纳米TiO_2修饰电极对鲁米诺电化学发光的增敏及TiO_2晶型的影响

该文水解合成并通过煅烧改变晶型,获得了金红石和锐钛矿两种晶型混合的二氧化钛纳米粒子。利用紫外可见分光光度法(UV-Vis)、激光粒度分析(LPSA)、X射线多晶衍射分析(XRD)和冷场发射扫描电镜(SEM)等方法对样品进行了表征。制备了以氧化铟锡(ITO)玻璃为基底的纳米TiO2修饰电极,并研究了晶型对鲁米诺电化学发光(ECL)的增敏作用的影响。结果表明,当粒径较小,经650℃煅烧处理形成混晶时,纳米TiO/ITO修饰电极对鲁米诺电化学发光的增敏效果最明显,为裸电极的7.5倍。     

氧化铟锡薄膜电极的表面修饰

氧化铟锡(ITO)薄膜电极具有良好的物理(导电性高、透光性好)和化学性能,对其表面进行修饰可进一步拓展其在电分析化学中的应用。该文根据目前的研究现状,简要介绍了ITO薄膜电极的制备和清洗方法,总结了ITO薄膜电极的表面修饰方法,着重介绍了应用较多的化学吸附、硅烷化、电化学接枝3类方法,并简要评述了ITO薄膜电极表面修饰方法面临的挑战及应用前景。     

电聚合苯胺过程的在线紫外-可见光谱

用在线紫外-可见光谱电化学的方法对0.5mol/L硫酸水溶液中苯胺在ITO导电玻璃电极上的电化学聚的过程进行了研究.结果表明在循环伏安条件下苯胺发生了电聚合,聚合速率与苯胺浓度成正关系;而且在线紫外-可见电化学光谱表明,在0.01mol/L苯胺溶液的电聚合过程的诱导期较长.恒电位条件下的在线紫外-可见电化学光谱显示苯胺浓度为0.05mol/L,电位为0.8V时,在ITO电极上苯胺低聚合物中间体可能产生于聚苯胺形成之前;而0.01mol/L苯胺在0.8V电位下不发生聚合,但在线紫外-可见光谱又显示此时在电极上可能存在小的苯胺低聚物的中间体;在线紫外-可见光谱表明这种中间体是可能产生并存在电极表面上的.     

三维有序结构的金掺杂纳米TiO_2修饰电极用于H_2O_2的测定

在ITO玻璃表面构建了三维有序多孔结构的金掺杂纳米Ti O2薄膜(3DOM GTD/ITO),同时制备了一种细胞色素c(Cyt c)酶生物传感器(Cyt c/3DOM GTD/ITO)。通过透射电镜(TEM)、扫描电镜(SEM)对修饰电极进行表征。紫外-可见光谱实验表明吸附在GTD上的Cyt c能够保持其生物活性,二级结构未被破坏。同时研究了Cyt c在3DOM GTD/ITO修饰电极表面的直接电化学及对H2O2的电催化行为。结果显示,Cyt c在3DOM GTD/ITO修饰电极上有显著的直接电化学响应,峰电流与扫描速度呈线性关系,说明该电极过程是表面电化学控制过程。Cyt c/3DOM GTD/ITO修饰电极对H2O2具有良好的催化性能,线性范围为3.0×10-7~1.70×10-5mol/L,检出限为3.6×10-8mol/L(S/N=3),响应时间为5 s,且该修饰电极具有较好的重现性和稳定性。     

聚灿烂甲酚蓝膜修饰电极测定抗坏血酸的研究

电化学聚合制备了聚灿烂甲酚蓝薄膜修饰玻碳电极,研究了修饰电极对抗坏血酸的电催化氧化作用。结果表明二步法电聚合制备的修饰电极性能优于一步法电聚合,在该电极上抗坏血酸的过电位降低320mV,催化氧化峰电流与抗坏血酸的浓度在2×10-5～5×10-3mol/L范围内呈良好的线性关系,相关系数0.9982。方法可用于药品及食品中抗坏血酸的分析。     

