基于MCM-41负载联吡啶钌的电致化学发光传感器

利用静电吸附作用将联吡啶钌[Ru(bpy)₃²⁺]负载到巯基化MCM-41介孔二氧化硅纳米颗粒上, 通过金-巯键修饰法将负载后的MCM-41固定在金电极表面, 发展了一种基于MCM-41负载联吡啶钌的电致化学发光传感器, 并研究了其电化学及电致化学发光行为. 基于三聚氰胺与增敏剂三正丙胺氨基结构的相似性, 将负载Ru(bpy)₃²⁺的MCM-41电致化学发光传感器用于三聚氰胺的检测, 获得了良好的检测效果, 为检测三聚氰胺提供了一种快速、简便的方法. 同时, 该研究为Ru(bpy)₃²⁺在电极表面的固定化提供了新思路.     

电化学发光法测定盐酸普鲁卡因

基于盐酸普鲁卡因对鲁米诺在中性介质中铂电极上电化学发光的催化增敏作用 ,建立了测定盐酸普鲁卡因电化学发光新方法。电化学发光强度与盐酸普鲁卡因质量浓度在 4 .0× 1 0 -7～6 .0× 1 0 -6g mL范围内有良好的线性关系 ,检测限为 2 .0× 1 0 -7g mL,相对标准偏差为 4 .4 %。该方法已用于针剂中盐酸普鲁卡因的测定     

Detection of thrombin using electrogenerated chemiluminescence based on Ru(bpy)3(2+)-doped silica nanoparticle aptasensor via target protein-induced strand displacement

A sensitive and selective aptasensor using tri(2,2′-bipyridyl)ruthenium(II)-doped silica nanoparticles (Ru(bpy)₃²⁺-doped SNPs) as DNA tags for detection of thrombin is developed based on the target protein-induced strand displacement of the DNA probe. For the proposed aptasensor, the aptamer was assembled on the surface of the Au electrode through Au-S binding. The hybridization event between the DNA probe labeled by the Ru(bpy)₃²⁺-doped SNPs and the aptamer was evaluated by electrogenerated chemiluminescence (ECL) measurements. Then, the DNA probe was displaced by thrombin and the binding event between the thrombin and the aptamer was monitored by ECL measurements again. The difference of ECL intensity (ΔI_ECL) of the two events could be used to quantify the thrombin. Other proteins, such as bovine serum albumin and bovine hemoglobin, had almost negligible ΔI_ECL. Under the optimal conditions, the ΔI_ECL was linearly related to the concentration of the thrombin in the range of 10 fM to 10 pM and the detection limit was down to 1.0 fM since SNPs containing a large number of Ru(bpy)₃²⁺ molecules were labeled on the DNA probe.     

Electrogenerated Chemiluminescence of Lucigenin in Ethanol Solution at a Polycrystalline Gold Electrode

The electrogenerated chemiluminescence (ECL) behavior of lucigenin in ethanol solution at a polycrystalline gold electrode was studied under conventional cyclic voltammetric conditions. Compared with the ECL of lucigenin in aqueous solution, one cathodic ECL peak (ECL‐1 at ?0.98 V versus SCE) with a shoulder (S₁ at ?0.42 V) and three new anodic ECL peaks (ECL‐2 at ?0.53 V, ECL‐3 at 0.20 V, and ECL‐4 at 0.51 V) were observed, respectively, on the curve of ECL intensity versus potential. The effects of initial potential scan direction, the presence of O₂ or N₂, potential scan ranges, supporting electrolyte and the concentration of lucigenin on these ECL peaks were examined. The electrochemistry of lucigenin in ethanol solution was also studied. The emitter of all ECL peaks was identified as N‐methylacridone (NMA) by analyzing the ECL spectra. The mechanism for these ECL peaks is proposed to be due to the reactions of lucigenin and its redox products such as Luc and DBA with dissolved oxygen or O₂ electrogenerated by the dissolved oxygen at different potentials. The formation of new anodic ECL peaks in ethanol solution is due to longer lifetime of superoxide ions and easier electro‐oxidation of DBA in nonaqueous solution, revealing that the solvent plays an important role in the lucigenin ECL reactions.     

