) complex and its electrocatalytic activity towards the oxidation of hydrogen peroxide were investigated by cyclic voltammetric technique in a 5.0×10⁻² mol/L NaClO₄+1.0×10⁻³ mol/L NaOH solution. It was found that Ni(II)-L acts as an effective catalyst for the oxidation of hydrogen peroxide. The modified electrode exhibited a linear response over a hydrogen peroxide concentrations in the range of 2.0×10⁻⁵−1.0×10⁻⁴ mol/L with a detection limit as low as 1.0×10⁻⁶ mol/L. The relative standard deviation was 3.5% for 5 successive determinations of H₂O₂ at 1.0×10⁻⁵ mol/L. The modified electrode was used successfully in rainwater analysis. Foundation item: Supported by the Natural Science Foundation of Hubei Province (98J040). Biography: Li Chun ya(1972-), Ph. D. candidate, research direction: electroanalysis and electrosynthesis.     

硫酸介质中3,5-二(2-吡啶基)-1,2,4-三唑对铜的缓蚀作用的电化学研究

利用动电位扫描、循环极化、循环伏安等电化学方法研究了3,5-二(2-吡啶基)-1,2,4-三唑(HBPT)在0.5 mol/L H2SO4介质中对铜的缓蚀性能.极化曲线研究表明3,5-二(2-吡啶基)-1,2,4-三唑在0.5 mol/L硫酸溶液中对铜的阳极反应起抑制作用,对铜的阴极反应起促进作用,属于阳极型缓蚀剂.循环伏安研究显示3,5-二(2-吡啶基)-1,2,4-三唑可能在电极表面产生吸附或与一价铜发生作用,从而在0.5 mol/L硫酸溶液中对铜起到缓蚀作用.     

HCO3-/CO32-浓度对X70管线钢钝化行为的影响

采用动电位扫描法、循环伏安法研究了X70管线钢在不同浓度的NaHCO₃ /Na₂CO₃ 溶液中的钝化行为。结果表明,材料在该体系中具有明显的钝化现象,随溶液浓度升高,X70钢钝化变得困难。利用Parkins的边界条件,确定了X70钢在1mol/LNaHCO3 +0.5mol/LNa₂CO₃ 溶液中发生应力腐蚀开裂的敏感电位区间为-560～-650mV。X70钢在钝化过程中表面发生的反应比较复杂,电极过程包含Fe的阳极溶解、生成钝化膜、钝化膜的化学溶解三种过程。用X-射线衍射分析了X70钢在活化钝化过渡区表面钝化膜的组成,证实了对电极过程的分析。     

水杨醛缩甘氨酸Schiff碱,2-氨基吡啶或甲醇混配Cu(Ⅱ),Zn(Ⅱ),Ni(Ⅱ)金属配合物的电化学合成及表征

采用金属Cu,Zn,Ni为"牺牲"阳极,在无隔膜电解槽和含配体水杨醛缩甘氨酸Schiff碱、2-氨基吡啶的甲醇溶液中首次电解合成了Cu(Ⅱ),Zn(Ⅱ),Ni(Ⅱ)配合物.利用元素分析、质谱、核磁、红外光谱、紫外光谱、热分析对配体和配合物进行了表征,确定了配合物的化学组成为ML.L.′nH2O[L=C9H7NO3,(M=Cu(Ⅱ),L′=CH3OH,n=0;M=Zn(Ⅱ)、Ni(Ⅱ),L′=2-氨基吡啶n=1)].电合成Zn(Ⅱ)、Ni(Ⅱ)配合物的电化学效率Ef接近0.5 mol.F-1,电极反应为2电子反应,电合成Cu(Ⅱ)配合物的电化学效率Ef接近1.0 mol.F-1,电极反应为1电子反应,Schiff碱配体均以三齿进行配位.Cu(Ⅱ)配合物中Cu(Ⅱ)(L)L′/Cu(I)(L)L′电对的可逆半波电位Er1/2为-1.225 V(vs SCE).     

钙基膨润土对水相中铜离子的吸附

通过考察吸附条件对吸附率及吸附负载量的影响,研究了钙基膨润土对水相中铜离子的吸附特性.实验结果表明,钙基膨润土对铜离子有较好的吸附效果;钙基膨润土对铜离子的吸附在15 min就达到吸附平衡;铜离子的吸附在15 min就达到吸附平衡;当铜离子初始质量浓度为190.6 mg/L,pH=6.03,t=20℃,吸附时间τ=15 min,吸附剂用量为10 g/L时,膨润土对铜离子的吸附率为94%.对初始质量浓度为635.4 mg/L的铜离子溶液,膨润土对铜离子的吸附率仍达57%.从吸附前后膨润土的扫描电镜图片和X射线衍射图谱对比分析可知,膨润土对铜离子的吸附不仅有表面和孔道吸附,还存在着晶层间吸附.     

