Voltammetric sensor based on carbon paste electrode modified with molecular imprinted polymer for determination of sulfadiazine in milk and human serum

A new sensitive voltammetric sensor for determination of sulfadiazine is described. The developed sensor is based on carbon paste electrode modified with sulfadiazine imprinted polymer (MIP) as a recognition element. For comparison, a non-imprinted polymer (NIP) modified carbon paste electrode was prepared. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) methods were performed to study the binding event and electrochemical behavior of sulfadiazine at the modified carbon paste electrodes. The determination of sulfadiazine after its extraction onto the electrode surface was carried out by DPV at 0.92 V vs. Ag/AgCl owing to oxidation of sulfadiazine. Under the optimized operational conditions, the peak current obtained at the MIP modified carbon paste electrode was proportional to the sulfadiazine concentration within the range of 2.0 × 10^? 7–1.0 × 10^? 4 mol L^? 1 with a detection limit and sensitivity of 1.4 × 10^? 7 mol L^? 1 and 4.2 × 10⁵ μA L mol^? 1, respectively. The reproducibility of the developed sensor in terms of relative standard deviation was 2.6%. The sensor was successfully applied for determination of sulfadiazine in spiked cow milk and human serum samples with recovery values in the range of 96.7–100.9%.     

Ligand exchange based paraoxon imprınted QCM sensor

In the present work, a paraoxon imprinted QCM sensor has been developed for the determination of paraoxon based on the modification of paraoxon imprinted film onto a quartz crystal combining the advantages of high selectivity of the piezoelectric microgravimetry using MIP film technique and high sensitivity of QCM detection. The paraoxon selective memories have formed on QCM electrode surface by using a new metal–chelate interaction based on pre-organized monomer and the paraoxon recognition activity of these molecular memories was investigated. Molecular imprinted polymer (MIP) film for the detection of paraoxon was developed and the analytical performance of paraoxon imprinted sensor was studied. The molecular imprinted polymer were characterized by FTIR measurements. Paraoxon imprinted sensor was characterized with AFM and ellipsometer. The study also includes the measurement of binding interaction of paraoxon imprinted quartz crystal microbalance (QCM) sensor, selectivity experiments and analytical performance of QCM electrode. The detection limit and the affinity constant (K_affinity) were found to be 0.06 μM and 2.25 × 10⁴ M^? 1 for paraoxon [MAAP–Cu(II)–paraoxon] based thin film, respectively. Also, it has been observed that the selectivity of the prepared paraoxon imprinted sensor is high compared to a similar chemical structure which is parathion.     

Extraction and purification of penicillin G from fermentation broth by water-compatible molecularly imprinted polymers

Highly selective molecularly imprinted polymer (MIP) was synthesized by using methacrylic acid as functional monomer, trimethylolpropane trimethacrylate as cross-linker, chloroform as porogen and penicillin G potassium as template molecule. These imprinted polymers were used as solid-phase extraction sorbent for the selective extraction of penicillin G from the fermentation broth samples. Various parameters affecting the extraction efficiency of the MIP particles such as; effects of pH, wash and eluent solutions were evaluated. Molecular recognition properties and selectivity of these MIPs were estimated and the obtained results revealed high affinity for the target antibiotic. Equilibrium binding experiments were done to assess the performance of the MIP relative to non imprinted polymer (NIP). After optimizing the extraction parameters in molecularly imprinted solid-phase extraction (MISPE), successful imprinting was confirmed by comparison of the recoveries from the fermentation broth, ranging between 24–26% (RSD 4.1–4.5%, n = 4) for the NIPs and 83–88% (RSD 3.1–3.4%, n = 4) for the MIPs.     

