Selective Electrochemical Determination of Salicylic Acid in Wheat Using Molecular Imprinted Polymers

Salicylic acid is a phytohormone, playing crucial roles in signal transduction, crop growth, and development, and defense to environmental challenges. In this study, a highly selective electrochemical sensor was designed and used to determine salicylic acid using molecularly imprinted polymers for recognition. The electrochemical sensor was fabricated via stepwise modification of gold nanoparticle–graphene–chitosan and molecularly imprinted polymers on a glassy carbon electrode. With electrochemical deposition, a gold nanoparticle–graphene–chitosan film was deposited on the glassy carbon electrode and enhanced the sensitivity. Molecularly imprinted polymers with adsorbed template salicylic acid were added to the surface of the modified electrode. Cyclic voltammetry and electrochemical impedance spectroscopy were used to characterize the modified electrodes. Salicylic acid in wheat was quantified by the sensor using the molecularly imprinted polymer/gold nanoparticle–graphene–chitosan/glassy carbon electrode. Concentrations of salicylic acid from 5?×?10^?10 to 5?×?10^?5?mol?L^?1 were determined showing that the developed sensor was suitable for the analysis of food.     

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.     

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.     

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.     

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.

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.     

Clopyralid detection by using a molecularly imprinted electrochemical luminescence sensor based on the “gate-controlled” effect

A new strategy for trace analysis was proposed by preparing a molecularly imprinted polymer (MIP) sensor. The template molecules of clopyralid were determined based on “gate-controlled” electrochemiluminescence (ECL) measurement. A dense polymer film was electropolymerized on an electrode surface to fabricate the MIP–ECL sensor. The process of template elution and rebinding acted as a gate to control the flux of probes, which pass through the cavities and react on the electrode surface. ECL measurement was conducted in the luminol–H₂O₂ system. A linear relationship between ECL intensity and clopyralid concentrations in the range of 1?×?10^?9 mol/L to 8?×?10^?7 mol/L exists, and the detection limit was 3.7?×?10^?10 mol/L. The prepared sensor was used to detect clopyralid in vegetables. Recoveries of 97.9 % to 102.9 % were obtained. The sensor showed highly selective recognition, high sensitivity, good stability, and reproducibility for clopyralid detection.     

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.     

Simultaneous preconcentration and determination of malachite green and fuchsine dyes in seafood and environmental water samples using nano-alumina-based molecular imprinted polymer solid-phase extraction

Molecular imprinted polymer for determination of malachite green (MG) and fuchsine basic (FU) dyes by spectrophotometry has been used, to develop a novel simultaneous extraction and preconcentration method. Molecularly imprinted layer-coated nano-alumina (MIP@Nano-Al₂O₃) as adsorbent was prepared by surface molecular imprinting technique, and characterised by FTIR spectroscopy, scanning electron microscopy, energy dispersive X-ray analysis (EDAX) and thermogravimetric analysis (TGA). The method is based on simultaneous extraction of MG and FU dyes from aqueous solution by using molecularly imprinted polymer and measuring the absorbance at 617 and 546 nm for MG and FU, respectively. Parameters which affect the extraction efficiency such as pH, volume of eluent and amount of adsorbent were investigated and optimised. Linear calibration curves were obtained in the range of 2–750 ng mL^?1 for MG and 1–240 ng mL^?1 for FU under optimum conditions. Detection limit based on three times the standard deviation of the blank (3S_b) was 0.655 and 0.245 ng mL^?1 (n = 10) for MG and FU, respectively. The relative standard deviation (RSD) for 100 ng mL^?1 of MG and FU was 2.35 and 3.06% (n = 7), respectively. The method was applied to the simultaneous determination of the dyes in different seafood and environmental water samples.     

Effect of dose rate on degradation of 2,6-dichlorophenol by electron beam irradiation

The effects of different dose rates on the degradation of 2,6-dichlorophenol (2,6-DCP) in aqueous solution were investigated at about 2?×?10⁴ Gy absorbed dose, using a 10 MeV electron beam accelerator. It was found that the removal efficiency decreased with increasing dose rate at all initial concentrations of 0.5, 1 and 2 g L^?1, and the effect was significantly diminished by addition of P25 TiO₂ nanoparticles. Alkaline medium were unfavorable for degradation of 2,6-DCP. Hydrogen peroxide (H₂O₂) could promote the removal efficiency at a lower dose rate rather than at a higher one.

