Preparation of Molecularly Imprinted Electrochemical Sensor for Detection of Vincristine Based on Reduced Graphene Oxide/Gold Nanoparticle Composite Film

An innovative molecularly imprinted electrochemical sensor was fabricated based on reduced graphene oxide (RGO) and gold nanocomposite (Au) for rapid detection of vincristine (VCR). The RGO‐Au composite membrane was obtained via direct one‐step electrodeposition technique of graphene oxide (GO) and chloroauric acid (HAuCl₄) on the surface of a glassy carbon electrode (GCE) by means of cyclic voltammetry (CV) in the potential range between ?1.5 and 0.6 V in phosphate buffer solution (PBS) of pH 9.18, which is capable of effectively utilizing its superior electrical conductivity, larger specific surface area due to its synergistic effect between RGO and Au. The molecularly imprinted polymers (MIPs) were synthesized on the RGO‐Au modified glassy carbon electrode surface with VCR as the template molecular, methyl acrylic acid (MAA) as the functional monomer, and ethylene glycol maleic rosinate acrylate (EGMRA) as a cross‐linker. The performance of the sensor was investigated by cyclic voltammetry (CV), differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS) in detail. Under the optimum conditions, the fabricated sensor exhibited a linear relationship between oxidation peak current and VCR concentration over the range of 5.0×10^?8–5.0×10^?6 mol·L ^minus;1 with a correlation coefficient of 0.9952 and a detection limit (S/N=3) of 2.6×10^minus;8 mol·L^minus;1. The results indicated that the imprinted polymer films exhibited an excellent selectivity for VCR. The imprinted sensor was successfully used to determine VCR in real samples with recoveries of 90% –120% by using the standard addition method.     

Graphene Doped Molecularly Imprinted Electrochemical Sensor for Uric Acid

A highly sensitive uric acid molecularly imprinted electrochemical sensor was prepared by using graphene doped chitosan as the functional matrix and uric acid as the template molecule; a electrodeposition technique was used to form a controllable graphene–chitosan–uric acid composited film on glassy carbon electrode whose uric acid was removed via electrochemical induce elution. Under the optimized preparation and detection conditions, the detection sensitivity of uric acid at graphene doped molecularly imprinted sensor was improved significantly compared with the undoped molecularly imprinted sensor. The mechanisms of sensitivity enhancement were studied by a.c. electrochemical impedance, adsorption model, and chronocoulometry. The observations suggest the effect of sensitivity enhancement resulted from magnified surface area and good electronic conduction of graphene. Additionally, the developed sensor exhibited specific recognition to uric acid against the competitors which consisted of structure liked substances and coexisting interference in blood serum.     

Development and application of the tartrazine voltammetric sensors based on molecularly imprinted polymers

A modified glassy carbon electrode was prepared as an electrochemical voltammetric sensor based on molecularly imprinted polymer film for tartrazine (TT) detection. The sensitive film was prepared by copolymerization of tartrazine and acrylamide on the carbon nanotube-modified glassy carbon electrode. The performance of the imprinted sensor was investigated by cyclic voltammetry, differential pulse voltammetry, and electrochemical impedance spectroscopy in detail. Under the optimum conditions, two dynamic linear ranges of 8?×?10^?8 to 1?×?10^?6?mol?L^?1 and 1?×?10^?6 to 1?×?10^?5?mol?L^?1 were obtained, with a detection limit of 2.74?×?10^?8?mol?L^?1(S/N?=?3). This sensor was used successfully for tartrazine determination in beverages.     

Acetylene black paste electrode modified with molecularly imprinted polymers/graphene for the determination of bisphenol A

A novel nanocomposite of molecularly imprinted polymers and graphene sheets was fabricated and used to obtain a highly conductive acetylene black paste electrode with high conductivity for the detection of bisphenol A. The two‐dimensional structure and the chemical functionality of graphene provide an excellent surface for the enhancement of the sensitivity of the electrochemical sensor and the specificity of molecularly imprinted polymers to improve detection of bisphenol A. The synergistic effect between graphene and molecularly imprinted polymers confers the nanocomposite with superior conductivity, broadened effective surface area and outstanding electrochemical performance. Factors affecting the performance of the imprinted sensor such as molecularly imprinted polymers concentration, foster time and scan rate are discussed. The sensor successfully detects bisphenol A with a wide linear range of 3.21 × 10^?10 to 2.8 × 10^?1 g/L (R = 0.995) and a detection limit of 9.63 × 10^?11g/L. The fabricated sensor also possessed high selectivity and stability and exhibits potential for environmental detection of contaminants and food safety inspection.     

