磷酸胆碱两性离子修饰的水溶性纳米银

用硼氢化钠还原硝酸银的方法制备了磷酸胆碱两性离子修饰的纳米银。通过紫外可见光谱研究显示磷酸胆碱两性离子修饰的纳米银在高盐浓度和血浆体系中均具有良好的稳定性。通过与硫普罗宁和柠檬酸钠修饰纳米银对比,磷酸胆碱两性离子修饰的纳米银在聚电解质和蛋白质溶液中显示出更好的生物稳定性,磷酸胆碱两性离子可能是一种更好的金属纳米微球稳定试剂。     

一步电沉积纳米铜/石墨烯/壳聚糖复合膜修饰玻碳电极测定邻苯二酚

用一步电沉积法制备了纳米铜/石墨烯/壳聚糖复合膜修饰玻碳电极。用循环伏安法(CV)和差分脉冲伏安法(DPV)对邻苯二酚在该修饰电极的电化学行为进行了研究。实验结果表明,在pH值为7.0的磷酸盐缓冲液(PBS)中,该修饰电极对邻苯二酚具有良好的电催化作用,其电化学信号与邻苯二酚的浓度在1.0×10-6～2.0×10-4mol/L范围内呈良好的线性关系,线性相关系数为0.991。检出限为1×10-7mol/L。结果表明,纳米铜/石墨烯/壳聚糖复合膜修饰电极显著提高了邻苯二酚的电化学响应信号,并表现出良好的选择性和重现性。该方法成功用于水样中邻苯二酚含量的测定。     

新型纳米银-磷酸锆-中性红复合膜修饰电极对过氧化氢电催化还原

制备了新型纳米银 磷酸锆复合材料 ,对中性红有强烈吸附。吸附的中性红表现出更强的氧化还原性 ,氧化还原中点电位与溶液中 (pH 7)相比正移约 2 0 0mV。将辣根过氧化酶与复合材料共同修饰在电极表面制成酶电极 ,对H2 O2 有显著电催化还原作用。催化电流在 2 .5× 1 0 - 6 ～ 2 .0× 1 0 - 3mol L范围内与H2 O2 浓度成正比 ;H2 O2 检出限为 2 .0× 1 0 - 7mol L(S N =3 ) ;传感器对 1 .0× 1 0 - 5mol LH2 O2 响应时间 <1 5s;RSD为1 4% (n=1 0 )。4℃保存 6个月该电极仍有 85 %以上初始响应。传感器有效消除了抗坏血酸等共存物质的干扰 ,回收率实验结果令人满意。     

载钯聚苯胺/聚砜复合膜修饰电极对甲酸的电催化氧化

采用电化学聚合法在铂电极表面制备了三维网状结构的聚苯胺(PAN)/聚砜(PSF)复合膜,并以此为载体制备了Pd/PAN/PSF复合膜电极,并用扫描电子显微镜对复合膜的微观形貌进行了表征。结果显示,此复合膜具有双层多孔结构,Pd纳米粒子在复合膜上平均粒径小、分散性好,有效地改善了Pd粒子的分散度和电极结构。电化学测试结果表明,Pd/PAN/PSF复合膜修饰电极对甲酸的电催化性能明显优于直接电沉积Pd的聚苯胺电极,并且表现出较高的稳定性。     

磷钼钒杂多酸/聚酰胺-胺复合膜修饰电极的制备及电催化性能

通过静电层层自组装方法在预修饰聚二烯丙基二甲基氯化铵的电极基片上制备了Dawson型磷钼钒杂多酸/聚酰胺-胺多层复合膜. 用X射线光电子能谱、紫外-可见光谱、循环伏安法和原子力显微镜分析表征了多层复合膜的形成过程; 用循环伏安法表征了该复合膜修饰电极的电化学性能, 研究结果表明, 该复合膜修饰的电极稳定性好, 对亚硝酸盐、溴酸盐的还原以及抗坏血酸的氧化具有良好的催化活性.     

