Fabrication of a New Electrochemiluminescent Sensing Interface Based on Zinc Oxide Nanorod

A new electrochemiluminescence (ECL) sensing interface was established based on the zinc oxide nanorod in this paper. Firstly, the zinc oxide (ZnO) nanorod was prepared on an indium tin oxide (ITO) electrode surface by the method of constant current cathodic electrodeposition, on which the Nafion film was then modified, and finally ruthenium(II) tris(bipyridine) (Ru(bpy)₃²⁺) was immobilized at the ZnO nanorod/Nafion composite‐modified electrode. The sensing interface shows well ECL behaviors and perfect stability after being constant temperature treatment at 80 °C. The composite electrode was characterized by EIS, SEM and XRD. The results showed that the good stability maybe related to the water content of Nafion film.     

Determination of nicotine and its metabolite cotinine in urine and cigarette samples by capillary electrophoresis coupled with electrochemiluminescence

In this paper, CE coupled with electrochemiluminesence (ECL) detection using a 76‐μm Pt disk as working electrode was developed for nicotine (NIC) determination. The major metabolite of NIC is cotinine (COT), which has a similar tertiary amine structure to NIC. However, there is a carbonyl group attached in the structure of COT, which leads to the great decrease in ECL response. In order to improve the ECL response of COT, NaBH₄ was used for carbonyl reduction. After reduction, NIC and COT were separated and detected by CE‐ECL. ECL response plotted with NIC concentration was linear between 5.0×10^?7 and 5.0×10^?5 mol/L (81–8100 μg/L), with LOD of 5.0×10^?8 mol/L (8.1 μg/L). The developed CE‐ECL method was applied for NIC determination in urine and cigarette samples.     

Electrochemiluminescence of SDBS‐Ru(bpy)32+‐CPM System and Its Application

When the concentration of dodecyl benzene sulfonic acid sodium salt (SDBS) is 0.7 mmol·L^?1, the electrochemical and electrochemiluminescence (ECL) intensity of Ru(bpy)₃²⁺‐chlorpheniramine maleate (CPM) system at the Au electrode were studied. The results showed that compared with the absence of SDBS, enhancement of the ECL intensity was 14‐fold at Au electrode. Base on this, an ECL method was established for efficient and simple determination of CPM at Au electrode. Under the optimum experimental condition, the enhanced ECL intensities had good linear relationship with the concentration of CPM in the range of 1.0×10^?4–1.0×10^?7 mol·L^?1, and a linear regression equation was obtained as follows: I (counts)=48.805×10⁶c+394.03 (r=0.9975), the detection limit for CPM was 1.4×10^?8 mol·L^?1. The RSD for 5 times determinations of 1.0×10^?5 mol·L^?1 CPM was 3.2%. The results of recovery test were between 96.3%–102.5%, and the RSD of recovery test (n=5) was 2.7%. In addition, eleven kinds of tertiary amines‐Ru(bpy)₃²⁺ systems were investigated in the absence and presence of SDBS. The results showed that the enhancement of SDBS on ECL intensity of tertiary amines‐Ru(bpy)₃²⁺ systems was universal.     

花状氧化锌纳米晶的制备及其电化学传感研究

本文以丙三醇为反应溶剂,在氧氧化钾体系中制备了两种花状氧化锌纳米晶.讨论了不同实验条件对氧化锌纳米晶形成影响,通过改变氢氧化钾浓度、反应温度和体系中水含量等条件来调节材料形貌.探讨了花状氧化锌纳米晶可能的形成过程.用X射线粉末衍射、扫描电子显微镜、紫外可见光谱等分析技术对制备的氧化锌纳米晶进行了表征.结果表明两种花状纳...     

