苏丹红I号在纳米金/碳球修饰硼掺杂金刚石电极上的电化学行为

采用纳米金/碳球(Au/CS)复合物修饰硼掺杂金刚石(BDD)电极,研究了苏丹红I号在Au/CS修饰BDD电极上的电化学行为,并据此建立了实际样品中的苏丹红I号的测定方法.结果表明,与裸BDD电极相比,苏丹红I号在Au/CS修饰BDD电极上的氧化峰电流由0.24μA增加到0.83μA,峰电位由0.809V负移到0.743V.在最优测试条件下,苏丹红I号浓度与其峰电流在4~100μmol/L范围内呈线性关系,线性方程为Ip=0.011 26c+0.116(R2=0.999),检出限为8.33μmol/L.采用本方法对实际样品中的苏丹红I号进行测定,测定结果及平均回收率均优于BDD电极法.     

测酚用的酪氨酸酶媒体玻碳电极的研制

通过聚乙烯亚胺(PEI)包埋和外覆Nafion膜 ,将酪氨酸酶固定在以天青—双氰胺 -甲醛聚合物修饰的玻碳电极表面。工作电位 -100mV(vs.SCE),电极对多种酚有响应 ,对苯酚测定的线性范围为0.20～96μmol/L,响应时间t95 小于50s ,用于测标样和炼焦废水样 ,精密度、准确度好。     

掺硼金刚石膜电极表面产生羟基自由基的原位ESR研究

建立了原位电化学-电子顺磁共振(ESR)方法,系统研究了掺硼金刚石(BDD)膜电极表面在水溶液中的羟基自由基(·OH)产生规律.结果表明,在高于析氧电位时,·OH的生成速率随着阳极电位的升高、电流密度的增加而增大,增加速率逐渐减缓.与此同时,与氢终端的BDD膜电极相比,氧终端的BDD膜电极表面因具有较好的亲水性而具有更高的·OH产生能力.在电化学氧化处理有机废水的过程中,电极表面处于氧终端的状态,有利于·OH产生并保持较高的活性.溶液pH值也在一定程度上影响·OH生成反应,酸性溶液中,BDD膜电极表面的·OH产生能力强于在中性或碱性溶液中.进一步研究发现,BDD膜电极表面还可能生成O3-·0自由基.本研究为深入探索BDD膜电极表面·OH的产生机制提供了研究手段,为阐述BDD膜电极电极在污染物处理中高效性的本质提供了有效的证据.     

阿昔洛韦在硼掺杂金刚石电极上的电化学行为及其与DNA相互作用的研究

利用硼掺杂金刚石(BDD)电极通过循环伏安法和微分脉冲伏安法研究了阿昔洛韦在0.10 mol/L磷酸盐缓冲溶液(pH 7.4)中的电化学行为及其与DNA的相互作用.与玻碳电极相比,阿昔洛韦在BDD电极上的循环伏安曲线在1.17 V处的氧化峰电流更大,背景电流较低.根据峰电位随溶液pH值和扫描速率的变化趋势考察了阿昔洛韦...     

多孔钛基掺硼金刚石电极结构对电催化降解阿司匹林性能的影响

利用扫描电子显微镜(SEM)和X射线衍射仪(XRD)对多孔Ti/BDD电极及传统平板Ti/BDD(BDD=钛基掺硼金刚石)电极进行了研究,通过循环伏安法考察了电极的背景电流和电化学窗口.以阿司匹林为模型污染物,研究了BDD电极结构对阿司匹林电催化降解的影响.结果表明,多孔Ti/BDD电极的总带电量,内、外部带电量,孔隙率和比表面积均高于平板Ti/BDD电极;多孔Ti/BDD在对COD和阿司匹林的去除率和能量消耗等方面均优于平板Ti/BDD电极.     

复合修饰电极测定p-硝基苯酚新方法的研究与探讨

将多壁碳纳米管分散在孔雀绿溶液中并滴涂在玻碳电极表面,再电聚合一层孔雀绿膜,制备了一种新型的聚孔雀绿/多壁碳纳米管复合膜修饰玻碳电极.用电化学方法对所制得的复合修饰电极进行了表征,并研究了p-硝基苯酚在该电极上的电化学行为.结果表明,所制备的复合修饰电极对P-硝基苯酚有良好的电催化作用,从而建立了一种直接测定P-硝基苯...     

