硬脂酸钠在蓖麻油/水界面上自组装动力学的研究

以电沉积铜为探针,循环伏安法研究硬脂酸钠在蓖麻油/水界面上自组装的动力学.在涂有蓖麻油的石墨粉-环氧树脂固态电极上,硬脂酸钠自组装膜形成过程可由电沉积铜阳极峰监测,遵从高斯函数生长动力学,生长速率常数为km=0.0006292(±0.0000294)s-1.硬脂酸钠自组装膜能较好地控制铜粒子的球形生长和生长尺度,形成硬脂酸钠自组装-铜纳米粒子复合膜.铜粒子在石墨粉-环氧树脂固态电极上为半球形生长,而在涂油和自组装电极上为球形生长.与蓖麻油涂层相比,石墨粉-环氧树脂固态电极与沉积铜间存在弱相互作用(ΔG0=3.86kJ/mol),而硬脂酸钠羧基与沉积铜也有较弱的相互作用(ΔG0=-2.412kJ/mol).     

细胞色素c在自组装纳米膜电极上的有效固定及直接电化学

采用自组装方法将壳聚糖-纳米金(Chi-Nano Au)修饰到金(Au)电极上,并经进一步自组装细胞色素c(Cyt c),制得自组装膜电极Cyt c/Chi-Nano Au/Au.测定了自组装膜电极的循环伏安曲线(CV)及稳定性.结果表明,利用自组装膜电极Chi-Nano Au/Au可以有效地固定Cyt c,并实现直接电子转移反应.Cyt c在0.13～0.28V(vs Ag/AgCl)之间显示一对明显的可逆氧化还原峰;峰电流与扫描速度呈现良好的线性关系,线性方程为Ipc=0.063 64+0.003 51υ,线性相关系数为r=0.997 2,这表明该电极过程受吸附控制.此外,所制备的膜电极稳定性良好.     

季铵酚离子在水／硝基苯界面的转移

油/水界面上的电化学研究是近年来电化学研究中的一个新领域,对膜电化学的发展具有重要意义。目前研究油/水界面电化学中普遍使用循环伏安(CV)法和循环线扫电流计时电位(CLC)法。有关抗生素在油/水界面的转移已有报导,本文用CLC法和CV法对肌肉松弛剂季铵酚离子在水/硝基苯界面的转移行为进行了研究。 所用三碘季铵酚为中国科学院生物化学研究所生产的化学试剂,其他试剂及仪器均与前文相同     

十烷基硫酸钠-全氟辛酸钠混合表面活性剂在四氯乙烯-水界面上的吸附及胶团形成

测定了在30℃、总离子强度为0.1m时不同比例混合的十烷基硫酸钠(C₁₀SN_a)-全氟辛酸钠(7CFNa)在四氯乙烯-水界面的界面张力,研究混合溶液的界面性质及胶团形成,结果表明:(1)7CFNa与C₁₀SNa在混合溶液中,基本上各自独立形成胶团;(2)混合表面活性剂在四氯乙烯-水界面上的吸附与在正庚烷-水界面上吸附规律相同;(3)测定C₁₀SNa、7CFNa在不同油-水界面上的界面张力,证实碳氟链与碳氯链之间具有“互憎性”。     

Au单晶表面氟表面活性剂FSN自组装膜的电化学行为

研究Au(111)和Au(100)表面非离子型氟表面活性剂FSN自组装膜的电化学行为.电化学扫描隧道显微术和循环伏安法测试表明,在0～0.8 V电位区间,FSN自组装膜未发生氧化还原,均一性好,可稳定地存在于电极表面,并显著抑制硫酸根离子在电极表面的吸附和Au单晶表面的重构.在FSN自组装膜Au单晶电极的初始氧化阶段,Au(111)表面有少量突起,而Au(100)表面呈现台阶剧烈变化,但FSN自组装膜的吸附结构没有改变.与Au(100)表面相比,Au(111)表面形成的FSN自组装膜可更有效地抑制Au表面的氧化.     

DHP和SWCNTs促进[Ru(bpy)2tatp]3+/2+在ITO上的电化学组装

应用循环伏安法和微分脉冲伏安法研究了[Ru(bpy)2tatp]3+/2+(bpy=2,2′-联吡啶, tatp=1,4,8,9-四氮三联苯)在ITO表面上的电化学组装及双十六烷基磷酸盐(DHP)和单壁碳纳米管(SWCNTs)对其组装效果的影响. 研究结果表明, [Ru(bpy)2tatp]2+在ITO电极上1.057 V(vs. Ag/AgCl)电位下呈现出清晰的扩散控制峰. 随着连续伏安扫描次数的增多, 微分脉冲伏安图逐渐呈现出明显的吸附控制峰. 当DHP浓度在0.05~0.22 mmol/L区间内时, 不管有无SWCNTs存在, DHP均能增强[Ru(bpy)2tatp]2+在缓冲溶液中的扩散系数和促进其在ITO上的电化学组装, 而SWCNTs在其中起减弱作用. 讨论了DHP和SWCNTs参与的[Ru(bpy)2tatp]3+/2+在ITO上的电化学组装机理.     

