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.     

Non-Aqueous Assay System for Phenobarbital Using Biomimetic Bulk Acoustic Wave Sensor Based on a Molecularly Imprinted Polymer

ABSTRACT

A new biomimetic bulk acoustic wave (BAW) sensor based on a molecularly imprinted polymer (MIP) was fabricated and applied for the determination of phenobarbital The MIP was synthesized using phenobarbital as the template molecule and methacrylic acid as the functional monomer by the non-covalent method. In absolute ethanol, the sensor exhibited good selectivity and sensitivity. A linear relationship between 9.0×10^?8 M and 5.0×10^?5 M was revealed. The determination limit was 5.0×10^?8 M. In harsh chemical environments such as high temperature, organic solvent, bases, acids, etc., the sensor still exhibited long-time stability. Satisfactory results of real sample assay were obtained by the proposed method.     

New sensing material of molecularly imprinted polymer for the selective recognition of sulfamethoxazole in foods and plasma and employing the Taguchi optimization methodology to optimize the carbon paste electrode

A new man-tailored biomimetic sensor for sulfamethoxazole host–guest interactions and potentiometric transduction is presented. The host cavity was shaped on a polymeric surface assembled with methacrylic acid monomers by radical polymerization. Molecularly imprinted particles (MIP) were mixed with graphite powder, paraffin oil and ionic site. Using the Taguchi method, this study analyzed the optimum conditions for preparing the carbon paste electrode. The controllable factors used in this study consisted the weights of (1) MIP, (2) paraffin oil, (3) graphite, and (4) the ionic site. The percentage contribution of each controllable factor was also determined. MIP-modified electrode exhibited a Nernstian response (57.2 mVdecade^?1) in a wide concentration range of 6.0 × 10^?8 to 3.1 × 10^?3 mol L^?1 with a lower detection limit of 3.5 × 10^?9 mol L^?1. The sensor was successfully applied to the determination of sulfamethoxazole concentrations in foods and plasma.     

Novel Potentiometric Sensors of Molecular Imprinted Polymers for Specific Binding of Chlormequat

Molecularly imprinted polymers (MIP) were used as potentiometric sensors for the selective recognition and determination of chlormequat (CMQ). They were produced after radical polymerization of 4‐vinyl pyridine (4‐VP) or methacrylic acid (MAA) monomers in the presence of a cross‐linker. CMQ was used as template. Similar non‐imprinted (NI) polymers (NIP) were produced by removing the template from reaction media. The effect of kind and amount of MIP or NIP sensors on the potentiometric behavior was investigated. Main analytical features were evaluated in steady and flow modes of operation. The sensor MIP/4‐VP exhibited the best performance, presenting fast near‐Nernstian response for CMQ over the concentration range 6.2×10⁻⁶–1.0×10⁻² mol L⁻¹ with detection limits of 4.1×10⁻⁶ mol L⁻¹. The sensor was independent from the pH of test solutions in the range 5–10. Potentiometric selectivity coefficients of the proposed sensors were evaluated over several inorganic and organic cations. Results pointed out a good selectivity to CMQ. The sensor was applied to the potentiometric determination of CMQ in commercial phytopharmaceuticals and spiked water samples. Recoveries ranged 96 to 108.5%.     

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.     

Preparation and Application of Urea Electrochemical Sensor Based on Chitosan Molecularly Imprinted Films

A novel urea electrochemical sensor was constructed based on chitosan molecularly imprinted films which were prepared by potentiostatic electrodeposition of chitosan in the presence of urea followed by eluting with 0.1 M KCl. Various techniques were carried out to investigate the formation of molecularly imprinted polymer (MIP) films and the performance of the sensor. According to our expectation, the urea MIP electrochemical sensor showed excellent selectivity to urea among the structural similarities and co‐existences, high linear sensitivity to urea in the range from 1.0×10^?8 to 4.0×10^?5 M with a detection limit of 5.0×10^?9 M. Furthermore, the recovery ranged from 96.3 % to 103.3 % and therefore offered great potential for clinical diagnosis applications.     

