荧光过氧化氢酶纳米传感器的制备及性能（英文）

过氧化氢(H_2O_2)是活性氧类的主要标志物,它与多种疾病如神经退行性疾病密切相关。本文设计了一种检测细胞内过氧化氢的荧光过氧化氢酶纳米传感器。这种纳米传感器由含多聚赖氨酸、辣根过氧化物酶的生物相容性外壳和含有氧探针的多孔聚合物基质的氧传感核组成。辣根过氧化物酶(HRP)催化H_2O_2生成氧,进而通过荧光氧气探针进行探测。该酶纳米传感器的流体动力学尺寸约为270 nm,zeta电位为-18 mV,具有良好的生物相容性。它的荧光比率和时间分辨荧光均对H_2O_2高度敏感。此外,该纳米传感器可以被活细胞有效地摄取,从而可以用TRF方式灵敏地检测细胞内的H_2O_2浓度。结果表明,本实验制备的酶纳米传感器有望进一步用于监测H_2O_2相关的细胞生化反应,如氧化应激。     

MnO_2/石墨烯复合电极材料的制备与储能性能

以葡萄糖为还原剂,天然石墨片为原料,采用Hummer法制备了石墨烯粉末(Graphene);并以该产物、KMnO4和HCl为原料,采用水热法制备了MnO2/Graphene复合材料。用扫描电子显微镜和X射线衍射对所制备的复合材料进行了表征,结果表明,水热法制备的MnO2材料为纯的α-MnO2相,且石墨烯粉末的加入并没有影响MnO2的晶体结构。在1mol/L Na2SO4电解液中进行了循环伏安和计时电位扫描测试,电极材料电化学性能稳定,具有较好的可逆性,在1.27mA/cm2电流密度下进行充放电测试时,电极比电容为147.9F/g;再循环1000次后,电极仍能保持稳定的电容,是一种理想的电化学电极材料。     

普鲁士蓝/壳聚糖/多壁碳纳米管修饰电极的制备及其电化学性质

制备了普鲁士蓝(PB)/壳聚糖(CS)/多壁碳纳米管(MWCNTs)修饰的玻碳电极.采用循环伏安法(CV),扫描电子显微镜、红外光谱技术对修饰电极进行表征,结果表明,PB纳米成功的修饰到电极表面,膜结构较均一,修饰量大,具有较强的空间结构性.此外,研究了不同pH值和不同扫描速率条件下PB/CS/MWCNTs修饰电极在0.1mol/L磷酸缓冲溶液中的电化学行为,结果表明该修饰电极具有良好的电化学性质,在电化学生物传感器领域具有潜在的应用价值.     

金纳米粒子和钼氧化物复合膜修饰电极的制备及应用 (cited: 1)

利用循环伏安法将金纳米粒子和钼氧化物共同电沉积在玻碳电极表面,制备了金纳米粒子和钼氧化物复合膜修饰电极,利用SEM和XPS研究了MoO_x/AuNPs复合膜的表面形态,并研究其修饰电极对葡萄糖的电催化氧化过程. 首次提出了阳极扫描极化反向催化伏安法,即在反向扫描过程中纯的催化氧化电流通过扣减背景电流的方法被提取出来. 显著提高电流测量灵敏度改善了信噪比. 制备的MoO_x/AuNPs复合膜修饰电极在0.01～4.0 mmol/L对葡萄糖具有线性响应,电流灵敏度为2.35 mA·L/(mmol·cm²),检测限为9.01 μmol/L(信噪比为3).     

基于氨基化石墨烯量子点荧光比率法超灵敏检测辣根过氧化物酶

荧光比率法超灵敏检测辣根过氧化物酶传感器的构建主要基于酶催化邻苯二胺氧化生成2,3-二氨基吩嗪,生成的2,3-二氨基吩嗪能猝灭氨基化石墨烯量子点440nm处的荧光强度,同时伴随2,3-二氨基吩嗪本身在553nm处的荧光信号增强。随着辣根过氧化物酶浓度的增加,2,3-二氨基吩嗪位于553nm处的荧光不断增强且氨基化石墨烯量子点440nm处的荧光逐渐减弱,形成荧光比率信号。当辣根过氧化物酶浓度在2~800fM范围时,其荧光比率信号与辣根过氧化物酶的浓度具有较好的线性关系,对辣根过氧化酶的检出限为0.21fM。该传感器具有良好的选择性和抗干扰能力,并能实现检测过程的可视性。     