Preparation of Luminol-doped Nanoparticle and Its Application in DNA Hybridization Analysis

Introduction The analysis of DNA sequence and DNA mutant detection play fundamental roles in the rapid development of molecular diagnostics and in the anticancer drug screening. Therefor many detection techniques of DNA sequence have been developed in recent years. These techniques mainly depend on the nucleic acid hybridization1 and their sensitivities are related to the specific activity of the label linked to the DNA probe. The degree of hybridization of probe to its complementary DN…     

Enhanced Electrochemiluminescence Performance of Ru(bpy)32+/CuO/TiO2 Nanotube Array Sensor for Detection of Amines

Tripropylamine (TPA) is a highly toxic and carcinogenic compound, therefore, TPA concentration in water must be monitored to protect health and the environment. In this paper, an electrochemiluminescent (ECL) sensor was fabricated by immobilising Ru(bpy)₃²⁺‐modified CuO nanoparticles (NPs) on a TiO₂ nanotube array (TN) electrode. Compared to an ECL sensor fabricated by immobilising Ru(bpy)₃²⁺ on a TN only electrode, the as‐prepared sensor displays a 30 % enhanced ECL signal and a detection limit of 9.6×10^?10 M at a signal‐to‐noise ratio=3 with the concentration of TPA in a range 1×10^?9 to 1×10^?5 M. The results from this study indicated a new approach for the enhancement of performance of ECL sensor in detecting TPA in water.     

Enhanced Anodic Electrochemiluminescence of Dissolved Oxygen with 2‐(Dibutylamino) ethanol at TiO2 Nanoparticles Modified Platinum Electrode for Dopamine Detection

The anodic electrochemiluminescence (ECL) of dissolved oxygen with 2‐(dibutylamino) ethanol (DBAE) on platinum electrode has been reported previously by our group. Interestingly, the ECL intensity can be greatly amplified at TiO₂ nanoparticles modified platinum electrode (TiO₂/Pt), which is due to the catalytic effect of TiO₂ nanoparticles to electrochemical oxidation of DBAE. It is the first case to obtain the enhanced ECL from luminophor by electrochemical catalysis of co‐reactant. The enhanced anodic ECL intensity can be quenched by dopamine sensitively. And the ECL intensity versus the logarithm of concentration of dopamine was linear over the 4.0×10^?12–1.8×10^?8 M (R²=0.9957), with the limit of detection of 2.7×10^?12 M (S/N=3).     

Determination of Hg2+ in Tap Water Based on the Electrochemiluminescence of Ru(phen)32+ and Thymine at Bare and Graphene Oxide‐Modified Glassy Carbon Electrodes

The electrochemiluminescence (ECL) of the Ru(phen)₃²⁺/thymine (T) system at bare and graphene oxide (GO)‐modified glassy carbon (GC) electrodes was utilized to determine Hg²⁺ in tap water. The ECL intensity of Ru(phen)₃²⁺ was considerably enhanced by the addition of thymine because of the occurrence of ECL reaction between them. Subsequently, the ECL intensity of Ru(phen)₃²⁺/T system rapidly decreased with the addition of Hg²⁺ because of the formation of a T‐Hg²⁺‐T complex. A linear response (R²=0.9914) was obtained over a Hg²⁺ concentration range of 1.0×10^?9 mol/L to 1.0×10^?5 mol/L with a detection limit of 3.4×10^?10 mol/L at a bare GC electrode in 0.1 mol/L phosphate buffer (pH=8.0). The detection limit can be further reduced to 4.2×10^?12 mol/L after modification of the GC electrode by GO. To verify its applicability, the proposed method was utilized to determine Hg²⁺ in tap water and simulated wastewater. The method exhibited good reproducibility and stability and thus reveals the possibility of developing a novel ECL detection method for Hg²⁺.     

Enhanced Iridium Complex Electrochemiluminescence Cytosensing and Dynamic Evaluation of Cell‐Surface Carbohydrate Expression

