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.     

Novel Ag@TiO2 nanocomposite synthesized by electrochemically active biofilm for nonenzymatic hydrogen peroxide sensor

A novel nonenzymatic sensor for H₂O₂ was developed based on an Ag@TiO₂ nanocomposite synthesized using a simple and cost effective approach with an electrochemically active biofilm. The optical, structural, morphological and electrochemical properties of the as-prepared Ag@TiO₂ nanocomposite were examined by UV–vis spectroscopy, X-ray diffraction, transmission electron microscopy and cyclic voltammetry (CV). The Ag@TiO₂ nanocomposite was fabricated on a glassy carbon electrode (GCE) and their electrochemical performance was analyzed by CV, differential pulse voltammetry and electrochemical impedance spectroscopy. The Ag@TiO₂ nanocomposite modified GCE (Ag@TiO₂/GCE) displayed excellent performance towards H₂O₂ sensing at ? 0.73 V in the linear response range from 0.83 μM to 43.3 μM, within a detection limit and sensitivity of 0.83 μM and ~ 65.2328 ± 0.01 μAμM^? 1 cm^? 2, respectively. In addition, Ag@TiO₂/GCE exhibited good operational reproducibility and long term stability.     

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.     

Direct electrochemistry and electrocatalysis of myoglobin immobilized on zirconia/multi-walled carbon nanotube nanocomposite

Zirconia/multi-walled carbon nanotube (ZrO₂/MWCNT) nanocomposite was prepared by hydrothermal treatment of MWCNTs in ZrOCl₂·8H₂O aqueous solution. The morphology and structure of the synthesized ZrO₂/MWCNT nanocomposite were characterized by transmission electron microscopy and X-ray diffraction analysis. It was found that ZrO₂ nanoparticles homogeneously distributed on the sidewall of MWCNTs. Myoglobin (Mb), as a model protein to investigate the nanocomposite, was immobilized on ZrO₂/MWCNT nanocomposite. Ultraviolet–visible spectroscopy and electrochemical measurements showed that the nanocomposite could retain the bioactivity of the immobilized Mb to a large extent. The Mb immobilized in the composite showed excellent direct electrochemistry and electrocatalytic activity to the reduction of hydrogen peroxide (H₂O₂). The linear response range of the biosensor to H₂O₂ concentration was from 1.0 to 116.0 μM with the limit of detection of 0.53 μM (S/N = 3). The ZrO₂/MWCNT nanocomposite provided a good biocompatible matrix for protein immobilization and biosensors preparation.     

Voltammetric determination of norepinephrine in the presence of acetaminophen using a novel ionic liquid/multiwall carbon nanotubes paste electrode

A novel multiwall carbon nanotubes (MWCNTs) modified carbon ionic liquid electrode (CILE) was fabricated and used to investigate the electrochemical behavior of norepinephrine (NP). MWCNTs/CILE was prepared by mixing hydrophilic ionic liquid, 1-methyl-3-butylimidazolium bromide (MBIDZBr), with graphite powder, MWCNTs, and liquid paraffin. The fabricated MWCNTs/CILE showed great electrocatalytic ability to the oxidation of NE. The electron transfer coefficient, diffusion coefficient, and charge transfer resistant (R_ct) of NE at the modified electrode were calculated. Differential pulse voltammetry of NE at the modified electrode exhibited two linear dynamic ranges with slopes of 0.0841 and 0.0231 μA/μM in the concentration ranges of 0.3 to 30.0 μM and 30.0 to 450.0 μM, respectively. The detection limit (3σ) of 0.09 μM NP was achieved. This modified electrode exhibited a good ability for well separated oxidation peaks of NE and acetaminophen (AC) in a buffer solution, pH 7.0. The proposed sensor was successfully applied for the determination of NE in human urine, pharmaceutical, and serum samples.     

