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Diazonium-functionalized horseradish peroxidase immobilized via addressable electrodeposition: direct electron transfer and electrochemical detection.

A simple one-step procedure is introduced for the preparation of diazonium-enzyme adducts. The direct electrically addressable deposition of diazonium-modified enzymes is examined for electrochemical sensor applications. The deposition of diazonium-horseradish peroxidase leads to the direct electron transfer between the enzyme and electrode exhibiting a heterogeneous rate constant, ks, of 10.3 +/- 0.7 s-1 and a DeltaEp of 8 mV (v = 150 mV/s). The large ks and low DeltaEp are attributed to the intimate contact between enzyme and electrode attached by one to three phenyl molecules. Such an electrode shows high nonmediated catalytic activity toward H2O2 reduction. Future generations of arrayed electrochemical sensors and studies of direct electron transfer of enzymes can benefit from protein electrodes prepared by this method.

Chemistry, Physical↗

Controllable template synthesis of superconducting Zn nanowires with different microstructures by electrochemical deposition.

A systematic study was conducted on the fabrication, structural characterization, and transport properties of Zn nanowires with diameters between 40 and 100 nm. Zinc nanowires were fabricated by electrodepositing Zn into commercially available polycarbonate (PC) or anodic aluminum oxide (AAO) membranes. By controlling the electrodeposition process, we found that the nanowires can be single-crystal, polycrystalline Zn, crystalline Zn/nanocrystalline ZnO composites, or entirely ZnO. The microstructure and chemistry was characterized by using transmission electron microscopy. Transport studies on single-crystal or polycrystalline Zn nanowire arrays embedded inside the membrane showed that the superconducting transition temperature, Tc, is insensitive to the nanowire diameter and morphology. The superconductivity shows a clear crossover from bulklike to quasi-1D behavior, as evidenced by residual low-temperature resistance, when the diameter of the wires is reduced to 70 nm (20 times smaller than the bulk coherence length).

Crystallization↗

Dynamic microscopy of nanoscale cluster growth at the solid-liquid interface.

Dynamic processes at the solid-liquid interface are of key importance across broad areas of science and technology. Electrochemical deposition of copper, for example, is used for metallization in integrated circuits, and a detailed understanding of nucleation, growth and coalescence is essential in optimizing the final microstructure. Our understanding of processes at the solid-vapour interface has advanced tremendously over the past decade due to the routine availability of real-time, high-resolution imaging techniques yielding data that can be compared quantitatively with theory. However, the difficulty of studying the solid-liquid interface leaves our understanding of processes there less complete. Here we analyse dynamic observations--recorded in situ using a novel transmission electron microscopy technique--of the nucleation and growth of nanoscale copper clusters during electrodeposition. We follow in real time the evolution of individual clusters, and compare their development with simulations incorporating the basic physics of electrodeposition during the early stages of growth. The experimental technique developed here is applicable to a broad range of dynamic phenomena at the solid-liquid interface.

Adsorption↗

PtRu/Ti anodes with varying Pt ratio: Ru ratio prepared by electrodeposition for the direct methanol fuel cell.

PtRu/Ti anodes with varying Pt ratio Ru ratio were prepared by electrodeposition of a thin PtRu catalyst layer onto Ti mesh for a direct methanol fuel cell (DMFC). The morphology and structure of the catalyst layers were analyzed by SEM, EDX and XRD. The catalyst coating layer shows an alloy character. The relative activities of the PtRu/Ti electrodes were assessed and compared in half cell and single DMFC experiments. The results show that these electrodes are very active for the methanol oxidation and that the optimum Ru surface coverage was ca. 9 at.% for DMFC operating at 20 degrees C and 11 at.% at 60 degrees C. The PtRu/Ti anode shows a performance comparable to that of the conventional carbon-based anode in a DMFC operating with 0.25 M or 0.5 M methanol solution and atmosphere oxygen gas at 90 degrees C.

Electric Power Supplies↗

Electrochemically deposited Pd islands on an organic surface: the presence of Coulomb blockade in STM I(V) curves at room temperature.

Palladium islands with a thickness of a few monolayers were deposited on top of a self-assembled monolayer (SAM) fabricated from 4-mercaptopyridine. In the I(V) curves obtained using the scanning tunneling microscope (STM) clearly the signature of Coulomb blockade is observed, explicitly demonstrating that these islands are coupled to the underlying gold substrate only via a tunneling barrier; this spectroscopic feature also allows to distinguish the palladium islands from similar morphological features present on the gold substrate prior to palladium deposition.

Adsorption↗

Periodic and chaotic oscillations of the electrochemical potential of p-Si in contact with an aqueous (CuSO4+HF) solution, caused by electroless Cu deposition.

