Electrochemical sensor based on PEDOT/CNTs-graphene oxide for simultaneous determination of hazardous hydroquinone, catechol, and nitrite in real water samples.

Hydroquinone (HQ), catechol (CC) and nitrite (NT) are considered aquatic environmental pollutants. They are highly toxic, harm humans' health, and damage the environment. Thus, in the present work we introduce a simple and efficient electrochemical sensor for determination of HQ, CC, and NT simultaneously in wastewater sample. The sensor is fabricated by modifying the surface of a glassy carbon electrode (GCE) by two successive thin films from poly(3,4-ethylenedioxythiophene) (PEDOT) and a mixture of carbon nanotubes-graphene oxide (CNT-GRO). Under optimized conditions the HQ, CC, and NT are successfully detected simultaneously in wastewater sample with changing their concentrations in the ranges (0.04 → 100 µM), (0.01 → 100 µM) and (0.05 → 120 µM), the detection limits are 8.5 nM, 3.8 nM and 6.1 nM, respectively. Good potential peak separations: 117 mV and 585 mV are obtained between the HQ-CC, and CC-NT. The sensor has an excellent catalytic capability toward the oxidation of HQ, CC, and NT due to good synergism between its composite components: PEDOT, GRO and CNTs. The features of the sensor are large active surface area, good electrical conductivity, perfect storage stability, good reproducibility, anti-interference capability and accepted recovery rate for HQ, CC, and NT determination in wastewater sample.

Electrochemical sensor for simultaneous determination of antiviral favipiravir drug, paracetamol and vitamin C based on host-guest inclusion complex of ß-CD/CNTs nanocomposite.

Favipiravir (FVI) is extensively used as an effective medication against several diverse infectious RNA viruses. It is widely administered as an anti-influenza drug. Combination therapy formed from FVI, paracetamol (PAR) and vitamin C (VC) is needed for treating patients diseased by RNA viruses. Thus, an efficient electrochemical sensor is developed for detecting FVI in human serum samples. The sensor is fabricated by casting a thin layer of carbon nanotubes (CNTs) over a glassy carbon (GC) electrode surface followed by electrodeposition of another layer of ß-cyclodextrin (ß-CD). Under optimized conditions, the sensor shows excellent catalytic effect for FVI, PAR and VC oxidation in the concentration ranges (0.08 µM → 80 µM), (0.08 µM → 50 µM) and (0.8 µM → 80 µM) with low detection limits of 0.011 µM, 0.042 µM and 0.21 µM, respectively. The combined effect of host-guest interaction ability of ß-CD for the drugs, and a large conductive surface area of CNTs improves the sensing performance of the electrode. The sensor exhibits stable response over 4 weeks, good reproducibility, and insignificant interference from common species present in serum samples. The reliability of using the sensor in serum samples shows good recovery of FVI, PAR and VC.

Electrochemical sensor for simultaneous determination of trifluoperazine and dopamine in human serum based on graphene oxide-carbon nanotubes/iron-nickel nanoparticles.

Trifluoperazine (TFLP) is an important psychiatric medication that balances the dopamine (DA) level in the brain for patients suffering from neurological disorder diseases. An efficient electrochemical sensor is developed for detecting TFLP in real human serum samples. The sensor is fabricated by casting the GC surface with two consecutive thin layers, namely a graphene oxide-carbon nanotubes mixture (GRO-CNT), and iron-nickel nanoparticles (Fe-Ni). The diffusion-controlled oxidation process of TFLP at the composite surface includes one electron transfer process. Under optimized conditions, the sensor in human serum shows excellent catalytic effect for simultaneous determination of TFLP and dopamine (DA) in the same concentration range (0.5 µM to 18 µM) with low detection limits of 0.13 µM and 0.32 µM respectively. The combined effect of a large conductive surface area and the excellent catalytic activity of the nanocomposite improves the sensor's performance. The sensor exhibits a stable current response over four weeks, excellent reproducibility, and insignificant interference from common species present in human serum samples. The reliability test of using the sensor in serum samples shows good recovery of TFLP.

New insight for simultaneous determination of hazardous di-hydroxybenzene isomers at crown ether modified polymer/carbon nanotubes composite sensor.