辣根过氧化物酶催化过氧化氢氧化邻苯二胺反应动力学的研究

本文对辣根过氧化物酶催化过氧化氢与氧化邻苯二胺合成 2 ,3 二氨基吩嗪反应动力学进行了研究。首先是用辣根过氧化物酶催化过氧化氢氧化邻苯二胺合成了氧化产物 ,并且对反应条件、酸度 ,温度 ,邻苯二胺 ,过氧化氢与辣根过氧化物酶不同的摩尔比等进行了研究。用紫外 可见光谱、红外光谱以及元素分析法对该产物进行了表征 ,结果表明 ,其产物为 2 ,3 二氨基吩嗪。然后用紫外可见分光光度法 ,根据Michaelis Menten(M M )方程研究了辣根过氧化物酶催化过氧化化氢氧化邻苯二胺反应 ,选择了最佳实验条件 ,确定了最大吸收波长λ =4 4 6 3nm ,pH =4 85和反应温度t=2 2℃ ,进行了一系列实验 ,从而确定了体系的反应级数 ,其结果表明 ,这个反应可以视为单底物反应进行处理 ,并且在实验和理论方面作出了论证 ,并且还求出Km =6 0 2× 10 - 3mol·L- 1 ,vm =7 2× 10 - 2 ΔA·min- 1 。     

以蛋白质作为模板的Au-CuO双金属簇中性葡萄糖传感器

本文提出以牛血清白蛋白为载体合成葡萄糖敏感复合材料. 首先以牛血清白蛋白作为模板,合成了Au-CuO双金属纳米团簇(Au-CuO/BSA),再与多壁碳纳米管(MWCNTs)复合,制备了新型葡萄糖传感材料(Au-CuO/BSA/MWCNTs). Au-CuO/BSA/MWCNTs能在中性条件下稳定且有效地检测葡萄糖. 利用扫描电子显微镜对Au-CuO/BSA/MWCNTs的形貌进行了表征. 使用循环伏安法测试了Au-CuO/BSA/MWCNTs的电化学性能. 葡萄糖检测实验表明,在中性环境中用Au-CuO/BSA/MWCNTs修饰的Au电极具有良好的葡萄糖检测能力,且具有较好的稳定性、准确性、重复性和选择性. 与现有的葡萄糖检测材料不同,使用牛血清白蛋白后,复合材料能在不用Nafion溶液的情况下牢固地固定在Au电极表面,减少使用Nafion固定敏感材料后存在的电流阻塞效应. 由于牛血清白蛋白的特殊效果,复合材料可以保存极长的时间;在室温下的封闭环境中,该复合材料能够保存3∽4个月后,仍具有超过80%的活性. 此外,使用牛血清白蛋白为模板制备葡萄糖敏感材料是可行性.     

催化分光光度法测定辣根过氧化物酶新方法研究

本文基于微量辣根过氧化物酶 (HRP)对过氧化氢氧化还原型罗丹明B这一显色反应的催化作用 ,建立了一个高灵敏度测定HRP及其酶标记结合物的催化光度新方法 ,探讨了该催化反应体系的反应条件及干扰情况 ,实验表明 β CD能显著增强还原型罗丹明B的稳定性 ,邻苯二胺对该催化反应有催化诱导作用。应用于测定痕量辣根过氧化物酶 ,其检出限为 12pg·mL-1,其线性范围为 15～ 2 5 0pg·10mL-1,RSD为4 2 5 % (n =10 )。     

锂离子电池Sn-Al薄膜电极的制备及电化学性能研究

采用磁控溅射沉积技术制备了纳米级Sn-Al合金薄膜电极材料,并用X射线衍射和扫描电子显微镜进行表征,用高精度电池测试系统进行充放电和循环伏安测试.结果表明直流DC与射频RF两种不同的溅射方法制备的Sn-Al薄膜电极具有很大的性能差异,前者DC法制备的材料颗粒细小,表现出稳定的循环性能,其首次放电容量为1060 mAh/g,首次效率为71.7％,电极经过50次循环后比容量保持在700 mAh/g以上.后者RF法制备的材料颗粒较大,放电比容量开始上升,第五次循环后接着逐渐衰减,表现出较差的循环性能. 关键词： 锂离子电池 磁控溅射 Sn-Al合金 电化学性能     

罗丹明染料荧光猝灭法测定超痕量辣根过氧化物酶

在HAC-NaAC缓冲液中,辣根过氧化物酶催化H₂O₂氧化KI生成I₂,过量的I-可与I₂结合形成I-₃,而I-₃分别与罗丹明S(RhS), 罗丹明G(Rh6G), 罗丹明B(RhB)和丁基罗丹明B(b-RhB)反应导致四体系在580,580,554和554 nm处的荧光强度降低。在选择条件下,对于RhS,Rh6G,RhB,b-RhB四体系,辣根过氧化物酶的浓度分别在8～6 400,40～4 000,32～3 200,40～6 400 pg·mL-1范围内与其荧光猝灭强度成线性关系,其检出限分别为3.2,3.0,2.4,3.7 pg·mL-1。其中RhS催化体系较好,用于酶联免疫乙肝试剂盒中辣根过氧化物酶活力的测定,结果比较满意。     

