Electrochemical study of atenolol at a carbon paste electrode modified with mordenite type zeolite

The electrochemical behavior of atenolol (ATN) at the surface of a carbon paste electrode modified with mordenite zeolite (MOR-MCPE) is described. The prepared electrode shows a good electrocatalytic activity toward the oxidation of atenolol, which is leading to considerable improvement of sensitivity (anodic current). Whereas at the surface of unmodified electrode an electrochemical activity for atenolol cannot be observed, a sharp anodic wave is obtained using the prepared modified electrode. The mechanism of oxidation of ATN at the surface of the MOR-MCPE containing various percents of mordenite is thoroughly investigated by cyclic and differential pulse voltammetry. Acetate, hydrogen phosphate and ammonium buffers were tested as the supporting electrolyte to find the optimal pH value. The optimal pH value was 5.0 for acetate buffer. A linear voltammetric response for ATN was obtained in the concentration range of 0.4 to 80 µM with a slope of 0.676 µA/µM. The LOD and LOQ of the electrode were 0.1 µM (26.6 µg/L) and 0.35 μM (93.1 µg/L), respectively. The results obtained for ATN in pharmaceutical formulations (tablets) was in agreement with compared reference method. In conclusion, this study has illustrated that the proposed electrode modified with mordenite is suitable for selective measurements of ATN.     

Electrosyntheses of high quality poly (5-nitroindole) films

High quality poly (5-nitroindole) (PNP) films were synthesized electrochemically by direct anodic oxidation of 5-nitroindole in boron trifluoride diethyl etherate (BFEE) containing additional 10% diethyl ether (by volume). The additional diethyl ether improved the solubility of the monomer in BFEE. In this medium, the oxidation potential onset of 5-nitroindole was measured to be only 1.04 V vs. SCE. PNP films obtained from this medium showed good electrochemical behavior with conductivity of 10^− 2 S cm^− 1. Structural studies showed that the polymerization of 5-nitroindole ring occurred at 2,3 position. As-formed PNP films could be dissolved in acetone, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), etc. Fluorescent spectral studies indicated that PNP was a good green light emitter with the best excitation and emission wavelength of 420 and 550 nm, respectively. To the best of our knowledge, this is the first time that nitro group-substituted high-quality conducting polymer films can be electrodeposited. These results will be greatly helpful for the understanding of the synthesis and properties of nitro-substituted conducting polymers and provide a new route for the post-functionalization of nitro-substituted conducting polymers through the reduction of nitro group.     

Determination of sulfamethoxazole in foods based on CeO2/chitosan nanocomposite-modified electrodes

An electrochemical immunosensor based on nanocomposite-modified glass carbon (GC) electrode has been developed. The biospecific surface was a CeO₂-chitosan (CHIT)-modified nanocomposite to which anti-sulfamethoxazole (SMX) polyclonal antibody (Ab) was immobilized. The assay was based on competition of SMX and horseradish peroxidase (HRP)–SMX to the antibody immobilized. Electrochemical voltammetry and impedance spectroscopy studies revealed that the presence of CeO₂-CHIT nanocomposite significantly enhanced conductivity of the electrode. The large electro-active surface area of nanoCeO₂-CHIT/GC electrode resulted in the high loading of anti-SMX polyclonal antibody. The electrochemical signals of the immunosensor mainly resulted from the HRP catalyzed hydrogen peroxide reduction in the presence of thionine. The immunosensor showed high sensitivity for the detection of SMX. The electrochemical response signals of the immunosensor were found to be linearly proportional to SMX concentration in the range from 5 × 10^? 7 to 5 × 10^? 4 mg mL^? 1 with a regression coefficient of 0.9935 and a detection limit of 3.25 × 10^? 7 mg mL^? 1. No cross-reactivity of antibodies with other antibiotics of sulfonamide family was found. Under optimal conditions, the immunosensor was successfully applied to the electrochemical determination of SMX in milk, honey and egg samples, showing excellent stability and anti-interference ability.     

pH-regulated release of dopamine from well-ordered self-assembled monolayers: Electrochemical studies

