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A glucose biosensor based on electrodeposition of palladium nanoparticles and glucose oxidase onto Nafion-solubilized carbon nanotube electrode.

Electrodeposition was used for the co-deposition of glucose oxidase (GOx) enzymes and palladium nanoparticles onto a Nafion-solubilized carbon nanotube (CNT) film. The co-deposited Pd-GOx-Nafion CNT bioelectrode retains its biocatalytic activity and offers an efficient oxidation and reduction of the enzymatically liberated H2O2, allowing for fast and sensitive glucose quantification. The combination of Pd-GOx electrodeposition with Nafion-solubilized CNTs enhances the storage time and performance of the sensor. An extra Nafion coating was used to eliminate common interferents such as uric and ascorbic acids. The fabricated Pd-GOx-Nafion CNT glucose biosensor exhibits a linear response up to 12 mM glucose and a detection limit of 0.15 mM (S/N = 3).

Biosensing Techniques↗

Amperometric protein sensor - fabricated as a polypyrrole, poly-aminophenylboronic acid bilayer.

An approach to the design of electrodes for the production of sensors, which show significant changes to the passage of current in response to the concentration of target protein molecules, is presented. Screen-printed platinum electrodes, modified with two separately applied conducting polymer layers, have been developed as a potential route to forming cheap disposable protein sensors. To achieve a heightened response for the target molecules, an initial layer of polypyrrole was formed on the electrode's surface by electro-deposition. This composite was then employed as a substrate for the subsequent electro-deposition of a relatively thin 'sensing layer' of poly-aminophenylboronic acid. Cyclic voltammetry (CV) of the prepared films revealed an excursion in the current versus potential curve in the anodic phase at approximately 0.0 to +0.2V. It was clearly shown that the introduction of proteins into the CV cell resulted in a measurable decrease in the passage of current in buffered aqueous media. Measured current reductions observed on introducing lysozyme (10ppm) into the test solution were 2.3x10(-6)A for an electrode formed with a poly-aminophenylboronic acid layer on platinum, and 1.75x10(-5)A for a composite electrode formed with poly-aminophenylboronic acid on a polypyrrole coated platinum substrate. The introduction of the competing analytes, dl adrenaline or dopamine, at concentrations typically found in human urine, had little effect on the sensor's response. Additionally, the sensing system was able to maintain a response to added target proteins with as much as 2vol.% urine in the test solution. Using the electrodes in high concentrations of competing physiological analytes, they were able to respond to protein concentrations as low as 0.5ppm in buffered solutions containing urea at a concentration representative of human urine (17,000ppm), which additionally contained glucose (1000ppm).

Biosensing Techniques↗

Electrodeposition of polypyrrole-multiwalled carbon nanotube-glucose oxidase nanobiocomposite film for the detection of glucose.

A nanobiocomposite film consisted of polypyrrole (PPy), functionalized multiwalled carbon nanotubes (cMWNTs), and glucose oxidase (GOx) were electrochemically synthesized by electrooxidation of 0.1M pyrrole in aqueous solution containing appropriate amounts of cMWNTs and GOx. Potentiostatic growth profiles indicate that the anionic cMWNTs is incorporated within the growing PPy-cMWNTs nanocomposite for maintaining its electrical neutrality. The morphology of the PPy-cMWNTs nanocomposite was characterized by scanning electron microscopy (SEM). The PPy-cMWNTs nanocomposite was deposited homogeneously onto glassy carbon electrode. The amperometric responses vary proportionately to the concentration of hydrogen peroxide at the PPy-cMWNTs nanocomposite modified electrode at an operating potential of 0.7V versus Ag/AgCl (3M). The results indicate that the electroanalytical PPy-cMWNTs-GOx nanobiocomposite film was highly sensitive and suitable for glucose biosensor based on GOx function. The GOx concentration within the PPy-cMWNTs-GOx nanobiocomposite and the film thickness are crucial for the performance of the glucose biosensor. The amperometric responses of the optimized PPy-cMWNTs-GOx glucose biosensor (1.5 mgmL(-1) GOx, 141 mCcm(-2) total charge) displayed a sensitivity of 95 nAmM(-1), a linear range up to 4mM, and a response time of about 8s.

Biosensing Techniques↗

Design and development of a highly stable hydrogen peroxide biosensor on screen printed carbon electrode based on horseradish peroxidase bound with gold nanoparticles in the matrix of chitosan.