基于2-(5-碘-2-吡啶偶氮-2-二甲氨基苯胺)捕获钴构置的肼传感器

将新型显色剂2-(5-碘-2-吡啶偶氮-2-二甲氨基苯胺)(5-I-PADMA)修饰在ITO玻璃电极上以捕获溶液中的钴离子,再将其在电极上原位还原,制备了纳米钴/ITO修饰电极,基于此建立了测定肼的电化学传感新方法。通过循环伏安法和安培法,对比研究了有无5-IPADM A的两种传感器的构置及传感响应。实验结果表明:5-I-PADM A形成的修饰膜,可以高稳定存在,并有效捕获溶液体系中的钴离子,构置的传感器性能显著优于无显色剂的情况。该结果表明,将显色剂引入电化学体系,在完成传统的重金属污染处理的同时,可以二次利用富集后的金属离子,实现对一些电活性物质环境污染物的测定。     

乙醇对双核酞菁钴掺杂聚苯胺膜修饰电极特性的影响

研究了乙醇对双核酞菁钴(b i-CoPc)掺杂聚苯胺(PAn)膜修饰电极特性的影响。用循环伏安法(CV)考察了乙醇浓度不同时,玻碳电极(GC)上双核酞菁钴掺杂聚苯胺的电聚合过程,用紫外-可见吸收光谱(UV-V is)、红外光谱(FTIR)和扫描电子显微镜(SEM)表征了在氧化铟锡玻璃(ITO)电极上b i-CoPc掺杂的PAn膜,研究了乙醇对膜以及该膜修饰电极对溶液中分子氧电催化性能的影响。结果表明,乙醇对苯胺的电聚合有促进作用,有助于增加b i-CoPc掺杂量,膜的光谱特性发生变化,表面形貌更加均匀。乙醇存在下制备的修饰电极对溶液中分子氧的电催化活性明显提高。当乙醇含量为10%时,制备的电极催化能力最强。     

亚甲紫的电化学聚合和亚硝酸根的电催化还原

运用循环伏安法在光谱纯石墨电极上制备了亚甲紫聚合修饰电极，在酸性，中性和碱性溶液中，亚甲紫单体均能在电极上进行电化学了和合得到性能稳定的亚甲紫聚合膜。研究了实验条件对膜生长过程的影响和亚甲紫聚合膜修饰电极的电化学行为，并讨论了该修饰电极对亚硝酸根的电催化还原作用。     

抗坏血酸在铂纳米粒子/碳纳米管/聚吡咯复合修饰电极上的电化学行为

研究了抗坏血酸在铂纳米粒子/碳纳米管/聚吡咯复合膜修饰电极上的电化学行为,发现复合修饰电极对抗坏血酸的电化学反应具有较好的电催化作用,与空白电极相比电化学氧化电流增加了7倍。用电化学阻抗谱研究了电子在修饰电极界面上的传输过程,发现修饰电极的电催化性能与修饰电极可以提高界面电子传输能力是相关的。同时研究了碳纳米管用量、支持电解质、扫速、电沉积条件等因素对抗坏血酸在修饰电极上电化学行为的影响。     

离子液体中吡咯的电化学聚合及性质研究

以1-丁基-3-甲基咪唑六氟磷酸盐离子液体作为溶剂和支持电解质,分别在铂电极和导电玻璃电极上电化学聚合得到了聚吡咯,聚合过程中发现,在离子液体中聚合的循环伏安图,其电流的变化和传统有机溶剂中的不同,通过交流阻抗技术研究了修饰电极的电化学性质,采用在线紫外、拉曼、红外谱对聚吡咯进行了光谱表征,得到了聚吡咯的特征峰,采用扫描电镜研究了聚合物的形貌。最后将修饰电极应用到了对对苯二酚的催化反应当中,显示了一定的催化作用。     

