An Electrochemical Sensor Based on Reduced Graphene Oxide,Gold Nanoparticles and Molecular Imprinted Over‐oxidized Polypyrrole for Amoxicillin Determination

An electrochemical sensor for amoxicillin (AMX) detection based on reduced graphene oxide (RGO), molecular imprinted overoxidized polypyrrole (MIOPPy) modified with gold nanoparticles (AuNPs) is described in this work. The electrochemical behavior of the imprinted and non‐imprinted polymer (NIP) was carried out by cyclic voltammetry (CV) and impedance spectroscopy (IS). The structure and morphology of the prepared MIP sensor were characterized by scanning electron microscopy (SEM), UV‐Visible, Fourier transform infrared spectroscopy (FTIR) and its experimental parameters such as monomer and template concentration, pH buffer solution, incubation time of AMX and AuNPs, scan rate as well as electropolymerization scan cycles were optimized to improve the performance of the sensor. The peak current obtained at the MIP electrode was proportional to the AMX concentration in the range from 10^?8 to 10^?3 mol L^?1 with a detection limit and sensitivity of 1.22 10^?6 mol L^?1 (Signal to noise ratio=3) and 2.52×10^?6 μAmol^?1 L, respectively. It was also found that this sensor exhibited reproducibility and excellent selectivity against molecules with similar chemical structures. Besides, the analytical application of the AMX sensor confirms the feasibility of AMX detection in milk and human serum.     

Highly Selective and Sensitive Voltammetric Sensor Based on Ruthenium Nanoparticle Anchored Calix[4]amidocrown‐5 Functionalized Reduced Graphene Oxide: Simultaneous Determination of Quercetin,Morin and Rutin in Grape Wine

In this report, ruthenium nanoparticles (RuNPs) and calix[4]amidocrown‐5 (C4A5) were synthesized and grafted onto the surface of reduced graphene oxide (RGO) nanocomposite (RuNPs/C4A5/RGO). The morphologies of the nanocomposites were characterized by transmission electron microscope, scanning electron microscope, atomic force microscope, electrochemical impedance spectroscopy and x‐ray photoelectron spectroscopy. The electrochemical experiments were performed by cyclic voltammetry, electrochemical impedance spectroscopy and square wave voltammetry. The simultaneous determination of quercetin, rutin and morin was performed on glassy carbon electrode modified with RuNPs/C4A5/RGO (RuNPs/C4A5/RGO/GCE). The linearity ranges and the detection limits of QR, RT and MR were 1.0×10^?10–1.0×10^?8 M and 2.0×10^?11 M respectively.     

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.     

A Biomimetic Potentiometric Sensor Using Molecularly Imprinted Polymer for the Cetirizine Assay in Tablets and Biological Fluids

Despite the increasing number of applications of molecularly imprinted polymers (MIPs) in analytical chemistry, the construction of a biomimetic potentiometric sensor remains still challenging. In this work, a biomimetic potentiometric sensor, based on a non‐covalent imprinted polymer was fabricated for the recognition and determination of cetirizine. The MIP was synthesized by precipitation polymerization, using cetirizine dihydrochloride as a template molecule, methacrylic acid (MAA) as a functional monomer and ethylene glycol dimethacrylate (EGDMA) as a cross linking agent. The sensor showed high selectivity and a sensitive response to the template in aqueous system. The MIP‐modified electrode exhibited Nernstian response (28.0±0.9 mV/decade) in a wide concentration range of 1.0×10^?6 to 1.0×10^?2 M with a lower detection limit of 7.0×10^?7 M. The electrode has response time of ca. 20 s, high performance, high sensitivity, and good long term stability (more than 5 months). The method was satisfactory and used to the cetirizine assay in tablets and biological fluids.     

