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–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.     

Potentiometric urea biosensor based on multi-walled carbon nanotubes (MWCNTs)/silica composite material

A novel potentiometric urea biosensor has been fabricated with urease (Urs) immobilized multi-walled carbon nanotubes (MWCNTs) embedded in silica matrix deposited on the surface of indium tin oxide (ITO) coated glass plate. The enzyme Urs was covalently linked with the exposed free –COOH groups of functionalized MWCNTs (F-MWCNTs), which are subsequently incorporated within the silica matrix by sol–gel method. The Urs/MWCNTs/SiO₂/ITO composite modified electrode was characterized by Fourier transform infrared (FTIR) spectroscopy, thermal gravimetric analysis (TGA) and UV–visible spectroscopy. The morphologies and electrochemical performance of the modified Urs/MWCNTs/SiO₂/ITO electrode have been investigated by scanning electron microscopy (SEM) and potentiometric method, respectively. The synergistic effect of silica matrix, F-MWCNTs and biocompatibility of Urs/MWCNTs/SiO₂ made the biosensor to have the excellent electro catalytic activity and high stability. The resulting biosensor exhibits a good response performance to urea detection with a wide linear range from 2.18 × 10^? 5 to 1.07 × 10^? 3 M urea. The biosensor shows a short response time of 10–25 s and a high sensitivity of 23 mV/decade/cm².     

Biopolymer-manganese oxide nanoflake nanocomposite films fabricated by electrostatic layer-by-layer assembly

Bio-nanocomposite films based on chitosan and manganese oxide nanoflake have been fabricated via the layer-by-layer (LBL) self-assembly technique. UV–vis absorption spectra showed that the subsequent growth of the nanocomposite film was regular and highly reproducible from layer to layer. X-ray photoelectron spectroscopy (XPS) spectra confirmed the incorporation of chitosan and manganese oxide nanoflake into the films. Scanning electron microscopy (SEM) images revealed that the nanocomposite film had a continuous surface and a layered structure. A sensitive hydrogen peroxide (H₂O₂) amperometric sensor was fabricated with the chitosan–manganese oxide nanoflake nanocompoite film. The sensor showed a rapid and linear response to H₂O₂ over the range from 2.5 × 10^? 6 to 1.05 × 10^? 3 M, with a sensitivity of 0.038 A M^? 1 cm^? 2.     

Electrocatalytical oxidation and sensitive determination of acetaminophen on glassy carbon electrode modified with graphene–chitosan composite

The electrochemical behaviors of acetaminophen (ACOP) on a graphene–chitosan (GR–CS) nanocomposite modified glassy carbon electrode (GCE) were investigated by cyclic voltammetry (CV), chronocoulometry (CC) and differential pulse voltammetry (DPV). Electrochemical characterization showed that the GR–CS nanocomposite had excellent electrocatalytic activity and surface area effect. As compared with bare GCE, the redox signal of ACOP on GR–CS/GCE was greatly enhanced. The values of electron transfer rate constant (k_s), diffusion coefficient (D) and the surface adsorption amount (Γ^?) of ACOP on GR–CS/GCE were determined to be 0.25 s^? 1, 3.61 × 10^? 5 cm² s^? 1 and 1.09 × 10^? 9 mol cm^? 2, respectively. Additionally, a 2e^?/2H⁺ electrochemical reaction mechanism of ACOP was deduced based on the acidity experiment. Under the optimized conditions, the ACOP could be quantified in the range from 1.0 × 10^? 6 to 1.0 × 10^? 4 M with a low detection limit of 3.0 × 10^? 7 M based on 3S/N. The interference and recovery experiments further showed that the proposed method is acceptable for the determination of ACOP in real pharmaceutical preparations.     

Study on electrochemical behaviors and the reaction mechanisms of dopamine and epinephrine at the pre-anodized inlaying ultrathin carbon paste electrode with nichrome as a substrate

In this paper, nichrome was adopted as a substrate, to fabricate the pre-anodized inlaying ultrathin carbon paste electrode (PAIUCPE). The electrochemical behaviors of dopamine (DA) and epinephrine (EP) at the electrode were investigated by cyclic voltammetry (CV). The reaction mechanisms of DA and EP have also been put forward. It was found that the electrode showed an excellent electrochemical behavior for electrode reaction of DA and EP. The cathodic potential difference of DA and EP was about 370 mV and the simultaneous determination of DA and EP was achieved based on it. The reduction peak current was proportional to the DA and EP concentrations in the range of 8.0 × 10^? 7–3.0 × 10^? 4 M and 2.0 × 10^? 6–1.5 × 10^? 4 M with the detection limits of 1.70 × 10^? 7 M and 3.27 × 10^? 7 M, respectively. Because the oxidation of ascorbic acid (AA) is an irreversible reaction at the PAIUCPE, the interferences of AA for determining DA and EP were eliminated. The method has been successfully applied to the determination of DA and EP in hydrochloride injection with satisfactory results.     