A newly prepared [(ppy)₂Ir(dcbpy)]⁺?PF₆^? (ppy: 2‐phenylpyridyl; dcbpy: 4,4′‐dicarboxy‐2,2′‐bipyridyl) and gold nanoparticle functionalized mesoporous silica nanoparticle (Au/Ir‐MSN) is reported. Based on the binding between concanavalin A (Con A) and mannose, the novel nanoparticle was applied to an ultrasensitive electrochemiluminescence (ECL) in situ cytosensing strategy and the dynamic evaluation of cell‐surface carbohydrate expression. The ECL activity of the presented Con A@Au/Ir‐MSN nanoprobe was greatly enhanced by employing a functionalized nanoparticle and graphene nanomaterial with an increased surface area and simultaneously improved electron‐transfer efficiency at the electrode interface. Under optimal conditions, the sandwich‐type ECL cytosensor showed a linear response to K562 cells at concentrations ranging from 1.0×10² to 1.0×10⁶ cells mL^?1 and realized a low detection limit of a single cell. The proposed method could also be successfully used for monitoring the dynamic variation of carbohydrate expression in cancer cells in response to external stimulation by an inhibitor.     

Electrochemiluminescent Detection Method for Glyphosate in Soybean on Carbon Fiber-ionic Liquid Paste Electrode

A carbon fiber paste electrode using ionic liquid as the binder (CFILE) was fabricated. The electrochemical characteristics of the electrode was examined in ferro‐/ferricyanide solution and showed better conductivity and reversibility when compared with graphite paste‐ionic liquid electrode (GPILE) and a little better than that on the carbon nanotube paste‐ionic liquid electrode (CNTILE). Glyphosate (GLY), a pesticide, exhibited excellent catalysis to the oxidation of Ru(bpy)²⁺₃ on CFILE and brought an obvious enhancement to the electrochemiluminescence (ECL) intensity of Ru(bpy)²⁺₃. Based on the catalytic ability of GLY, a simple ECL method for GLY detection had been established. Under optimum conditions, the enhanced ECL intensities were found to had linearly respond to the GLY concentration between 3.0×10^?7 and 3.0×10^?5 mol/L, and the detection limit (S/N=3) was 2.0×10^?7 mol/L. The electrode also showed excellent sensitivity in detecting GLY‐spiked soybean samples. The linear range for GLY in soybean samples was 1.0×10^?6–4.0×10^?5 mol/L and the detection limit was 5.0×10^?7 mol/L, equal to 8.45 µg GLY in per gram of soybean. The detection limit in soybean sample was lower than the USA, EU regulation and so on. If the method is coupled with the separation technology, it can be applied to detect the GLY in the contaminated samples.     

Highly Sensitive Electrogenerated Chemiluminescence Isoniazid with NiO Nanoparticles‐modified Graphite Electrode

Abstract

NiO nanoparticles (NiO NPs) were prepared with chemical precipitation method and modified on the surface of vaseline‐impregnated graphite electrode with chitosan. It was found that, based on the catalysis of the NiO NPs for the chemiluminescent reaction of the ECL process, the enhancing effect of isoniazid on the weak electrogenerated chemiluminescence (ECL) signal of luminol at a NiO NPs‐chitosan modified electrode was stronger than that at a bare graphite electrode. Under the optimum experimental conditions, the relative ECL intensity was linear with isoniazid concentration over the range 3.0×10^?10～1.0×10^?6 g/ml at the NiO NPs‐chitosan modified electrode with a detection limit of 1.0×10^?10 g/ml.     

Graphene Oxide/ZnO Nano Composite for Sensitive and Selective Electrochemical Sensing of Levodopa and Tyrosine Using Modified Graphite Screen Printed Electrode

Determination of levodopa and tyrosine as two important species for treatment of Parkinson's disease is described. A novel electrochemical sensor involving graphene oxide/ZnO nanorods (GR/ZnO) nano composite and the graphite screen‐printed electrodes (GSPE) was developed for the simultaneous detection of levodopa and tyrosine. The screen‐printed electrodes with several advantages, including low cost, versatility and miniaturization were employed. On the other hand, the graphene oxide/ZnO nanorods nano composite was casted on the surface of GSPE to obtain GR/ZnO/SPE. The proposed nano sensor has excellent performance such as high sensitivity, good selectivity and analytical application in real samples. The combination of graphene oxide/ZnO nanorods nano composite with the screen‐printed electrode is favorable for amplifying electrochemical signals. Under optimized conditions square wave voltammetry (SWV) exhibited linear dynamic ranges from 1.0×10^?6 to 1.0×10^?3 M and 1.0×10^?6 to 8.0×10^?4 M with detection limits of 4.5×10^?7 M and 3.4×10^?7 M for levodopa and tyrosine respectively.     