     

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.     

Surface-enhanced Raman scattering for quantitative detection of ethyl carbamate in alcoholic beverages

Ethyl carbamate, a by-product of fermentation and storage with widespread occurrence in fermented food and alcoholic beverages, is a compound potentially toxic to humans. In this work, a new approach for quantitative detection of ethyl carbamate in alcoholic beverages, based on surface-enhanced Raman scattering (SERS), is reported. Individual silver-coated gold nanoparticle colloids are used as SERS amplifiers, yielding high Raman enhancement of ethyl carbamate in three kinds of alcoholic beverages (vodka, Obstler, and white rum). The characteristic band at 1,003 cm^-1, which is the strongest and best reproducible peak in the SERS spectra, was used for quantitative evaluation of ethyl carbamate. The limit of detection, which corresponds to a signal-to-noise ratio of 3, was 9.0?×?10^-9 M (0.8 μg?·?L^-1), 1.3?×?10^-7 M (11.6 μg?·?L^-1), and 7.8?×?10^-8 M (6.9 μg?·?L^-1), respectively. Surface-enhanced Raman spectroscopy offers great practical potential for the in situ assessment and identification of ethyl carbamate in the alcoholic beverage industry.     

A new molecularly imprinted polymer for selective extraction and pre‐concentration of guaifenesin in different samples: Adsorption studies and kinetic modeling

This paper describes the synthesis of a molecularly imprinted polymer by chemical oxidation of pyrrole as the functional monomer, and at the presence of guaifenesin as the template. The prepared polymer was used as adsorbent in molecularly imprinted solid‐phase extraction followed by spectrophotometric determination. Different parameters in the solid‐phase extraction including sample pH, adsorbent weight, washing solution, and elution solvent were studied to determine optimum conditions for isolation and enrichment of guaifenesin. The results showed guaifenesin was quantitatively adsorbed on the molecularly imprinted polymer at pH 6.0 and completely eluted with an ethanol–water solution (50% v/v). An enrichment factor of four with satisfactory recoveries (87.0–95.0%) was obtained. The solid‐phase extraction columns could be used for up to six consecutive elution‐loading cycles without significant decreases in the analyte recoveries. The method had a dynamic range of 3.0 × 10^?6–1.5 × 10^?4 mol/L with a limit of detection and limit of quantification of 1.4×10^?6 and 4.5×10^?6 mol/L, respectively. The proposed procedure was used for the extraction and determination of guaifenesin in different pharmaceutical formulations, with satisfying results being achieved.     

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.     

Electrochemical sensor for determination of aflatoxin B1 based on multiwalled carbon nanotubes-supported Au/Pt bimetallic nanoparticles

A sensitive and selective imprinted electrochemical sensor for the determination of aflatoxin B₁ (AFB₁) was constructed on a glassy carbon electrode by stepwise modification of functional multiwalled carbon nanotubes (MCNTs), Au/Pt bimetallic nanoparticles (Au/PtNPs), and a thin imprinted film. The fabrication of a homogeneous porous poly o-phenylenediamine (POPD)-grafted Au/Pt bimetallic multiwalled carbon nanotubes nanocomposite film was conducted by controllable electrodepositing technology. The sensitivity of the sensor was improved greatly because of the nanocomposite functional layer; the proposed sensor exhibited excellent selectivity toward AFB₁ owing to the porous molecular imprinted polymer (MIP) film. The surface morphologies of the modified electrodes were characterized using a scanning electron microscope. The performance of the imprinted sensor was investigated by cyclic voltammetry, differential pulse voltammetry, and electrochemical impedance spectroscopy in detail. A linear relationship between the sensor response signal and the logarithm of AFB₁ concentrations ranging from 1?×?10^?10 to 1?×?10^?5 mol L^?1 was obtained with a detection limit of 0.03 nmol L^?1. It was applied to detect AFB₁ in hogwash oil successfully.     