Periodic and chaotic oscillations were observed for the potential of p-type Si(111) immersed in an aqueous (HF+CuSO(4)) solution, accompanied by electroless Cu deposition on p-Si. They were, to our knowledge, the first examples of open-circuit potential oscillations observed for semiconductor electrodes. The oscillations appeared only when the Cu deposit formed a continuous porous film composed of mutually connected submicrometer-sized particles. Besides, the Si surface was kept flat within the size less than 50 nm even after the prolonged oscillation for a few hours, though the Si surface should be etched considerably with HF for this time. A plausible model is proposed for the periodic oscillation, in which interestingly coupling of autocatalytic shift in the flat-band potential of Si (U(fb)) caused by the change in the coverage of the Si oxide and the connection and disconnection of the Cu film with the Si surface plays the key role. The appearance of the chaotic oscillation is also explained by taking into account an oscillation-coupled change in the HF or Cu(2+) concentration near the Si surface.

Catalysis↗

A prospective cohort study of chromium plating workers in Japan.

A prospective cohort study was conducted in 415 small-scale chromeplating plants in Japan to examine the mortality of platers employed between 1970 and 1976. A group of 1,193 male metal platers was identified in 1976 and divided into a chromium plater subgroup (n = 626) and a nonchromium plater subgroup (n = 567). Both subgroups were followed from 1976 through December 1987. Among specific causes of death, only lung cancer was found to be significantly higher than expected for all platers (16 observed, 8.9 expected; SMR 179; 95% CI 102-290). This elevated SMR, however, was not statistically significant in either of the two plater subgroups. The SMR for lung cancer of the chromium plater subgroup was highest among those exposed for the shortest period and among those exposed in the most remote calendar years.

Adult↗

Application of advanced oxidation processes for the treatment of cyanide containing effluent.

Batch experiments were carried out for the removal of cyanide in the effluent of plating industry by the application of advanced oxidation processes. Four systems with different modes of oxidation in combination of ultra violet (UV) light with hydrogen peroxide and/or ozone were investigated. Of all the applied systems, UV-light with two oxidants, i.e. O3 (32 mg min(-1)), and H2O2 (1.36 g l(-1)) was found successful in bringing down the amount of cyanide from 157.32 mg l(-1) to 1.0 mg l(-1), which is the limit set by the Ministry of Environment of Korea for cyanide-containing discharges. Other systems, however, could not bring the cyanide abatement to the targeted value even with higher dosage of oxidants and an extended period of reaction time. Regardless of the oxidation modes applied, all the heavy metal ions in the treated effluent were reduced to 90%. Ultra violet light with the combination of two oxidants had the economic preference over the other systems since a relatively lower dosage of UV-light (2484 W-S cm(-2)) was found effective at achieving the targeted level of cyanide removal.

Cyanides↗

Comparison of discharge silver concentrations from electrolytic plating and metallic replacement silver recovery units.

Silver-based photographic X-ray film is made of solid crystals of silver chloride or silver bromide suspended in a gelatin and then coated on a film. During the X-ray developing process, the image is processed and the nonimage areas containing solid silver chloride or silver bromide crystals are removed in a solution called the fixer. There may be local environmental regulations that regulate the amount of silver discharged from a facility. To meet these regulations, many facilities have added silver recovery units to their processes. Two different types of recovery processes are in use in a large hospital and three clinics under study. All of the units were claimed by their respective manufacturers to be able to recover silver down to concentrations of 5 mg/L. This concentration would ensure that the building that houses each unit would meet the local county limit of 0.5 mg/L silver for total building silver discharge. The hypothesis for this research is that one system, newer and more expensive, consisting of so-called electrolytic plating units (EPUs) (which are followed by so-called metallic replacement units [MRUs] as a backup), will have better silver recovery than MRUs alone. A total of six units were sampled, three EPUs (in combination with MRUs) and three MRUs. The units were sampled once or twice a day for 10 days for a total of 17 samples from each. The samples then were analyzed by inductively coupled plasma spectroscopy, and an analysis of variance was performed on the results. The range for the electrolytic plating unit/metallic replacement unit combinations was 0.20-99.9 mg/L (mean of 35.15 mg/L; median of 33.8 mg/L). The range for the MRUs alone was 7.2-1112 mg/L (mean of 565.5 mg/L; median of 720 mg/L). Many individual results exceeded 5 mg/L, such that extensive dilution would be required to ensure the building effluent did not exceed 0.5 mg/L. It is suggested that the metallic replacement units be changed to EPUs (with metallic replacement backup units) because they had better silver recovery. Also, the EPU combinations need to be sampled regularly to ensure that their silver concentrations are at acceptable levels.

Conservation of Natural Resources↗

Performance evaluation of pilot scale sulfur-oxidizing denitrification for treatment of metal plating wastewater.