Co-immobilization of polymeric luminol,iron(II) tris(5-aminophenanthroline) and glucose oxidase at an electrode surface,and its application as a glucose optrode

The anodic polymerization of 3-aminophthalhydrazide (luminol) and iron(II) tris 5-aminophenanthroline (Fe(phen-NH2)3(2+)) has been reported in this paper. A bilayer electrode was developed based on these polymers and the ITO conductive glass (denoted ITO[Fe(phen-NH2)3(2+)]luminol electrode). This electrode emitted light (lambdaem: 430 nm) as it was brought into contact with H2O2. At pH 10, the resulting electrochemiluminescence (ECL) showed a linear relationship with the concentration of H2O2 in the range of 10 microM(-1) mM. This bilayer electrode also showed an application potential for the detection of glucose after being further modified with glucose oxidase (denoted ITO[Fe(phen-NH2)3(2+)]luminol]GOx electrode). Although the resulting ECL decayed more rapidly in concentrated glucose solutions (e.g., I M) because of the consumption of luminol during use, the decay became less severe in diluted glucose solutions (e.g., 10 mM). According to the flow injection analysis, a linear relationship existed between the ECL and the concentration of glucose from 10(-5)-10(-3) M at pH 9. The detection limit could reach a level of 5 x 10(-5) M at this pH.     

Intensification of electrochemiluminescence of luminol on TiO2 supported Au atomic cluster nano-hybrid modified electrode

With TiO(2) nanoparticles as carrier, a supported nano-material of Au atomic cluster/TiO(2) nano-hybrid was synthesized. It was then modified onto the surface of indium tin oxide (ITO) by Nafion to act as a working electrode for exciting the electrochemiluminescence (ECL) of luminol. The properties of the nano-hybrid and the modified electrode were characterized by XRD, XPS, electronic microscopy, electrochemistry and spectroscopy. The experimental results demonstrated that the modification of this nano-hybrid onto the ITO electrode efficiently intensified the ECL of luminol. It was also revealed that the ECL intensity of luminol on this modified electrode showed very sensitive responses to oxygen and hydrogen peroxide. The detection limits for dissolved oxygen and hydrogen peroxide were 2 μg L(-1) and 5.5 × 10(-12) M, respectively. Besides the discussion of the intensifying mechanism of this nano-hybrid for ECL of luminol, the developed method was also applied for monitoring dissolved oxygen and evaluating the scavenging efficiency of reactive oxygen species of the Ganoderma lucidum spore.     

A Highly Sensitive Electrochemiluminescence Choline Biosensor Based on Poly(aniline‐luminol‐hemin) Nanocomposites

Poly(aniline‐luminol‐hemin) nanocomposites are prepared on an electrode surface through electropolymerization, and a highly sensitive electrochemiluminescence (ECL) biosensor for choline is developed based on the poly(aniline‐luminol‐hemin) nanocomposites and an enzyme catalyzed reaction of choline oxidase (CHOD). The obtained nanocomposites are characterized by scanning electron microscopy (SEM), atomic absorption spectrometry (AAS) and ECL. The results indicate that hemin can be incorporated into the poly(aniline‐luminol) nanocomposites using the facile electropolymerization method, and the poly(aniline‐luminol‐hemin) nanocomposites are rod shaped porous nanostructure. Moreover, the poly(aniline‐luminol‐hemin) nanocomposites exhibit higher ECL intensity than poly(aniline‐luminol) nanocomposites in alkaline media due to the catalytic effect of hemin on the ECL of the polymerized luminol and the electron transfer ability of hemin in the nanocomposites. CHOD is immobilized on the surface of the poly(aniline‐luminol‐hemin) nanocomposites modified electrode with glutaraldehyde, and the ECL biosensor based on poly(aniline‐luminol‐hemin)/CHOD exhibits a wider linear range for the choline detection. The enhanced ECL signals are linear with the logarithm of concentration of choline over the range of 1.0×10^?11～1.0×10^?7 mol L^?1 with a low detection limit of 1.2×10^?12 mol L^?1. Moreover, the proposed biosensor is successfully applied to the detection of choline in milk.     