Flow-based method for epinephrine determination using a solid reactor based on molecularly imprinted poly(FePP–MAA–EGDMA)

A solid phase reactor based on molecularly imprinted poly(iron (III) protoporphyrin-methacrylic acid-ethylene glycol dimethacrylate) (MIP–MAA) has been synthesized by bulk method and applied as an selective material for the epinephrine determination in the presence of hydrogen peroxide. In order to prove the selective behaviour of MIP, two blank polymers named non-imprinted polymer (NIP1), non-imprinted polymer in the absence of hemin (NIP2) as well as a poly(iron (III) protoporphyrin-4-vynilpyridine-ethylene glycol dimethacrylate) (MIP–4VPy) were synthesized. The epinephrine-selective MIP–MAA reactor was used in a flow injection system, in which an epinephrine solution (120 μL) at pH 8.0 percolates in the presence of hydrogen peroxide (300 μmol L^? 1) through MIP–MAA. The oxidation of epinephrine by hydrogen peroxide is increased by using MIP–MAA, being the product formed monitored by amperometry at 0.0 V vs. Ag/AgCl. The MIP–MAA showed better selective behaviour than NIP1, NIP2 and MIP–4VPy, demonstrating the effectiveness of molecular imprinting effect. Highly improved response was observed for epinephrine in detriment of similar substances (phenol, ascorbic acid, methyl-l-DOPA, p-aminophenol, catechol, l-DOPA and guaiacol). The method provided a calibration curve ranging from 10 to 500 μmol L^? 1 and a limit of detection of 5.2 μmol L^? 1. Kinetic data indicated a value of maximum rate V_max (0.993 μA) and apparent Michaelis–Menten constant of K_m^app(725.6 μmol L^? 1). The feasibility of biomimetic solid reactor was attested by its successful application for epinephrine determination in pharmaceutical formulation.     

Determination of Pb2+ ions by a modified carbon paste electrode based on multi-walled carbon nanotubes (MWCNTs) and nanosilica

A novel carbon paste ion selective electrode for determination of trace amount of lead was prepared. Multi-walled carbon nanotubes (MWCNTs) and nanosilica were used for improvement of a lead carbon paste sensor response. MWCNTs have a good conductivity which helps the transduction of the signal in carbon paste electrode. The electrode composition of 20 wt% paraffin oil, 57% graphite powder, 15% ionophore (thiram), 5% MWCNTs, and 3% nanosilica showed the stable potential response to Pb²⁺ ions with the Nernstian slope of 29.8 (±0.2) mV decade^?1 over a wide linear concentration range of 10^?7–10^?2 mol L^?1. The electrode has fast response time, and long term stability (more than 2 months). The proposed electrode was used to determine the concentration of lead ions in waste water and black tea samples.     

Ascorbic acid sensor based on molecularly imprinted polymer-modified hanging mercury drop electrode

Ascorbic acid sensor based on molecularly imprinted polymer (MIP) is reported for sensitive and selective analysis, without any cross-reactivity or matrix effect, in aqueous, blood serum and pharmaceutical samples. The sensor was developed by the direct coating of ascorbic acid-imprinted polymer, prepared from melamine and chloranil, on the surface of a hanging mercury drop electrode (HMDE) at + 0.4 V (vs. Ag/AgCl). The molecular recognition of ascorbic acid was highly specific using non-covalent (hydrophobically driven hydrogen-bonding and electrostatic) interactions. The analyte was preconcentrated and oxidised instantaneously in the imprinted polymer layer giving voltammetric signal on cathodic stripping at optimised operational conditions: accumulation potential + 0.4 V (vs. Ag/AgCl), polymer deposition time 120 s, template accumulation time 120 s, pH 7.0, scan rate 10 mV s^? 1, pulse amplitude 25 mV. The proposed MIP sensor is able to enhance sensitivity substantially so as to detect serum ascorbic acid level as low as 0.26 ng mL^? 1 (R.S.D. 0.5%, S/N 3) for the diagnosis of hypovitaminosis C (Vitamin C deficiency).     