A new insight is presented in the fabrication of a reliable electrochemical sensor for di-hydroxybenzene isomers; hydroquinone (HQ), catechol (CC), and resorcinol (RC) which have been considered as common pollutants in environment and water samples. The sensor is based on modifying the glassy carbon electrode (GC) with successive layers, multi-walled carbon nanotubes (CNT), poly-hydroquinone (PHQ) and benzo-12-crown-4 (CE); GC/CNT/PHQ/CE. CE is introduced for the first time as a receptor for the di-hydroxybenzene isomers based on host-guest size matching. Other cycling compound with different cavity diameter as ß-cyclodextrin (ß-CD) (6.0-6.5 Å) was examined displaying lower current responses. CE exhibited "fit" cavity size (1.20-1.50 Å). Thus, the inclusion complexes formed between ß-CD and di-hydroxybenzene isomers are less stable. The layered sensor showed highly electro-catalytic activity for simultaneous determination of isomers; HQ, CC and RC in the concentration ranges of 0.03-100 µM, 0.01-100 µM and 0.05-100 µM with low detection limit values of 0.156 nM, 0.118 nM and 0.427 nM, respectively. The practical impact of the sensor was illustrated for determination of di-hydroxybenzene isomers in real water matrices from two different sources. Moreover, anti-interference ability of the layered sensor for determination of di-hydroxybenzene isomers was successfully achieved in presence of common interfering ions and organic pollutants.

Novel Design of a Layered Electrochemical Dopamine Sensor in Real Samples Based on Gold Nanoparticles/ß-Cyclodextrin/Nafion-Modified Gold Electrode.

Change in the level of dopamine (DA) concentration in the human body causes critical diseases such as schizophrenia and Parkinson's disease. Therefore, the determination of DA concentration and monitoring its level in human body fluids is of great importance. An electrochemical sensor based on modification of the gold electrode surface with Nafion (NF), ß-cyclodextrin (CD), and gold nanoparticles (AuNPs) was fabricated for the determination of DA in biological fluids. Combined impact of all the modifiers enhances the catalytic activity of the sensor. Gold nanoparticles increase the surface area of the sensor and enhance the electron transfer rate. CD plays a main role in enhancing the accumulation of protonated DA and forming stable complexes via electrostatic interactions and hydrogen bond formation. In addition, extra preconcentration of positively charged DA is achieved through ionic selectivity of NF. High electrocatalytic activity was achieved using the modified sensor for determination of DA in real urine samples in a wide concentration range, 0.05-280 µM with a low detection limit of 0.6 nM in the small linear dynamic range, 0.05-20 µM. Furthermore, common overlapped oxidation peaks of DA in presence of biologically interfering compounds at the gold electrode were resolved by using the modified sensor. Excellent recovery results were obtained using the proposed method for determination of DA in real urine samples.

Synthesis, structural and morphological characterizations of nano-Ru-based perovskites/RGO composites.

Highly-dispersed Ru-based perovskites supported on reduced graphene oxide (A-RG) nanocomposites are prepared using different A-metal salts (Sr(NO3)2, Ba(NO3)2 and Ca(NO3)2). The procedure is based on a redox reaction between the metal precursors and graphene oxide (GO) using two different routes of reaction initiation: through thermal heating or by microwave-assisted heating. The resulting nanocomposites do not require further calcination, making this method less energy-demanding. In addition, no additional chemical reagents are required for either the GO reduction or the metal precursor oxidation, leading to an overall simple and direct synthesis method. The structure and morphology of the as-prepared A-RG (non-calcined) nanocomposites are characterized using various structural analyses including XRD, XPS, SEM/EDX and HR-TEM. Changing metal A in the perovskite as well as the "activation method" resulted in significant structural and morphological changes of the formed composites. SrRuO3 and BaRuO3 in combination with RuO2 are obtained using a conventional combustion method, while SrRuO3 (~1 nm size) in combination with Ru nanoparticles are successfully prepared using microwave irradiation. For the first time, a microwave-assisted synthesis method (without calcination) was used to form crystalline nano-CaRuO3.

Energy and cost-efficient nano-Ru-based perovskites/RGO composites for application in high performance supercapacitors.