脱氧核糖核酸在硬脂酸铝离子膜上固定杂交及BAR基因片段检测

将石墨粉、固体石蜡和硬脂酸按一定比例混合制得表面富含羧基的碳糊电极,然后在电极表面组装荷正电的铝离子膜。在硬脂酸铝离子膜上进行DNA探针的固定和与目标基因的杂交。以亚甲蓝为杂交指示剂,用循环伏安法优化了DNA的固定和杂交条件。应用该电化学生物传感器以微分脉冲伏安法对转基因玉米外源BAR基因片段进行了检测,结果令人满意。     

荧光性自组装双层膜的制备及其性能研究

借助Au-S化学键的作用,在金基底上组装DL-半胱氨酸,利用DL-半胱氨酸与1-萘胺乙酸(NAA)的静电吸引作用在金表面间接组装荧光试剂NAA,从而构建了双层自组装膜NAA/Cys/Au.该自组装膜有较强的荧光信号,能被Cu²⁺猝灭,并具有较好的可逆再生性能,可用于超痕量铜离子的界面荧光测定,对Cu²⁺的检出下限为7.87×10^-11mol/L.同时采用电化学、荧光光谱及电子能谱等方法表征自组装膜的结构,并采用电化学阻抗谱技术和循环伏安法研究自组装膜在K₃[Fe(CN)₆]/K₄[Fe(CN)₆]溶液中的电化学行为研究.结果表明,金表面组装的单层膜具有良好的“针孔”效应,组装上荧光试剂之后形成的无“针孔”缺陷的自组装双层膜对溶液与基底间的界面电子转移有强烈的阻碍作用.     

新型巯基化合物自组装膜修饰电极对铜离子的检测

合成了一种新型的巯基化合物,在金电极上形成自组装膜,以循环伏安法和电化学阻抗法(EIS)对自组装膜进行表征,基于其末端的氨基对铜离子的配位效应,实现了对铜离子的快速检测,并优化了沉积时间、pH、静止时间、沉积电压等检测条件.同时研究了铜离子与人血清白蛋白的相互作用.结果表明,该组装膜在2×10-7 ～2.5×10-3 mol/L范围内对铜离子有线性响应,检出限为0.05 μmol·L-1,其与蛋白的结合常数为2.20×103 L/mol.银离子、锌离子等对铜离子的测定几乎没有干扰.     

不同中心离子对自组装三元配合物膜光诱导

在ITO(indium-tin-oxide)透明电极上,按照一种新的自组装策略分别制备了3种以四价金属离子Sn4+,Zr4+和Ce4+为桥连中心离子、以苝四羧酸为功能染料配体分子、以草酸为连接配体的光电功能自组装膜.用接触角、紫外光谱、X射线光电子能谱(XPS)和电化学循环伏安作了表征.并测定了这3种自组装膜体系的光电转换性质及电子给体、偏压、光强等因素的影响.     

Adsorption behavior of copper ions on Mucor rouxii biomass through microscopic and FTIR analysis

Mucor rouxii biomass (MRB) was found to be most potent sorbent for the removal of copper from its aqueous solution. Maximum adsorption was noted within pH range 5.0-6.0, and the process follows Langmuir adsorption isotherm (r2=0.998). Adsorption process is very fast initially and reaches equilibrium very quickly following pseudo second order rate kinetics. Amino, carboxyl and phosphate groups present on the cell surface of the biomass are involved in chemical interaction with copper ion as revealed from FTIR and SEM-EDX study and also by blocking experiments. Both SEM and AFM micrographs revealed the formation of metal nanostructure on the biomass surface due to copper adsorption. Biomass surface modification indicates the major involvement of amino functional group for the binding probably through the chelation. Copper ion can be eluted from the adsorbed biomass with 0.1M hydrochloric acid.     