基于离子缔合效应电化学发光分析法测定十二烷基苯磺酸钠

研究发现,丁基罗丹明B与十二烷基苯磺酸钠(SDBS)在0.02mol/LHCl介质中形成的疏水性离子缔合物,可被选择性地萃取到以液体石蜡为粘合剂的碳糊电极表面。当该电极置于0.1mol/LNaOH介质且施加1.3V电解电位时,富集于碳糊电极表面的丁基罗丹明B可被电化学氧化而产生强烈的电化学发光信号,且电化学发光强度与SDBS的浓度成正比。据此,建立了一种选择性好、灵敏度高的测定SDBS的电化学发光新方法。在最佳实验条件下,相对电化学发光强度与SDBS的浓度在2.0×10-6~8.0×10-3g/L范围内呈线性关系,其线性回归方程为ΔIECL=5.1c 44.3,检出限为5.0×10-7g/L,相关系数为0.9983。     

Flow-injection chemiluminescence determination of tetracyclines with in situ electrogenerated bromine as the oxidant

By designing a novel flow-through electrolytic cell (FEC), bromine was produced near to the surface of the platinum electrode by electrochemical oxidation of acidic KBr. The fast and weak chemiluminescence signal produced by the chemical reaction of the electrogenerated bromine with H₂O₂ was greatly enhanced by tetracyclines Based on these observations, a new, sensitive and simple electrogenerated chemiluminescence (ECL) method for the determination of tetracyclines was developed. Under the optimum experimental conditions, the calibration graphs are linear over the range 3.0×10⁻⁸ to 5.0×10⁻⁵ g ml⁻¹ for tetracycline, 2.0×10⁻⁷ to 2.4×10⁻⁵ g ml⁻¹ for oxytetracycline and 1.0×10⁻⁷ to 5.0×10⁻⁵ g ml⁻¹ for chlortetracycline. The limits of detection (S/N=3) are 1.0×10⁻⁸ g ml⁻¹ for tetracycline, 7.0×10⁻⁸ g ml⁻¹ for oxytetracycline and 1.5×10⁻⁷ g ml⁻¹ for chlortetracycline. For the determination 5.0×10⁻⁷ g ml⁻¹ tetracycline, the relative standard deviation was <5%. The proposed method was used to determine tetracyclines in pharmaceutical formulations.     

Analysis of Choline in Milk Powder Using Electrogenerated Chemiluminescence Including a Mechanism Study

A novel and simple method for detection of choline in milk powder using electrogenerated chemiluminescence (ECL) without prior separation was developed and its mechanism was studied thoroughly. Choline could not strengthen ECL signals of tris(2,2′-bipyridine)ruthenium(II) (Ru(bpy)3²⁺) to be detected. Heated to its melting point, choline decomposed into two new compounds, trimethylamine and N,N-dimethyl-2-aminoethanol. Both of them were tertiary amines and could act as ECL co-reactants to strengthen the ECL signals of Ru(bpy)3²⁺ sharply. The detection method overcame the defects of the commonly used method based on enzyme procedures and liquid chromatography-mass spectrometric technique.     

Tris(2,2′‐bipyridyl)ruthenium(II) Electrogenerated Chemiluminescence Sensor Based on Platinized Carbon Nanotube–Zirconia–Nafion Composite Films

Mesoporous films of platinized carbon nanotube–zirconia–Nafion composite have been used for the immobilization of tris(2,2′‐bipyridyl)ruthenium (II) (Ru(bpy)₃²⁺) on an electrode surface to yield a solid‐state electrogenerated chemiluminescence (ECL) sensor. The composite films of Pt–CNT–zirconia–Nafion exhibit much larger pore diameter (3.55 nm) than that of Nafion (2.82 nm) and thus leading to much larger ECL response for tripropylamine (TPA) because of the fast diffusion of the analyte within the films. Due to the conducting and electrocatalytic features of CNTs and Pt nanoparticles, their incorporation into the zirconia–Nafion composite films resulted in the decreased electron transfer resistance within the films. The present ECL sensor based on the Pt–CNT–zirconia–Nafion gave a linear response (R²=0.999) for TPA concentration from 3.0 nM to 1.0 mM with a remarkable detection limit (S/N=3) of 1.0 nM, which is much lower compared to those obtained with the ECL sensors based on other types of sol‐gel ceramic–Nafion composite films such as silica–Nafion and titania–Nafion.     

Application of DNA aptamers as sensing layers for detection of carbofuran by electrogenerated chemiluminescence energy transfer

In this study, an electrogenerated chemiluminescence (ECL) sensing platform for carbofuran detection was constructed based on ECL energy transfer (ECRET) and carbon dot (C-dot)-tagged aptamers as the recognition element. Fullerene (C60)-loaded gold nanoparticles (C60-Au) were used as the energy donor, modified on a glassy carbon electrode. C-dot-tagged DNA aptamers were used as the receptor, and ECRET then occurred between C60-Au and C-dots. After accepting the energy, the C-dots acted as a signal indicator and showed decreased signal intensity in the presence of targets, which competitively bound to DNA aptamers and blocked energy transfer. Using this robust, straight-forward strategy, the sensor showed a linear ECL response to carbofuran at concentrations from 2.0 × 10⁻¹¹ mol L⁻¹ to 8.0 × 10⁻⁹ mol L⁻¹. The detection limit of this assay was shown to be 8.8 × 10⁻¹³ mol L⁻¹. Thus, the sensing approach described in this study could be adapted for use in the detection of various pesticide residue targets.