Preparation of Zn-doped TiO2 nanotubes electrode and its application in pentachlorophenol photoelectrocatalytic degradation

Zn-doped titanium oxide （TiO2） nanotubes electrode was prepared on a titanium plate by direct anodic oxidation and immersing method in sequence. Field emission scanning electron microscopy （FESEM） showed that the Zn-doped TiO2 nanotubes were well aligned and organized into high density uniform arrays with diameter ranging from 50 to 90 nm. The length and the thickness were about 200 and 15 nm respectively. TiO2 anatase phase was identified by X-ray diffraction （XRD）. X-ray photoelectronspectroscopy （XPS） indicated that Zn ions were mainly located on the surface of TiO2 nanotubes in form of ZnO clusters. Compared with TiO2 nanotubes electrode, about 20 nm red shift in the spectrum of UV-vis absorption was observed. The degradation of pentachlorophenol （PCP） in aqueous solution under the same condition （initial concentration of PCP： 20 mg/L; concentration of Na2SO4：0.01 mol/L and pH： 7.03） was carried out using Zn-doped TiO2 nanotubes electrode and TiO2 nanotubes electrode. The degradation rates of PCP using Zn-doped TiO2 nanotubes electrode were found to be twice and 5.8 times as high as that using TiO2 nanotubes electrode by UV radiation （400 μw/cm^2） and visible light radiation （4500 μw/cm^2）, respectively. 73.5% of PCP was removed using Zn-doped TiO2 nanotubes electrode against 45.5% removed using TiO2 nanotubes electrode in 120 min under UV radiation. While under visible light radiation, the degradation efficiency of PCP was 18.4% using Zn-doped TiO2 nanotubes electrode against 3.2% using TiO2 nanotubes electrode in 120 min. The optimum concentration of Zn doping was found to be 0.909%. The PCP degradation efficiencies of the 10 repeated experiments by Zn-doped TiO2 nanotubes electrode were rather stable with the deviation within 3.0%.     

碳纳米管修饰碳糊电极吸附溶出伏安法测定铜

制备了羧基化碳纳米管修饰碳糊电极（MWCNT/CPE）,并研究了Cu（Ⅱ）-SPAPT络合物在该电极上的吸附伏安行为,建立了一种测定痕量铜的新方法。采用二阶导数线性扫描溶出伏安法进行分析。结果表明：在0.1 mol/L的HAc-NaAc（pH=4.0）中,于-400 mV处搅拌富集一定时间,从-400~600 mV范围内以250 mV/s的扫描速度线性扫描,络合物吸附在MWCNT/CPE表面,于66 mV（vs.SCE）处产生一灵敏的阳极溶出峰,其峰电流与Cu（Ⅱ）浓度在4×10-11mol/L-8×10-9mol/L和8×10-9mol/L-1×10-7mol/L范围内分两段呈良好的线性关系,检出限（S/N=3）为2.2×10-11mol/L（富集时间240 s）。同时,探讨了电极反应机理。该方法操作简便、灵敏度高,应用于人发中铜含量的测定,结果满意。     

石墨烯/聚苯胺复合膜修饰玻碳电极测定多巴胺

采用原位聚合法制备石墨烯/聚苯胺复合物,利用X射线衍射技术和红外光谱进行表征,通过滴涂法制备修饰电极,对多巴胺进行电化学测定。分别对支持电解质、pH值和扫描速率等实验条件进行了优化,建立了测定多巴胺的新方法。实验结果表明,经石墨烯/聚苯胺修饰后的玻碳电极对多巴胺具有很好的催化氧化作用。在0.1mol/L磷酸盐缓冲溶液中(pH值为4.0),多巴胺的线性响应范围为8.0×10-7~5.0×10-3 mol/L,相关系数为0.994,检出限为9.8×10-8 mol/L。该法用于实际样品中多巴胺的测定,回收率为97.1%~103.4%。     

Equilibrium dialysis study on the interaction between Cu(II) and HSA or BSA

The interaction of Cu(II) and human serum albumin (HSA) or bovine serum albumin (BSA) at physiological pH is studied by equilibrium dialysis. The successive stability constants are obtained by non-linear least square methods fitting Bjerrum formula. For both the Cu(II)-HSA and Cu(II)-BSA systems, the order of magnitude of K₁ and K₂ was found to be ≈10⁴ mol⁻¹· dm³. There are about twenty stoichiometry binding sites found in one HSA or BSA molecule. They can be divided into two or three sets. Results of equilibrium dialysis experiments suggest that there exists one strong metal binding site in both Cu(II)-HSA and Cu (II)-BSA. It is the imidazol group nitrogen atoms of His³ that are primarily concerned with copper binding site. After reaching dialysis equilibrium, there is the interaction among the different binding sites, the values ofK all deviate from the simple statistical effect except forK ₁ and K₂ in both Cu(II)-HSA and Cu(II)-BSA systems, and the positive cooperative effect is found.     