Preparation and characterization of copper nanoparticles/zinc oxide composite modified electrode and its application to glucose sensing

We report a new method for selective detection of d(+)-glucose using a copper nanoparticles (Cu-NPs) attached zinc oxide (ZnO) film coated electrode. The ZnO and Cu-NPs were electrochemically deposited onto indium tin oxide (ITO) coated glass electrode and glassy carbon electrode (GCE) by layer-by-layer. In result, Cu-NPs/ZnO composite film topography was characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM), respectively. SEM and AFM confirmed the presence of nanometer sized Cu-NPs/ZnO composite particles on the electrode surface. In addition, X-ray diffraction pattern revealed that Cu-NPs and ZnO films were attached onto the electrode surface. Indeed, the Cu-NPs/ZnO composite modified electrode showed excellent electrocatalytic activity for glucose oxidation in alkaline (0.1 M NaOH) solution. Further, we utilized the Cu-NPs/ZnO composite modified electrode as an electrochemical sensor for detection of glucose. This glucose sensor showed a linear relationship in the range from 1 × 10^? 6 M to 1.53 × 10^? 3 M and the detection limit (S/N = 3) was found to be 2 × 10^? 7 M. The Cu-NPs/ZnO composite as a non-enzymatic glucose sensor presents a number of attractive features such as high sensitivity, stability, reproducibility, selectivity and fast response. The applicability of the proposed method to the determination of glucose in human urine samples was demonstrated with satisfactory results.     

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.     

Preparation of nano-TiO2/activated carbon composite and its electrochemical characteristics in non-aqueous electrolyte

The composite of nano-TiO₂/activated carbon (ACT) was prepared by hydrolytic precipitation of TiO₂ from TiCl₄ in a mixed aqueous solution containing activated carbon and followed by calcination at 450 °C. The physical characteristics of the activated carbon and ACT composite have been studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectronic spectroscopy (XPS) and nitrogen adsorption–desorption measurements at 77 K. Three electrode systems with lithium metal as reference electrode were assembled to study the electrochemical performance of ACT composite and the activated carbon. It is found from galvanostatic charge–discharge tests that the mass specific capacitance and the area specific capacitance of ACT composite in the electrolyte of 1 M LiPF₆–ethylene carbonate (EC)/diethyl carbonate (DEC)/dimethyl carbonate (DMC) increase by 20% and 50%, respectively compared to the pure activated carbon on average. The a.c. impedance spectra show that the ACT composite electrode has higher interfacial electron transfer resistance (R_t) but lower equivalent series resistance (R_s) than the pure activated carbon electrode has. Therefore ACT composite is a promising electrode active material for electrochemical capacitors.     

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.     

Electrochemical deposition of precious metal on carbon nanotube for methanol oxidation

Precious metal nanoparticles were prepared on carbon nanotube (CNT) by sequential and simultaneous deposition methods for the electrocatalytic study of methanol oxidation. All electrochemical measurements were carried out in a three-electrode cell. A Platinum wire and Ag/AgCl were used as auxiliary and reference electrodes, respectively. Suspension of the CNT and Nafion were mixed and dropped on glassy carbon as a working electrode. Cyclic voltammograms in H₂SO₄ electrolyte solution are attributable to hydrogen adsorption and hydrogen desorption resulting in promising electrochemical performance of the prepared precious metal nanoparticles. Cyclic voltamograms of methanol electrooxidation studied in 2 M CH₃OH in 1 M H₂SO₄ show a distinguishing shape with a prominent oxidation wave in the anodic scan contributed to methanol oxidation while the cathodic scan is associated with the accumulation of carbonaceous species.     

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.     