Electrochemical Studies of Polymeric Carbons. II. Surface Layer Formation on Glassy Carbon Electrodes in Chloride Solutions as Studied by Radiotracer Techniques

The interaction of chloride ions with glassy carbon electrodes is studied by means of ³⁶Cl as radiotracer. Chloride ions are bonded on the electrode in case of anodization depending on electrode potential and duration of the polarization. Strong interaction is observed at electrode potentials more positive than +1.3 V. A significant part of the chloride ions bonded at the glassy carbon can not be displaced neither by cathodic polarization nor by rinsing with water or non-labelled solutions. It is concluded that chloride ions are chemically bonded at the surface and the surface region of glassy carbon.     

in situ FTIR Spectroscopic Characterization of Absorbed Species on Carbon Electrode,Part II: TCNE Anion Radical from Acetonitrile Solution

The reduction of tetracyanoethylene (TCNE) to its anion radicals on glassy carbon has been studied using in situ FTIR spectroscopy. In contrast to its adsorption behavior on a platinum electrode, TCNE was found to adsorb on a carbon surface not only as the dianion but also as the tricyanovinyl alcoholate (TVA) ion. A mechanism for the formation of the TVA ion involving the presence of surface functional groups on the carbon electrode is proposed.     

Electrocatalytic properties of glassy carbon electrodes modified with hydroxy derivatives of 9,10-anthraquinone for oxygen reduction reaction

The electrochemical and electrocatalytic behavior of glassy carbon electrodes modified by one mono and four dihydroxy derivatives of anthra-9,10-quinone compounds have been investigated by cyclic voltammetric technique. The stability of the modified electrodes was ascertained in acidic and neutral media. The surface morphology of modified electrode was characterized by scanning electron microscope. The influence of pH on the electrochemical and electrocatalytic behavior was studied and pH?6.0 or 7.0 was chosen as the optimum working pH by comparing the shift in oxygen reduction potential. The anthraquinone-adsorbed glassy carbon electrodes possess excellent electrocatalytic ability for oxygen reduction with overpotential ranging from 388 to 547?mV lower than that at a plain glassy carbon electrode. Hydrodynamic volatammetric studies were performed to determine the heterogeneous rate constants for the reduction of O₂ at the surface of the modified electrodes, mass specific activity of the anthraquinones used, and the apparent diffusion coefficient of O₂ in buffered aqueous O₂-saturated solutions.     

Spectroscopic and Electrochemical Characterization of Benzoylglycine-Modified Glassy Carbon Electrode: Electrocatalytic Effect Towards Dioxygen Reduction in Aqueous Media

Present work aims to create a benzoylglycine (BG)-modified glassy carbon (GC) substrate exploiting the electroreduction of diazonium salts. Dopamine was used to confirm the attachment of benzoylglycine molecules onto the glassy carbon surface by observing the blockage of the electron transfer using cyclic voltammetry (CV). BG-modified GC surface (BG-GC) was also characterized by Raman spectroscopy and electrochemical impedance spectroscopy (EIS) techniques. The ellipsometric thickness of the BG film was measured as approximately 14 nm for seven CV cycles. The electrocatalytic effect of BG-GC electrode surface against dioxygen reduction was investigated. The catalytic effect for dioxygen reduction of the BG-GC surface was compared with that of 2-benzo[c]cinnoline, 2-benzo[c]cinnoline 6-oxide- and diethylene glycol bis(2-aminophenyl)ether-modified GC surfaces to clarify the mechanism of catalysis of the surfaces in terms of molecular structure.     

A voltammetric sensor based on GO–MWNTs hybrid nanomaterial-modified electrode for determination of carbendazim in soil and water samples

A voltammetric sensor for the determination of carbendazim was developed at a glassy carbon electrode modified with a hybrid nanomaterial (graphene oxide–multi-walled nanotubes/glassy carbon (GO–MWNTs/GC)). Its surface electrochemical property was studied with UV–Vis spectroscopy, TEM analysis, and electrochemical impedance spectroscopy. The electrochemical behavior of carbendazim was investigated on the modified electrode with cyclic voltammetry and differential pulse voltammetry. The influence of modifier dosage, buffer solution, pH, accumulation time, and scan rates on the determination was discussed. The results indicated that the reaction of carbendazim on the electrode was controlled by diffusion and was an irreversible process with two electrons. The effective area of GO–MWNTs/GC, anodic transfer coefficient, and apparent diffusion coefficient were calculated. The anodic peak current of carbendazim was linear with the concentration of carbendazim from 10 nM to 4 μM with a detection limit of 5 nM (S/N?=?3). The proposed sensor was successfully applied to the determination of carbendazim in soil and tap water.     