A novel electrochemical sensor based on molecularly imprinted polymers for caffeine recognition and detection

A sensitive and selective electrochemical sensor based on molecularly imprinted polymers (MIPs) was developed for caffeine (CAF) recognition and detection. The sensor was constructed through the following steps: multiwalled carbon nanotubes and gold nanoparticles were first modified onto the glassy carbon electrode surface by potentiostatic deposition method successively. Subsequently, o-aminothiophenol (ATP) was assembled on the surface of the above electrode through Au–S bond before electropolymerization. During the assembled and electropolymerization processes, CAF was embedded into the poly(o-aminothiophenol) film through hydrogen bonding interaction between CAF and ATP, forming an MIP electrochemical sensor. The morphologies and properties of the sensor were characterized by scanning electron microscopy, cyclic voltammetry, and differential pulse voltammetry. The recognition and determination of the sensor were observed by measuring the changes of amperometric response of the oxidation-reduction probe, [Fe(CN)₆]^3?/[Fe(CN)₆]^4?, on modified electrode. The results demonstrated that the prepared sensor had excellent selectivity and high sensitivity for CAF, and the linear range was 5.0?×?10^?10?~?1.6?×?10^?7?mol?L^?1 with a detection limit of 9.0?×?10^?11?mol?L^?1 (S/N?=?3). The sensor was also successfully employed to detect CAF in tea samples.     

Construction of a novel electrochemical sensor based on molecularly imprinted polymers for the selective determination of chlorpyrifos in real samples

We present a novel electrochemical sensor based on an electrode modified with molecularly imprinted polymers for the detection of chlorpyrifos. The modified electrode was constructed by the synthesis of molecularly imprinted polymers by a precipitation method then coated on a glassy carbon electrode. The surface morphology of the modified electrode was characterized by using field‐emission scanning electron microscopy and transmission electron microscopy. The performance of the imprinted sensor was thoroughly investigated by using cyclic voltammetry and differential pulse voltammetry. The imprinted electrochemical sensor displayed high repeatability, stability, and selectivity towards the template molecules. Under the optimal experimental conditions, the peak current response of the imprinted electrochemical sensor was linearly related to the concentration of chlorpyrifos over the range 1 × 10⁻¹⁰–1 × 10⁻⁵ mol/L with a limit of detection of 4.08 × 10⁻⁹ mol/L (signal‐to‐noise ratio = 3). Furthermore, the proposed molecularly imprinted electrochemical sensor was applied to the determination of chlorpyrifos in the complicated matrixes of real samples with satisfactory results. Therefore, the molecularly imprinted polymers based electrochemical sensor might provide a highly selective, rapid, and cost‐effective method for chlorpyrifos determination and related analysis.     

Determination of Oxytetracycline with a Gold Electrode Modified by Chitosan-Multiwalled Carbon Nanotube Multilayer Films and Gold Nanoparticles

A molecularly imprinted electrochemical sensor was fabricated based on a gold electrode modified by chitosan-multiwalled carbon nanotube composite (CS-MWCNTs) multilayer films and gold nanoparticles (AuNPs) for convenient and sensitive determination of oxytetracycline (OTC). The multilayer of CS-MWCNTs composites and AuNPs were used to augment electronic transmission and sensitivity. The molecularly imprinted polymers (MIPs) were synthesized using OTC as the template molecule and o-phenylenediamine (OPD) as the functional monomer. They were modified on a gold electrode by electropolymerization. The electrochemical behavior of OTC at the imprinted sensor was characterized by cyclic voltammetry (CV), scanning electron microscopy (SEM), and amperometry. The molecularly imprinted sensor showed high selectivity and excellent stability toward OTC. The linear range was from 3.0 × 10^?8 to 8.0 × 10^?5 mol/L, with a limit of detection (LOD) of 2.7 × 10^?8 mol/L (S/N = 3). The developed sensor showed good recovery in spiked samples analysis.     