邻苯二甲酸二甲酯在三维多孔钛基掺硼金刚石薄膜电极上的电催化氧化行为

以邻苯二甲酸二甲酯(DMP)作为模型污染物,研究了不同结构的钛基体对掺硼金刚石薄膜(Ti/BDD)电极电催化性能的影响.结果表明,三维多孔电极为氧化还原反应提供了更多的反应活性位点,表现出更快的电子传递速率.通过循环伏安法和线性扫描法验证了DMP在BDD电极上的电催化氧化行为属于直接电氧化过程,且在低浓度下近似为一级反应,DMP浓度较高时会在BDD电极表面发生成膜现象.在不同浓度的DMP溶液中使用平板Ti/BDD电极及多孔Ti/BDD电极进行直接电催化氧化时,DMP的电催化氧化过程与理论推断一致;多孔电极由于其电活性面积的优势在COD和DMP的去除方面均优于平板电极.     

掺硼金刚石电极的再生性清洗方法研究

掺硼金刚石电极(BDD)是一种化学和电化学稳定性高、不易吸附污染物的电极.但是多次重复检测较高浓度神经递质如多巴胺、羟色胺后,产生了电极污染.特别是经过表面改性的电极,其表面吸附物难以简单去除.以Fe(CN)3-/4-氧化还原对为探针,通过二次水、乙醇、异丙醇等不同液体超声清洗,发现异丙醇是较好的清洗剂.未改性电极表面...     

季铵盐化纳米金刚石-肌红蛋白修饰电极的电化学行为

通过一系列的化学反应对纳米金刚石(ND)表面进行修饰,成功制备了季铵盐化纳米金刚石:ND-CO-NH-CH2-CH2-N(CH3)3+·I-(QAS-ND),通过FT-IR、元素分析、电化学等手段对目标产物QAS-ND进行了表征。将肌红蛋白(Mb)与QAS-ND混合液滴加在玻碳(GC)电极表面,制备QAS-ND/Mb/GC修饰电极。在0.1 mol/L磷酸盐缓冲溶液(pH 7.0)中,固定在膜内的Mb表现出良好的直接电化学性质,并显示了很好的稳定性。同时,探讨了此修饰电极表面固定的Mb对H2O2的催化还原,结果表明,此修饰电极可作为H2O2生物传感器,实现对H2O2的快速、准确检测,检出限为3.5μmol/L(S/N=3)。     

十六烷基三甲基溴化胺/凹土复合物修饰玻碳电极差分脉冲伏安法测定苯酚

采用物理涂附法将十六烷基三甲基溴化胺(CTAB)与凹凸棒土(ATT)的复合物固定在玻碳电极表面,制成CTAB/ATT复合物修饰电极,并研究了苯酚在该修饰电极上的电化学行为。结果表明,苯酚在CTAB/ATT修饰电极上具有良好的灵敏度和稳定性。在优化的实验条件下,利用差分脉冲伏安法(DPV)测定其峰电流,苯酚的浓度在4.0×10-6～5.0×10-5mol/L范围内与差分脉冲电流呈线性关系,相关系数R=0.9988,检出限为5.0×10-8mol/L。     

Photografting and patterning of oligonucleotides on benzophenone-modified boron-doped diamond

Irradiation of a patterned benzophenone-terminated boron-doped diamond (BDD) surface with UV light (lambda = 350 nm) in the presence of a 15(mer) oligonucleotide resulted in the covalent linking of the DNA strand to the BDD interface.     

The application of boron-doped diamond electrodes in amperometric biosensors

Boron-doped diamond (BDD) electrodes outperform conventional electrodes in terms of high stability, chemical inertness, wide potential window and low background current. Combining the superior properties of BDD electrodes with the merits of biosensors, such as specificity, sensitivity, and fast response, amperometric biosensors based on BDD electrodes have attracted the interests of many researchers. In this review, the latest advances of BDD electrodes with different surfaces including hydrogen-terminated, oxygen-terminated, metal nanoparticles-modified, amine-terminated, and carboxyl-terminated thin films, and microelectrodes, for the construction of various biosensors or the direct detection of biomolecules were demonstrated. The future trends of BDD electrodes in biosensing were also discussed.     