Nano-Ru-based perovskites RGO are prepared simultaneously in presence of various A-metal salts (A = Sr, Ba or Ca salts) using two different methods for reaction initiation. No further calcination step is needed for the formation of well-defined perovskite structure. Graphene oxide (GO) is used as a fuel to prepare various Ru-based perovskites for the first time. The resulted low-Ru content nanocomposites are used as supercapacitor electrodes in a neutral electrolyte (1.0 M NaNO3). The results show that the specific capacitance of the resulted nanocomposites strongly depends on the method of their preparation as well as the type of A-site of the nanocomposites. Ru-based perovskites RGO nanocomposites that are prepared by combustion method show higher specific capacitance than those prepared by microwave irradiation. The maximum specific capacitance of Sr-, Ba- and Ca-RG-C composites at scan rate 2 mV s-1 are 564 (598 mF cm-2), 460 (487 mF cm-2) and 316 (336 mF cm-2) F g-1, respectively. This value is higher than our previous work using a physical mixture between the individually prepared RGO and SrRuO3. Lowest values for specific capacitance are obtained when using CaRuO3/RGO prepared using microwave-assisted method (Ca-RG-M). The resulted A-RG-nanocomposites show very high cycling stability and good specific capacitance compared to other Ru-based structures previously reported in the literature. A correlation is defined between the structure and specific capacitance of the nanocomposites. It is confirmed that the nanocomposite size, morphology and distribution over the RGO matrix influence the supercapacitor characteristics.

Rapid and simple electrochemical detection of morphine on graphene-palladium-hybrid-modified glassy carbon electrode.

A hybrid of reduced graphene oxide-palladium (RGO-Pd) nano- to submicron-scale particles was simultaneously chemically prepared using microwave irradiation. The electrochemical investigation of the resulting hybrid was achieved using cyclic voltammetry and differential pulse voltammetry. RGO-Pd had a higher current response than unmodified RGO toward the oxidation of morphine. Several factors that can affect the electrochemical response were studied, including accumulation time and potential, Pd loading, scan rate, and pH of electrolyte. At the optimum conditions, the concentration of morphine was determined using differential pulse voltammetry in a linear range from 0.34 to 12 µmol L(-1) and from 14 to 100 µmol L(-1), with detection limits of 12.95 nmol L(-1) for the first range. The electrode had high sensitivity toward morphine oxidation in the presence of dopamine (DA) and of the interference compounds ascorbic acid (AA) and uric acid (UA). Electrochemical determination of morphine in a spiked urine sample was performed, and a low detection limit was obtained. Validation conditions including reproducibility, sensitivity, and recovery were evaluated successfully in the determination of morphine in diluted human urine.

Novel sensor based on carbon paste/Nafion® modified with gold nanoparticles for the determination of glutathione.

Several problems for the direct electrochemical oxidation of reduced glutathione (GSH) challenge the usage of electroanalytical techniques for its determination. In this work, the electrochemical oxidation of GSH catalyzed by gold nanoparticles electrodeposited on Nafion modified carbon paste electrode in 0.04 mol L(-1) universal buffer solution (pH 7.4) is proved successful. The effect of various experimental parameters including pH, scan rate and stability on the voltammetric response of GSH was investigated. At the optimum conditions, the concentration of GSH was determined using differential pulse voltammetry (DPV) in two concentration ranges: 0.1 × 10(-7) to 1.6 × 10(-5) mol L(-1) and 2.0 × 10(-5) to 2.0 × 10(-4) mol L(-1) with correlation coefficients 0.9988, 0.9949 and the limit of detections (LOD) are 3.9 × 10(-9) mol L(-1) and 8.2 × 10(-8) mol L(-1), respectively, which confirmed the sensitivity of the electrode. The high sensitivity, wide linear range, good stability and reproducibility, and the minimal surface fouling make this modified electrode useful for the determination of spiked GSH in urine samples and in tablet with excellent recovery results obtained.

Probing cysteine self-assembled monolayers over gold nanoparticles--towards selective electrochemical sensors.