The design and development of a screen printed carbon electrode (SPCE) on a polyvinyl chloride substrate as a disposable sensor is described. Six configurations were designed on silk screen frames. The SPCEs were printed with four inks: silver ink as the conducting track, carbon ink as the working and counter electrodes, silver/silver chloride ink as the reference electrode and insulating ink as the insulator layer. Selection of the best configuration was done by comparing slopes from the calibration plots generated by the cyclic voltammograms at 10, 20 and 30 mM K(3)Fe(CN)(6) for each configuration. The electrodes with similar configurations gave similar slopes. The 5th configuration was the best electrode that gave the highest slope. Modifying the best SPCE configuration for use as a biosensor, horseradish peroxidase (HRP) was selected as a biomaterial bound with gold nanoparticles (AuNP) in the matrix of chitosan (HRP/AuNP/CHIT). Biosensors of HRP/SPCE, HRP/CHIT/SPCE and HRP/AuNP/CHIT/SPCE were used in the amperometric detection of H(2)O(2) in a solution of 0.1M citrate buffer, pH 6.5, by applying a potential of -0.4V at the working electrode. All the biosensors showed an immediate response to H(2)O(2). The effect of HRP/AuNP incorporated with CHIT (HRP/AuNP/CHIT/SPCE) yielded the highest performance. The amperometric response of HRP/AuNP/CHIT/SPCE retained over 95% of the initial current of the 1st day up to 30 days of storage at 4 degrees C. The biosensor showed a linear range of 0.01-11.3mM H(2)O(2), with a detection limit of 0.65 microM H(2)O(2) (S/N=3). The low detection limit, long storage life and wide linear range of this biosensor make it advantageous in many applications, including bioreactors and biosensors.

Biosensing Techniques↗

Electrogenerated indium tin oxide-coated glass surface with photosensitive interfaces: surface analysis.

We present herein a photo-immobilization technique for the localized and specific conjugation of biochip platforms with different proteinaceous bioreceptors, such as antigen or antibodies. This methodology based on a photoactivable electrogenerated polymer film, pyrrole-benzophenone, allows the covalent immobilization of biomolecules through light mediation. The surface-conductive glass platform electropolymerized with poly(pyrrole-benzophenone) thin film may then be used to affinity-coat the chip with molecular recognition probes. This glass chip electroconductive surface modification is done by the deposition of a thin layer of indium tin oxide (ITO). Thereafter, pyrrole-benzophenone monomers are electropolymerized onto the conductive metal oxide surface and then exposed to an antigen Staphylococcal Enterotoxin B (SEB)) solution and illuminated with UV light (wavelength approximately 345 nm) through a mask. As a result of the photochemical reaction, a pattern thin layer of the antigen was covalently bound to the benzophenone-modified surface. Then the sample to be analyzed, along with its specific target antibody (anti-SEB antibodies), is introduced onto the glass surface and left to react with the previously photo-immobilized antigen. When the immuno-reaction is completed, the specifically attached immunoglobulin analytes are detected by using secondary antibodies conjugated with Fluorescein isothiocyanate (FITC). The fluorescence signal emanating from the biochip surface is then quantified by two methods, using a filtered intensified charge-coupled device (CCD) camera and a grating spectrometer.

Antibodies↗

Application of saccharose as copper(II) ligand for electroless copper plating solutions.

Saccharose, forming sufficiently stable complexes with copper(II) ions in alkaline solutions, was found to be a suitable ligand for copper(II) chelating in alkaline (pH>12) electroless copper deposition solutions. Reduction of copper(II)-saccharose complexes by hydrated formaldehyde was investigated and the copper deposits formed were characterized. The thickness of the compact copper coatings obtained under optimal operating conditions in 1h reaches ca. 2 microm at ambient temperature. The plating solutions were stable and no signs of Cu(II) reduction in the bulk solution were observed. Results were compared with those systems operating with other copper(II) ligands.

Chelating Agents↗

Effect of chromium(VI) on the status of plasma lipid peroxidation and erythrocyte antioxidant enzymes in chromium plating workers.