In the present work, gold electrode modified with novel aldehyde-terminated self-assembled monolayers (SAMs) was used for controllable load and release of dopamine molecules by pH triggering. Electrochemical techniques including cyclic voltammetry (CV) and electrochemcial impedance spectroscopy (EIS) were employed to investigate the SAMs characteristic on the gold electrode surface. The electrochemical experiments indicated Faradaic behavior for the electrode surface after its modification with dopamine. Notably, it was observed that decreasing the conditioning pH, results in a decrease of peak currents, presumably due to the hydrolysis of the terminal imine bonds and releasing the dopamine moiety into the solution. Moreover, the preliminary kinetics studies were done for dopamine release from the SAMs surface as a model to design future drug delivery systems. Finally, the rate constant of dopamine release from the SAMs modified surface estimated to be 0.167 day^? 1 at pH = 3.     

Application of graphene-ionic liquid-chitosan composite-modified carbon molecular wire electrode for the sensitive determination of adenosine-5′-monophosphate

In this paper, a graphene (GR) ionic liquid (IL) 1-octyl-3-methylimidazolium hexafluorophosphate and chitosan composite-modified carbon molecular wire electrode (CMWE) was fabricated by a drop-casting method and further applied to the sensitive electrochemical detection of adenosine-5′-monophosphate (AMP). CMWE was prepared with diphenylacetylene (DPA) as the modifier and the binder. The properties of modified electrode were examined by scanning electron microscopy, cyclic voltammetry and electrochemical impedance spectroscopy. Electrochemical behaviors of AMP was carefully investigated with enhanced responses appeared, which was due to the presence of GR-IL composite on the electrode surface with excellent electrocatalytic ability. A well-defined oxidation peak of AMP appeared at 1.314 V and the electrochemical parameters were calculated by electrochemical methods. Under the selected conditions, the oxidation peak current of AMP was proportional to its concentration in the range from 0.01 μM to 80.0 μM with the detection limit as 3.42 nM (3σ) by differential pulse voltammetry. The proposed method exhibited good selectivity and was applied to the detection of vidarabine monophosphate injection samples with satisfactory results.     

Development of a modified electrode with amine-functionalized TiO2/multi-walled carbon nanotubes nanocomposite for electrochemical sensing of the atypical neuroleptic drug olanzapine

In this work, using of amine-functionalized TiO₂/multi-walled carbon nanotubes (NH₂-TiO₂-MWCNTs) nanocomposite for modification of glassy carbon electrode (GCE) was investigated. The nanocomposite was characterized by Fourier transformed infrared spectroscopy, transmission electron microscopy and scanning electron microscopy. The efficiency of modified electrode for electrocatalytic the oxidation of olanzapine was studied by cyclic voltammetry, square wave voltammetry and chronoamperometry. The electrochemical measurements were carried out in phosphate-buffered solution (PBS, pH 5.0). The NH₂-TiO₂-MWCNTs/GCE provided high surface area and more sensitive performance. The charge transfer coefficient (α) and the apparent charge transfer rate constant (k_s) were calculated to be equal to 0.42 and 0.173 s^? 1, respectively. The square wave voltammetry exhibited two linear dynamic ranges and a detection limit of 0.09 μM of olanzapine. In addition, the modified electrode was employed for the determination of olanzapine in pharmaceutical and human blood serum samples in order to illustrate the applicability of proposed method.     

Simple route for the synthesis of supercapacitive Co–Ni mixed hydroxide thin films

Facile synthesis of Co–Ni mixed hydroxides films with interconnected nanoparticles networks through two step route is successfully established. These films have been characterized by X-ray diffraction (XRD), Fourier transform infrared technique (FTIR), scanning electron microscopy (SEM) and wettability test. Co–Ni film formation is confirmed from XRD and FTIR study. SEM shows that the surface of Co–Ni films is composed of interconnected nanoparticles. Contact angle measurement revealed the hydrophilic nature of films which is feasible for the supercapacitor. The electrochemical performance of the film is evaluated by cyclic voltammetry, and constant-current charge/discharge cycling techniques. Specific capacitance of the Co–Ni mixed hydroxide electrode achieved 672 F g^?1. Impedance analysis shows that Co–Ni mixed hydroxide electrode provides less resistance for the intercalation and de-intercalation of ions. The Co–Ni mixed electrode exhibited good charge/discharge rate at different current densities. The results demonstrated that Co–Ni mixed hydroxide composite is very promising for the next generation high performance electrochemical supercapacitors.     