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.     

High conductive ethylene vinyl acetate composites filled with reduced graphene oxide and polyaniline

A conductive network composed of reduced graphene oxide (RGO) planes and polyaniline (PANI) chains was designed and fabricated by in situ polymerization of aniline monomer on the RGO planes. It was further used for fabrication of conductive composites with a polymer matrix–ethylene vinyl acetate (EVA). The composites achieve improved conductivity at a low filler loading although the host polymer–EVA–is of insulator. For instance, compared to the pure EVA polymer, the conductivity of the composite filled with 4.0 wt.% RGO and 8.0 wt.% PANI increases from 1.2 × 10^?14 S cm^?1 to 1.07 × 10^?1 S cm^?1. In addition, thermal stability of the composites is also enhanced by the filler loading.     

Structural,optical and electrical characterization of ZnO:Ga thin films for organic photovoltaic applications

Gallium-doped zinc oxide (ZnO:Ga) films were prepared on glass substrates by RF magnetron sputtering. The effect of growth temperature on microstructure, optical and electrical properties of the films was investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), UV–visible spectrophotometer and four-point probe. The results show that all the films are polycrystalline and (002) oriented, and that the growth temperature significantly affects the microstructure and optoelectrical properties of the films. The film deposited at 670 K has the largest grain size of 71.9 nm, the lowest resistivity of 8.3 × 10^? 4 Ω?cm and the highest figure of merit of 2.1 × 10^? 2 Ω^? 1. Furthermore, the optical energy gaps and optical constants were determined by optical characterization methods. The dispersion behavior of the refractive index was also studied using the Sellmeir's dispersion model and the oscillator parameters of the films were obtained.     

Amperometric choline biosensors based on multi-wall carbon nanotubes and layer-by-layer assembly of multilayer films composed of Poly(diallyldimethylammonium chloride) and choline oxidase

A layer-by-layer deposition technique combined with Multi-wall carbon nanotubes (MWCNTs) was employed for fabricating choline sensors. The terminals and side-walls were linked with oxygen-containing groups when MWCNTs were treated with concentrated acid mixtures. A film of MWCNTs was initially prepared on the platinum electrode surface. Based on the electrostatic interaction between positively charged polyallylamine (PAA) and negatively charged MWCNTs and poly(vinyl sulfate) (PVS), a polymer film of (PVS/PAA)₃ was alternately adsorbed on the modified electrode continuously to be used as a permselective layer. Then poly(diallyldimethylammonium) (PDDA) and choline oxidase(ChOx) multilayer films were assembled layer-by-layer on the pretreated electrode, so an amplified biosensor toward choline was constructed. The choline sensor showed a linear response range of 5 × 10^? 7 to 1 × 10^? 4 M with a detection limit of 2 × 10^? 7 M estimated at a signal-to-noise ratio of 3, and a sensitivity of 12.53 μA/mM with a response time of 7.6 s in the presence of MWCNTs. Moreover, it exhibited excellent reproducibility, long-term stability as well as good suppression of interference. This protocol could be used to immobilize other enzymes for biosensor fabrication.     

Determination of benzalkonium chloride preservative in pharmaceutical formulation of eye and ear drops using new potentiometric sensors