Study of spectrophotometric method for determination of trace copper after the separation and enrichment with solid phase extractant-microcrystalline phenolphthalein

A new method of using phenolphthalein loaded with 1-(2-pyridylazo)-2-naphthol (PAN) as solid phase extractant to separate and enrich trace copper in diverse water samples has been developed. The ef- fects of different parameters, such as the amounts of PAN and phenolphthalein, stirring time, various salts and metal ions on the enrichment yield of Cu(II) have been investigated to select the experimental conditions. Under the optimum conditions, Cu(II) can be totally adsorbed on the surface of microcrys- talline phenolphthalein. By controlling appropriate acidity (pH=1.0), Cu(II) is completely separated from Cd(II), Pb(II), Mn(II), Co(II), Fe(III), Ni(II), Al(III), Zn(II) and Hg(II) in the solution. The possible reaction mechanism of the enrichment of copper is discussed in detail in this paper. The detection limit of this proposed method is found to be 0.03 μg·L-1 with the enrichment factor of 200. The recovery is in a range of 96.8%―105%. The standard deviation is less than 2.5%. The proposed method has been successfully applied to the determination of trace copper in different water samples with satisfactory results.     

Synthesis and structure of Cu5(BTA)6(TTA)4 · 5DMF, a copper-nitrogen cluster containing η Π3-benzotriazolate

The title cluster compound—Cu₅(BTA)₆(TTA)₄·5DMF was prepared using thenyltrifluoroacetone and benzotriazolate ligands. The crystal structure indicates that a tetrahedral array of Cu(1), Cu(2), Cu(3) and Cu(4) ions surrounding a central Cu(5) ion are held together by bridging tridentate BTA^- and terminated by TTA^- bond cap. The three nitrogen atoms of a BTA^- bond three different copper ions to form a η³-benzotriazolate. The central Cu ion has a distorted octahedral structure and the surrounding Cu ions are 5 coordinated forming distorted tetragonal structures. The distances between the surrounding Cu(Ⅱ) ions and the central Cu(Ⅱ) ion are in the range of 0.3561—0.3755 nm and those between the surrounding Cu(Ⅱ) ions are in the range of 0.5785—0.6301 nm.     

基于金纳米线构建电化学传感器间接检测碱性磷酸酶活性

在临床实践中，碱性磷酸酶（ALP）是最常检测的酶之一，已被广泛用作肝病、骨病、乳腺癌、前列腺癌以及糖尿病等多种疾病的重要检测指标.通过自组装方法在氧化铟锡（ITO）导电玻璃上制备金纳米线（AuNWs），利用4-巯基苯甲酸（4-MBA）修饰AuNWs，对其进行改性，与铜离子（Cu²⁺）螯合形成Cu²⁺-AuNWs/ITO电极.在ALP活性检测中，电解液中的焦磷酸根阴离子（PPi）与电极表面Cu²⁺结合，湮灭了Cu²⁺的电化学信号.ALP的加入使底物PPi水解并释放出Cu²⁺，电化学信号增加.构建的Cu²⁺-AuNWs/ITO电极对ALP活性检测范围为60~180 U·L^-1，且抗干扰性能良好.     

The adsorption of 2,5-dimer-capto-1,3,4-thiadiazole (DMTD) on copper surface and its binding behavior

The interaction mechanism of 2,5-dimercapto- 1,3,4-thiadiazole (DMTD) on copper surface was studied by surface-enhanced Raman scattering (SERS), infrared (IR) and X-ray photoelectron spectroscopy (XPS) techniques. The SERS spectra were obtained. We found that DMTD bound with the copper via its two-excocyclic mercapto groups. The monosulphide salt was formed. At the same time, DMTD coordinated with the Cu⁺ ion through the excocyclic mercapto groups and polymerized via the Cu⁺ ion into a one- dimensional polymer chain on the copper surface.     

Metal Ions Induced Vesicle Formation of Single-Chained Hydrocarbon Surfactants with Coordinated Headgroups

0IntroductionApmrpotheiipnhsil ceasn s augchgr eagsa tseurifnatcota an tvsa r,ileitpyid osf , stcroupcotluyrmeser (se a.ngd.micelles ,bilayers ,vesicles and biological membranes ,etc .)inaqueous solutions , which can transformfrom one to anotherwhen the solutionconditions are changed,such as the electro-lyte concentration or the value of pH[1]. The forces that holdamphiphilic molecules together in aggregates are not due tostrong covalent orionic bonds but arisingfromweaker van derWaals ,hydrop…