Peptide immobilization on amine-terminated boron-doped diamond surfaces

This paper reports on the formation and characterization of semicarbazide termination on aminated boron-doped diamond (BDD) surfaces, and further preparation of peptide microarray through site-specific alpha-oxo semicarbazone ligation. Hydrogen-terminated BDD electrodes were first aminated using NH3 plasma treatment and then reacted with triphosgene and Fmoc-protected hydrazine to yield a protected semicarbazide termination. Subsequent deprotection and chemical reaction with glyoxylyl peptides led to the covalent immobilization of the peptides on the surface through site-specific ligation. The resulting surfaces were characterized using X-ray photoelectron spectroscopy (XPS) and fluorescence measurements.     

Electrochemical behavior of nitrogen gas species adsorbed onto boron-doped diamond (BDD) electrodes

The adsorption of nitrogen species, in neutral electrolyte solutions, onto boron-doped diamond (BDD) electrode surfaces from dissolved NO2, NO, and N2O gases was induced at 0 V/SCE. Modified BDD electrode surfaces showed a different electrochemical response toward the hydrogen evolution reaction than did a nonmodified electrode surface in electrolyte base solution. The formation of molecular hydrogen and nitrogen gaseous species was confirmed by the online differential electrochemical mass spectrometry (DEMS) technique. Among the three nitrogen oxides gases, NO2 substantially modifies the electrolyte via hydrolysis leading to the formation of NO3- and its adsorption on the BDD electrode surface. The BDD/(NO3-) interface was the only N2O and N2 species generating system.     

Diamond Electrodes for High Sensitivity Mercury Detection in the Aquatic Environment: Influence of Surface Preparation and Gold Nanoparticle Activity

This work compares polished and unpolished boron doped diamond (BDD) electrodes decorated with two sizes of gold nanoparticles (AuNPs) for use as robust mercury sensors in aquatic environments. The size of the catalytically active AuNPs on the electrode surfaces was demonstrated to have a less significant effect on the sensitivity for mercury detection than the surface preparation of the BDD. The lowest limits of detection were achieved with the polished BDD electrodes, which both detected mercury at a concentration of 1 pM, six orders of magnitude greater sensitivity than the lowest detection limit of 5 μM achieved with an unpolished BDD electrode, and high in comparison with other reported electrode systems.     

Sensitive Electrochemical Detection of Oxalate at a Positively Charged Boron‐Doped Diamond Surface

Allyltriethylammonium bromide (ATAB) was covalently attached to the surface of hydrogen‐terminated boron‐doped diamond (BDD) thin films using a photochemical method to fabricate positively charged electrode surfaces. The anodic current for oxalate oxidation both in cyclic voltammetry and in flow‐injection analysis with amperometry was found to be up to two times larger at ATAB‐modified BDD (ATAB‐BDD) than at an unmodified BDD electrode, which may be based on the electrostatic interaction between the oxalate anion and the electrode surface. In addition, the stability of the electrochemical detection of oxalate was improved at the ATAB‐BDD electrode compared to the unmodified electrode.     

Effect of the doping level on the biological stability of hydrogenated boron doped diamond electrodes

Fouling of electrode surfaces by electrode reaction products or by biological spectator species is known to inactivate electrochemical sensors and thus limit their use in biological conditions. Here we present an investigation on the stability of boron doped diamond (BDD) electrodes with different levels of doping. Three different doping levels were used (0.1, 1 and 5% in the carbon phase). The highly doped (5%) BDD is of particular interest as it is here used for the first time for biological applications. Three different redox reactions were examined based on their electrode reaction characteristics: ruthenium(III) hexaammine (outer sphere), ferrocyanide (surface dependent), dopamine (adsorption mediated). The effect of albumin at blood concentration was studied. All results were compared with glassy carbon. There were no significant differences for the outer sphere electrochemistry, but all the BDDs showed improved resistance to fouling for the ferrocyanide oxidation. The electrocatalytic activity of BBD towards dopamine oxidation increased with increased boron content. However, this appears to be due to a larger number of defect sites which also increases the vulnerability to fouling by albumin and by electrode reaction products and the 5% BDD had similar properties to glassy carbon in this regard. These results suggest that it is possible to optimise the BDD performance for specific applications and that the large potential window for BDD may be due, at least in part, to its relatively poor electrocatalytic activity.     