OBJECTIVES: The present study was carried out to determine the effect of chromium(VI) on the status of plasma lipid peroxidation and erythrocyte antioxidant enzymes in workers exposed to chromium during chromium plating process. METHODS: Fifty subjects working in chromium plating process formed the study group. An equal number of age-sex matched subjects working in administrative units formed the control group. The control subjects were residing in the same city but away from the work place of study group subjects. Urinary chromium levels were determined by using a graphite furnace atomic absorption spectrophotometer. The plasma lipid peroxidation and erythrocyte antioxidant enzymes were determined by using spectrophotmetric methods. RESULTS: A significant increase of plasma lipid peroxidation and a significant decrease of superoxide dismutase and glutathione peroxidase levels were noted in the study group as compared with the controls. The level of plasma lipid peroxidation was positively and erythrocyte antioxidant enzymes were negatively and significantly correlated with chromium levels in urine. Multiple regression analysis was assessed the oxidative stress associated with chromium and life style confounding factors such as BMI, coffee, tea, alcohol and smoking. The multiple regression analysis showed that the urine chromium levels >10 micro g/g of creatinine, smoking, consumption of green vegetables and BMI variables were significantly associated with the levels of oxidative stress. CONCLUSION: The results show that the increased plasma lipid peroxidation and decreased antioxidant enzymes (superoxide dismutase and glutathione peroxidase) observed in chromium-exposed workers could be used as biomarkers of oxidative stress.

Adult↗

Precision control of the surface structure of gelatin films using micropit plates.

We attempted to use micropit plates as a silicon mold in order to control the surface structures of gelatin films. The three-dimensional micropit plates, fabricated with micromachining technology, have uniform quadrangular or circular pits with side lengths or diameters from 25-400 microm and depths of 40 microm. The micropit plates were originally hydrophilic because of silanol groups on the surface. In order to facilitate peeling the aqueous gelatin film from the micropit plates, the plate was therefore modified with hexamethyldisilazane. Gelatin films with precisely microfabricated structures on the surfaces were obtained by using the modified micropit plates. The release behavior of the films with different surface structures was examined.

Electroplating↗

A case study on algal response to raw and treated effluents from an aluminum plating plant and a pharmaceutical plant.

The algal growth responses to the effluents of an aluminum plating plant and to the wastewater from an analgesic/antiinflammatory-drug-producing pharmaceutical plant were investigated. Growth response of the marine alga Dunaliella tertiolecta was monitored by measuring the two response parameters optical density (OD(640)) and in vitro chlorophyll fluorescence for a period of 14 days. Generally, the two response measurements gave similar results for all effluents but the raw effluents of the aluminum plating plant due to the composition of the wastewater. All wastes affected algal growth either by inhibition only or by stimulation at low concentrations and inhibition at high concentrations. Since pollutant tolerance of algae biased toxicity test results, acclimation of algae to the raw effluent of the aluminum plating plant was examined. Although the water quality parameters of treated effluent of both plants were in the permitted range reported by the Turkish Water Pollution Control Act, they inhibited growth at higher concentrations, implying that the two treatment plants were inefficient. Therefore, the importance of toxicity tests in wastewater discharge regulations was emphasized.

Aluminum↗

Evolving into epilepsy: Multiscale electrophysiological analysis and imaging in an animal model.

Epilepsy research for the design of seizure detection/prediction neuroprosthetics has been faced with the search for electrophysiologic control parameters that can be used to infer the epileptic state of the animal and be leveraged at a later time to deliver neurotherapeutic feedback. The analysis presented here uses multi-microelectrode array technology to provide an electrophysiologic quantification of a hippocampal neural ensemble during the latent period of epileptogenesis. Through the use of signal processing system identification methodologies, we were able to assess the spatial and temporal interrelations of ensembles of hippocampal neurons and relate them to the evolution of the epileptic condition. High-field magnetic resonance (MR) imaging was used to determine the location of electrode placement and to evaluate hippocampal pyramidal cell structural damage. Long-term single unit activity analysis suggests that hippocampal neurons in both CA1-2 and dentate regions increase the number of occurrences and duration of their bursting activity after injury to the contra-lateral hippocampus. The trends inferred from both single neuron and ensemble analysis suggests that the evolution into epilepsy is not abrupt but modulates gradually from the time of injury.

Action Potentials↗

Nafion-coated bismuth film and nafion-coated mercury film electrodes for anodic stripping voltammetry combined on-line with ICP-mass spectrometry.