Towards development of colorimetric test-systems for phenols detection based on computationally-designed molecularly imprinted polymer membranes

Colorimetric test-system for the express-control of phenols content in water was developed. The system consisted of free-standing molecularly imprinted polymer (MIP) membranes which contained synthetic binding sites capable of phenol binding. The MIP membranes were obtained by co-polymerisation of a functional monomer (e.g. itaconic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, acrylamide or methacrylic acid) with triethyleneglycoldimethacrylate and oligourethaneacrylate. Rational choice of the functional monomers was based on the results of computational modelling. The phenol-selective MIP membranes were used as a basis for the colorimetric test-system for measuring phenol in aqueous samples. Phenol molecules were selectively adsorbed by the MIP membranes and quantified using color reaction with 4-aminoantipyrine. The intensity of the membranes' staining was proportional to the phenol concentration in the analysed sample. The optimised colorimetric test-system based on MIP membranes demonstrated a low detection limit (50 nM), a wide working range — 50 nM–0.5 mM and an excellent storage stability at room temperature (12 months). As compared to the traditional methods of phenols detection the developed test-system is superior because of simplicity of operation, small size and low cost.     

Comparison of different methodologies for integration of molecularly imprinted polymer and electrochemical transducer in order to develop a paraoxon voltammetric sensor

In this work a paraoxon voltammetric sensor was introduced. Different methods for integration of molecularly imprinted polymer (MIP) and electrochemical transducer were investigated. Three techniques including MIP particles embedding in the carbon paste (CP) (MIP-CP), coupling of MIP with the glassy carbon electrode (GC) surface by using poly epychloro hydrine (PECH) (MIP/PECH-GC) and MIP/graphite mixture thin layer attachment onto the glassy carbon electrode (MIP/Graphite-PECH-GC) were tested. The prepared electrodes were applied for paraoxon measurement by using a three-step procedure including analyte extraction in the electrode, electrode washing and electrochemical measurement of paraoxon. The washing of electrodes, after paraoxon extraction, led to high selectivity of electrode for paraoxon. It was found that MIP-CP electrode had higher response to paraoxon in comparison to other tested electrodes. Besides, the washing process decreased response magnitude of MIP/PECH-GC and MIP/Graphite-PECH-GC but, the response of MIP-CP was not affected considerably by the washing. Parathion was chosen to evaluate the selectivity of MIP based sensors. It was proved that the MIP-CP had better selectivity, wider linear range and lower detection limit in comparison to other tested electrodes. The developed MIP-CP electrode was used as a high selective sensor for paraoxon determination in water and vegetable samples.     

Selective determination of sucrose based on electropolymerized molecularly imprinted polymer modified multiwall carbon nanotubes/glassy carbon electrode

A novel and selective electrochemical sensor was successfully developed for the determination of sucrose by integrating electropolymerization of molecularly imprinted polymer with multiwall carbon nanotubes. The sensor was prepared by electropolymerizing of o-phenylenediamine in the presence of template, sucrose, on a multiwall carbon nanotube-modified glassy carbon electrode. The sensor preparation conditions including sucrose concentration, the number of CV cycles in the electropolymerization step, pH of incubation solution, extraction time of template from the imprinted film and the incubation time were optimized using response surface methodology (RSM). A mixture of acetonitrile/acetic acid was used to remove the template. Hexacyanoferrate(II) was used as a probe to characterize the sensor using electrochemical impedance spectroscopy, cyclic voltammetry and differential pulse voltammetry. Capturing of sucrose by the modified electrode causes decreasing the response of the electrode to hexacyanoferrate(II). Calibration curve was obtained in the sucrose concentration range of 0.01–10.0 mmol L^? 1 with a limit of detection 3 μmol L^? 1. This sensor provides an efficient way for eliminating interferences from compounds with similar structures to sucrose. The sensor was successfully used to determine sucrose in sugar beet juices with satisfactory results.     

Selective voltammetric determination of norepinephrine in the presence of acetaminophen and tryptophan on the surface of a modified carbon nanotube paste electrode

A new electrochemical sensor for the determination of norepinephrine (NE), acetaminophen (AC) and tryptophan (TRP) is described. The sensor is based on carbon paste electrode (CPE) modified with 5-mino-3′,4′-dimethyl-biphenyl-2-ol (5ADB) and takes the advantages of carbon nanotubes (CNTs), which makes the modified electrode highly sensitive for the electrochemical detection of these compounds. Under the optimum pH of 7.0, the oxidation of NE occurs at a potential about 170 mV less positive than that of the unmodified CPE. Also, square wave voltammetry (SWV) was used for the simultaneous determination of NE, AC and TRP at the modified electrode.     