Highly Selective and Sensitive Copper(II) Membrane Sensors Based on 6‐Methyl‐4‐(1‐phenylmethylidene)amino‐3‐thioxo‐1,2,4‐triazin‐5‐one as a New Neutral Ionophore

A new Cu(II) ion‐selective PVC membrane sensor based on 6‐methyl‐4‐(1‐phenylmethylidene)amino‐3‐thioxo‐1,2,4‐triazin‐5‐one (MATTO) as an excellent sensing material was developed. The electrode exhibits a Nernstian slope of 29.2±0.4 mV per decade over a very wide concentration range between 1.0×10^?1 and 1.0×10^?6 M, with a detection limit of 4.8×10^?7 M (30.5 ng/mL). The sensor possesses the advantages of short conditioning time, fast response time (<10 s), and especially, very good selectivity towards transition and heavy metal, and some mono, di and trivalent cations. The proposed electrode was successfully applied to the determination of copper in wastewater of copper electroplating samples and as an indicator electrode in potentiometric titration of Cu(II) ions with EDTA.     

Nanomolar Determination of Methyldopa in the Presence of Large Amounts of Hydrochlorothiazide Using a Carbon Paste Electrode Modified with Graphene Oxide Nanosheets and 3‐(4′‐Amino‐3′‐hydroxy‐biphenyl‐4‐yl)‐acrylic Acid

A novel electrochemical sensor for sensitive detection of methyldopa at physiological pH was developed by the bulk modification of carbon paste electrode (CPE) with graphene oxide nanosheets and 3‐(4′‐amino‐3′‐hydroxy‐biphenyl‐4‐yl)‐acrylic acid (3,′AA). Applying square wave voltammetry (SWV), in phosphate buffer solution (PBS) of pH 7.0, the oxidation current increased linearly with two concentration intervals of methyldopa, one is 1.0×10^?8–1.0×10^?6 M and the other is 1.0×10^?6–4.5×10^?5 M. The detection limit (3σ) obtained by SWV was 9.0 nM. The modified electrode was successfully applied for simultaneous determination of methyldopa and hydrochlorothiazide. Finally, the proposed method was applied to the determination of methyldopa and hydrochlorothiazide in some real samples.     

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.     

A Highly Selective and Sensitive Barium(II)‐Selective PVC Membrane Based on Dimethyl 1‐Acetyl‐8‐oxo‐2,8‐dihydro‐ 1H‐pyra‐zolo[5,1‐a]isoindole‐2,3‐dicarboxylate

A poly(vinyl chloride)‐based membrane of dimethyl 1‐acetyl‐8‐oxo‐2,8‐dihydro‐1H‐pyra‐zolo[5,1‐a]isoindole‐2,3‐dicarboxylate as a neutral carrier with sodium tetraphenylborate (NaTPB) as an anion excluder and 2‐nitrophenyl octyl ether (NPOE) as plasticizer was prepared and investigated as a Ba(II)‐selective electrode. The electrode exhibits a Nernstian slope of 29.7±0.4 mV per decade over a wide concentration range (1.0×10^?6 to 1.0×10^?1 M) with a detection limit of 7.6×10^?7 M between pH 3.0 and 11.0. The response time of the sensor is about 10 s and it can be used over a period of 2 months without any divergence in potential. The proposed membrane sensor revealed good selectivity for Ba(II) over a wide variety of other metal ions. It was successfully used in direct determination of barium ions in industrial wastewater samples.     

A Self‐assembled L‐Cysteine and Electrodeposited Gold Nanoparticles‐reduced Graphene Oxide Modified Electrode for Adsorptive Stripping Determination of Copper

Glassy carbon electrode (GCE) modified with L‐cysteine and gold nanoparticles‐reduced graphene oxide (AuNPs‐RGO) composite was fabricated as a novel electrochemical sensor for the determination of Cu²⁺. The AuNPs‐RGO composite was formed on GCE surface by electrodeposition. The L‐cysteine was decorated on AuNPs by self‐assembly. Physicochemical and electrochemical properties of L‐cysteine/AuNPs‐RGO/GCE were characterized by scanning electron microscopy, atomic force microscopy, energy dispersive spectroscopy, Raman spectroscopy, X‐ray diffraction, cyclic voltammetry and adsorptive stripping voltammetry. The results validated that the prepared electrode had many attractive features, such as large electroactive area, good electrical conductivity and high sensitivity. Experimental conditions, including electrodeposition cycle, self‐assembly time, electrolyte pH and preconcentration time were studied and optimized. Stripping signals obtained from L‐cysteine/AuNPs‐RGO/GCE exhibited good linear relationship with Cu²⁺ concentrations in the range from 2 to 60 μg L⁻¹, with a detection limit of 0.037 μg L⁻¹. Finally, the prepared electrode was applied for the determination of Cu²⁺ in soil samples, and the results were in agreement with those obtained by inductively coupled plasma mass spectrometry.     