Nafion-coated bismuth film electrodes (NCBFEs) and Nafion-coated mercury film electrodes (NCMFEs) were used to electrochemically preconcentrate metal analytes for subsequent analysis by inductively coupled plasma-mass spectrometry (ICP-MS). Either type of electrodes is part of a thin-layer electrochemical flow cell that is positioned upstream of a microconcentric nebulizer for the ICP-MS. Performances of these electrodes were compared in terms of the analytical "figures of merit" (e.g., dynamic ranges, reproducibility, hydrodynamic stability, and elimination of matrix effects detrimental to ICP-MS). The coupled technique (ASV-ICP-MS) is found to possess a wide dynamic range (at least 4 to 5 orders of magnitude) and to be reproducible. Both electrodes are much more stable than the thin mercury film electrode (TMFE) traditionally used for ASV-ICP-MS, with the lifetime of the NCBFE exceeding 8 h. Adopting these electrodes for ASV-ICP-MS overcomes the problems associated with a TMFE, the erosion of which decreases the sample throughput, affects the analysis precision, and contaminates conventional glass nebulizers and spray chambers of the spectrometer. The medium exchange procedure inherent in ASV is successfully implemented with a two-valve flow injection system for the accumulation of trace Cd2+ into the electrode from a certified seawater sample, followed by stripping Cd into a solution that is compatible to the ICP-MS operation.

Adsorption↗

Bioreductive deposition of platinum nanoparticles on the bacterium Shewanella algae.

An environmentally friendly method using the metal ion-reducing bacterium Shewanella algae was proposed to deposit platinum nanoparticles. Resting cells of S. algae were able to reduce aqueous PtCl(6)(2-) ions into elemental platinum at room temperature and neutral pH within 60min when lactate was provided as the electron donor. Biogenic platinum nanoparticles of about 5nm were located in the periplasm--a preferable, cell surface location for easy recovery of biogenic nanoparticles.

Biodegradation, Environmental↗

A novel and simple biomolecules immobilization method: electro-deposition ZrO2 doped with HRP for fabrication of hydrogen peroxide biosensor.

For the first time, a very novel and simple immobilization method for fabrication of hydrogen peroxide biosensor was reported in this paper. The biocompatible composite HRP-ZrO(2) thin films were synthesized on gold electrode surface based on electro-deposition zirconia doped with horseradish peroxidase (HRP) by cyclic voltammetry scanning in KCl solution containing ZrO(2) and HRP. The fabricated process of biosensor was characterized by electrochemical impedance spectroscopy (EIS) and the surface topography of the prepared films was imaged by atomic force microscope (AFM). The HRP in HRP-ZrO(2) thin films kept its bioactivity and exhibited excellent electrocatalytical response to the reduction of H(2)O(2). Experimental conditions influencing the biosensor performance such as pH, potential were optimized. The resulting biosensor (HRP-ZrO(2)/Au electrode) showed a linear response to H(2)O(2) over a concentration range from 0.02 to 9.45mM with a detection limit of 2muM based on a signal-to-noise ratio of 3 under optimized conditions. The apparent Michaelis-Menten constant (K(M)(app)) was evaluated to be 8.01mM, which indicated the HRP in HRP-ZrO(2) thin films kept its native bioactivity and had high affinity for H(2)O(2). Moreover, the proposed biosensor showed high sensitivity, good reproducibility and long-term stability. What is more, this immobilization methodology widened biosensor application in biomolecules immobilization and could further develop for other protein and biomolecules immobilization.

Biocompatible Materials↗

The role of electrochemical reactions during electrophoretic particle deposition.

Platinum microelectrodes were fabricated on a sapphire substrate by lithographic patterning and used to manipulate 1.58 microm silica particles in the plane of the substrate. A digital video system captured the motion of particles far from the electrodes and their deposition onto the working electrode during application of a DC potential. The role of electrode reversibility was investigated by comparing as-deposited electrodes with electrodes modified by electrolytic plating of platinum. Particles were also observed adhering to the substrate before reaching the electrode. The zeta potential of the particles and substrate was measured. The differing surface chemistry of the two systems and a local reduction in pH due to the production of hydrogen ion at the anode can explain the adhesion phenomena. Force distance curves were recorded using a colloid probe atomic force microscopy technique to directly measure the interaction of the silica particles with the sapphire substrate. These data validated the observed adhesion at the electrode and provided further support for the temporal and spatial reduction in pH. The role of Faradaic processes and the diffusion of potential determining ions in electrophoretic deposition were also considered.