Investigations into the electroreduction of copper(II) ions on chalcocite in ammonia solutions using the rotating disc electrode method

Investigations into the electroreduction of copper(II) ions in ammonia solutions on a disc electrode made of synthetic chalcocite having a deficiency of copper atoms have been presented. It has been concluded that within the range of the diffusion controlled process copper(II) ions are the diffusing substance, at the same time in the course of the reaction two electrons are exchanged. The kinetic parameters for the electroactivating process have been estimated. With a higher concentration of copper in solution an inhibition process has been observed, probably caused by a slow transport rate of the species in the material of the electrode. In the system studied the phenomenon of a partially blocked electrode surface does not occur according to the Landsberg model.     

Behaviors and mechanisms of copper adsorption on hydrolyzed polyacrylonitrile fibers

Polyacrylonitrile fiber (PANF) was hydrolyzed in a solution of sodium hydroxide and the hydrolyzed polyacrylonitrile fiber (HPANF) was used as an adsorbent to remove copper ions from aqueous solution. Scanning electron microscopy (SEM) showed that the hydrolysis process made the surface of HPANF rougher than that of PANF. Fourier transform infrared (FTIR) spectroscopy revealed that the HPANF contained conjugated imine (-Cz=Nz-) sequences. Batch adsorption results indicated that the HPANF was very effective in adsorbing copper, and the adsorption equilibrium could be reached within 10-20 min. Atomic force microscopy (AFM) showed that some aggregates formed on the surface of the HPANF after copper ion adsorption and the average surface roughness (R(a)) value of the HPANF changed from 0.363 to 3.763 nm due to copper adsorption. FTIR analysis indicated that copper adsorption caused a decrease of the light adsorption intensity of the imine (-Cz=Nz-) groups at 1573 and 1406 cm(-1) wavenumbers, and X-ray photoelectron spectroscopy (XPS) showed that the binding energy (BE) of some of the nitrogen atoms in the HPANF increased to a greater value due to copper adsorption. The FTIR and XPS results suggest that the adsorption of copper ions to the HPANF is attributed to the imine groups on the surface of the HPANF.     

Initial stages of copper electrocrystallization on polycrystalline platinum and glassy carbon in the presence of acetonitrile

The kinetics of formation of copper adlayer, three-dimensional nucleation, and the deposit growth on polycrystalline platinum and glassy carbon in the 0.5 M H₂SO₄ + 10 mM CuSO₄ + (0–2) M acetonitrile (AcN) solutions at the cathodic overvoltages is studied using the methods of cyclic voltammetry and potentiostatic current transients on a ring-disc electrode. At [AcN] = 2 M, the process of formation of copper adatoms on platinum is significantly retarded. In the solutions with high contents of AcN, the processes of Cu⁺ ion production, the formation of their complexes with acetonitrile, hydrogen evolution, copper nucleation, and the deposit growth proceed in parallel. The contribution of any process to the overall current depends on the amount of adsorbed AcN at the surface of substrate and copper deposit and on the electrode potential. At [AcN] = 2 M, an increase in the cathodic overvoltage to 0.32 V leads to an abnormal increase in the current of Cu⁺ ion production on platinum, which is caused by insufficiently rapid formation of copper atoms in the reduction of Cu⁺(AcN) _x complexes.     

Characterization and Optimization of Polymeric Bispicolamine Chelating Resin: Performance Evaluation via RSM Using Copper in Acid Liquors as a Model Substrate through Ion Exchange Method

Advanced technologies of electronics industries have led to environmental contamination concerns, especially waste print circuit boards containing a very high concentration of copper (II) ions, which can be discharged in wastewater containing many contaminated metals. A low pH is a necessity for treating industrial wastewater containing heavy metals to meet engineering process design. A novel polymeric bispicolamine chelating resin, Dowex-M4195, was applied as an alternative for investigating the behavior of copper (II) in acidic solution via an ion exchange method in a batch experiment system. Characterization of physical and chemical properties before and after ion exchange were also explored through BET, SEM-EDX, FTIR and XRD. Response surface methodology was also applied for optimization of copper (II) removal capacity using design of experiment for selective chelating resin at a low pH. The results indicate that H⁺ Dowex-M4195 chelating resin had a high-carbon content and specific surface area of >64% and 26.5060 m²/g, respectively. It was predominantly macropore porous in nature due to the N₂ gas adsorption isotherm and exhibited type IV with insignificant desorption hysteresis loop of H1-type. It was spherical and cylindrical. After the ion exchange process of copper (II)-loaded H⁺ Dowex-M4195, the specific surface area and total pore volume decreased by about 17.82% and 5.39%, respectively, as compared to H⁺ Dowex-M4195. Hysteresis loop, isotherm and pore size distribution were also similar. Regarding the functional group, the surface morphology and crystalline structures of H⁺ Dowex-M4195 showed copper (II) compound based on the structure of chelating resin that confirmed effective ion exchange behavior. The design of optimization indicated that copper (II) removal capacity of about 31.33 mg/g was achieved, which could be obtained at 6.96 h, pH of 2 (a desirable low pH), dose of 124.13 mg and concentration of 525.15 mg/L. The study indicated that the H⁺ Dowex-M4195 (which is commercially available on the market) can successfully be applied as an alternative precursor through the ion exchange method for further reuse and regeneration of the copper (II) in the electronic waste industries and other wastewater applications needed to respond the policy of biocircular green economy in Thailand.     