A full-scale and two pilot-scale upflow sulfur-oxidizing denitrification (SOD) columns were evaluated using metal plating wastewater as feed. The sludge was autotrophically enriched, and inoculated in the SOD columns attached to the effluent line of three metal plating wastewater treatment facilities. The effects of activated carbon and aeration were also studied, and found effective for the removal of suspended solids and ammonia, respectively. The results showed that the constituents, such as the total nitrogen, nitrates, nitrites, ammonia, chemical oxygen demand (COD), and heavy metals, were effectively removed. The pH was observed to be maintained at 7-8 due to the alkalinity supplied by the sulfur-calcium carbonate (SC) pellet. The denitrification efficiency and start-up period were observed to be affected by the influent quality. Chromium, iron, nickel, copper, and zinc--the major heavy metal components of the influent--were effectively reduced at certain concentrations. Other metal ions were also detected and reduced to undetectable concentrations, but no trends in the comparison with denitrification were observed. From the results it can be concluded that SOD is effective for the removal of nitrogen, particularly nitrates, without a drastic pH change, and can effectively remove minute concentrations of heavy metals and COD in metal plating wastewaters.

Bacteria↗

A demonstration of NIOSH push-pull ventilation criteria.

This paper summarizes the results of a study performed on an actual chrome plating tank in order to validate criteria for push-pull ventilation systems developed by Huebener and Hughes at NIOSH. Validation of the criteria was made by taking area industrial hygiene samples for hexavalent and total chrome at ten locations around the plating tank. The sampling was performed during actual production runs or while the tank was operating with a dummy load. The sampling data are summarized. The data show that the push-pull system, operating at Huebener's criteria, could control emissions to below the current standards and guidelines. Conclusions and recommendations are included.

Air Pollutants, Occupational↗

Treatment of Cr(VI) and phenol by illuminated TiO2.

Industrial wastewater from organic chemical manufacturing and metal plating industries may contain significant amounts of refractory organic matter and heavy metals. Heavy metals such as Cr(VI) and refractory organic matter like phenol were simultaneously removed by reduction and mineralization, respectively, during photocatalytic process. Therefore, this study was carried out to evaluate the effects of phenol on the removal of Cr(VI) in several environmental conditions. Cr(VI) and phenol were more effectively eliminated in UV/TiO2 condition than either by UV or TiO2-alone. The removal efficiencies of Cr(VI) increased as the pH of the TiO2 slurry decreased, the concentration of phenol increased up to 10 mg L(-1), and nitrogen gas was used. Otherwise, the removal efficiencies of phenol were higher at O2-purged system and neutral pH. Without regard to purging gases, complete Cr(VI) removal was observed at pH 4 after 80 min while 90% phenol destruction and 60% mineralization were found after 120 min. It wasfound that application of photocatalytic reaction by using illuminated TiO2 to treat wastewater containing both Cr(VI) and phenol was possible.

Carcinogens, Environmental↗

Temperature selective deposition of Parylene-C.

A new method for selectively depositing conformal, biocompatible coatings of Parylene-C on implantable integrated circuit structures is described. The technique consists of using thin film or diffused resistors to electrically heat the area where an opening in the Parylene is desired. Theoretically predicted and actual Parylene-C thickness are compared.

Biomedical Engineering↗

Electrodeposited iridium oxide for neural stimulation and recording electrodes.

Iridium oxide films formed by electrodeposition onto noniridium metal substrates are compared with activated iridium oxide films (AIROFs) as a low impedance, high charge capacity coating for neural stimulation and recording electrodes. The electrodeposited iridium oxide films (EIROFs) were deposited on Au, Pt, PtIr, and 316 LVM stainless steel substrates from a solution of IrCl4, oxalic acid, and K2CO3. A deposition protocol involving 50 potential sweeps at 50 mV/s between limits of 0.0 V and 0.55 V (versus Ag AgCl) followed by potential pulsing between the same limits produced adherent films with a charge storage capacity of >25 mC/cm2. Characterization by cyclic voltammetry and impedance spectroscopy revealed no differences in the electrochemical behavior of EIROF on non-Ir substrates and AIROF. The mechanical stability of the oxides was evaluated by ultrasonication in distilled water followed by dehydration and rehydration. Stability under charge injection was evaluated using 200 micros, 5.9 A/cm2 (1.2 mC/cm2) cathodal pulses. Loss of iridium oxide charge capacity was comparable for AIROFs and the EIROFs, ranging from 1% to 8% of the capacity immediately after activation or deposition. The EIROFs were deposited and evaluated on silicon microprobe electrodes and on metallized polyimide electrodes being developed for neural recording and stimulation applications.

Electric Capacitance↗

A high-yield fabrication process for silicon neural probes.

There is a great need for silicon microelectrodes that can simultaneously monitor the activity of many neurons in the brain. However, one of the existing processes for fabricating silicon microelectrodes-reactive-ion etching in combination with anisotropic KOH etching-breaks down at the wet-etching step for device release. Here we describe a modified wet-etching sidewall-protection technique for the high-yield fabrication of well-defined silicon probe structures, using a Teflon shield and low-pressure chemical vapor deposition (LPCVD) silicon nitride. In the proposed method, a micro-tab holds each individual probe to the central scaffold, allowing uniform anisotropic KOH etching. Using this approach, we obtained a well-defined probe structure without device loss during the wet-etching process. This simple method yielded more accurate fabrication and an improved mechanical profile.

Action Potentials↗