Molecularly Imprinted Electrochemical Sensor for the Detection of Organophosphorus Pesticide Profenofos

The presence of profenofos (PFF) in food has been strictly limited by legislation due to its genotoxic and toxic effects on health. It is therefore very important to establish simple and rapid analytical methods to detect traces of this insecticide. A reusable molecularly imprinted polypyrrole MIP(O-PPy) on a glassy carbon electrode (GCE) has been developed to measure PFF. The PPy was polymerized by cyclic voltammetry (CV) in the presence of template molecules (PFF) in an acidic solution on a GCE. The various experimental parameters such as film thickness, analyte/monomer ratio, and removal/rebinding requirements were examined and optimized. The signal of the redox probe (ferrocyanide/ferrocyanide) was used for the electrochemical detections. All steps of the sensor manufacturing, removal/rebinding of template molecules, and response to different PFF concentrations were tested by cyclic voltammetry (CV), differential pulse voltammetry (DPV), and electrochemical impedance spectroscopy (EIS). The MIP sensor was able to detect PFF in the linear ranges of 1.0×10⁻⁹ to 1.0×10⁻⁶ M and 1.0×10⁻⁹ to 5.0×10⁻⁶ M, with detection limits, a signal-to-noise ratio (S/N) of three was used to estimate LOD, of about 1 nM using DPV and EIS, respectively. The MIP (PPy) GCE provided excellent PFF recognition performance and was successfully used to quantify PFF in sweet pepper samples, yielding recoveries not greater than 108 %.     

Development of an Electrochemical Sensor for Selective Determination of Dopamine Based on Molecularly Imprinted Poly(p-aminothiophenol) Polymeric Film

In this study, a molecularly imprinted electrochemical sensor (MIP/DA) was investigated for selective and sensitive determination of dopamine (DA) by electrochemical polymerization of p-aminothiophenol in the presence of DA on gold electrode. According to electrochemical behaviour of the sensor, gained through cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), MIP/DA sensor showed distinctive electron transfer characteristics in comparison to the non-imprinted (NIP/DA) sensor. Besides the MIP/DA sensor showed high selectivity for dopamine through its analyte specific cavities. The sensor had a broad working range of 5.0×10⁻⁸–2.0×10⁻⁷ M with a limit of detection (LOD) of 1.8×10⁻⁸ M and the developed sensor was successfully applied for determination of dopamine in pharmaceutical samples.     

Using an Electrochemical MIP Sensor for Selective Determination of 1-Naphthol in Oilfield Produced Water

A molecularly imprinted polymer (MIP) sensor was successfully constructed on glassy carbon electrode for the determination of 1-naphthol (1-Nph). The sensor was constructed by electropolymerization on bare GCE in the presence of the target molecule. The recognition of 1-Nph was conducted indirectly using [Fe(CN)₆]^3−/4− as redox probe. The MIP sensor presented wide linear working range and limit of detection of 1.5×10⁻⁹ mol L⁻¹. The MIP sensor was applied for the determination of 1-Nph in oilfield produced water. The results obtained showed good selectivity and sensitivity of the proposed sensor in terms of 1-Nph quantification.     

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.     

Polyaniline-ZnO−NiO Nanocomposite Based Non-enzymatic Electrochemical Sensor for Malathion Detection

An electrochemical sensor based on polyaniline-ZnO−NiO (PANI-ZnO−NiO) nanocomposite was developed for the non-enzymatic detection of malathion. The structure, surface morphology, and optical properties of the as-prepared nanocomposite were studied by XRD, FTIR, SEM, and UV-Vis spectroscopy. The electrochemical behavior of the nanocomposite based sensor was first evaluated through cyclic voltammetry (CV). Under optimum conditions, differential pulse voltammetry (DPV) was further utilized for malathion detection, which proved the PANI-ZnO−NiO/GCE electrode as an effective electrochemical sensor. The developed electrochemical sensor showed a low detection limit of 1.0×10⁻⁸ M with a wider linear range of 10 to 70 nM for malathion.     