A novel approach for determination of low concentrations of the preservative, benzalkonium chloride (BCCl), in pharmaceutical formulation constitutes is presented. New chemically modified carbon paste electrodes (CMCPEs) are developed. The first is based on an ion-association of BCCl with phosphomolybdic acid (PMA) as the ion-exchanger (BC–PM) dissolved in the mixed plasticizers dibutyl phthalate (DBP) and dioctyl sebacate (DOS) encoded sensor A. In the other electrode, encoded sensor B, the plasticizers DBP and dioctyl phthalate (DOP) are more suitable solvent mediators for the paste. These electrodes exhibit a Nernstian slope of 58.2 ± 0.6 and 62.3 ± 0.7 mV/decade in concentration range 1.3 × 10^? 7–1.7 × 10^? 4 M and 2.5 × 10^? 7–1.7 × 10^? 4 M with the limit of detection of 1.0 × 10^? 7 M and 1.6 × 10^? 7 for sensors A and B, respectively. The sensors have short and stable response time 5–8 s, good reproducibility and can be used in pH range of 5.7–8.6. The present electrodes show good discrimination of BCCl from several inorganic, organic ions and some common drug excipients. These characteristics of the electrodes make them useful in successful determination of BCCl in its pharmaceutical preparations (eye and ear drops) and aqueous solutions. The results obtained were satisfactory with excellent percentage recovery comparable and sometimes better than those obtained by other routine methods for the assay.     

New potentiometric sensor for the determination of iodine species

The characteristics, performance and application of novel triiodide potentiometric sensor based on ion-pair of Rhodamine B triiodide as a membrane carrier are described. The electrode has a linear dynamic range between 1 × 10^? 6 and 1 × 10^? 1 M, with a Nernstian slope of 68 ± 1 mV pC^? 1 and detection limit of 3.9 × 10^? 7 M. Fast and stable response, good reproducibility, long-term stability, very good selectivity over a large number of common organic and inorganic anions, applicability over a pH range of 2–10 are demonstrated. The proposed sensor has been applied for potentiometric determination of some iodine species.     

Iodide selective membrane electrodes based on a Molybdenum–Salen as a neutral carrier

A new polymeric membrane electrode (PME) and a coated platinum disk electrode (CPtE) based on Schiff base complex of Mo(VI) as a suitable carrier for I^? ion were described. The influence of membrane composition, pH and possible interfering anions were investigated on the response properties of the electrodes. The electrodes exhibited a Nernstian slope of 63.0 ± 0.5 (CPtE) and 60.3 ± 0.4 (PME) mV decade^? 1 in I^? ion over a wide concentration range from 7.9 × 10^? 7 to 1.0 × 10^? 1 M for CPtE and 9.1 × 10^? 6 to 1.0 × 10^? 1 M I^? for PME. The potentiometric response of the electrodes was independent of the pH of the test solution in the pH range 2.0–8.5 with a fast response time (< 10 s). The process of transfer of iodide across the membrane interface was investigated by use of the AC impedance technique. The proposed sensors were successfully applied to direct determination of iodide in samples containing interfering anions, waste water and as indicator electrodes in precipitation titrations.     

ZnO film with ultra-low background electron concentration grown by plasma-assisted MBE using Mg film as the buffer layer

High quality ZnO epilayer with background electron concentration as low as 2.6 × 10¹⁴ cm^?3 was obtained by plasma-assisted MBE on c-sapphire using a thin Mg film as the buffer layer. High-resolution XRD measurement shows a sharp (0 0 2) peak with full width at half maximum (FWHM) of only 0.029°. Photoluminescence spectroscopy presents a weak defect-related near-edge emission. A metal–semiconductor–metal (MSM) typed photodetector based on the material demonstrates a response of ～43 A/W under the bias of 1 V and an ON/OFF ratio of 10⁴. This un-doped ZnO with ultra-low background electron concentration could be a promising starting material for p-type doping.     

A new silver(I)-selective electrode based on derivatized MWCNTs@SiO2 nanocomposites as a neutral carrier

For the first time a novel carbon paste electrode (CPE) for the detection of trace silver(I) was designed by using derivatized silica-coated multi-walled carbon nanotubes (MWCNTs@SiO₂) nanocomposites as a neutral carrier. This proposed electrode, with optimum composition, exhibits a wide dynamic range of 8.6 × 10^? 8 to 1.0 × 10^? 1 M toward silver(I) with a detection limit of 8.0 × 10^? 8 M and a Nernstian slope of 60.8 ± 0.2 mV dec^? 1. Meanwhile, it also shows a good selectivity and a relatively fast response time (~ 20 s), a long lifetime (1 month) and a wide pH range (4.0–9.0). Finally, the developed CPEs were successfully applied in the potentiometric titration of potassium bromide and determination of Cl^? ions in different water samples.     

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.     