Aluminum Oxide↗

The behavior of organic components in copper recovery from electroless plating bath effluents using 3D electrode systems.

An electrochemical method was applied for the recovery of copper both from the spent solutions and from the rinse waters of electroless copper plating baths, containing copper sulfate, formaldehyde, quadrol, and NaOH. Experiments were conducted in a rotating packed cell (Rollschichtzelle) to investigate the effects of current density, electrolyte composition, temperature, and pH on the copper recovery. All the copper (final CCu=0.1 ppm) was recovered from the waste and rinse waters of chemical copper plating plants with 70% current efficiency by the electrochemical treatment in a rotating packed cell at 130 A/m2 current density, room temperature, with 5mm diameter cathode granules, with the presence of formaldehyde, and with a specific energy consumption of 3.2-3.5 kW h/kg Cu. On the other hand, final copper concentrations of 5 ppm were reached with 62% current efficiency and 5.5-5.8 kW h/kg Cu specific energy consumption, with electrolytes containing no formaldehyde.

Copper↗

Characterization of the catalytic films formed on stainless steel anodes employed for the electrochemical treatment of cuprocyanide wastewaters.

Surface composition changes at stainless steel anodes in an electrochemical reactor applied for the electrochemical treatment of cuprocyanide-containing wastewaters operating under different hydrodynamic conditions were investigated. Under highly alkaline conditions in situ generation of a surface film on the anode with catalytic properties towards cyanide electrolysis was observed. X-ray photoelectron spectroscopy (XPS) results demonstrated that only copper oxi-hydroxide compounds constitute the surface film developed on the stainless steel anodes, as no traces of N- and C-containing compounds were observed. The collected XPS spectra revealed relevant details concerning the oxidation states of copper in the film, and the products Cu2O, CuO and Cu(OH)2 were identified on the surface of the anodes. However, the quantitative proportions of the individual products differ and depend on the type of mixing employed during reactor operation.

Catalysis↗

Sulfidation of zinc plating sludge with Na2S for zinc resource recovery.

A high amount of zinc disposed in the landfill sites as a mixed-metal plating sludge represents a valuable zinc source. To recover zinc from the plating sludge, a sulfidation treatment is proposed in this study, while it is assumed that ZnS formed could be separated by flotation. The sulfidation treatment was conducted by contacting simulated zinc plating sludge with Na(2)S solution at S(2-) to Zn(2+) molar ratio of 1.5 for a period of 1-48 h, while changing the solid to liquid (S:L) ratio from 0.25:50 to 1.00:50. The conversion of zinc compounds to ZnS was determined based on the consumption of sulfide ions. The reaction products formed by the sulfidation of zinc were identified by X-ray diffraction (XRD). As a result, it was found that the conversion of zinc compounds to ZnS increased with an increase in S:L ratio. A maximum conversion of 0.809 was obtained at an S:L ratio of 1.00:50 after 48 h. However, when the zinc sludge treated at S:L ratio of 1.00:50 for 48 h was subjected to XRD analyses, only ZnS was identified in the treated zinc sludge. The result suggested that the rest of zinc sludge remained unreacted inside the agglomerates of ZnS. The formation behavior of ZnS was predicted by Elovich equation, which was found to describe the system satisfactorily indicating the heterogeneous nature of the sludge.

Electroplating↗

Enhanced photo-catalytic activity of TiO2 films with doped La prepared by micro-plasma oxidation method.

Mesoporous thin titanium dioxide films have been prepared on titanium plates through micro-plasma oxidation. To increase the films' photo-catalytic activity, La ions with different concentrations (0, 0.025, 0.005, 0.075, 0.1g/L) were added into the H(2)SO(4) electrolyte solution. X-ray diffraction, X-ray photoelectron spectroscopy, atomic force microscopy, and scanning electron microscopy techniques were applied to characterize the modified films. A kind of typical textile industry pollutant (Rhodamine B) was used to evaluate the photo-catalytic activity of the films. The results showed that this activity of the films had been improved by adding La ions into the electrolyte solution. The enhanced photo-catalytic activities might be resulted from the increase of mesopores' number, producing more reactive sites to absorb and oxidize pollutants. Also, the improvement was related to the forming of titanium dioxide lattice distortion, which could accept more photoexcitated holes and produce more strong surface free radicals to oxidate adsorptive molecules.

Catalysis↗