Electrochemical sensor for uric acid based on a molecularly imprinted polymer brush grafted to tetraethoxysilane derived sol-gel thin film graphite electrode

Determination of uric acid in human serum and urine is useful to provide treatment guidelines to hyperuricemic patients. An electrochemical sensor was developed for selective and quantitative recognition of uric acid by using a preanodised sol-gel coated graphite electrode with a molecularly imprinted polymer brush of poly(melamine–co-chloranil) grafted to its exterior surface. During a preconcentration step at (+ 2.0 V versus saturated calomel electrode), the encapsulated analyte recapture involved hydrophobically induced hydrogen-bondings in outwardly exposed MIP cavities in aqueous environment (pH 7.0), instantly oxidised as dications, and then cathodically stripped off as corresponding lactam responding differential pulse, cathodic stripping voltammetric signal. The uric acid was selectively detected without any cross reactivity in the windows of 14.56–177.42 µg mL^? 1 (aqueous medium), 4.78–106.96 µg mL^? 1 (blood serum), and 7.81–148.42 µg mL^? 1 (urine) indicating detection limits in the range of 3.71–4.10 µg mL^? 1 (3σ, RSD = 1.9%).     

Selective electrochemical detection of dopamine based on molecularly imprinted poly(5-amino 8-hydroxy quinoline) immobilized reduced graphene oxide

The dopamine-imprinted conducting polymer film of 5-amino 8-hydroxy quinoline (AHQ) was electrodeposited on reduced graphene oxide (rGO)-modified glassy carbon (GC) electrode and was applied as a molecular recognition element for the selective determination of dopamine. The molecularly imprinted polymer (MIP)-modified electrode showed an excellent affinity towards dopamine due to the presence of imprinted site through hydrogen bonding interaction between dopamine and poly (AHQ) membrane. The molecular recognition ability of MIP-modified electrode was analyzed by cyclic voltammetric and differential pulse voltammetric techniques. The most stable geometry of the template–monomer complex in the pre-polymerization mixture was calculated by computational approaches. The rGO modification augmented both surface area and electron transfer kinetics of the bare electrode. The GC/rGO/MIP electrode possessed 2.83 fold current enhancements when compared to GC/MIP electrode, indicating the improvement in sensitivity due to rGO modification. The limit of detection and sensitivity of GC/rGO/MIP electrode was observed to be 32.7 nM and 13.3 AM^?1 cm^?2, respectively. The imprinting methodology provided an exceptional selectivity towards the detection of dopamine even in the presence of high concentration of possible physiological interferents. Moreover, the fabricated electrode was successfully employed for the detection of dopamine in human blood plasma samples proving the effectiveness of the sensor for the sensitive detection of dopamine from real samples.     

Electrochemical sensor for selective determination of N-acetylcysteine in the presence of folic acid using a modified carbon nanotube paste electrode

In the present paper, a novel benzoylferrocene (BF) modified carbon nanotube paste electrode (BFCNPE) was prepared. The modified electrode was further used for the successful determination of N-acetylcysteine (NAC), and it showed an excellent electrocatalytic oxidation activity toward NAC with a lower overvoltage, pronounced current response, and good sensitivity. Under the optimized experimental conditions, the proposed electrochemical NAC sensor exhibited a linear calibration plot that ranged from 3.0 × 10^? 7 to 7.0 × 10^? 4 M with a detection limit of 9.0 × 10^? 8 M. Also, Square wave voltammetry (SWV) was used for simultaneous determination of NAC and folic acid (FA) at the modified electrode. Finally, the proposed method was applied to the determination of NAC in NAC tablets.     