Cysteine forms self-assembled monolayers over gold nanoparticles. Based on this knowledge, a novel electrochemical sensor (Au-Au(nano)-Cys-SDS) has been constructed by the formation of self-assembly monolayer (SAM) of cysteine on gold-nanoparticles modified gold electrode (Au-Au(nano)-Cys) to be utilized for determination of dopamine in the presence of sodium dodecyl sulfate (SDS). Electrochemical investigation and characterization of the modified electrode sensor was achieved using cyclic voltammetry, electrochemical impedance spectroscopy, scanning electron, and atomic force microscopies. Au-Au(nano)-Cys electrode in the presence of SDS gave comparable high current response to that of the gold nanoparticles modified gold electrode (Au-Au(nano)). The Au-Au(nano)-Cys-SDS electrode current signal was remarkably stable via repeated cycles and long term stability due to the strong AuS bond. Very small peak separation, almost zero or 15 mV peak separation was also obtained by repeated cycles indicating unusual high reversibility. The oxidation peak current was determined to be linearly dependent on the dopamine concentration. A resulting calibration curve using square wave voltammetry (SWV) was obtained over concentration range of 30-100 µmol L(-1) and 120-320 µmol L(-1) with correlation coefficients of 0.996 and 0.994 and a limit of detection of 16 and 57 nmol L(-1), respectively. Using differential pulse voltammetry (DPV), a highly selective and simultaneous determination of tertiary mixture of ascorbic acid AA, dopamine, and acetaminophen APAP was explored at this modified electrode. It has been demonstrated that Au-Au(nano)-Cys-SDS electrode can be used as a sensor with excellent reproducibility, sensitivity, and long term stability.

A novel sensor of cysteine self-assembled monolayers over gold nanoparticles for the selective determination of epinephrine in presence of sodium dodecyl sulfate.

A novel sensor of cysteine self-assembled monolayers over gold nanoparticles modified gold electrode has been constructed for the determination of epinephrine in presence of sodium dodecyl sulfate (Au/Au(nano)-CysSDS). Electrochemical investigation and characterization of the modified electrode are achieved using cyclic voltammetry, linear sweep voltammetry, and scanning electron microscopy. The Au/Au(nano)-CysSDS electrode current signal is remarkably stable via repeated cycles and long term stability, due to the strong Au-S bond, compared to the Au/Au(nano) electrode. The catalytic oxidation peak currents obtained from linear sweep voltammetry (LSV) increased linearly with increasing epinephrine concentrations in the range of 2 to 30 µmol L(-1) and 35 to 200 µmol L(-1) with correlation coefficients of 0.9981 and 0.9999 and a limit of detection of 0.294 nmol L(-1) and 1.49 nmol L(-1), respectively. The results showed that Au/Au(nano)-CysSDS can selectively determine epinephrine in the coexistence of a large amount of uric acid and glucose. In addition, a highly selective and simultaneous determination of tertiary mixture of ascorbic acid, epinephrine, and acetaminophen is explored at this modified electrode. Excellent recovery results were obtained for determination of epinephrine in spiked urine samples at the modified electrode. Au/Au(nano)-CysSDS can be used as a sensor with excellent reproducibility, sensitivity, and long term stability.

Determination of morphine at gold nanoparticles/Nafion® carbon paste modified sensor electrode.

A novel and effective electrochemical sensor for the determination of morphine (MO) in 0.04 mol L(-1) universal buffer solution (pH 7.4) is introduced using gold nanoparticles electrodeposited on a Nafion modified carbon paste electrode. The effect of various experimental parameters including pH, scan rate and accumulation time on the voltammetric response of MO was investigated. At the optimum conditions, the concentration of MO was determined using differential pulse voltammetry (DPV) in a linear range of 2.0 × 10(-7) to 2.6 × 10(-4) mol L(-1) with a correlation coefficient of 0.999, and a detection limit of 13.3 × 10(-10) mol L(-1), respectively. The effect of common interferences on the current response of morphine namely ascorbic acid (AA) and uric acid (UA) is studied. The modified electrode can be used for the determination of MO spiked into urine samples, and excellent recovery results were obtained.

Poly(3,4-ethylene-dioxythiophene) electrode for the selective determination of dopamine in presence of sodium dodecyl sulfate.