Amperometric thiol sensor based on Prussian blue-modified glassy carbon electrode

This paper describes the performance of an amperometric sensor for thiol detection. The sensor was designed based on a Prussian blue (PB) glassy carbon (GC) electrode. Prussian blue was chemically deposited onto the glassy carbon electrode by a dropletting method. Thiol compounds were detected at the PB-modified GC electrode by electrooxidation. A PB-modified glassy carbon electrode was applied to detect thiol at an applied potential of +0.25 V versus the Ag/AgCl electrode. This sensor showed an excellent electrochemical response for thiol compounds below μmol level with high sensitivity and selectivity and short response time. In the case of aminoethanethiol, the sensor showed a wide linearity range with RSDs <4% for the whole analyses, which reflected the highly reproducible sensor performance. The optimal conditions were investigated. By using the optimized conditions, the detection limit was found to 0.4 μM for aminoethanethiol (based on S/N = 3).     

High sensitive determination of theophylline based on manganese oxide nanoparticles/multiwalled carbon nanotube nanocomposite modified electrode

Ionics - In this study, the preparation of a glassy carbon electrode (GCE) modified with multiwall carbon nanotubes|MnO2 nanoparticles (MWNT|MnO2) was developed for electrocatalytic detection of...     

Acoustically fabricated random microelectrode assemblies

We report the insonation of bismuth, silver, copper and tungsten metal particles suspended in octane in the vicinity of a glassy carbon electrode. AFM and voltammetry reveal that metal particles are immobilised onto the electrode substrate. In the case of bismuth, silver and copper, the possible melting of the metal particles due to the high sonochemical conditions cannot unambiguously be ruled out. However, it is likely that the immobilisation of the metal particles occurs predominantly through mechanical attachment due to the high rates of mass transport, evidenced from the fact that tungsten can be immobilised at a glassy carbon surface which has a melting point (mp 3410 degrees C) outside the likely sonochemical conditions. The immobilised particles are found to be in electrical contact with the glassy carbon electrodes which can then act as random assemblies of microelectrodes. Proof-of-concept for use in electro-analysis is examined for the possible detection of arsenic and cadmium at a silver and bismuth random microelectrode assemblies, respectively. This approach suggests a simple generic methodology for the construction of microelectrode assemblies via abrasive attachment induced by insonation with power ultrasound.     

Hydrogen peroxide biosensor based on gold nanoparticles/thionine/gold nanoparticles/multi-walled carbon nanotubes-chitosans composite film-modified electrode

In this paper, an amperometric electrochemical biosensor for the detection of hydrogen peroxide (H₂O₂), based on gold nanoparticles (GNPs)/thionine (Thi)/GNPs/multi-walled carbon nanotubes (MWCNTs)-chitosans (Chits) composite film was developed. MWCNTs-Chits homogeneous composite was first dispersed in acetic acid solution and then the GNPs were in situ synthesized at the composite. The mixture was dripped on the glassy carbon electrode (GCE) and then the Thi was deposited by electropolymerization by Au-S or Au-N covalent bond effect and electrostatic adsorption effect as an electron transfer mediator. Finally, the mixture of GNPs and horseradish peroxidase (HRP) was assembled onto the modified electrode by covalent bond. The electrochemical behavior of the modified electrode was investigated by scanning electron microscope, cyclic voltammetry and chronoamperometry. This study introduces the in situ-synthesized GNPs on the other surface of the modified materials in H₂O₂ detection. The linear response range of the biosensor to H₂O₂ concentration was from 5 × 10⁻⁷ mol L⁻¹ to 1.5 × 10⁻³ mol L⁻¹ with a detection limit of 3.75 × 10⁻⁸ mol L⁻¹ (based on S/N = 3).     

Glassy carbon - A promising substrate material for pulsed laser deposition of thin Li1+xMn2O4−δ electrodes

The spinel LiMn₂O₄ is a promising candidate for future battery applications. If used as a positive electrode in a battery, the charging capacity of such a battery element is limited by the formation of a solid electrolyte interphase like layer between the electrolyte and the spinel. To study the electrolyte-electrode interaction during electrochemical cycling, spinel thin films are deposited as model electrodes on glassy carbon substrates by pulsed laser ablation. The obtained polycrystalline oxide thin films show a well defined surface morphology and are electrochemical active. Adhesion of these thin films on glassy carbon is in general poor, but can be improved considerably by a surface pretreatment or adding a thin metallic coating to the substrate prior deposition. The best adhesion is obtained for films deposited on argon plasma pretreated as well as Pt coated glassy carbon substrates. During the electrochemical characterization of Li_1.06Mn₂O_3.8 thin film electrodes, no additional reactions of the substrate are observed independent of the used electrolyte. The best cycle stability is achieved for films on Pt coated glassy carbon substrates.