Novel Potentiometric Sensor Based on Molecular Imprinted Polyacrylamide for the Determination of Shikimic Acid in Herbal Medicine

ABSTRACT

A novel potentiometric sensor based on a molecular imprinted polymer was developed for the determination of shikimic acid in herbal medicine. The imprinted polymer was synthesized via bulk polymerization of the functional monomer in the presence of trimethylolpropane triacrylate as the cross-linker with 2,2′-azo-bisisobutyronitrile as the initiator and shikimic acid as the template. The sensing membrane was constructed by the inclusion of imprinted polymer in the polyvinyl chloride matrix. The effect of the identity of the imprinted polymer on the potentiometric response was observed. The optimal imprinted polyacrylamide was characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The performance of the imprinted membrane based sensor, including the effects of pH, response time and selectivity coefficient, was investigated. The imprinted sensor exhibited a fast near-Nernstian response in the concentration range of 1?×?10^?5 to 1?×?10^?1?mol/L with a detection limit of 9?×?10^?6?mol/L. The analytical performance of the sensor supported the direct determination of shikimic acid in herbs, and the obtained results were validated by ultraviolet-visible absorption spectrophotometry. Advantages of the potentiometric sensor include enhanced sensitivity, high selectivity, long-term stability and low-cost fabrication, suggesting the device offers promise for the analysis of Chinese herbal medicine.     

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.     

Design and Development of Imprinted Polymer Inclusion Membrane‐Based Field Monitoring Device for Trace Determination of Phorate (O,O‐Diethyl S‐Ethyl Thiomethyl Phophorodithioate) in Natural Waters

A biomimetic potentiometric field monitoring device was developed for the trace determination of phorate (O,O‐diethyl S‐ethyl thiomethyl phophorodithioate) in natural waters. The sensing element was fabricated by the inclusion of phorate imprinted polymer materials in the polyvinyl chloride (PVC) matrix. The sensor surface can be reused without conditioning unlike most other conventional sensors. Operational parameters such as amount and nature of plasticizers sensing material, pH and response time were optimized. The response characteristics of the non‐imprinted (NIPIM) and imprinted polymer inclusion membrane (IPIM) sensors for phorate were compared under optimum conditions. The IPIM sensor responds linearly to phorate in the concentration in the ranges 1×10^?9 to 1×10^?6 M and 1×10^?6 to 1×10^?5 M of different slopes with a detection limit of 1×10^?9 M. The selectivity was tested with various common organophosphorous (OP) pesticides and herbicides. In addition to superior sensitivity and selectivity of IPIM over NIPIM‐based sensor, IPIM‐based phorate sensor was found to be stable for 3 months and can be used for more than 40 times without any loss in sensitivity. The applicability for analyzing ground, river and tap‐water samples was successfully demonstrated via recovery studies.     

Electrochemical Sensor Prepared from Molecularly Imprinted Polymer for Recognition of 1,3-Dinitrobenzene (DNB)

An electrochemical sensor was modified with multi‐wall carbon nanotubes (MWCNT) and molecularly imprinted polymer (MIP) material synthesized with acrylamide and ethylene glycol dimethacrylate (EGDMA) in the presence of 1,3‐dinitrobenzene (DNB) as the template molecule. The MWCNT and MIP layers were successively modified on the surface of a glassy carbon electrode (GCE), of which the MIP film works as an artificial receptor due to its specific molecular recognition sites. The MIP material was characterized by FT‐IR and electrochemical methods of square wave voltammetry (SWV). The interferences of other nitroaromatic compounds (NAC) such as 2,4,6‐trinitrotoluene (TNT), 1,3,5‐trinitrobenzene (TNB) and 2,4‐dinitrotoluene (DNT) to DNB were also investigated by the prepared MIP/MWCNT electrode. Compared with other traditional sensors, the MIP/MWCNT modified electrode shows good selectivity and sensitivity. In addition, the current responses to DNB are linear with the concentration ranging from 4.5×10^?8 to 8.5×10^?6 mol/L with the detection limits of 2.5×10^?8 (?0.58 V) and 1.5×10^?8 mol/L (?0.69 V) (S/N=3). The construction process of MIP/MWCNT modified electrode was also studied as well. All results indicate that the MIP/MWCNT modified electrode established an improving way for simple, fast and selective analysis of DNB.     