Assessment of metabolic activity of human cells in solution and in polymer matrix with the use of metabolite-sensitive sensors

We developed metabolite-sensitive electrochemical sensors on the basis of electrodes modified with a thick film of carbon nanotubes. Modified electrodes provide efficient pre-adsorption of cellular metabolites and their sensitive detection using anodic square-wave voltammetry. On the electrode surface both adhered and non-adhered human cells produce three oxidation peaks at the potentials of + 0.82, + 1.05, and + 1.17 V attributed to three groups of cellular metabolites: amino acid-derived antioxidants including glutathione, guanine nucleotides, and also adenine nucleotides including ATP. The electrochemical response was well correlated with cell viability, intracellular ATP level and induction of apoptosis, as determined by independent assays. Developed sensors allow for robust and cost-effective assessment of ATP in cells in contrast to enzyme-based electrodes and conventional bioluminescent assay. Results can be used for rapid analysis of human cells for the purpose of medical diagnostics, transplantology, and toxicological screening. Additionally, we combined modified electrodes with human cells entrapped in agarose matrix. The resulting biosensor allowed for electrochemical monitoring of metabolic activity and death of cells within polymeric matrix that is of interest for tissue engineering applications.     

Characterization of carbon nanotubes decorated with NiFe2O4 magnetic nanoparticles as a novel electrochemical sensor: Application for highly selective determination of sotalol using voltammetry

A magnetic nano‐composite of multiwall carbon nanotube, decorated with NiFe₂O₄ nanoparticles, was synthesized with citrate sol–gel method. The multiwall carbon nanotubes decorated with NiFe₂O₄ nanoparticles (NiFe₂O₄–MWCNTs) were characterized with different methods such as Fourier transform infrared spectroscopy (FT‐IR), transmission electron microscopy (TEM), atomic force microscopy (AFM), vibrating sample magnetometer (VSM), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The new nano-composite acts as a suitable electrocatalyst for the oxidation of sotalol at a potential of 500 mV at the surface of the modified electrode. Linear sweep voltammetry exhibited two wide linear dynamic ranges of 0.5–1000 μmol L^? 1 sotalol with a detection limit of 0.09 μmol L^? 1. The modified electrode was used as a novel electrochemical sensor for the determination of sotalol in real samples such as pharmaceutical, patient and safe human urine.     

Fabrication of GNPs/CDSH-Fc/nafion modified electrode for the detection of dopamine in the presence of ascorbic acid

A novel dopamine sensor was fabricated by forming the inclusion complex between mono-6-thio-β-cyclodextrin (CD-SH) and ferrocene (Fc) functionalized gold nanoparticles (GNPs) films on a platinum electrode. The properties of the GNPs/CDSH-Fc nanocomposite were characterized by Fourier transform infrared spectra, UV–visible absorption spectroscopy, transmission electron microscopy and cyclic voltammetry. The electrochemistry of dopamine (DA) was investigated by cyclic voltammetry (CV) and differential pulse voltammograms (DPV). The electrooxidation of dopamine could be catalyzed by Fc/Fc⁺ couple as a mediator and had a higher electrochemical response due to the unique performance of GNPs/CDSH-Fc. The anodic peaks of DA and ascorbic acid (AA) in their mixture can be well separated by the prepared electrode. Under optimum conditions linear calibration graphs were obtained over the DA concentration range 2.0 × 10^? 6 to 5.0 × 10^? 5 M with a correlation coefficient of 0.998 and a detection limit of 9.0 × 10^? 8 M (S/N = 3). The modified electrode had been effectively applied for the assay of DA in dopamine hydrochloride injections. This work provides a simple and easy approach to selectively detect DA in the presence of AA.     

Colorimetric response of fluorescein-modified multilayer thin films induced by electrolysis of water

The surface of an indium–tin oxide (ITO) electrode was coated with layer-by-layer (LbL) thin films composed of fluorescein-modified poly(allylamine) (F-PAH) and poly(styrenesulfonic acid) (PSS) and their UV–visible absorption spectra were recorded under the influence of electrode potential. The LbL films were prepared by an alternate deposition of F-PAH and PSS on the surface of ITO electrode through an electrostatic force of attraction. The intensity of the absorption band around 500 nm originating from fluorescein residues in the LbL film depended on the pH of the solution in which the LbL film is immersed. The intensity of the absorption band decreased when the electrode potential higher than + 1.2 V was applied, while virtually no response was observed at lower electrode potential. The spectral change was suppressed in solutions with higher buffer capacity. The results were discussed in terms of the changes in local pH in the vicinity of the electrode surface, which in turn was induced by electrolysis of H₂O on the electrode surface.     