Accumulation and trace measurement of paraquat at kaolin-modified carbon paste electrode

The carbon paste electrode modified by kaolin (KCPE) has been utilized for the determination of pesticides with high sensitivity based on their redox behavior. The experiment is performed on the use of cyclic and square wave voltammetry. Experimental conditions were optimized by varying the accumulation time, kaolin loading and measuring solution pH. Square wave voltammetric response showed a linear calibration curve in the range from 3.9 × 10^? 9 to 9 × 10^? 5 mol L^? 1 with a detection limit of 2 × 10^? 10 mol L^? 1 at kaolin-modified carbon paste electrode. As a result, it was found that there was feasibility in the use of kaolin to improve the carbon paste electrode properties.     

Application of ionic liquid–TiO2 nanoparticle modified carbon paste electrode for the voltammetric determination of benserazide in biological samples

An ionic liquid–TiO₂ nanoparticle modified carbon paste electrode (IL–TiO₂/CPE) was used as a fast and sensitive tool for the investigation of the electrochemical oxidation of benserazide using voltammetry. This modified electrode has been fabricated using hydrophilic ionic liquid (n-hexyl-3-methylimidazolium hexafluoro phosphate) as a binder. The modified electrode offers a considerable improvement in voltammetric sensitivity toward benserazide, compared to the bare electrode. Using differential pulse voltammetry (DPV), the electrocatalytic oxidation peak current of benserazide shows a linear calibration curve in the range of 1.0–600 μmol L^? 1 benserazide. The limit of detection was equal to 0.4 μmol L^? 1. The relative standard deviation (RSD%) for eight successive assays of 10 μmol L^? 1 benserazide was 1.1%. Finally, the proposed method was successfully applied to the determination of benserazide in real samples such as blood serum and urine.     

Designing and synthesis of bis(2,4-dihydroxybenzylidene)-1,6-diaminohexane and its efficient application as neutral carrier for preparation of new copper selective electrode

A new copper carbon paste electrode (CPE) based on incorporation bis(2, 4-dihydroxybenzyliden)-1,6-diaminohexane (DHBDAH) in graphite powder matrix has been described. The influence of variables including an amount of graphite, sodium tetraphenylborate (NaTPB), DHBDAH and nujol on the Cu²⁺ carbon paste electrode response was studied and optimized. The optimum carbon paste composition was set as follows, graphite powder: NaTPB: Nujol: DHBDAH with amount of 150:2.3:30:4 mg, respectively. At the optimum conditions, the potential response is linear over the concentration range of 5.0 × 10^? 8 to 1.0 × 10^? 1 mol L^? 1 with a Nernstian slope of 29.5 ± 1.1 mV per decade of Cu²⁺ ion concentration. The good performance of electrode such as low detection limit of (LOD) (4 × 10^? 8 mol L^? 1), wide applicable pH range (2.5–5.5), fast response time (?10 s) and adequate shelf life (69 days) indicate the utility of the proposed electrode for evaluation of Cu²⁺ ion content in various analysis. Due to moderate potentiometric selectivity coefficients of proposed electrode obtained by fixed interference method (FIM) and separate solution method (SSM), the proposed electrode successfully can be applied for the determination of Cu²⁺ ions content in some real samples.     

A simple and efficient electrochemical sensor for folic acid determination in human blood plasma based on gold nanoparticles–modified carbon paste electrode

Folic acid (FA) is a water soluble vitamin that exists in many natural species. The lack of FA causes some deficiencies in human body, so finding a simple and sensitive method for determining the FA is important. A new chemically modified electrode was fabricated for determination of FA in human blood plasma using gold nanoparticles (AuNPs) and carbon paste electrode (CPE). Gold nanoparticles–modified carbon paste electrode (AuNPs/CPE) was characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The experimental parameters such as pH, scan rate (ν) and amount of modifier were studied by cyclic voltammetry and the optimized values were chosen. The electrochemical parameters such as diffusion coefficient of FA (D_FA), electrode surface area (A) and electron transfer coefficient (α) were calculated. Square wave voltammetry as an accurate technique was used for quantitative calculations. A good linear relation was observed between anodic peak current (i_pa) and FA concentration (C_FA) in the range of 6 × 10^? 8 to 8 × 10^? 5 mol L^? 1, and the detection limit (LOD) achieved 2.7 × 10^? 8 mol L^? 1, that is comparable with recently studies. This paper demonstrated a novel, simple, selective and rapid sensor for determining the FA in the biological samples.     