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.     

Electrochemical Sensor Based on Molecularly Imprinted Polymer Film Prepared with Functional Abietic‐Type Acids as Cross‐Linker for the Determination of Quinine

A novel cross‐linker (functional abietic‐type acids) for preparing highly sensitive, molecularly imprinted sensors was proposed for quinine determination. A MIP film was created on a glassy carbon electrode for determination of quinine using free radical polymerization method. The modification procedure was characterized via electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The interaction between functional monomer and target molecule was observed by UV spectrometric methods. Under the optimal experimental conditions, the peak currents were proportional to the concentrations of quinine in the range from 8.0×10^?7 to 2.6×10^?4 M with a detection limit of 2.0×10^?8 M. Meanwhile the prepared sensor showed sensitive and selective binding sites for quinine. Determination of quinine in tonic water showed good recovery.     

A Novel Molecularly Imprinted Photoelectrochemical Sensor Based on g‐C3N4‐AuNPs for the Highly Sensitive and Selective Detection of Triclosan

A novel molecularly imprinted polymer (MIP) photoelectrochemical sensor was fabricated for the highly sensitive and selective detection of triclosan. The MIP photoelectrochemical sensor was fabricated using graphite‐like carbon nitride (g‐C₃N₄) and gold nanoparticles (AuNPs) as photoelectric materials. The MIP/g‐C₃N₄‐AuNPs sensor used photocurrent as the detection signal and was triggered by ultraviolet light (UV‐Light 365 nm). g‐C₃N₄‐AuNPs was immobilized on indium tin oxide electrodes to produce the photoelectrochemically responsive electrode of the MIP/g‐C₃N₄‐AuNPs sensor. A MIP layer of poly‐o‐phenylenediamine was electropolymerized on the g‐C₃N₄‐AuNPs‐modified electrode to act as the recognition element of the MIP/g‐C₃N₄‐AuNPs sensor and to enable the selective adsorption of triclosan to the sensor through specific binding. Under optimal experimental conditions, the designed MIP/g‐C₃N₄‐AuNPs sensor presented high sensitivity for triclosan with a linear range of 2×10⁻¹² to 8×10⁻¹⁰ M and a limit of detection of 6.01×10⁻¹³ M. Moreover, the MIP/g‐C₃N₄‐AuNPs sensor showed excellent selectivity. The sensor had been successfully applied in the analysis of toothpaste samples.     

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.     

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.     

An Enzyme‐free H2O2 Sensor Based on Poly(2‐Aminophenylbenzimidazole)/Gold Nanoparticles Coated Pencil Graphite Electrode

A poly(2‐aminophenylbenzimidazole)/gold nanoparticles (P2AB/AuNPs) coated disposable pencil graphite electrode (PGE) was fabricated as an enzyme‐free sensor for the H₂O₂ determination. P2AB/AuNPs and P2AB were successfully synthesized electrochemically on PGE in acetonitrile for the first time. The coatings were characterized by scanning electron microscopy, X‐ray diffraction spectroscopy, Energy‐dispersive X‐ray spectroscopy, Surface‐enhanced Raman spectroscopy, and UV‐Vis spectroscopy. AuNPs interacted with P2AB as carrier enhances the electrocatalytic activity towards reduction of H₂O₂. The analytical performance was evaluated in a 100 mM phosphate buffer solution at pH 6.5 by amperometry. The steady state current vs. H₂O₂ concentration is linear in the range of 0.06 to 100 mM (R²=0.992) with a limit of detection 3.67×10^?5 M at ?0.8 V vs. SCE and no interference is caused by ascorbic acid, dopamine, uric acid, and glucose. The examination for the sensitive determination of H₂O₂ was conducted in commercially available hair oxidant solution. The results demonstrate that P2AB/AuNPs/PGE has potential applications as a sensing material for quantitative determination of H₂O₂.     