Determination of Hydrogen Peroxide by Electrochemiluminescence Using a Chitosan–graphene Composite Film Doped Cadmium-Tellurium Quantum Dot Modified Glassy Carbon Electrode

Here is reported the novel determination of hydrogen peroxide by electrochemiluminescence using a chitosan–graphene composite film doped cadmium-tellurium quantum dot modified glassy carbon electrode. The cadmium-tellurium quantum dots were studied by absorption and fluorescence spectroscopy. Scanning electron microscopy and electrochemical impedance spectroscopy were used to characterize the structure morphology of the composite matrix. The electrochemiluminescence emission was linear with the concentration of hydrogen peroxide in the range of 3.5?×?10^?7 to 1.1?×?10^?5?M with a determination limit of 2.1?×?10^?7?M. Furthermore, the modified electrode showed excellent reproducibility and stability.     

Electrochemical Behavior of Caffeic Acid Assayed with Gold Nanoparticles/Graphene Nanosheets Modified Glassy Carbon Electrode

A gold nanoparticle (AuNP) and graphene nanosheet (GN) modified glassy carbon electrode (GCE) is proposed as voltammetric sensor for caffeic acid assay. The sensor exhibits a surface‐confined and reversible process for oxidation of caffeic acid revealed by cyclic voltammetry. The results show more favorable electron transfer kinetics than the bare GCE. The linear response of the sensor is from 5×10^?7 to 5×10^?5 M with a detection limit of 5×10^?8 M (S/N=3). The AuNP/GN nanocomposite shows more favorable electrochemical activity and should be a kind of more robust and advanced functional material, which provides a promising platform for electrochemical sensors and biosensors. The method was successfully applied to detect caffeic acid in pharmaceutical tablets with satisfactory results.     

Enhanced electrochemiluminescence of luminol at the gold nanoparticle/carbon nanotube/electropolymerised molecular imprinting composite membrane interface for selective recognition of triazophos

This paper reports a surface molecular self-assembly strategy for imprinting triazophos in the electropolymerised poly(aminthiophenol) (PATP) membranes at the surface of gold nanoparticle (AuNP)/carbon nanotube (CNT) composites modified glassy (GC) electrode for electrochemiluminescent (ECL) detection of pesticide triazophos. The electrochemical and ECL behaviours of luminol at the imprinted PATP/AuNP/CNT/GC electrode were investigated before and after the rebinding of triazophos. It was also found that the ECL intensity was strikingly enhanced by the adsorbed triazophos molecules in the imprinted PATP/AuNP/CNT composite membranes, which was about 5.2-fold as compared with the blank ECL intensity. On this basis, the molecularly imprinted polymer (MIP)-ECL sensor is established for high sensitive and selective detection of triazophos residues in vegetable samples. The resulting MIP-ECL sensor shows wide linear ranges from 3.1 × 10^?8 to 3.1 × 10^?5 g L^?1 with lower detection limit of 3.1 × 10^?9 g L^?1 for triazophos. Moreover, the MIP-ECL sensor has the advantages of high sensitivity, speed, specificity, stability and can become a promising technique for organophosphate pesticide detection.     