电化学聚合法制备聚中性红膜修饰电极及其应用

以正交试验法研究了影响电聚合中性红制备膜修饰电极的具体条件 ,通过较少次数的试验得到了最佳条件 ,并依此制得了聚中性红膜修饰电极。用抗坏血酸对其电化学性能进行了表征 ,该修饰电极对抗坏血酸有较强的催化氧化作用 ,氧化电流与抗坏血酸的浓度在 1 .0× 1 0 - 5mol/L～ 2 .5× 1 0 - 2 mol/L之间呈线性关系 ,相关系数r=0 .9994,氧化电位为 3 3 0mV ,比裸玻碳电极负移 2 3 0mV左右 ,而且电极重现性良好。     

新型聚N，N-二甲基苯胺/多壁碳纳米管修饰电极的制备、表征与应用

采用多壁碳纳米管(MWNT)改性聚N,N-二甲基苯胺(PDMA)膜,制备了新型复合膜修饰玻碳电极,并用SEM、电化学方法对修饰电极进行表征。 结果表明,无论MWNT是以掺杂还是先滴涂MWNT再聚合DMA多层修饰方式,均会改变PDMA膜的形貌和电化学性能。 复合膜修饰电极比单一PDMA膜修饰电极大幅度提高了比表面积和电活化面积,同时使PDMA和MWNT更好地协同发挥其优良的电化学特性。 实验结果表明,层层修饰制备的聚N,N-二甲基苯胺/多壁碳纳米管复合膜修饰电极对香草醛的电化学响应远大于基体电极和其它方法制备的修饰电极,电催化作用显著提高,其过电位降低了148 mV,氧化峰电流约增加了6倍;其电极反应是吸附控制的不可逆氧化过程,转移电子数n为2,质子数m为1,传递系数α为0.4062,吸附量为Γ=3.527×10-9 mol/cm2;检出下限为8.0×10-7 mol/L,样品平均回收率为99.87%。     

聚中性红/纳米二氧化硅复合修饰电极直接测定抗坏血酸

用滴涂法和电化学聚合法制备了聚中性红/纳米二氧化硅修饰电极(PNR/nano-SiO2/GCE),并用循环伏安法和交流阻抗法研究了修饰电极表面的电化学行为。实验表明,该修饰电极对抗坏血酸(AA)表现出良好的电催化氧化性能,探讨了复合修饰电极协同增效作用的机理。用线性扫描伏安法研究了AA浓度与峰电流之间线性关系,在pH2.0的磷酸盐缓冲溶液中,AA氧化峰电流在1.8×10-6～5.0×10-3mol/L浓度范围内呈良好的线性关系,检出限为5.4×10-7mol/L(S/N=3)。该修饰电极制备简单,可用于药品及果蔬食品中抗坏血酸的直接测定。     

TiO2-石墨烯-Nafion复合膜修饰玻碳电极同时测定多巴胺和尿酸

利用在玻碳电极上修饰了TiO2-石墨烯-Nafion复合膜制得的修饰电极进行多巴胺(DA)和尿酸(UA)的同时测定。用循环伏安法(CV)和差分脉冲伏安法(DPV)研究了该修饰电极的电化学行为。在pH为7.0的磷酸盐缓冲液(PBS)中,修饰电极对于DA和UA的电化学氧化具有良好的电催化性能。DA和UA的氧化峰电流分别在2～120和60～300μmol/L浓度范围内呈良好的线性关系,检出限分别为0.066和0.102μmol/L。实验结果表明,TiO2-石墨烯-Nafion复合膜修饰电极显著提高了检测的灵敏度,并表现出良好的选择性和重现性。     

纳米银/石墨烯修饰电极测定青蒿素

本文建立一种新型的青蒿素传感器。首先,在玻碳电极上滴涂氧化石墨,通过电化学方法将氧化石墨还原为石墨烯,然后,在石墨烯上沉积纳米银得到石墨烯/纳米银修饰电极,它作为检测青蒿素的电化学传感器。用此电极对青蒿素进行测定,并通过循环伏安法、差分脉冲伏安法、交流阻抗法等研究其电化学行为。该修饰电极在测定青蒿素溶液时,表现出较正的还原电位和较大的峰电流等优势;对其实验条件如电解质溶液的p H、应用电势等进行了探查,该电化学传感器在青蒿素溶液浓度范围为1.0×10-8~3.0×10-5mol/L时与其还原峰电流呈现良好的线性关系,最低检出限为1.2×10-9mol/L(S/N=3)。此外,对该传感器的稳定性和重现性等也进行了研究,获得令人满意的结果。     