Lead(II) Potentiometric Sensor Based on 1,4,8,11‐Tetrathiacyclotetradecane Neutral Carrier and Lipophilic Additives

A potentiometric sensor for lead(II) ions based on the use of 1,4,8,11‐tetrathiacyclotetradecane (TTCTD) as a neutral ionophore and potassium tetrakis‐(p‐chlorophenyl)borate as a lipophilic additive in plasticized PVC membranes is developed. The sensor exhibits linear potentiometric response towards lead(II) ions over the concentration range of 1.0×10^?5–1.0×10^?2 mol L^?1 with a Nernstian slope of 29.9 mV decade^?1 and a lower limit of detection of 2.2×10^?6 mol L^?1 Pb(II) ions over the pH range of 3–6.5. Sensor membrane without a lipophilic additive displays poor response. The sensor shows high selectivity for Pb(II) over a wide variety of alkali, alkaline earth and transition metal ions. The sensor shows long life span, high reproducibility, fast response and long term stability. Validation of the method by measuring the lower limit of detection, lower limit of linear range, accuracy, precision and sensitivity reveals good performance characteristics of the proposed sensor. The developed sensor is successfully applied to direct determination of lead(II) in real samples. The sensor is also used as an indicator electrode for the potentiometric titration of Pb(II) with EDTA and potassium chromate. The results obtained agree fairly well with data obtained by AAS.     

Molecularly Imprinted Poly-o-phenylenediamine Electrochemical Sensor for Entacapone

We have developed a molecularly imprinted polymer (MIP) electrochemical sensor for entacapone (ETC) based on an electropolymerised polyphenylenediamine (Po-PD) on a glassy carbon electrode (GCE) surface. The direct electropolymerisation of the o-phenylenediamine monomer (o-PD) was carried out with ETC as a template. The steps of electropolymerization process, template removal and binding of the analyte were tested by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) using [Fe(CN)₆]³⁻/[Fe(CN)₆]^{4 −} as a redox probe. The operation of the sensor has been investigated by differential pulse voltammetry (DPV). Under optimal experimental conditions, the response of the DPV was linearly proportional to the ETC concentration between 1.0×10⁻⁷ and 5.0×10⁻⁶ M ETC with a limit of detection (LOD) of 5.0×10⁻⁸ M. The developed sensor had excellent selectivity without detectable cross-reactivity for levodopa and carbidopa. The MIP sensor was successfully used to detect ETC in spiked human serum samples.     

A novel sensor based on multi-walled carbon nanotubes and boron-doped double-layer molecularly imprinted membrane for the analysis of SCZ in pharmaceutical and biological samples

ABSTRACT

A molecularly imprinted electrochemical sensor for the rapid detection of the anti-parasitic drug Secnidazole (SCZ) is reported. In this work, the build electrochemical sensor was based on a carbon paste electrode (CPE) modified with multi-wall carbon nanotubes (MWCNTs) and boron-embedded duplex molecularly imprinted composite membranes (B-DMICMs), that significantly increased the efficiency of the sensor for the detection of template molecule SCZ. Density functional theory (DFT) was employed to study the interactions between the template and monomers to select appropriate functional monomers for rational design of the B-DMICMs.The optimal experimental conditions were optimised for the factors affecting the performance of the sensor. Under the optimal conditions, the reduction peak currents of SCZ by differential pulse voltammetry increased linearly with SCZ concentration in the range from 3.0 × 10^?4 to 1.0 × 1.0^?6 mol L^?1 and 1.0 × 1.0^?6 to 1.91 × 10^?8 mol L^?1 with a detection limit of 1.72 × 10^?8 mol L^?1 for secnidazole, which is significantly lower than those in the currently used methods and in previous reports. This method offers low cost, sensitive and effective determination of SCZ and can potentially be used for detection of SCZ in pharmaceutical and biological samples with good precision and accuracy.     

Facile Synthesis and Characterization of 5-[(3-Methylthiophene-2-yl-methyleneamino)]-2-mercaptobenzimidazole and Its Potentiometric Sensor Application in a Polyvinyl Chloride Membrane for the Determination of Copper(II)

A novel Schiff base designated as 5-[(3-methylthiophene-2-yl-methyleneamino)]-2-mercaptobenzimidazole was synthesized and characterized. A polyvinyl chloride-membrane potentiometric copper(II)-selective sensor was prepared by using the synthesized 5-[(3-methylthiophene-2-yl-methyleneamino)]-2-mercaptobenzimidazole compound. The prepared polyvinyl chloride-membrane copper(II)-selective sensor exhibited very good selectivity and sensitive potentiometric response towards copper(II) ions compared to a wide variety of other cations. The sensor had a fast response time of <5?s, and showed a linear Nerstian behavior to copper(II) ions over a wide concentration range from 1.0?×?10^?5 to 1.0?×?10^?1 mol L^?1 with a slope of 29.2?±?0.7 and correlation coefficient of 0.9998. The prepared polyvinyl chloride-membrane copper(II)-selective sensor was used for 14 weeks without any significant change in its potentiometric response. The potentiometric response of the developed sensor was highly repeatable. Additionally, the developed sensor was used as an indicator electrode for the potentiometric titration of copper(II) ion with ethylenediaminetetraacetic acid. The sensor was also successfully applied to the direct determination of copper(II) ions in tap water, river water, and dam water samples.     