Sensitive and Selective Electrochemical Sensor Based on Molecularly Imprinted Polypyrrole Hybrid Nanocomposites for Tetrabromobisphenol A Detection

Abstract

A sensitive and selective electrochemical sensor based on electropolymerized molecularly imprinted polypyrrole and gold nanoparticles–multiwalled carbon nanotubes (AuNPs–MWCNTs) hybrid nanocomposites was developed for the determination of tetrabromobisphenol A (TBBPA). A glassy carbon electrode (GCE) was modified with MWCNTs, and the AuNPs–MWCNTs/GCE was prepared by an electrodeposition method in HAuCl₄ solution. The AuNPs–MWCNTs nanocomposite showed high electrocatalytic activity, good conductivity, and sufficient reactive sites for the direct electro-oxidation of TBBPA. The molecularly imprinted polymers (MIPs) as recognition elements were synthesized through in situ electro-polymerization of pyrrole as functional monomers in the presence of the TBBPA template molecules. Under the optimal conditions, the developed sensor exhibited good selectivity towards TBBPA compared with structural analogs, high sensitivity, and excellent producibility. The electrochemical responses of the sensor toward TBBPA were obtained in the linear range from 0.5?nM to 1?μM with a limit of detection equal to 0.24?nM at a signal-to-noise ratio of 3.     

Ultra-sensitive electrochemical DNA biosensor based on signal amplification using gold nanoparticles modified with molybdenum disulfide,graphene and horseradish peroxidase

We have developed an ultra-sensitive electrochemical DNA biosensor by assembling probe ssDNA on a glassy carbon electrode modified with a composite made from molybdenum disulfide, graphene, chitosan and gold nanoparticles. A thiol-tagged DNA strand coupled to horseradish peroxidase conjugated to AuNP served as a tracer. The nanocomposite on the surface acts as relatively good electrical conductor for accelerating the electron transfer, while the enzyme tagged gold nanoparticles provide signal amplification. Hybridization with the target DNA was studied by measuring the electrochemical signal response of horseradish peroxidase using differential pulse voltammetry. The calibration plot is linear in the 5.0?×?10^?14 and 5.0?×?10^?9 M concentration range, and the limit of detection is 2.2?×?10^?15 M. The biosensor displays high selectivity and can differentiate between single-base mismatched and three-base mismatched sequences of DNA. The approach is deemed to provide a sensitive and reliable tool for highly specific detection of DNA.

A Polypyrrole‐Imprinted Electrochemical Sensor Based on Nano‐SnO2/Multiwalled Carbon Nanotubes Film Modified Carbon Electrode for the Determination of Oleanolic Acid

A sensitive molecularly imprinted electrochemical sensor with specific recognition ability for oleanolic acid was synthesized by modification of multiwalled carbon nanotubes (MWNTs) decorated with tin oxide nanoparticles (nano‐SnO₂/MWNTs) and polypyrrole‐imprinted polymer on a carbon electrode. The morphology and electrochemical performance of the imprinted sensor were investigated by using scanning electron microscope (SEM), X‐ray diffraction (XRD), cyclic voltammetry (CV), linear sweep voltammetry (LSV) and amperometric i–t curve. The results showed that the imprinted sensor displayed excellent selectivity toward oleanolic acid. A linear relationship between the response currents and oleanolic acid concentrations ranging from 5.0×10^?8 g/L to 2.0×10^?5 g/L was obtained for the imprinted sensor. The limit of detection (LOD) of the imprinted sensor toward oleanolic acid was calculated as 8.6×10^?9 g/L at a signal to noise ratio (S/N) of 3. This imprinted sensor was successfully applied to the determination of oleanolic acid in Acitinidia deliciosa root samples.     

Surface‐Imprinting Sensor Based on Carbon Nanotubes/Graphene Composite for Determination of Bovine Serum Albumin

A novel molecularly imprinted sensor was firstly prepared based on a carbon nanotubes/graphene composite modified carbon electrode (MIPs/CNT/GP/CE) for the selective determination of bovine serum albumin. The molecularly imprinted sensor was tested by differential pulse voltammetry (DPV) to investigate the relationship between the response current and bovine serum albumin concentration. The results showed that a wide linear range (1.0×10^?4 to 1.0×10^?10 g mL^?1) for the detection of bovine serum albumin with a low detection limit of 6.2×10^?11 g mL^?1 for S/N=3 was obtained. The novel imprinted sensor exhibited high selectivity, sensitivity, and reproducibility, which provided an applicable way for sensor development.     