Green Synthesis of Silver Nanoparticles Using Ionic Liquid and Application for the Detection of Dissolved Oxygen

The electrochemical synthesis of silver nanoparticles (nano‐Ag) has been successfully carried out on glassy carbon electrode (GCE) and indium tin oxide electrode (ITO) using 1‐butyl‐3‐methylimidazolium tetrafluoroborate (BMT) as green electrolytes. Further the electrodeposited nano‐Ag modified ITO electrode has been examined using atomic force microscopy (AFM), and X‐ray diffraction studies (XRD). The electrodeposited Ag nanoparticles on ITO were found in the size range of 5 to 35 nm. The nano‐Ag film modified GCE was further coated with nafion (Nf) and BMT (1 : 1 ratio) mixture and found to be stable in BMT and in pH 7 phosphate buffer solution (PBS). The nano‐Ag/BMT‐Nf film modified GCE successfully applied for the oxygen reduction reaction in neutral pH (pH 7.0 PBS). The proposed film modified GCE successfully reduces the over potential and show well defined reduction peaks for the detection of dissolved oxygen using cyclic voltammetry (CV) and rotating disc voltammetry (RDE). The film also applied for the detection of dissolved oxygen using electrochemical impedance spectroscopic studies (EIS).     

Electrocatalysis of Hemoglobin in ZnO Nanoparticle/Ionic Liquid Composite Film Modified Glassy Carbon Electrode

A nanobiocompatible composite containing hemoglobin (Hb), ZnO nanoparticles (nano‐ZnO) and ionic liquid 1‐butyl‐3‐methylimidazolium hexafluorophosphate (BMIMPF₆) was fabricated and further modified on the glassy carbon electrode (GCE). The electrochemical behaviours of Hb in the composite film were carefully studied and a pair of quasi‐reversible redox peaks appeared in pH 7.0 phosphate buffer solution, which was attributed to the electrode reaction of Hb heme Fe(III)/Fe(II) redox couple. The presences of nano‐ZnO and BMIMPF₆ in the film can retain the bioactivity of Hb and greatly enhance the direct electron transfer of Hb. The immobilized Hb showed high stability and good electrocatalytic ability to the reduction of hydrogen peroxide and O₂.     

Amperometric Biosensors for Glucose Based on Layer‐by‐Layer Assembled Functionalized Carbon Nanotube and Poly (Neutral Red) Multilayer Film

Abstract

Multiwalled carbon nanotubes (MWNTs) were treated with a mixture of concentrated sulfuric and nitric acid to introduce carboxylic acid groups to the nanotubes. Conducting polymer film was prepared by electrochemical polymerization of neutral red (NR). By using a layer‐by‐layer method, homogeneous and stable MWNTs and poly (neutral red) (PNR) multilayer films were alternately assembled on glassy carbon (GC) electrodes. With the introduction of PNR, the MWNTs/PNR multilayer film system showed synergy between the MWNTs and PNR, with a significant improvement of redox activity due to the excellent electron‐transfer ability of carbon nanotubes (CNTs) and PNR. The electropolymerization is advantageous, providing both prolonged long‐term stability and improved catalytic activity of the resulting modified electrodes. The MWNTs/PNR multilayer film modified glassy carbon electrode allows low potential detection of hydrogen peroxide with high sensitivity and fast response time. As compared to MWNTs and PNR‐modified GC electrodes, the magnitude of the amperometric response of the MWNTs/PNR composite‐modified GC electrode is more than three‐fold greater than that of the MWNTs modified GC electrode, and nine‐fold greater than that of the PNR‐modified GC electrode. With the immobilization of glucose oxidase onto the electrode surface using glutaric dialdehyde, a biosensor that responds sensitively to glucose has been constructed. In pH 6.98 phosphate buffer, nearly interference‐free determination of glucose has been realized at ?0.2 V vs. SCE with a linear range from 50 µM to 10 mM and response time <10s. The detection limit was 10 µM glucose (S/N=3).     