An Electrochemical Sensor for L-Tryptophan Using a Molecularly Imprinted Polymer Film Produced by Copolymerization of o-Phenylenediamine and Hydroquinone

An electrochemical sensor for L-tryptophan based on a molecularly imprinted polymer was developed. The sensing film was prepared by the co-electropolymerization of o-phenylenediamine and hydroquinone on a gold electrode in the presence of L-tryptophan as the template. The performance of the L-tryptophan sensor was characterized by cyclic voltammetry, differential pulse voltammetry, and alternating current impedance. Under the optimal experimental conditions, the relative current change was linear to the concentration of L-tryptophan in the range of 1.0 × 10^?8 to 1.0 × 10^?6 mol/L and a detection limit of 0.50 × 10^?8 mol/L was obtained. The sensor showed high sensitivity and selectivity for L-tryptophan. The imprinting factor was 3.58 and selectivity factors of L-tryptophan compared to analogs were larger than 2. The sensor also demonstrated good resistance to acidic, basic, and organic environments.     

A Novel Sulfate Polymeric Membrane Sensor Based on a New Bis‐Pyrylium Derivative

A novel ion‐selective polymeric membrane sensor based on pyrylium‐4,4‐(1,4‐phenylen) bis[2,6‐bis(2‐naphthyl)]‐bis[tetrafluoroborate] (PBGNB) as an excellent sensing material is successfully developed. The electrode possesses the advantages of a very low detection limit (5.0×10^?8 M), a wide working concentration range (1.0×10^?8?1.0×10^?1 M) and specially, a high sulfate selectivity over most common organic and inorganic anions. The sensor displays Nernstian behavior (slope of 29.5±0.5 mV per decade) in a wide pH range (3.0–8.5). It shows a short response time in the whole concentration range (ca. 10 s). The electrode was used as an indicator electrode in the potentiometric titration of sulfate ions with barium ions. The proposed sensor was successfully applied to the direct determination of salbutamol sulfate and paromomycin sulfate.     

Molecularly imprinted polymer based potentiometric sensor for the determination of hydroxyzine in tablets and biological fluids

Molecular imprinting is a useful technique for the preparation of functional materials with molecular recognition properties. In this work, a biomimetic potentiometric sensor, based on a non-covalent imprinted polymer, was fabricated for the recognition and determination of hydroxyzine in tablets and biological fluids. The molecularly imprinted polymer (MIP) was synthesized by precipitation polymerization, using hydroxyzine dihydrochloride as a template molecule, methacrylic acid (MAA) as a functional monomer and ethylene glycol dimethacrylat (EGDMA) as a cross-linking agent. The sensor showed a high selectivity and a sensitive response to the template in aqueous system. The MIP-modified electrode exhibited a Nernstian response (29.4 ± 1.0 mV decade⁻¹) in a wide concentration range of 1.0 × 10⁻⁶ to 1.0 × 10⁻¹ M with a lower detection limit of 7.0 × 10⁻⁷ M. The electrode demonstrated a response time of ∼15 s, a high performance and a satisfactory long-term stability (more than 5 months). The method has the requisite accuracy, sensitivity and precision to assay hydroxyzine in tablets and biological fluids.     

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 %.     

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.     

Preparation of Cu (II) imprinted polymer electrode and its application for potentiometric and voltammetric determination of Cu (II)

The Cu (II) imprinted polymer glassy carbon electrode (GCE/Cu-IP) was prepared by electropolymerization of pyrrole at GCE in the presence of methyl red as a dopant and then imprinting by Cu²⁺ ions. This electrode was applied for potentiometric and voltammetric detection of Cu²⁺ ion. The potentiometric response of the electrode was linear within the Cu²⁺ concentration range of 3.9 × 10^?6 to 5.0 × 10^?2 M with a near-Nernstian slope of 29.0 mV decade^?1 and a detection limit of 5.0 × 10^?7 M. The electrode was also used for preconcentration anodic stripping voltammetry and results exhibited that peak currents for the incorporated copper species were dependent on the metal ion concentration in the range of 1.0 × 10^?8 to 1.0 × 10^?3 M and detection limit was 6.5 × 10^?9 M. Also the selectivity of the prepared electrode was investigated. The imprinted polymer electrode was used for the successful assay of copper in two standard reference material samples.