A Novel Electrochemical Sensor Based on Copper‐based Metal‐Organic Framework for the Determination of Dopamine

A glassy carbon electrode (GCE) modified with a copper‐based metal‐organic framework (MOF) [HKUST‐1, HKUST‐1 = Cu₃(BTC)₂ (BTC = 1,3,5‐benzenetricarboxylicacid)] was developed as a highly sensitive and simple electrochemical sensor for the determination of dopamine (DA). The MOF was prepared by a hydrothermal process, and the morphology and crystal phase of the MOF were characterized by scanning electron microscopy (SEM) and X‐ray diffraction (XRD), respectively. Meanwhile, the electrochemical performance was investigated using cyclic voltammetry (CV), differential pulse voltammetry (DPV), and electrochemical impedance spectroscopy (EIS). Under optimized conditions, the modified electrode showed excellent electrocatalytic activity and high selectivity toward DA. The linear response range was from 5.0 × 10⁻⁷ to 1.0 × 10⁻⁴ M and the detection limit was as low as 1.5 × 10⁻⁷ M. Moreover, the electrochemical sensor was used to detect DA in real samples with excellent results. MOF‐based sensors hold great promise for routine sensing applications in the field of electrochemical sensing.     

A Study of Preparation and Performance of a Dichlorvos Electrochemical Sensor Based on Molecularly Imprinted Technique

A new dichlorvos molecularly imprinted electrochemical sensor was prepared. The sensitive membrane sensor was fabricated by electro-polymerizing on an Au electrode surface using o-aminophenol as a monomer and dichlorvos as a template. The 5 mmol/L K₃[Fe(CN)₆] containing 0.1 mol/L KCl was used as the test background solution, while cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were used to study the properties of the senor. The changes of oxidation peak current versus dichlorvos concentration showed linearity in the range of 0.12–0.42 µmol/L (R ² = 0.9432) and 0.45–15 µmol/L (R ² = 0.9516) with a detection limit of 0.06 µmol/L (S/N = 3). Moreover, the selectivity and repeatability properties of the dichlorvos electrochemical sensor were examined. Results showed that the senor had excellent repeatability (RSD = 3.92%, n = 5), good selectivity to the dichlorvos in detection, and only a ten minute response time. Organophosphorus insecticides have some response signals in the detections.     

Sol-Gel Imprinted Polymers Based Electrochemical Sensor for Paracetamol Recognition and Detection

Molecular imprinting and sol-gel technique were combined to develop a molecular imprinted polymer (MIP) based electrochemical sensor in this work. With the successive modification of multi-walled carbon nanotubes (MWNTs) and gold nanoparticles (GNPs), a modified glassy carbon electrode (GCE) was immersed in a sol-gel solution in the presence of paracetamol (PR) for the electropolymerization to fabricate an imprinted sensor. Scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS), and differential pulse voltammetry (DPV) were employed to characterize the constructed sensor. The factors for the sensor preparation, the electropolymerization potential range, the monomer concentration, and the scan rate for the sensor preparation were optimized. The sensor displayed an excellent recognition capacity toward PR compared with other analogues. Additionally, the DPV peak current was linear to the PR concentration in the range from 8.0 × 10^?8 to 5.0 × 10^?5 mol/L, with a detection limit of 4.0 × 10^?8 mol/L. The prepared sensor also showed satisfactory reproducibility and regeneration capacity.     

Molecularly Imprinted Impedimetric Sensor for Determination of Mycotoxin Zearalenone

The mycotoxin zearalenone (ZEA) prompts reproductive toxicity due to its strong estrogenic effects. In this work, an electrochemical sensor for determination of ZEA was developed by electropolymerization of a molecularly imprinted poly (o‐phenylenediamine) (PPD) film on screen‐printed gold electrode (SPGE) surface. The sensor was examined by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) using K₃[Fe(CN)₆]/K₄[Fe(CN)₆] as redox probe. The molecularly imprinted polymer (MIP) sensor showed a wide determination range from 2.50 to 200.00 ngmL^?1 for ZEA. The Limit of detection (LOD) was calculated to be 0.20 ngmL^?1, based on the signal to noise (S/N) ratio equal to 3.0. The sensor displayed good repeatability, with RSD values≤4.6 %, and maintained 93.2 % of its initial response after storage for 10 days in air at room temperature. The developed method was successfully applied for the determination of ZEA in corn flakes with mean recoveries ranged from 96.2 % to 103.8 % and RSDs within the interval of 2.1 % to 3.8 %.     