Electrode Based on Nickel‐containing SBA‐15 for the Determination of Copper in Ethanol Biofuel

A sensor based in a graphite–polyurethane composite electrode modified with the mesoporous nanostructured silica with hexagonal array of pores called Santa Barbara Amorphous type material (SBA‐15) containing nickel was built. The presence of Ni, incorporated during the synthesis of SBA‐15, resulted in an increase in sensitivity when compared to the other electrodes based on the unmodified SBA‐15. A procedure was proposed for the determination of Cu²⁺ in ethanol biofuel by square wave stripping voltammetry with linear response in concentration levels of 1.0×10^?8 and 1.0×10^?7 mol L^?1, resulting in a limit of detection of 1.83×10^?10 mol L^?1 and precision (RSD) of 2.09 %.     

Determination of Reduced Nicotinamide Adenine Dinucleotide Based on Immobilization of Tris(2,2′‐bipyridyl) Ruthenium(II) in Multiwall Carbon Nanotubes/Nafion Composite Membrane

Abstract

An electrochemiluminescence (ECL) method for reduced nicotinamide adenine dinucleotide (NADH) was proposed by immobilizing tris(2,2′‐bipyridyl) ruthenium(II) (Ru(bpy)₃ ²⁺) in multiwall carbon nanotubes (MWCNTs)/Nafion composite membrane that was formed on glassy carbon electrode surface. The electrochemical and ECL behaviors of the immobilized Ru(bpy)₃ ²⁺ were investigated. The cyclic votammogram of the modified electrode in pH 7.0 phosphate buffer solution showed a couple of redox peaks at +1190 and +1060 mV at 100 mV/s. The composite film had a more open structure and a large surface area allowing faster diffusion of Ru(bpy)₃ ²⁺. The presence of MWCNTs resulted in the improved ECL sensitivity and longer‐term stability of the modified electrode. The modified electrode showed a linear response to NADH in the concentration range of 1.0×10^?6 to 1.6×10^?5 M with a detection limit of 8.2×10^?7 M.     

Ultrasensitive Eletrogenerated Chemiluminescence Immunoassay by Magnetic Nanobead Amplification

An ultrasensitive electrogenerated chemiluminescence (ECL) immunoassay was proposed by using magnetic nanobeads (MNBs) as the carrier of ECL labels for ECL emission amplification. Carcinoembryonic antigen (CEA) and MNBs were initially immobilized on a platform in 1 : 1 molar ratio via sandwich immunoreaction. Subsequently, the MNBs were released from the platform and labeled with Ru(bpy)₃²⁺ species. After the MNBs with Ru(bpy)₃²⁺ were immobilized on an Au electrode, ECL of the Ru(bpy)₃²⁺ was measured for CEA determination. A linear relation between the ECL intensity and CEA concentration was obtained in a range of 1×10^?14 to 3×10^?13 mol/L (2.0 to 60 pg/mL) with a limit of detection of 8.0×10^?15 mol/L (1.6 pg/mL).     

Zn(II)‐Selective Membrane Electrode Based on Tetraazamacrocycle [Bzo2Me2Ph2(16)hexaeneN4]

A PVC membrane electrode using [Bzo₂Me₂Ph₂(16)hexaeneN₄] ( I ) as ionophore, oleic acid as lipophilic additive and o‐nitrophenyloctyl ether as plasticizer has been investigated as Zn(II)‐selective electrode. The membrane incorporating 34.9% (w/w) PVC, 2.3% I , 4.7% OA and 58.1% o‐NPOE gave linear response over the concentration range 2.82×10^?6?1.0×10^?1 M with a Nernstian slope of 28.5±0.2 mV/decade of concentration with a detection limit of 2.24×10^?6 M (0.146 ppm) and showed a response time of less than 10 s and could be used in pH range 2.5–8.5. High selectivity was obtained over a wide variety of metal ions. The proposed electrode was successfully used as an indicator electrode in potentiometric titration of zinc ions with EDTA and for determination of zinc in real samples.     