Preparation of Carbon Nanotubes/Neutral Red Composite Film Modified Electrode and Its Catalysis on Rutin

Neutral red was directly electropolymerized onto the carbon nanotubes modified electrode. A polymerized neutral red/carbon nanotubes composite film was characterized by scanning electron micrograph (SEM) and cyclic voltammetry (CV). Well‐defined voltammetric responses are observed for [Fe(CN)₆]^4?/3? on the composite film modified glassy carbon electrode. And it's found that this modified electrode has good catalysis on the redox of rutin. Differential pulse voltammetry method was used to determinate the concentration of rutin and obtain a linear equation between the current and concentration in a certain range. The modified electrode is satisfied with us for its good sensibility and stability.     

Electrocatalytic Oxidation of Dopamine at a Nanocuprous Oxide‐Methylene Blue Composite Glassy Carbon Electrode

Cuprous oxide nanowhisker was prepared by using cetyltrimethyl ammonium bromide (CATB) as soft template, and was characterized by XRD and TEM methods. The electrochemical properties of nano‐Cu₂O and nano‐Cu₂O‐methylene blue (MB) modified electrode were studied. The experimental results indicate that nano‐Cu₂O shows a couple of redox peaks corresponding to the redox of Cu(II)/Cu(I), the peak currents are linear to the scan rates which demonstrate that the electrochemical response of Cu₂O is surface‐controlled. The composite nano‐Cu₂O‐Nafion‐MB modified electrode shows a trend of decrease of peak currents corresponding to the Cu (II)/Cu (I). However, the electrocatalytic ability of nano‐Cu₂O‐MB composite film to dopamine increases dramatically. At this composite electrode, dopamine shows a couple of quasireversible redox peaks with a peak separation of 106 mV, the peak current increases about 8 times and the oxidation peak potential decreases about 200 mV as compared to that at bare glassy carbon electrode. The peak currents change linearly with concentration of dopamine from 1×10^?7 to 3.2×10^?4 mol/L, the detection limit is 4.6×10^?8 mol/L. The composite electrode can effectively eliminate the interference of ascorbic acid and has better stability and excellent reproducibility.     

Electrochemical Studies of Oxidation of Lomefloxacin and Interaction with Calf Thymus DNA at Nano‐SnO2/DHP Modified Electrode

A nanoparticle thin film modified electrode has been constructed using a glassy carbon electrode (GCE) coated with a nano‐tin oxide/dihexadecylphosphate (nano‐SnO₂/DHP). In pH 6.0 phosphate buffer solutions (PBS), lomefloxacin (LMF) appeared as an anodic peak with peak potential of 1.35 V at nano‐SnO₂/DHP modified electrode. In comparison with a bare GCE or a nano‐SnO₂ modified electrode, the nano‐SnO₂/DHP modified electrode exhibited an enhanced effectiveness for the oxidation of LMF. Cyclic voltammetry (CVs) coupled with fluorescence and UV/vis absorbance spectra techniques were used to study the interaction of LMF with Calf thymus DNA (ctDNA) in phosphate buffer solutions (PBS). The interaction of LMF and ctDNA could result in a considerable decrease in the peak currents and positive shift in the peak potential, as well as changes of fluorescence, UV/vis adsorption spectra and gel electrophoresis. All the acquired data showed that the new adduct between LMF and ctDNA was formed. Electrochemistry coupled with spectroscopy techniques could provide a relatively easy way to obtain useful information about the molecular mechanism of LMF‐ctDNA interactions.     