A novel biosensor using poly(3,4-ethylene dioxythiophene) (PEDOT) modified Pt electrode was developed for selective determination of dopamine (DA) in presence of high concentrations of ascorbic acid (AA) and uric acid (UA) with a maximum molar ratio of 1/1000, and 1/100 in the presence of sodium dodecyl sulfate (SDS). SDS forms a monolayer on PEDOT surface with a high density of negatively charged end directed outside the electrode. The electrochemical response of dopamine was improved by SDS due to the enhanced accumulation of protonated dopamine via electrostatic interactions. The common overlapped oxidation peaks of AA, UA and DA can be resolved by using SDS as the DA current signal increases while the corresponding signals for AA and UA are quenched. The use of SDS in the electrochemical determination of dopamine using linear sweep voltammetry at modified electrode PEDOT/Pt resulted in detecting dopamine at relatively lower concentrations. The DA concentration could be measured in the linear range of 0.5 to 25µmol L(-1) and 30µmol L(-1) to 0.1mmol L(-1) with correlation coefficients of 0.998 and 0.993 and detection limits 61nmol L(-1) and 86nmol L(-1), respectively. The validity of using this method in the determination of dopamine in human urine was also demonstrated.

Computational investigation and synthesis of a sol-gel imprinted material for sensing application of some biologically active molecules.

A hybrid sol-gel material was molecularly imprinted with a group of neurotransmitters. Imprinted material is a sol-gel thin film that is spin coated on the surface of a glassy carbon electrode. Imprinted films were characterized electrochemically using cyclic voltammetry (CV) and the encapsulated molecules were extracted from the films and complementary molecular cavities are formed that enable their rebind. The films were tested in their corresponding template solutions for rebinding using square wave voltammetry (SWV). Computational approach for exploring the primary intermolecular forces between templates and hydrolyzed form of the precursor monomer, tetraethylorthosilicate (TEOS), were carried out using Hartree-Fock method (HF). Interaction energy values were computed for each adduct formed between a monomer and a template. Analysis of the optimized conformations of various adducts could explain the mode of interaction between the templates and the monomer units. We found that interaction via the amino group is the common mode among the studied compounds and the results are in good agreement with the electrochemical measurements.

Simultaneous determination of catecholamines, uric acid and ascorbic acid at physiological levels using poly(N-methylpyrrole)/Pd-nanoclusters sensor.

An interesting electrochemical sensor has been constructed by the electrodeposition of palladium nanoclusters (Pd(nano)) on poly(N-methylpyrrole) (PMPy) film-coated platinum (Pt) electrode. Cyclic voltammetry, electrochemical impedance spectroscopy (EIS), and scanning electron microscopy were used to characterize the properties of the modified electrode. It was demonstrated that the electroactivity of the modified electrode depends strongly on the electrosynthesis conditions of the PMPy film and Pd(nano). Moreover, the modified electrode exhibits strong electrocatalytic activity toward the oxidation of a mixture of dopamine (DA), ascorbic acid (AA), and uric acid (UA) with obvious reduction of overpotentials. The simultaneous analysis of this mixture at conventional (Pt, gold [Au], and glassy carbon) electrodes usually struggles. However, three well-resolved oxidation peaks for AA, DA, and UA with large peak separations allow this modified electrode to individually or simultaneously analyze AA, DA, and UA by using differential pulse voltammetry (DPV) with good stability, sensitivity, and selectivity. This sensor is also ideal for the simultaneous analysis of AA, UA and either of epinephrine (E), norepinephrine (NE) or l-DOPA. Additionally, the sensor shows strong electrocatalytic activity towards acetaminophen (ACOP) and other organic compounds. The calibration curves for AA, DA, and UA were obtained in the ranges of 0.05 to 1mM, 0.1 to 10 microM, and 0.5 to 20 microM, respectively. The detection limits (signal/noise [S/N]=3) were 7 microM, 12 nM, and 27 nM for AA, DA, and UA, respectively. The practical application of the modified electrode was demonstrated by measuring the concentrations of AA, DA, and UA in injection sample, human serum, and human urine samples, respectively, with satisfactory results. The reliability and stability of the modified electrode gave a good possibility for applying the technique to routine analysis of AA, DA, and UA in clinical tests.

Smart electrochemical sensor for some neurotransmitters using imprinted sol-gel films.