A sensitive and selective sensor‐coated molecularly imprinted sol–gel film incorporating β‐cyclodextrin‐multi‐walled carbon nanotubes and cobalt nanoparticles‐chitosan for oxacillin determination

A sensitive and selective imprinted electrochemical sensor for the determination of oxacillin was developed based on indium tin oxide electrode. The proposed sensor was decorated with imprinted sol–gel film and cobalt nanoparticles‐chitosan/β‐cyclodextrin‐multiwalled carbon nanotubes nanocomposites. The surface morphologies of the modified electrodes were characterized by scanning electron microscopy and transmission electron microscope. The stepwise assembly process and electrochemical behavior of the novel sensor were characterized by differential pulse voltammetry, cyclic voltammetry and Amperometric i‐t response. The imprinted sensor displayed excellent selectivity toward oxacillin. Meanwhile, the introduced cobalt nanoparticles‐chitosan and β‐cyclodextrin‐multi‐walled carbon nanotubes exhibited noticeable amplified electrochemical response signal. The differential voltammetric anodic peak current was linear to oxacillin concentration in the range from 2.0 × 10^?7 to 1.0 × 10^?4 mol·l^?1, and the detection limit was 6.9 × 10^?9 mol·l^?1. The proposed imprinted sensor was applied to the determination of oxacillin in human blood serum samples successfully. Copyright © 2011 John Wiley & Sons, Ltd.     

Selective Electrochemical Determination of Dopamine with Molecularly Imprinted Poly(Carbazole‐co‐Aniline) Electrode Decorated with Gold Nanoparticles

Dopamine (DA) is a significant neurotransmitter in the central nervous system, coexisting with uric acid (UA) and ascorbic acid (AA). UA and AA are easily oxidizable compounds having potentials close to that of DA for electrochemical analysis, resulting in overlapping voltammetric response. In this work, a novel molecularly imprinted (MI) electrochemical sensor was proposed for selective determination of DA (in the presence of up to 80‐fold excess of UA and AA), relying on gold nanoparticles (Au_nano)‐decorated glassy carbon (GC) electrode coated with poly(carbazole (Cz)‐co‐aniline (ANI)) copolymer film incorporating DA as template (DA imprinted‐GC/P(Cz‐co‐ANI)‐Au_nano electrode, DA‐MIP‐Au_nano electrode). The DA recognizing sensor electrode showed great electroactivity for analyte oxidation in 0.2 mol L^?1 pH 7 phosphate buffer. Square wave voltammetry (SWV) was performed within 10^?4–10^?5 mol L^?1 of DA, of which the oxidation peak potential was observed at 0.16 V. The limit of detection (LOD) and limit of quantification (LOQ) were 2.0×10^?6 and 6.7×10^?6 mol L^?1, respectively. Binary and ternary synthetic mixtures of DA‐UA, DA‐AA and DA‐UA‐AA yielded excellent recoveries for DA. Additionally, DA was quantitatively recovered from a real sample of bovine serum spiked with DA, and determined in concentrated dopamine injection solution. The developed SWV method was statistically validated against a literature potentiodynamic method using a caffeic acid modified‐GC electrode.     

Preparation of an amperometric sensor for norfloxacin based on molecularly imprinted grafting photopolymerization

A sensitive amperometric sensor for norfloxacin (NF) was introduced. The receptor layer was prepared by molecularly imprinted photopolymerization of acrylamide and trimethylolpropane trimethacrylate on the surface of a gold electrode. The binding mechanism of the molecularly imprinted polymer was explored by ultraviolet (UV) and infrared (IR) spectroscopy. The chemosensor was characterized by cyclic voltammetry (CV), differential pulse voltammetry (DPV), electrochemical impedance (EI), and scanning electron microscopy (SEM). The electrode prepared by photopolymerization has a better recognition ability to template molecules than that of electropolymerization and NIP. Some parameters affecting sensor response were optimized. Norfloxacin was detected by measurements of an amperometric i–t curve. The linear relationships between current and logarithmic concentration are obtained from 1.0?×?10^?9 to 1.0?×?10^?3?mol?L^?1. The detection limit of the sensor was 1.0?×?10^?10?mol?L^?1. The proposed method is sensitive, simple, and cheap, and is applied to detect NF in human urine successfully.