A Highly Sensitive Electrochemical Impedance Spectroscopy Immunosensor for Determination of 1‐Pyrenebutyric Acid Based on the Bifunctionality of Nafion/Gold Nanoparticles Composite Electrode

A simple, highly sensitive and label‐free electrochemical impedance spectroscopy (EIS) immunosensor was developed using Nafion and gold nanoparticles (nano‐Au/Nafion) composites for the determination of 1‐pyrenebutyric acid (PBA). Under the optimal conditions, the amount of immobilized antibody was significantly improved on the nano‐Au/Nafion electrode due to the synergistic effect and biocompatibility of Nafion film and gold nanoparticles composites. The results showed that the sensitivity and stability of nano‐Au/Nafion composite electrode for PBA detection were much better than those of nano‐Au modified glassy carbon electrode (nano‐Au/GCE). The plot of increased electron transfer resistances (R_ets) against the logarithm of PBA concentration is linear over the range from 0.1 to 150 ng·mL^?1 with the detection limit of 0.03 ng·mL^?1. The selectivity and accuracy of the proposed EIS immunosensor were evaluated with satisfactory results.     

DNA／聚（3-甲基噻吩）复合膜修饰电极的制备及其应用于研究8-羟基-2＇-脱氧鸟嘌呤核苷的伏安行为及测定

首先通过电聚合方法在玻碳电极表面制备了聚（3-甲基噻吩）（P3MT）修饰膜,然后在一定电位下将DNA分子电沉积到P3MT表面,制备了DNA／（P3MT）复合膜修饰玻碳电极．研究了8-羟基-2’-脱氧鸟嘌呤核苷（8-OH-dG）在该复合膜修饰电极上的伏安行为以及扫描速度、pH值和尿酸对其伏安行为和检测的影响．实验结果表明,该复合膜修饰电极结合了P3MT和DNA两者的优点,使8-OH-dG在复合膜修饰电极上的电化学行为明显改善,而且具有很好的重现性和稳定性．在0．1mol／LpH7．0的磷酸盐缓冲溶液（PBS）中,8-OH-dG的氧化峰电流与其浓度在0．28～4．2μmol／L和4．2～19．6μmol／L两个范围内成良好的线性关系,检出限为56nmol／L（S／N=3）．该研究可以为制备HPLC或毛细管电泳电化学检测器检测8-OH—dG打下一定的基础,因此在检测尿样中8-OH-dG的研究方面具有潜在的应用价值．     

A novel nano-sized bionic function interface for enhancing the ability of red blood cells to carry oxygen

A nano-sized bionic function interface was prepared by immobilizing red blood cells onto a silver electrode, which was modified with cysteamine and colloidal gold. Scanning electron microscopy and electrochemical impedance spectroscopy were used to characterize its surface. Cyclic voltammograms in phosphate buffer solution of pH?7.0 exhibited a pair of redox peaks for oxygen at -378 and -207 mV, respectively. The reduction peak currents at -378 mV were linearly proportional to the oxygen concentration in the range from 12.6 µM to 1.39 mM. Cyclic voltammetry also indicated that the functional surface enhanced the ability of red blood cells to transport oxygen.     

新型聚中性红膜修饰碳糊电极的制备、表征及应用

运用一种新型的化学引发-电聚合方式将中性红膜固定到碳糊电极表面,制备出聚中性红薄膜修饰碳糊电极(PNR/CPE)。利用循环伏安法(CV)和交流阻抗谱(EIS)对修饰电极的电化学性能进行研究,借助于扫描电子显微镜(SEM)对修饰电极表面进行表征,并采用红外吸收光谱法(IR)和紫外可见吸收光谱法(UV-Vis)对PNR薄膜结构进行测试。结果表明,中性红成功地固定在碳糊电极表面,修饰电极的表面呈现特定的立体化结构,表面的电活性位点增多,电催化性能增大。在优化条件下,将该电极应用于鲱鱼精DNA(hs DNA)的检测,PNR电极上出现了1对较强的氧化还原峰,峰电流与其浓度在1.0×10~(-6)~8.0×10~(-5)mol/L范围内呈良好的线性关系,检出限为1.0×10~(-7)mol/L。