A polydopamine-based molecularly imprinted polymer on nanoparticles of type SiO<Subscript>2</Subscript>@rGO@Ag for the detection of λ-cyhalothrin via SERS

A new method is described for the determination of the pesticide λ-cyhalothrin (LC). It combines SERS detection with molecular imprinting and largely improves selectivity. A multilayer surface imprinted nanocomposite was synthesized in two steps on a nanostructure of type SiO₂@rGO@Ag acting as a substrates. Firstly, the surface of the SiO₂@rGO@Ag composite was modified with self-polymerized dopamine. Secondly, surface-initiated polymerization was carried out to prepare a molecularly imprinted polymer (MIP) using LC as the template. The use of this SiO₂@rGO@Ag-MIP allows for excellent SERS based detection and has high selectivity for LC. The Raman intensity and LC concentration present perfect linear relationship between 10^?5 to 10^?9 mol L^?1 and the detection limit is 3.8×10^?10 mol L^?1. All the procedures are conducted in aqueous or ethanol solution.

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Graphical abstract Schematic of a new method for determination of the pesticide λ-cyhalothrin. It combines SERS detection with molecular imprinting and largely improves selectivity. A multilayer surface imprinted nanocomposite was synthesized in two steps on a nanostructure of type SiO₂@rGO@Ag acting as a substrates.

     

Man‐Tailored Biomimetic Sensor of Molecularly Imprinted Materials for the Potentiometric Measurement of Rivastigmine in Tablets and Biological Fluids and Employing the Taguchi Optimization Methodology to Optimize the MIP‐Based Membranes

This work proposes a novel biomimetic sensor for the potentiometric transduction of rivastigmine based on molecularly imprinted polymer (MIP). Using the Taguchi method, this study analyzed the optimum conditions for preparing the MIP‐based membranes. The rank order of each controllable factor was also determined. MIP‐based membranes exhibited a Nernstian response (30.7±1.1 mV decade^?1) in a concentration range from 1.0×10^?5 to 1.0×10^?2 mol L^?1 with a LOD of 6.3×10^?6 mol L^?1. The sensor was successfully applied to the determination of rivastigmine concentrations in human serum, plasma, urine, rat brain and tablets.     

Electrochemical Determination of the KRAS Genetic Marker for Colon Cancer with Modified Graphete and Graphene Paste Electrodes

The determination of KRAS was performed using electrochemical sensing devices based on graphite and graphene pastes, modified with a phthalocyanine-boron dipyrromethene (BODIPY) and azulenes dyes. The limits of quantification for KRAS were 1.54?×?10^?4?µg/mL using the sensor based on the phthalocyanine-BODIPY dye and graphite, 2.64?×?10^?7?µg/mL using the sensor based on 2,6-bis((E)-2-(furan-2-yl)vinyl)-4-(4,6,8-trimethylazulen-1-yl)pyridine/TiO₂Pt/reduced graphene oxide, and 3.84?×?10^?3?µg/mL using the sensor based on 2,6-bis((E)-2-(thiophen-3-yl)vinyl)-4-(4,6,8-trimethylazulen-1-yl)pyridine/TiO₂Pt/reduced graphene oxide. Recovery measurements demonstrated the suitable analytical performance of these sensors for the early detection of colon cancer by the analysis of whole blood samples.     

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.     

Electrochemical oxidation determination and voltammetric behaviour of 4-nitrophenol based on Cu2O nanoparticles modified glassy carbon electrode

Cu₂O nanoparticles (nano-Cu₂O) modified glassy carbon electrode (GCE) was fabricated and used to investigate the electrochemical behaviour of 4-nitrophenol (4-NP) by cyclic voltammetry (CV), chronoamperometry (CA), chronocoulometry (CC) and differential pulse voltammetry (DPV). Compared with GCE, a remarkable increase in oxidation peak current was observed. It indicates that nano-Cu₂O exhibits remarkable enhancement effect on the electrochemical oxidation of 4-NP. Under the optimised experimental conditions, the oxidation peak currents were propotional to 4-NP concentration in the range from 1.0?×?10^?6 to 4.0?×?10^?4?mol?L^?1 with a detection limit of 5.0?×?10^?7?mol?L^?1 (S/N?=?3). The fabricated electrode presented good repeatability, stability and anti-interference. Finally, the proposed method was applied to determine 4-NP in water samples. The recoveries for these samples were from 94.60% to 105.5%.