A hybrid sol-gel material formed by acid hydrolysis of a mixture of tetraethylorthosilicate (TEOS) and phenyltriethylorthosilicate (PTEOS) as functional monomers was imprinted by tyramine and dopamine as template molecules for the purpose of molecular recognition. Imprinted materials were spin coated as thin films on the surface of glassy carbon electrodes and then were characterized using cyclic voltammetry (CV). After extraction of the encapsulated molecules, imprinted films were tested in solutions of their templates and other molecules. Rebinding experiments were followed by electrochemical characterization using square wave voltammetry (SWV). Imprinted films showed higher affinities toward their template molecules compared to other structurally similar molecules especially for tyramine imprinted film. With the exception of tyramine and norepinephrine, the interference level did not exceed 5% for all compounds studied for dopamine-imprinted films. Tyramine-imprinted films however showed high affinity to tyramine with dopamine 40% interference. Some factors related to the rebinding ability process like pH of solution, concentration of template were studied. The sensing surface lifetime extended to 2 weeks with decay in response signal that ranged from 22%, 40% to 60% for dopamine, tyramine and norepinephrine, respectively. The standard deviation from the mean of measurements for the repeated experiments is 7.4%. Electrochemical impedance spectroscopy (EIS) measurements confirmed the results obtained by electrochemical measurements. Morphological characteristics of the imprinted thin films and their thickness were investigated using scanning electron microscope (SEM).

Poly(3-methylthiophene)/palladium sub-micro-modified sensor electrode. Part II: Voltammetric and EIS studies, and analysis of catecholamine neurotransmitters, ascorbic acid and acetaminophen.

Promising voltammetric sensors based on the modification of Pt and poly(3-methylthiophene) (PMT) electrodes with Pd nanoparticles were achieved for the determination of catecholamine neurotransmitters, ascorbic acid and acetaminophen. Electrochemistry of the indicated compounds was studied at these electrodes and interesting electrocatalytic effects were found. Furthermore, simple, easily prepared one electrochemical step Pd-modified Pt electrode (Pt/Pd) is reported for the first time. Cyclic voltammetry (CV) and chronocoulometry (CC) were used for the determination of the apparent diffusion coefficients in different electrolytes at these electrodes and the values are in the range from 10(-4) to 10(-5)cm(2)s(-1). Furthermore, it was found that the method of polymer formation had a substantial effect on the synergism between the polymer film and the loaded metal particles towards the oxidation of dopamine (DA) in different supporting electrolytes. This was confirmed by the CV, CC and EIS (electrochemical impedance spectroscopy) as well as SEM (Scanning Electron Microscopy) results. Pt and PMT electrodes modified with Pd nanoparticles showed excellent results for the simultaneous determination of tertiary and quaternary mixtures of the studied compounds.

Effect of surfactants on the voltammetric response and determination of an antihypertensive drug.

The effect of adding surface-active agents to electrolytes containing terazosin, an antihypertensive drug, on the voltammetric response of glassy carbon electrode was studied. The current signal due to the oxidation process was a function of the amount of terazosin, pH of the medium, type of surfactant, and accumulation time at the electrode surface. Two surfactants were used, an anionic type, sodium dodecyl sulfate (SDS) and a cationic type, cetyl trimethyl ammonium bromide (CTAB). Addition of SDS to the terazosin-containing electrolyte was found to enhance the oxidation current signal while CTAB showed an opposite effect. Beside the interfacial interaction of the surfactant with the electrode surface in reference to the bias applied potential and the charge of surfactant, terazosin-surfactant interaction in the electrolytic solution was found to be critical to the magnitude of current signal. Addition of SDS to terazosin-containing buffer solution resulted in a decrease in the drug absorption spectrum both in the ultra-violet and visible (UV-vis) regions. Moreover, NMR measurements showed considerable chemical shifts for the aromatic protons of the quinazolinyl moiety of the terazosin in presence of SDS. The affected aromatic protons are positioned next to the interacting protonated amino-group of the terazosin with the charged sulfonate-group of SDS. On the other hand, addition of CTAB did not cause noticeable changes both to the UV-vis and NMR spectra of the drug. The use of SDS in the electrochemical determination of terazosin using linear sweep voltammetry and differential pulse voltammetry at solid glassy carbon electrode enhanced the detection limit from 6.00x10(-7)molL(-1) in absence of surfactant to 4.58x10(-9)molL(-1) when present. The validity of using this method in the determination of drug active ingredient in urine samples and tablet formulations was also demonstrated.