Simultaneous electrochemical determination of dopamine and tryptophan using a TiO2-graphene/poly(4-aminobenzenesulfonic acid) composite film based platform

TiO₂-graphene/4-aminobenzenesulfonic acid composite film modified glassy carbon electrode (TiO₂-GR/4-ABSA/GCE) was first employed for the simultaneous determination of dopamine (DA) and tryptophan (Trp). TiO₂-GR/4-ABSA/GCE displayed excellent electrochemical catalytic activities toward the redox of DA and Trp. The cathodic peaks potentials of DA and Trp decreased significantly and their cathodic current peaks increased dramatically at TiO₂-GR/4-ABSA/GCE. Differential pulse voltammograms (DPV) was used for the simultaneous determination of DA and Trp in their dualistic mixture. The peak separation between DA and Trp was large up to 177 mV. The calibration curves for simultaneous determination of DA and Trp were obtained in the range of 1–400 μM. The detection limits (S/N = 3) were 0.1 μM and 0.3 μM for DA and Trp, respectively. The present method was applied to the determination of DA and Trp in human serum samples.     

Highly sensitive amperometric sensor for micromolar detection of trichloroacetic acid based on multiwalled carbon nanotubes and Fe(II)–phtalocyanine modified glassy carbon electrode

A highly sensitive electrochemical sensor for the detection of trichloroacetic acid (TCA) is developed by subsequent immobilization of phthalocyanine (Pc) and Fe(II) onto multiwalled carbon nanotubes (MWCNTs) modified glassy carbon (GC) electrode. The GC/MWCNTs/Pc/Fe(II) electrode showed a pair of well-defined and nearly reversible redox couple correspondent to (Fe(III)Pc/Fe(II)Pc) with surface-confined characteristics. The surface coverage (Γ) and heterogeneous electron transfer rate constant (k_s) of immobilized Fe(II)–Pc were calculated as 1.26 × 10^? 10 mol cm^? 2 and 28.13 s^? 1, respectively. Excellent electrocatalytic activity of the proposed GC/MWCNTs/Pc/Fe(II) system toward TCA reduction has been indicated and the three consequent irreversible peaks for electroreduction of CCl₃COOH to CH₃COOH have been clearly seen. The observed chronoamperometric currents are linearly increased with the concentration of TCA at concentration range up to 20 mM. Detection limit and sensitivity of the modified electrode were 2.0 μM and 0.10 μA μM^? 1 cm^? 2, respectively. The applicability of the sensor for TCA detection in real samples was tested. The obtained results suggest that the proposed system can serve as a promising electrochemical platform for TCA detection.     

Electrochemical oxidation of adenosine-5′-triphosphate on a chitosan–graphene composite modified carbon ionic liquid electrode and its determination

In this paper a new electrochemical method was proposed for the determination of adenosine-5′-triphosphate (ATP) based on a chitosan (CTS) and graphene (GR) composite film modified carbon ionic liquid electrode (CTS–GR/CILE). CILE was fabricated by using ionic liquid 1-butyl-3-methylimidazolium dihydrogen phosphate ([BMIM]H₂PO₄) as the binder, which was further modified by GR and CTS composite. The modified electrode exhibited an excellent electrocatalytic activity toward the oxidation of ATP with the increase of the oxidation peak current and the decrease of the oxidation peak potential. The electrochemical parameters of ATP on CTS–GR/CILE were calculated with the electron transfer coefficient (α) as 0.329, the electron transfer number (n) as 2.15, the apparent heterogeneous electron transfer rate constant (ks) as 3.705 × 10^? 5 s^? 1 and the surface coverage (Γ_T) as 9.33 × 10^? 10 mol cm^? 2. Under the optimal conditions the oxidation peak current was proportional to ATP concentration in the range from 1.0 × 10^? 6 to 1.0 × 10^? 3 M with the detection limit of 0.311 μM (S/N = 3). The proposed electrode showed excellent reproducibility, stability, anti-interference ability and further successfully applied to the ATP injection sample detection.     