Direct electrodeposition of gold nanotube arrays of rough and porous wall by cyclic voltammetry and its applications of simultaneous determination of ascorbic acid and uric acid

Gold nanotube arrays of rough and porous wall has been synthesized by direct electrodeposition with cyclic voltammetry utilizing anodic aluminum oxide template (AAO) and polycarbonate membrane (PC) during short time (only 3 min and 2 min, respectively). The mechanism of the direct electrodeposition of gold nanotube arrays by cyclic voltammetry (CV) has been discussed. The morphological characterizations of the gold nanotube arrays have been investigated by scanning electron microscopy (SEM). A simultaneous determination of ascorbic acid (AA) and uric acid (UA) by differential pulse voltammetry (DPV) was constructed by attaching gold nanotube arrays (using AAO) onto the surface of a glassy carbon electrode (GCE). The electrochemical behavior of AA and UA at this modified electrode has been studied by CV and differential pulse voltammetry (DPV). The sensor offers an excellent response for AA and UA and the linear response range for AA and UA were 1.02 × 10^? 7–5.23 × 10^? 4 mol L^? 1 and 1.43 × 10^? 7–4.64 × 10^? 4 mol L^? 1, the detection limits were 1.12 × 10^? 8 mol L^? 1 and 2.24 × 10^? 8 mol L^? 1, respectively. This sensor shows good regeneration, stability and selectivity and has been used for the determination of AA and UA in real human urine and serum samples with satisfied results.     

Potentiometric determination of ketoprofen and piroxicam at a new PVC electrode based on ion associates of Rhodamine 6G

The characteristics, performance and application of ion-selective electrodes for ketoprofen and piroxicam ions based on Rhodamine 6G as electrode-active substances are described. These electrodes respond with sensitivities of (58.0 ± 1.0) and (57.0 ± 2.0) mV/decade over the range 1.0 × 10^? 4–1.0 × 10^? 1 and 1.0 × 10^? 4–5.0 × 10^? 2 mol/l at pH 5–9 and 6–10 and a detection limit of 6.3 × 10^? 5 and 3.2 × 10^? 5 mol/l for ketoprofen and piroxicam, respectively. The electrodes are easily constructed at a relatively low cost, have a fast response time and can be used for a period of 5 months without any considerable divergence in potential. The proposed sensor displayed good selectivity for ketoprofen and piroxicam in the presence of several substances and inorganic anions. It was used for the direct assay of ketoprofen and piroxicam in commercial pharmaceutical preparations.     

A novel ratiometric fluorescent Yb3+ sensor based on a N′-(1-oxoacenaphthylen-2(1H)-ylidene)furan-2-carbohydrazide as a suitable fluorophore

N′-(1-oxoacenaphthylen-2(1H)-ylidene)furan-2-carbohydrazide (L) was synthesized for the first time and used as a ratiometric fluorescent chemosensor for high selective recognition of Yb³⁺ ions in acetonitrile (MeCN) solution. The L–Yb³⁺ complexation quench the fluorescence of L at 420 nm and induces new fluorescent enhancement at 516 nm. Due to the formation of a 2:1 metal ligand complex in acetonitrile solution, the red shift of fluorescent emission spectrum occurred. The sensor shows a linear response toward Yb³⁺ ion concentration in the range of 3.3 × 10^? 7 M to 1.0 × 10^? 4 M with detection limit of 1.2 × 10^? 7 M. The fluorescent probe exhibits high selectivity for Yb³⁺ ion over the other common mono-, di-, and trivalent cations.     

Potentiometric detection of silver (I) ion based on carbon paste electrode modified with diazo-thiophenol-functionalized nanoporous silica gel

For the first time, triazene compound functionalized silica gel was incorporated into carbon paste electrode for the potentiometric detection of silver (I) ion. A novel diazo-thiophenol-functionalized silica gel (DTPSG) was synthesized, and the presence of DTPSG acted as not only a paste binder, but also a reactive material. The electrode with optimum composition, exhibited an excellent Nernstian response to Ag⁺ ion ranging from 1.0 × 10^? 6 to 1.0 × 10^? 1 M with a detection limit of 9.5 × 10^? 7 M and a slope of 60.4 ± 0.2 mV dec^? 1 over a wide pH range (4.0–9.0) with a fast response time (50 s) at 25 °C. The electrode also showed a long-time stability, high selectivity and reproducibility. The response mechanism of the proposed electrode was investigated by using AC impedance. Moreover, the electrode was successfully applied for the determination of silver ions in radiology films, and for potentiometric titration of the mixture solution of Cl^? and Br^? ions.