Electrogenerated Chemiluminescence (ECL) Determination of Ephedrine with a Self-Assembly Multilayer Ni(II)-Polyluminol Modified Electrode

By combining the layer-by-layer (LBL) self-assembly technique with the electrochemical polymerization method, multilayer Ni(II)-polyluminol films were modified on the surface of a vaseline-impregnated graphite electrode. It was found that, compared with an electrode modified by direct electrochemical polymerization, this modified electrode offered a suitable ECL reaction micro-environment created by the special multilayer films, which was beneficial to the ephedrine hydrochloride enhancing effect for luminol ECL intensity. The ECL enhancing effect of ephedrine hydrochloride on the electro-oxidation luminol was improved on this modified electrode. Based on this finding, a new sensitive ECL method was developed for ephedrine hydrochloride determination under the optimal conditions. At the same time, a new idea is proposed for improving the analytical performance of the luminol ECL system by modifying the ECL reaction micro-environment with the layer-by-layer self- assembly method. Under the optimum experimental conditions, the ephedrine hydrochloride concentration in the range of 2.0 × 10⁻⁸–7.0 × 10⁻⁶ mol L⁻¹ was proportional to the enhanced ECL signal, and it offered an 8.0 × 10⁻⁹ mol L⁻¹ detection limit for ephedrine hydrochloride.     

Gold nanoparticle-modified ITO electrode for electrogenerated chemiluminescence: well-preserved transparency and highly enhanced activity

Although it is desirable to use transparent indium tin oxide (ITO)-coated glass substrates as working electrodes for electrogenerated chemiluminescence (ECL), their applications in ECL studies of the Ru(bpy)32+ (bpy, 2,2'-bipyridine)/tri-n-propylamine (TPrA) system have been limited because of the large overpotential of TPrA oxidation and the instability of the ITO surface at high anodic potentials. Here, we describe a simple method to achieve high ECL activity using ITO electrodes modified with gold nanoparticles (GNPs). The GNPs have been capped with fluorosurfactant ligands (i.e., Zonyl FSO). Much more facile TPrA oxidation was achieved by using the modified electrode, and an intense low-oxidation-potential (LOP) ECL signal was observed at approximately 0.88 V versus SCE. The electrode transmittance drop upon modification was generally less than 5% over the visible spectrum when small-sized GNPs (approximately 4 nm) were employed. The well-preserved transparency and highly enhanced activity make the modified electrode promising for ECL studies.     

The enhanced electrochemiluminescence of luminol on the nickel phthalocyanine modified electrode

A glassy carbon electrode (GCE) modified with nickel(II) tetrasulfophthalocyanine (NiTSPc) and Nafion was used for the investigation of the catalytic oxidation of luminol. The modified electrode was found to much more effectively improve the emission of electrochemiluminescence(ECL) of luminol in a solution containing hydrogen peroxide. The enhanced ECL signal corresponded to the catalytic oxidation of both luminol and H(2)O(2) by NiTSPc. Attached Ni(II) on GCE was oxidised to Ni(III) and then used as the catalyst for the chemiluminescence of luminol. The enhanced stability of the ECL signal with Nafion would mainly result from the prevention of the dissolution of NiTSPc and the adsorption of the oxidation product of luminol on the electrode surface. The proposed method enables a detection limit for luminal of 6.0 x 10(-8) mol L(-1) to be achieved in the presence of H(2)O(2) in the neutral solution. The enhanced ECL intensity had a linear relationship with the concentration of luminol in the range of 1.0 x 10(-7)-8.0 x 10(-6) mol L(-1).     