Multi-walled carbon nanotube modified carbon paste electrode as an electrochemical sensor for the determination of epinephrine in the presence of ascorbic acid and uric acid

A biocompatible electrochemical sensor for selective detection of epinephrine (EP) in the presence of 1000-fold excess of ascorbic acid (AA) and uric acid (UA) was fabricated by modifying the carbon paste electrode (CPE) with multi-walled carbon nanotubes (MWCNTs) using a casting method. The electro-catalytic activity of the modified electrode for the oxidation of EP was investigated. The current sensitivity of EP was enhanced to about five times upon modification. A very minimum amount of modifier was used for modification. The voltammetric response of EP was well resolved from the responses of AA and UA. The electrochemical impedance spectroscopic (EIS) studies reveal the least charge transfer resistance for the modified electrode. The AA peak that is completely resolved from that of EP at higher concentrations of AA and the inability of the sensor to give an electrochemical response for AA below a concentration of 3.0 × 10^? 4 M makes it a unique electrochemical sensor for the detection of EP which is 100% free from the interference of AA. Two linear dynamic ranges of 1.0 × 10^? 4–1.0 × 10^? 5 and 1.0 × 10^? 5–5.0 × 10^? 7 M with a detection limit of 2.9 × 10^? 8 M were observed for EP at modified electrode. The practical utility of this modified electrode was demonstrated by detecting EP in spiked human blood serum and EP injection. The modified electrode is highly reproducible and stable with anti fouling effects.     

Preparation of nano-sized Pb2+ imprinted polymer and its application as the chemical interface of an electrochemical sensor for toxic lead determination in different real samples

In this work, a new nano-structured ion imprinted polymer (IIP) was synthesized by copolymerization of methacrylic acid-Pb(2+) complex and ethylene glycol dimethacrylate according to the precipitation polymerization. Methacrylic acid acted as both functional monomer and complexing agent to create selective coordination sites in a cross-linked polymer. A carbon paste electrode modified with IIP-nanoparticles was used for fabrication of a Pb(2+) sensitive electrode. Differential pulse stripping voltammetry method was applied as the determination technique, after open circuit sorption of Pb(2+) on the electrode and its reduction to metallic form. The IIP modified electrode showed a considerably higher response, compared to the electrode embedded with non-imprinted polymer (NIP). This indicated that the suitable recognition sites were created in the IIP structure in the polymerization stage. Various factors, effective on the response behavior of the electrode, were investigated and optimized. The introduced sensor showed a linear range of 1.0 × 10(-9) to 8.1 × 10(-7)M and detection limit of 6.0 × 10(-10)M (S/N=3). The sensor was successfully applied for the trace lead determination in different samples.     

Simultaneous determination of phenylhydrazine and hydrazine by a nanostructured electrochemical sensor

In the present paper, the use of a nanostructured electrochemical sensor was described for simultaneous determination of phenylhydrazine (PhH) and hydrazine (HZ). This electrochemical sensor was prepared by a simple and rapid method by modification of carbon paste electrode with a derivative of hydroquinone and TiO₂ nanoparticles. The modified electrode showed an excellent character for electrocatalytic oxidation of PhH. Using differential pulse voltammetry, a highly selective and simultaneous determination of PhH and HZ has been explored at the modified electrode. Differential pulse voltammetry peak currents of PhH and HZ increased linearly with their concentration at the ranges of 2.0 × 10^? 6 to 1.0 × 10^? 3 M and 7.5 × 10^? 5–1.0 × 10^? 3 M, respectively and the detection limits for PhH and HZ were 7.5 × 10^? 7 M and 9.0 × 10^? 6 M, respectively.