Highly Selective PVC‐Based Membrane Electrode Based on 2,6‐Diphenylpyrylium Fluoroborate

A highly selective PVC‐membrane electrode based on 2,6‐diphenylpyrylium fluoroborate is presented. The electrode reveals a Nernstian potentiometric response for sulfate ion over a wide concentration range (5.0 × 10^?6‐1.0 × 10^?1 M). The electrode has a response time of about 10 s and can be used for at least 2 months without any divergence. The proposed sensor revealed very good selectivities for sulfate over a wide variety of common organic and inorganic anions and could be used over a wide pH range (2.5–9.5). The detection limit of the sensor is 3.0 × 10^?6 M. It was successfully applied to the direct determination of salbutamol, paramomycin tablets, and as an indicator electrode for potentiometric titration of sulfate ions with barium ions.     

Chromium(III) Potentiometric Sensor Based on Para‐Tertiary‐Butyl Calix[4]arene

A new chromium(III) PVC membrane sensor incorporating p‐tertiary‐butyl calix[4]arene as ionophore, potassium tetrakis as additive and dibutyl phthalate (DBP) as plasticizer was constructed. The electrode exhibited an excellent potentiometric response over a wide concentration range of 1.0×10^?7–1.0×10^?1 M with a Nernstian slope of 20±0.5 mV per decade. The detection limit was 5.0×10^?8 M. The electrode showed a better performance over a pH range of 3.0–8.0, and had a short response time of about <15 s.The electrode was successfully applied to potentiometric titration of Cr (III) with EDTA and for direct determination of chromium(III) in waste water.     

A Copper(II) Ion‐Selective Potentiometric Sensor Based on N,N′,N″,N′′′‐Tetrakis(2‐pyridylmethyl)‐1,4,8,11‐tetraazacyclotetradecane in PVC Matrix

The simple PVC‐based membrane containing N,N′,N″,N′′′‐tetrakis(2‐pyridylmethyl)‐1,4,8,11‐tetraazacyclotetradecane (tpmc) as an ionophore and dibutyl phthalate as a plasticizer, directly coated on a glassy carbon electrode was examined as a new sensor for Cu²⁺ ions. The potential response was linear within the concentration range of 1.0×10^?1–1.0×10^?6 M with a Nernstian slope of 28.8 mV/decade and detection limit of 7.0×10^?7 M. The electrode was used in aqueous solutions over a wide pH range (1.3–6). The sensor exhibited excellent selectivity for Cu²⁺ ion over a number of cations and was successfully used in its determination in real samples.     

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.     

Be(II) Graphite Coated Membrane Sensor Based on a Recently Synthesized Benzo‐9‐Crown‐3 Derivative

A highly sensitive and selective membrane electrode with 9‐crown‐3 derivative (CD) as ionophore, potassium tetrakis‐(p‐chlorophenyl) borate as anionic additive (KTB), acetophenone (AP) as solvent mediator was prepared and investigated as a Be(II) sensor. The best performance was observed with the membrane having the percent ratio 30% PVC: 8% CD: 6% KTB: 56% Acetophenone. The poly(vinyl chloride) PVC membrane containing 9‐crown‐3 derivative (CD) directly coated on a graphite electrode, shows a Nernstian response for Be(II) ions over a very wide concentration range (1.0×10^?1?1.0×10^?7 M) with a detection limit of 8.0×10^?8 M (ca. 0.72 ng/mL). It has a fast response time of ca. 20 s and can be used for at least 10 weeks without any major deviation in potential. The proposed sensor exhibits very good selectivity with respect to common alkali, alkaline earth, transition and heavy metal ions. The proposed sensor was used as end point indicator electrode in the titration of Be(II) ions with EDTA. It was also applied to determination of Be(II) in real sample.