基于抗原决定基的胰岛素分子印迹电化学传感器

采用抗原决定基法制备了胰岛素电化学分子印迹传感器.以胰岛素C端多肽作为模板分子,定向自组装在Au电极上,以邻苯二胺为功能单体,电化学聚合制备分子印迹聚合膜.以NaOH为洗脱液,洗脱模板分子,形成的与胰岛素C端多肽三维结构相匹配的分子印迹孔穴能特异性识别胰岛素.重吸附胰岛素分子后,以K3[Fe(CN)6]/K4[Fe(CN)6]为探针,通过测量探针在电极表面产生的电流大小实现胰岛素的间接测定.在1.0 × 10-14~5.0 × 10-13 mol/L浓度范围内,传感器的电流响应值与胰岛素浓度呈良好的线性关系,检出限为7.24 × 10-15 mol/L(3σ).此传感器具有较好的选择性和稳定性,并成功用于血清样品中胰岛素的测定.     

Screen-printed electrochemical sensors for label-free potentiometric and impedimetric detection of human serum albumin

Herein, two electrochemical methods based on potentiometric and impedimetric transductions were presented for albumin targeting, employing screen-printed platforms (SPEs) to make easy and cost-effective sensors with good detection merits. The SPEs incorporated ion-to-electron multi-walled carbon nanotubes (MWCNTs) transducer. Sensors were constructed using either tridodecyl methyl-ammonium chloride (TDMACl) (sensor I) or aliquate 336S (sensor II) in plasticized polymeric matrices of carboxylated poly (vinyl chloride) (PVC-COOH). Analytical performances of the sensors were evaluated using the above-mentioned electrochemical techniques. For potentiometric assay, constructed sensors responded to albumin with −81.7 ± 1.7 (r² = 0.9986) and −146.2 ± 2.3 mV/decade (r² = 0.9991) slopes over the linearity range 1.5 μM–1.5 mM with 0.8 and 1.0 μM detection limits for respective TDMAC- and aliquate-based sensors. Interference study showed apparent selectivity for both sensors. Impedimetric assays were performed at pH = 7.5 in 10 mM PBS buffer solution with a 0.02 M [Fe(CN)₆]^−3/−4 redox-active electrolyte. Sensors achieved detection limits of 4.3 × 10⁻⁸ and 1.8 × 10⁻⁷ M over the linear ranges of 5.2×10⁻⁸–1.0×10⁻⁴ M and 1.4×10⁻⁶–1.4×10⁻³ M, with 0.09 ± 0.004 and 0.168 ± 0.009 log Ω/decade slopes for sensors based on TDMAC and aliquate, respectively. These sensors are characterized with simple construction, high sensitivity and selectivity, fast response time, single-use, and cost-effectiveness. The methods were successfully applied to albumin assessment in different biological fluids.     

基于石墨烯修饰的铜离子印迹电化学传感器研制与应用

以铜离子为模板离子,多巴胺为功能单体,采用电聚合法在石墨烯修饰碳电极表面成功制备对铜离子有高选择性和高灵敏性的印迹电化学传感器。采用差分脉冲伏安法和循环伏安法对该印迹传感器的电化学行为进行详细研究。优化检测条件,该印迹电化学传感器的响应电流与铜离子浓度的负对数在5×10_-6~5×10_-11 mol/L的浓度范围内呈良好的线性关系,最低检测限为1.0 × 10_-11mol/L。该印迹电化学传感器成功用于实际水样中的微量铜离子分析。     

Titanium Dioxide/Multi-walled Carbon Nanotubes Composite Modified Pencil Graphite Sensor for Sensitive Voltammetric Determination of Propranolol in Real Samples

A very effective electrochemical sensor for the analysis of propranolol was constructed using TiO₂/MWCNT film deposited on the pencil graphite electrode as modifier. The modified electrode represented excellent electrochemical properties such as fast response, high sensitivity and low detection limit. The proposed sensor showed an excellent selective response to propranolol in the presence of foreign species and other drugs. The electrochemical features of the modified electrode were investigated by cyclic voltammetry and electrochemical impedance spectroscopy (EIS) technique which indicated a decrease in resistance of the modified electrode versus bare PGE and MWCNT/PGE. The surface morphology for the modified electrode was determined by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and Fourier transform infrared spectroscopy (FT-IR). Differential pulse technique (DPV) was used to determine propranolol which showed a good analytical response in the linear range of 8.5×10⁻⁸-6.5×10⁻⁶ M with a limit of detection 2.1×10⁻⁸ M. The TiO₂/MWCNT/PGE sensor was conveniently applied for the measurement of propranolol in biological and pharmaceutical media.     