Biofouling and in situ electrochemical cleaning of a boron-doped diamond free chlorine sensor

Biofouling presents a significant obstacle to the long-term use of electrochemical sensors in complex media. Drinking water biofilms reduce performance of sensors by insulating electrode surfaces by inter alia inhibiting mass transport. Boron-doped diamond (BDD) electrodes are relatively resistant to biofouling and inert at high potentials. These qualities can be exploited to create a drinking water quality sensor that resists biofouling to meet performance criteria for longer, and to enable electrochemical cleaning of the sensor surface in situ using high potentials without disconnecting or disassembling the sensor.A purpose-built BDD wall-jet sensor was compared with a glassy carbon (GC) sensor in ability to determine free chlorine, detect biofilm and remove biofilm in situ. It was found that the BDD produced accurate and reliable readings with a 4.86% standard error and a LOD of 0.18 ppm. The BDD could be electrochemically cleaned in situ whereas this was less successful with the GC electrode. The BDD electrode could also detect electroactive pyocyanin, secreted in the biofilm of the drinking water biofilm indicator organism Pseudomonas aeruginosa, potentially enabling biofouling and non-biological fouling such as scaling to be distinguished. Observed changes in flow sensitivity and current-voltage curves that correspond to fouling provide multiple fouling detection methods, resulting in an accurate, sensitive, water quality sensor that can be cleaned without disassembly or replacement of parts and can identify when cleaning is required.     

Influence of the surface termination on the electrochemical properties of boron-doped diamond (BDD) interfaces

The paper reports on the electrochemical study of heavily boron-doped diamond (BDD) in aqueous media. Cyclic voltammetry and Mott-Schottky analysis were used to evaluate the influence of the surface termination on the electrochemical properties of BDD electrodes. The behavior of aminated BDD (NH₂–BDD) interfaces, prepared from hydrogen-terminated BDD using NH₃ plasma and from photochemically oxidized BDD (HO–BDD) using 3-aminopropyltrimethoxysilane (APTMES), are investigated and compared to those of H–BDD and HO–BDD. While H–BDD and HO–BDD electrodes show classical semiconductor behavior, amine-terminated BDD interfaces exhibit metallic behavior at pH < 10 and a semiconductor behavior at more basic pH.     

Electrochemical impedance sensing of DNA hybridization on conducting polymer film-modified diamond

The impedimetric sensing of DNA hybridization on polyaniline/polyacrylate (PANI/PAA)-modified boron-doped diamond (BDD) electrode has been investigated. An ultrathin film of PANI-PAA copolymer was electropolymerized onto the diamond surfaces to provide carboxylic groups for tethering to DNA sensing probes. The electrochemical impedance and the intrinsic electroactivity of the polymer-diamond interface were analyzed after the hybridization reaction with target and non-target DNA. The impedance measurement shows changes in the impedance modulus as well as electron-transfer resistance at the stage of probe DNA immobilization (single-strand), as well as after hybridization with target DNA (double-strand). DNA hybridization increases the capacitance of the polymer-DNA layer and reduces the overall impedance of the DNA-polymer-diamond stack significantly. The polymer-modified BDD electrode shows no detectable nonspecific adsorption, with good selectivity between the complementary DNA targets and the one-base mismatch targets. The detection limit was measured to be 2 x 10(-8) M at 1000 Hz. Denaturing test on the hybridized probe and subsequent reuse of the probe indicates chemical robustness of the sensor. Our results suggest that electropolymerization followed by the immobilization of biomolecules is a simple and effective way of creating a functional biomolecular scaffold on the diamond surface. In addition, label-free electrochemical impedance method can provide direct and noninvasive sensing of DNA hybridization on BDD.