Study of the Preparation of a Modified Lubricant Using a W/O Microemulsion Reactor and a Cyclic Voltammetry Study of Rubbing Steel S45C with Lubricants

A successful preparation of a Schiff base copper complex was carried out directly in rap oil, using a W/O microemulsion reactor. The prepared Schiff base copper complex dispersed equably and spontaneously in the oil. Owing to a modification of the rap oil, by addition of 2%wt of Cu (II) chelate of bissalicylaldehyde-ethylenediamine, the friction coefficient decreased by 80% compared to that of the original one. It was verified by energy dispersive spectroscopy (EDS) and x-ray photoelectron spectroscopy (XPS) analyses that steel/steel rubbing pairs underwent a selective transferring process with such modified lubricants. It was suggested that the mechanism for the improvement in the tribological characteristics of the modified lubricants was due to a selective transferring effect. The Cu (II) chelate of bissalicylaldehyde-ethylenediamine not only served as an additive in the rap oil, but also self-assembled on the surface of the 100Cr6 steel. The self-assembled monolayer (SAM) was examined using SEM techniques. The SAM was characterized with cyclic voltammetry (CV). It indicated that the SAM could activate the rubbing surface of 100Cr6 steel, which benefited the tribological chemical reaction.     

高强度黏附力可调控的水下超疏油铜网膜的制备

通过调控在铜网表面电镀铜的时间制备了一系列具有不同黏附性的水下超疏油铜网表面,并进一步在铜网表面包覆一层磷酸二氢铝(ADP)纳米涂层.在保持铜网表面原有微结构形貌不变的前提下,ADP纳米涂层有效增强了铜网表面微纳结构的机械强度及表面浸润特征的稳定性.研究结果表明,铜网表面不同微结构赋予了表面与油滴之间不同的接触状态,从而产生了不同的黏附性; ADP包覆后铜网表面微结构机械强度的增加,得益于包覆后表面微观结构在外力作用下最大应力和最大横向位移的明显降低.     

Redox buffering in an electrospray ion source using a copper capillary emitter.

An electrospray ion source used in electrospray mass spectrometry is a two-electrode, controlled-current electrochemical flow cell. Electrochemical reactions at the emitter electrode (oxidation and reduction in positive and negative ion modes respectively) provide the excess charge necessary for the quasi-continuous production of charged droplets and ultimately gas-phase ions with this device. We demonstrate here that a copper capillary emitter, in place of the more commonly used stainless-steel capillary emitter, can be utilized as a redox buffer in positive ion mode. Anodic corrosion of the copper capillary during normal operation liberates copper ions to solution and in so doing maintains the interfacial potential at this electrode near the equilibrium potential for the copper corrosion process [E degrees = 0.34 V versus standard hydrogen electrode (SHE)]. Fixing the interfacial potential at the emitter electrode provides control over the electrochemical reactions that take place at this electrode. It is shown that the oxidation of N-phenyl-1,4-phenylenediamine to N-phenyl-1,4-phenylenediimine (E(p/2) = 0.48 V versus SHE) can be completely avoided using the copper emitter, whereas this analyte is completely oxidized with a stainless-steel capillary emitter under the same conditions. Moreover, using N-phenyl-1,4-phenylenediimine, we demonstrate that reduction reactions can occur at the copper emitter electrode in positive ion mode. Emitter corrosion, in addition to redox buffering, provides a convenient means to introduce metal ions into solution for analytical use in electrospray mass spectrometry.     

多元醇法制备Cu2O/CNTs复合材料的研究

以Cu(CH₃COO)₂•H₂O和经硝酸处理的CNTs作为原料, 采用多元醇法成功合成了纳米氧化亚铜均布于碳纳米管表面的复合光催化剂. 用透射电镜(TEM), 高分辨透射电镜(HRTEM), X射线粉末衍射(XRD)对样品进行了表征, 测试结果表明大小为2～5 nm的氧化亚铜纳米颗粒均匀分散于碳纳米管的表面. 讨论了反应条件对Cu₂O在CNTs上负载效果的影响并就多元醇法合成Cu₂O/CNTs复合材料的反应机理作了初步探讨.