基于石墨烯分子印迹电化学传感器测定芦丁

将石墨烯(GR)滴涂至裸Au电极表面,并以邻氨基酚为功能单体,芦丁为模板分子,制备了芦丁分子印迹膜电化学传感器,利用循环伏安法(CV)和差分脉冲伏安法(DPV)对制得的传感器进行了电化学性能研究,并且对制备条件和测定条件进行了优化。结果表明,与裸Au电极相比,该GR修饰的Au电极在[Fe(CN)_6]~(3-/4-)溶液中峰电流明显增大,显著提高了芦丁分子印迹传感器的灵敏度。在最优实验条件下,基于GR分子印迹电化学传感器在4.40×10~(-6)~2.80×10~(-4) mol/L范围内呈良好的线性关系,检测限为1.46×10~(-6) mol/L。用该传感器测定了黑茶中芦丁的含量,获得较好结果。     

Indigo Carmine as New Label in PNA Biosensor for Detection of Short Sequence of p53 Tumor Suppressor Gene

A new electrochemical PNA hybridization biosensor for detection of a 15‐mer sequence unique to p53 using indigo carmine (IC) as an electrochemical detector is described in this work. This genosensor is based on the hybridization of target oligonucleotide with its complementary probe immobilized on the gold electrode by self‐assembled monolayer formation. Because this label is electroactive in acidic medium, the interaction between IC and short sequence of p53 is studied by differential pulse voltammety (DPV) in 0.1 M H₂SO₄. The results of electrochemical impedance spectroscopy and cyclic voltammetry in the solution of [Fe(CN)₆]^3?/4? shows no breakage in PNA‐DNA duplex. A decrease in the voltammetric peak currents of IC is observed upon hybridization of the probe with the target DNA. The influence of probe concentration on effective discrimination against non‐complementary oligonucleotides is investigated and a concentration of 10^?7 M is selected. The diagnostic performance of the PNA sensor is described and the detection limit is found to be 4.31×10^?12 M.     

Lithium Ferrocyanide Catholyte for High-Energy and Low-cost Aqueous Redox Flow Batteries**

Aqueous redox flow batteries (ARFBs) are a promising technology for grid-scale energy storage, however, their commercial success relies on redox-active materials (RAM) with high electron storage capacity and cost competitiveness. Herein, a redox-active material lithium ferrocyanide (Li₄[Fe(CN)₆]) is designed. Li⁺ ions not only greatly boost the solubility of [Fe(CN)₆]⁴⁻ to 2.32 M at room temperature due to weak intermolecular interactions, but also improves the electrochemical performance of [Fe(CN)₆]^4−/3−. By coupling with Zn, ZIRFBs were built, and the capacity of the batteries was as high as 61.64 Ah L⁻¹ (pH-neutral) and 56.28 Ah L⁻¹ (alkaline) at a [Fe(CN)₆]⁴⁻ concentration of 2.30 M and 2.10 M. These represent unprecedentedly high [Fe(CN)₆]⁴⁻ concentrations and battery energy densities reported to date. Moreover, benefiting from the low cost of Li₄[Fe(CN)₆], the overall chemical cost of alkaline ZIRFB is as low as $11 per kWh, which is one-twentieth that of the state-of-the-art VFB ($211.54 per kWh). This work breaks through the limitations of traditional electrolyte composition optimization and will strongly promote the development of economical [Fe(CN)₆]^4−/3−-based RFBs in the future.     