Hydrothermal synthesis of SnO2/SnS2 nanocomposite with high visible light-driven photocatalytic activity

SnO₂/SnS₂ nanocomposite with a heterojunction structure (that is, SnO₂ nanoparticles-decorated SnS₂ nanoplates) was synthesized via the hydrothermal reaction between SnO₂ nanoparticles and thioacetamide in 5 vol.% acetic acid aqueous solution at 150 °C for 3 h, and characterized by X-ray diffraction, transmission electron microscopy, high-resolution transmission electron microscopy and UV–vis diffuse reflectance spectra. The photocatalytic activity of the hydrothermally synthesized SnO₂/SnS₂ nanocomposite was tested by degrading methyl orange in distilled water under visible light (λ > 420 nm) irradiation. It was found that the hydrothermally synthesized SnO₂/SnS₂ nanocomposite exhibited superior photocatalytic activity to SnO₂ nanoparticles, SnS₂ nanoplates and physically mixed SnO₂/SnS₂ nanocomposite. The heterojunction structure of the hydrothermally synthesized SnO₂/SnS₂ nanocomposite, which can facilitate interfacial electron transfer and reduce the self-agglomeration of two components, was considered to play an important role in achieving its higher photocatalytic activity.     

Application of graphene–pyrenebutyric acid nanocomposite as probe oligonucleotide immobilization platform in a DNA biosensor

A stable and uniform organic–inorganic nanocomposite that consists of graphene (GR) and pyrenebutyric acid (PBA) was obtained by ultrasonication, which was characterized by scanning electron microscopy (SEM) and UV–vis absorption spectra. The dispersion was dropped onto a gold electrode surface to obtain GR–PBA modified electrode (GR–PBA/Au). Electrochemical behaviors of the modified electrode were characterized by cyclic voltammetry and electrochemical impedance spectroscopy using [Fe(CN)₆]^3 ?/4 ? as the electroactive probe. A novel DNA biosensor was constructed based on the covalent coupling of amino modified oligonucleotides with the carboxylic group on PBA. By using methylene blue (MB) as a redox-active hybridization indicator, the biosensor was applied to electrochemically detect the complementary sequence, and the results suggested that the peak currents of MB showed a good linear relationship with the logarithm values of target DNA concentrations in the range from 1.0 × 10^? 15 to 5.0 × 10^? 12 M with a detection limit of 3.8 × 10^? 16 M. The selectivity experiment also showed that the biosensor can well distinguish the target DNA from the non-complementary sequences.     

One-step mechanical synthesis of the nanocomposite granule of LiMnPO4 nanoparticles and carbon

The nanocomposite granule of LiMnPO₄ nanoparticles and carbon were directly and rapidly created from the starting powder materials by one-step mechanical method without extra heat assistance. The primary particle size and the granule particle size obtained by this method were less than 20 nm and around 20 μm, respectively. The granules could be compacted easily to be the electrode for high packing density. The cathode electrode made by the granules also consisted of the network structure of LiMnPO₄ and that of carbon, thus reduced the lithium ion diffusion path and achieved high electron conductivity. Although, the specific capacity was still 60% of the theoretical capacity, it is expected to be innovative energy-saving process for manufacturing lithium ion batteries by better control of the granule structure in future.     

Electrochemical horseradish peroxidase biosensor based on dextran–ionic liquid–V2O5 nanobelt composite material modified carbon ionic liquid electrode

Direct electrochemistry of horseradish peroxidase (HRP) was realized in a dextran (De), 1-ethyl-3-methylimidazolium ethylsulphate ([EMIM]EtOSO₃) and V₂O₅ nanobelt composite material modified carbon ionic liquid electrode (CILE). Spectroscopic results indicated that HRP retained its native structure in the composite. A pair of well-defined redox peaks of HRP appeared in pH 3.0 phosphate buffer solution with the formal potential of ?0.213 V (vs. SCE), which was the characteristic of HRP heme Fe(III)/Fe(II) redox couple. The result was attributed to the specific characteristics of De–IL–V₂O₅ nanocomposite and CILE, which promoted the direct electron transfer rate of HRP with electrode. The electrochemical parameters of HRP on the composite modified electrode were calculated and the electrocatalysis of HRP to the reduction of trichloroacetic acid (TCA) was examined. Under the optimal conditions the reduction peak current increased with TCA concentration in the range from 0.4 to 16.0 mmol L^?1. The proposed electrode is valuable for the third-generation electrochemical biosensor.     

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.     

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.