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.     

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.     

Poly(N-vinyl carbazole) and carbon nanotubes based composites and their application to rechargeable lithium batteries

In order to prepare poly(N-vinyl carbazole) (PVK) and carbon nanotube (CNs) based composites, electrochemical polymerization of N-vinyl carbazole (NVK) was studied by cyclic voltammetry (CV) in LiClO₄/acetonitrile solutions. Cyclic voltammograms recorded on a blank Pt electrode and those obtained when single or multi-walled carbon nanotubes (SWNTs or MWNTs) films were previously deposited onto the Pt electrode show a down-shift of the VK reduction peak potential in the latter case. The influence of monomer concentration and supporting electrolyte on the polymerization conditions and electrochemical properties of these composite materials were also investigated. Morphologic aspects as well as the photoluminescence properties of the PVK/CNs composite were also investigated. A covalent functionalization of carbon nanotubes with PVK is suggested on the basis of infrared (IR) spectroscopic studies. Using the PVK/CN composite as a positive electrode and an electrolytic solution containing LiPF₆, a higher specific discharge capacity of the rechargeable lithium cells, ∼45 and 115 mA h g⁻¹, are reported for PVK functionalized SWNTs and MWNTs, respectively.     

ZnO films and nanorod/shell arrays electrodeposited on PET-ITO electrodes

In this work, ZnO films, nanorod and nanorod/shell arrays were synthesized on the surface of PET-ITO electrodes by electrochemical methods. ZnO films with high optical transmittance were prepared from a zinc nitrate solution using a pulsed current technique with a reduced pulse time (3 s). The X-ray diffraction pattern of ZnO film deposited on PET-ITO electrode showed that it has a polycrystalline structure with preferred orientations in the directions [0 0 2] and [1 0 3]. ZnO nanorods were synthesized on electrochemical seeded substrate in an aqueous solution containing zinc nitrate and hexamethylenetetramine. In order to increase the stability of PET-ITO electrode to electrochemical and chemical stresses during ZnO nanorods deposition the surface of the electrode was treated with a 17 wt% NH₄F aqueous solution. Electrochemical stability of PET-ITO electrode was evaluated in a solution containing nitrate ions and hexamethylenetetramine. ZnO nanorod/shell arrays were fabricated using eosin Y as nanostructuring agent. Photoluminescence spectra of ZnO nanorod and ZnO nanorod/shell arrays prepared on the surface of PET-ITO electrode were discussed comparatively. By employing the 1.5 μm-length ZnO nanorod/shell array covered with a Cu₂O film a photovoltaic device was fabricated on the PET-ITO substrate.     

Electrochemical sensor for ranitidine determination based on carbon paste electrode modified with oxovanadium (IV) salen complex

The preparation and electrochemical characterization of a carbon paste electrode modified with the N,N-ethylene-bis(salicyllideneiminato)oxovanadium (IV) complex ([VO(salen)]) as well as its application for ranitidine determination are described. The electrochemical behavior of the modified electrode for the electroreduction of ranitidine was investigated using cyclic voltammetry, and analytical curves were obtained for ranitidine using linear sweep voltammetry (LSV) under optimized conditions. The best voltammetric response was obtained for an electrode composition of 20% (m/m) [VO(salen)] in the paste, 0.10 mol L^? 1 of KCl solution (pH 5.5 adjusted with HCl) as supporting electrolyte and scan rate of 25 mV s^? 1. A sensitive linear voltammetric response for ranitidine was obtained in the concentration range from 9.9 × 10^? 5 to 1.0 × 10^? 3 mol L^? 1, with a detection limit of 6.6 × 10^? 5 mol L^? 1 using linear sweep voltammetry. These results demonstrated the viability of this modified electrode as a sensor for determination, quality control and routine analysis of ranitidine in pharmaceutical formulations.     