Incorporation of Tetrazolium Blue (TB)/Gold Nanoparticles (GNPs) into Carbon Paste Electrode: Application as an Electrochemical Sensor for the Sensitive and Selective Determination of Sotalol in Micellar Medium

The electrochemical oxidation of Sotalol (SOT) based on Tetrazolium Blue (TB)/gold nanoparticles (GNPs)‐modified carbon paste electrodes (CPE) have been studied in the presence of sodium lauryl sulphate (SLS). Cyclic voltammetry (CV), differential pulse voltammetry (DPV), chronoamperometry and electrochemical impedance spectroscopy (EIS) techniques have all been utilized within this study. GNPs and TB have a synergetic effect‐giving rise to highly improved electrochemical responses and provide an advantageous platform for the basis of an electrochemical sensor with excellent performance. The experimental parameters, electrodeposition time, pH and scan rate have all been examined and optimized. The sensing of SOT via DPV is found to exhibit a wide linear dynamic range of 1.0×10⁻⁷–7.5×10⁻⁴ M in pH 2. LOD and LOQ were calculated and found to correspond to 2.5×10⁻⁸ M and 8.3×10⁻⁸ M, respectively. The suggested sensor has been used successfully for SOT determination in pharmaceutical samples and human urine as real samples. Satisfactory recoveries of analyte from these samples are demonstrated indicating that the suggested sensor is highly suitable for clinical analysis, quality control and a routine determination of SOT in pharmaceutical formulations.     

Electrochemical Sensor for trans‐Resveratrol Determination Based on Indium Tin Oxide Electrode Modified with Molecularly Imprinted Self‐Assembled Films

A voltammetric sensor for sensitive and specific determination of trans‐resveratrol (RES) were prepared based on immobilization of an RES‐imprinted film on the surface of functionalized Indium Tin Oxide (ITO) electrode, which was modified with γ‐methacyloxypropyl trimethoxysilane (γ‐MPS). Cyclic Voltammetry (CV) was presented to extract RES from the molecularly imprinted polymer film and RES were extracted rapidly and completely. The binding performance of the imprinted electrode with the template RES were investigated using differential pulse voltammetry (DPV). The results showed that the imprinted ITO film can give selective recognition to the template RES over that of structurally analogous molecules. A linear response to RES in the concentration range of 2.0×10^?6 M to 2.0×10^?5 M was observed with a correlation coefficient of 0.992, and the detection limit of the electrochemical sensor was 8.0×10^?7 M. Whereas, binding to the reference nonimprinted electrode, made in the same way but without the addition of template RES, there was almost no response to RES.     

Molecular imprinting polymer electrosensor based on gold nanoparticles for theophylline recognition and determination

An electrochemical sensor for theophylline (ThPh) was prepared by electropolymerizing o-phenylenediamine on a glassy carbon electrode in the presence of ThPh via cyclic voltammetry, followed by deposition of gold nanoparticles using a potentiostatic method. The effects of pH, ratio between template molecule and monomer, number of cycles for electropolymerization, and of the solution for extraction were optimized. The current of the electro-active model system hexacyanoferrate(III) and hexacyanoferrate(IV) decreased linearly with successive addition of ThPh in the concentration range between 4.0?×?10^?7?~?1.5?×?10^?5 mol·L^?1 and 2.4?×?10^?4?~?3.4?×?10^?3 mol·L^?1, with a detection limit of 1.0?×?10^?7 mol·L^?1. The sensor has an excellent recognition capability for ThPh compared to structurally related molecules, can be regenerated and is stable.

Simultaneous determination of catechol and hydroquinone by carbon paste electrode modified with hydrophobic ionic liquid-functionalized SBA-15

Hydrophobic ionic liquid-functionalized SBA-15 modified carbon paste electrode (CPSPE) was fabricated, and its electrochemical performance was investigated by cyclic voltammetry, electrochemical impedance spectra, and chronocoulometry in K₃Fe(CN)₆/K₄Fe(CN)₆ solution. Compared with carbon paste electrode (CPE) and SBA-15 modified carbon paste electrode (CSPE), the electron transfer ability was in the sequence as: CPSPE>CSPE>CPE. Meanwhile, the electrocatalytic activity of CPSPE to catechol and hydroquinone was evaluated by cyclic voltammetry, and then, the linear concentration ranges were obtained by the amperometric detection from 2.0?×?10^-5 to 3.2?×?10^-4 M for catechol and 5.0?×?10^-5 to 5.5?×?10^-4 M for hydroquinone, with the detection limits of 5.0?×?10^-7 and 6.0?×?10^-7 M, respectively. The advantages of both ionic liquids and heterogeneous supports made CPSPE exhibit high electrocatalytic activity towards the redox of catechol and hydroquinone by significantly improving their reversibility and enhancing their peak currents. In addition, the present method was applied to the determination of catechol and hydroquinone in artificial wastewater sample, and the results were satisfactory.