Molecularly Imprinted Electrochemical Sensor Based on Modified Reduced Graphene Oxide‐gold Nanoparticles‐polyaniline Nanocomposites Matrix for Dapsone Determination

This work was designed to develop an electrochemical sensor based on molecular imprinted polyaniline membranes onto reduced graphene oxide (RGO) and gold nanoparticles (AuNPs) modified glassy carbon (GC) electrode for dapsone (DDS) determination. The prepared RGO/AuNPs/PANI‐MIPs nanocomposite was characterized by Ultra‐Violet‐Visible (UV‐Vis), Fourier transform infrared spectroscopy (FT‐IR) and scanning electronic microscopy (SEM) images. The feature of the imprinted electrode was evaluated by cyclic voltammetry (CV), differential pulse voltammetry (DPV) and impedance spectroscopy (IS). Throughout this study several analytical parameters, such as incubation time, pH value, concentration of monomer/template molecules and electro‐polymerization cycles were investigated. Under the optimized conditions, the experimental results showed best analytical performances for DDS detection with a sensitivity of 0.188 Ω/mol L^?1, a linear range from 1.0×10^?7 M to 1.0×10^?3 M and a detection limit of 6.8×10^?7 M. The bioanalytical sensor was applied to the determination of dapsone in real samples with high selectivity and recovery.     

Electrochemical Determination of Dopamine Using a Poly(3,4-Ethylenedioxythiophene)-Reduced Graphene Oxide-Modified Glassy Carbon Electrode

Poly(3,4-ethylenedioxythiophene) was deposited on a reduced graphene oxide-decorated glassy carbon electrode through an electrochemical polymerization. The resulting glassy carbon electrode-reduced graphene oxide-poly(3,4-ethylenedioxythiophene) electrode was applied as an electrochemical biosensor for the determination of dopamine in the presence of ascorbic acid and uric acid. The material deposited on glassy carbon electrode was investigated in terms of morphology and structural analysis. The comparison of electrochemical behavior of the glassy carbon electrode-reduced graphene oxide-poly(3,4-ethylenedioxythiophene) electrode with the glassy carbon electrode-graphene oxide, glassy carbon electrode-reduced graphene oxide, and glassy carbon electrode-poly(3,4-ethylenedioxythiophene) electrodes exhibited high electrocatalytic activity for dopamine detection. Electrochemical kinetic parameters of glassy carbon electrode-reduced graphene oxide-poly(3,4-ethylenedioxythiophene), including the charge transfer coefficient α (0.49) and electron transfer rate constant k_s (1.04), were determined and discussed. The glassy carbon electrode-reduced graphene oxide-poly(3,4-ethylenedioxythiophene) electrode was studied for the determination of dopamine by differential pulse voltammetry and exhibited a linear range from 19.6 to 122.8?µM with a sensitivity of 3.27?µA?µM^?1?cm^?2 and a detection limit of 1.92?µM. The developed biosensor exhibited good selectivity toward dopamine with high reproducibility and stability.     

利巴韦林原位聚合分子印迹电化学传感器的研制

利用原位聚合分子印迹技术,以3-氨基苯硼酸(3-ABBA)为功能单体,利巴韦林(RIB)为目标分子,以硼酸和顺式二醇在不同酸碱度条件下可逆形成环内酯键为原理,在玻碳电极表面原位聚合形成利巴韦林分子印迹膜,研制了测定利巴韦林的分子印迹电化学传感器。采用循环伏安法(CV)和差分脉冲法(DPV)对印迹膜性能进行研究。DPV测试表明:在最优实验条件下,利巴韦林的浓度在5.0×10~(-8)~1.0×10~(-5)mol/L范围内与峰电流呈良好的线性关系,相关系数(r~2)为0.995 3,检出限(S/N=3)为1.5×10~(-8)mol/L。特异性实验表明制备的传感器对利巴韦林的选择性良好。该分子印迹电化学传感器可用于食品中利巴韦林的检测。