Enhanced Electrochemiluminescence of TiO2 Nanoparticles Modified Electrode by Nafion Film and Its Application in Selective Detection of Dopamine

In this work, a simple and effective approach to obtain stable, nontoxic and strong electrochemiluminescence (ECL) interfaces is provided by coating TiO₂ nanoparticles (NPs) modified glassy carbon electrode (GCE) surfaces with Nafion. Unlike a decrease of the current resulting from the blocked diffusion usually displayed in electrochemical processes by Nafion coating, a Nafion/TiO₂ NPs modified electrode not only shows a highly stable ECL, but also shows an 8‐fold increase of ECL intensity and a reduction of the overpotential of ca. 300 mV in the presence of K₂S₂O₈ as co‐reactant, compared with those of bare TiO₂ NPs modified electrodes. The roles of Nafion coating on TiO₂ NPs in the ECL process are proposed to be twofold: to provide refuge for the free radicals and to enhance the electron‐hole recombination. Benefiting from its excellent ECL performance, the cationic exchange function of Nafion and the susceptible to being oxidized performance of dopamine (DA) by holes, the Nafion/TiO₂ composite electrode could be used to sensitively and selectively detect DA with a detection limit of 1.0×10^?11 M and a linear range of 1.0×10^?11–6.0×10^?7 M. The coexisting anionic species such as excess ascorbic acid show little interference on DA detection.     

Electrocatalytic oxidation of formaldehyde and methanol on Ni(OH)2/Ni electrode

A nickel hydroxide-modified nickel electrode (Ni(OH)₂/Ni) was successfully prepared by the cyclic voltammetry (CV) method and the electrocatalytic properties of the electrode for formaldehyde and methanol oxidation have been investigated respectively. The Ni(OH)₂/Ni electrode exhibits high electrocatalytic activity in the reaction. A new method has been developed for formaldehyde determination at the nickel hydroxide-modified nickel electrode and the experimental parameters were optimized. The oxidation peak current is linearly proportional to the concentration of formaldehyde in the range of 7.0 × 10^?5 to 1.6 × 10^?2 M with a detection limit of 2.0 × 10^?5 M. Recoveries of artificial samples are between 93.3 and 103.5%. The effect of scan rate and methanol concentration on the electrochemical behavior of methanol were investigated respectively.     

Highly Sensitive Electrogenerated Chemiluminescence Detecting Ranitidine Based On Chemically Modifying Microenvironment of the Chemiluminescence Reaction

Using a graphite electrode modified with vaseline and NiO, ranitidine showed a strongly ECL enhancing effect for the weak ECL signal of electrooxidation of luminol. Based on this finding, a more sensitive ECL method for ranitidine was firstly proposed. Under the optimum experimental conditions, the ranitidine hydrochloride concentration in the range of 3.0×10^?8–9.0×10^?6 mol/L was proportional to the enhancing ECL signal and offered a 9×10^?9 mol/L detection limit for ranitidine hydrochloride. At the same time, based on the investigation on this ECL reaction mechanism, a new concept, to improve the suitable ECL reaction micro‐environment with chemically modified electrode technique for the better analytical performances of ECL analysis was also firstly proposed.     

First Electrochemical Report for Simultaneous Determination of Norepinephrine,Tyrosine and Nicotine Using a Nanostructure Based Sensor

A carbon paste electrode was modified with ZnO nanorods and 3‐(4′‐amino‐3′‐hydroxy‐biphenyl‐4‐yl)‐acrylic acid (3,4′AAZCPE) to cause electrocatalysis of norepinephrine oxidation. It has been found that the oxidation of norepinephrine at the surface of modified electrode occurs at a potential of about 180 mV less positive than that of an unmodified carbon paste electrode. Square wave voltammetry (SWV) exhibits linear dynamic range from 1.0×10^?7 to 8.0×10^?5 M and a detection limit of 3.9×10^?8 M for norepinephrine. In addition, this modified electrode was used for simultaneous determination of norepinephrine, tyrosine and nicotine.