鲁米诺/氨基磺酸电化学发光及其多巴胺检测应用

在本文中,我们首次观察到氨基磺酸可以显著增强鲁米诺电化学发光,而且鲁米诺电化学发光的强度随着氨基磺酸浓度在0.1 μmol·L^-1至500 μmol·L^-1范围增加而线性增加。同时,我们观察到多巴胺可以显著猝灭鲁米诺-氨基磺酸电化学发光。基于该猝灭现象,我们建立了多巴胺的电化学发光分析方法,该方法的线性范围为0.5至20 μmol·L^-1,检出限为30 nmol·L^-1。该方法具有较好的选择性,尿酸、抗坏血酸、糖和一些氨基酸对电化学发光影响较小。采用标准加入法,成功地将鲁米诺-氨基磺酸体系用于尿液中多巴胺的电化学发光测定,回收率为103% ~ 105%。另外,我们还考察了多巴胺的猝灭机理,并用Stern-Volmer方程计算了的动态猝灭常数。     

鲁米诺在铂电极上阳极电致化学发光的机理研究

研究了碱性鲁米诺溶液在多晶铂电极上的阳极电致化学发光(ECL)行为,观察到电极的预极化处理和溶解氧跟发光峰强度和峰形有直接关系。结合XPS谱图和Pt,Pt|S~a~d~s修饰电极的循环伏安特性,给出了鲁米诺阳极ECL两个发光通道的可能反应机理:(1)鲁米诺阴离子在表面有新鲜Pt原子的电极上氧化生成鲁米诺自由基,然后迅速与溶液中的氧反应形成0.22V(vs.Ag)处的发光肩峰;(2)电极表面的铂氧化物能加速原子态氧的发生过程,并增大0.60V(vs.Ag)附近ECL主峰的发光强度。     

Comparative studies on electrogenerated chemiluminescence of luminol on gold nanoparticle modified electrodes

Comparative studies on the electrogenerated chemiluminescence (ECL) behavior of luminol on various electrodes modified with gold nanoparticles of different size were carried out in neutral solution by conventional cyclic voltammetry (CV). The results demonstrated that the gold nanoparticle modified electrodes could generate strong luminol ECL in neutral pH conditions. The catalytic performance of gold nanoparticle modified electrodes on luminol ECL depended not only on the gold nanoparticles but also on the substrate. Gold electrode and glassy carbon electrode were the most suitable substrates for the self-assembly of gold nanoparticles. Moreover, the gold nanoparticle modified gold and glassy carbon electrode had satisfying stability and reproducibility and did not need tedious pretreatment of electrode surface before each measurement. It was also found that luminol ECL behavior depended on the size of gold nanoparticles. The most intense ECL signals were obtained on a 16-nm-diameter gold nanoparticle modified electrode. The modified electrode prepared by the self-assembly method exhibited much better catalytic effect on luminol ECL than that prepared by the electrically deposited method. The ECL behavior of luminol on a gold nanoparticle self-assembled gold electrode was also investigated by other transient-state electrochemical techniques, such as chronoamperometry, differential pulse voltammetry, normal pulse voltammetry, and square wave voltammetry. The strongest ECL intensity was obtained under square wave voltammetric condition.     

The Sensitized Solid‐Phase Electrochemiluminescence of Electrodeposited Poly‐Luminol/Aniline on AuAg/TiO2 Nanohybrid Functionalized Electrode for Flow Injection Analysis

In this study, a copolymer of luminol with aniline is electrochemically deposited onto the AuAg/TiO₂ nanohybrid functionalized indium tin oxide coated glass. It is used as a reagentless electrochemiluminescent (ECL) electrode for flow‐injection‐analysis (FIA). The properties of this solid phase ECL electrode are characterized by cyclic voltammetry, electrochemical impedance spectroscopy and scanning electron microscopy etc. It has stronger ECL emission, sensitive response for target analytes and excellent stability. The so‐prepared ECL electrode shows sensitive response to reactive oxygen species thereafter to be applied for determination of hydrogen peroxide with FIA mode. Under optimized conditions, a mass detection limit of 0.822 pg of hydrogen peroxide was obtained. Thus the hydrogen peroxide residues in samples were detected with satisfactory result.