Synthesis of biomaterial thin films by pulsed laser technologies: Electrochemical evaluation of bioactive glass-based nanocomposite coatings for biomedical applications

The surface of biomedical titanium implants has been covered with thin films of bioactive glass and bioactive glass + poly(methyl methacrylate nanocomposite) in order to increase the resistance to corrosion and improve the bioactivity of their area in contact with bone tissue. To this purpose Pulsed Laser Deposition and Matrix Assisted Pulsed Laser Evaporation with an excimer laser source have been applied.The layer assessments under conditions that simulate their biological interaction with the human body fluids and resistance to degradation have been studied by electrochemical polarization and electrochemical impedance spectroscopy. The poly(methyl methacrylate) addition to bioglass has reduced the bone ability to bond but resulted in a significant increase of the shielding efficiency against corrosion of the applied coatings.The obtained results support the application of bioactive glass and composite bioactive glass + poly(methyl methacrylate) coatings for the development of advanced highly stable implants and prostheses that cannot be affected by corrosion.     

Electrospun chitosan/PEDOT nanofibers

Plasma-modified chitosan and poly(3,4-ethylenedioxythiophene) were blended to obtain conducting nanofibers with polyvinyl alcohol as a supporting polymer at various volumetric ratios by electrospinning method. Chemical compositions and molecular interactions among nanofiber blend components were determined using Fourier transform infrared spectroscopy (FTIR). The conducting blends containing plasma-modified chitosan resulted in a superior antibacterial activity and thinner fiber formation than those containing chitosan without plasma-modification. The obtained nanofiber diameters of plasma-modified chitosan were in the range of 170 to 200 nm and those obtained from unmodified chitosan were in the range of 190 to 246 nm. The electrical and electrochemical properties of nanofibers were also investigated by four-point probe conductivity and cyclic voltammetry measurements.     

Modified gold surfaces by 6-(ferrocenyl)hexanethiol/dendrimer/gold nanoparticles as a platform for the mediated biosensing applications

An electrochemical biosensor mediated by using 6-(Ferrocenyl) hexanethiol (FcSH) was fabricated by construction of gold nanoparticles (AuNPs) on the surface of polyamidoamine dendrimer (PAMAM) modified gold electrode. Glucose oxidase (GOx) was used as a model enzyme and was immobilized onto the gold surface forming a self assembled monolayer via FcSH and cysteamine. Cyclic voltammetry and amperometry were used for the characterization of electrochemical response towards glucose substrate. Following the optimization of medium pH, enzyme loading, AuNP and FcSH amount, the linear range for the glucose was studied and found as 1.0 to 5.0 mM with the detection limit (LOD) of 0.6 mM according to S/N = 3. Finally, the proposed Au/AuNP/(FcSH + Cyst)/PAMAM/GOx biosensor was successfully applied for the glucose analysis in beverages, and the results were compared with those obtained by HPLC.     

New approach to immobilization and specific-sequence detection of nucleic acids based on poly(4-hydroxyphenylacetic acid)

Immobilization and hybridization of oligonucleotides or specific-gene PCR product (DENV-1), a conserved genomic sequence of the dengue virus, onto graphite electrode modified with poly(4-hydroxyphenylacetic acid), were carried out with success using both direct electrochemical oxidation of guanine or redox electroactive indicator ethidium bromide.Studies of oligonucleotides hybridization with the complementary target showed a decrease of both guanosine and adenosine current peaks, when compared with the peak previously obtained before the hybridization. Immobilized ssDNA, DENV-1, was hybridized with various concentrations of target DNA. The interaction between DENV-1 hybridized onto the modified graphite electrodes surface and the intercalator, ethidium bromide, was observed by differential pulse voltammetry, monitoring the current change generated to the DNA intercalator accumulated onto the modified electrode after DNA hybridization. For the determination of complementary target, the proposed method exhibited a good dynamic range (12–42 nmol L^? 1) and a low detection limit (7.12 nmol L^? 1).AFM images showed that the oligonucleotides or single-stranded DNA, DENV-1, before hybridization, had roughness values lower than the double stranded obtained after hybridization.The new surface obtained in these work, as well as the possibility of utilization of the same to monitor hybridization events is a promising strategy for the development of DNA electrochemical biosensors.