Studies on the Electrocatalytic Reduction of Hydrogen Peroxide on a Glassy Carbon Electrode Modified With a Ruthenium Oxide Hexacyanoferrate Film

The electrocatalytic reduction of hydrogen peroxide on a glassy carbon (GC) electrode modified with a ruthenium oxide hexacyanoferrate (RuOHCF) was investigated using rotating disc electrode (RDE) voltammetry aiming to improve the performance of the sensor for hydrogen peroxide detection. The influence of parameters such as rotation speed, film thickness and hydrogen peroxide concentration indicated that the rate of the cross-chemical reaction between Ru(II) centres immobilized into the film and hydrogen peroxide controls the overall process. The kinetic regime could be classified as LSk mechanism, according to the diagnostic table proposed by Albery and Hillman, and the kinetic constant of the mediated process was found to be 706 mol(-1) cm(3) s(-1). In the LSk case the reaction layer is located at a finite layer close to the modifier layer/solution interface

Continuous monitoring of ascorbate transport through neuroblastoma cells with a ruthenium oxide hexacyanoferrate modified microelectrode

The uptake of ascorbate by neuroblastoma cells using a ruthenium oxide hexacyanoferrate (RuOHCF)-modified carbon fiber disc (CFD) microelectrode (r = 14.5 mu m) was investigated. By use of the proposed electrochemical sensor the amperometric determination of ascorbate was performed at 0.0 V in minimum essential medium (MEM, pH = 7.2) with a limit of detection of 25 mu mol L(-1). Under the optimum experimental conditions, no interference from MEM constituents and reduced glutathione (used to prevent the oxidation of ascorbate during the experiments) was noticed. The stability of the RuOHCF-modified electrode response was studied by measuring the sensitivity over an extended period of time (120 h), a decrease of around 10% being noticed at the end of the experiment. The rate of ascorbate uptake by control human neuroblastoma SH-SY5Y cells, and cells transfected with wild-type Cu,Zn-superoxide dismutase (SOD WT) or with a mutant typical of familial amyotrophic lateral sclerosis (SOD G93A), was in agreement with the level of oxidative stress in these cells. The usefulness of the RuOHCF-modified microelectrode for in vivo monitoring of ascorbate inside neuroblastoma cells was also demonstrated.

Effects of acid treatments of carbon on N2O and NO reduction by carbon-supported copper catalysts

The influences of HCl, HNO3 and HF treatments of carbon on N2O and NO reduction with 20 wt% Cu-loaded activated carbon were studied. The order of activity in both N2O and NO is as follows: Cu20/AC-HNO3>Cu20/AC>Cu20/AC-HF>Cu20/AC-HCl. The same sequence was also observed for the amount of CO2 evolved during TPD experiments of supports acid for the catalyst dispersion. On the other hand, N2O exhibited a higher reaction rate than NO and a higher sensitivity to acid treatments, and the presence of gas-phase O-2 had opposite effects in N2O and NO reduction. The key role of carbon surface chemistry is examined to rationalize these findings and the relevant mechanistic and practical implications are discussed. The effects of oxygen surface groups on the pore structure of supports and catalysts are also analyzed, (C) 2000 Elsevier Science Ltd. All rights reserved.

Atmospheric corrosion of copper at Heron Island

Atmospheric corrosion tests have been conducted at Heron Island, Queensland, a low SO2 marine environment. The corrosion rates for copper followed the linear bi-logarithmic law. X-ray diffraction identified atacamite (basic copper chloride) and cuprite (cuprous oxide) as the predominant corrosion products. Biogenic and anthropogenic sources of pollution did not have a measurable influence.

Clinical observations of cattle and buffalos with experimentally induced chronic copper poisoning

The susceptibility of cattle and buffalos to chronic copper poisoning (CCP) was compared by using cattle (n = 10) and buffalo (n = 10) steers distributed into two copper supplemented (n = 6) and two control (n = 4) groups. Supplemented animals received 2 mg copper (Cu)/kg body weight daily for one week, with an additional 2 mg weekly until the end of the experiment (day 105). Three liver biopsies (day 0, 45, and 105) were obtained for mineral analyses; clinical examinations and blood samples were obtained every 15 days. Three supplemented cattle and two buffalos with typical manifestations of CCP died. There were no differences in the frequency of mortality between cattle and buffalos; hepatic copper concentration was higher in cattle than buffalos. These findings suggest that buffalos and cattle might be equally susceptible to CCP. However, buffalos accumulate less liver copper than cattle and have a lower threshold of hepatic Cu accumulation, which leads to clinical manifestation of CCP. (c) 2009 Elsevier Ltd. All rights reserved.

Changes in zinc and copper homeostasis in human livers and kidneys associated with exposure to environmental cadmium

This study was undertaken to assess changes in zinc and copper homeostasis in human tissues that could be attributed to human exposure to environmental cadmium, using samples of lung, liver and kidney cortex of 61 Queensland residents, aged 2 to 89 years, who had died of accidental causes. None of the subjects were exposed to cadmium in the workplace. Levels of zinc in liver and kidney cortex samples showed inverse associations with donor age whereas zinc in lung only showed inverse association with gender. Lung zinc levels in females were 14% lower than in males. Zinc in liver and kidney cortex samples were found to exist in at least two pools; one was associated with cadmium that bound to metallothionein (MT) and the other was associated with non - MTbound copper. In liver, the amounts of zinc in the MT pool were smaller compared to those in non-MT pool given that only 7% of zinc variations were explained by cadmium whereas 22% of the liver zinc Variations were accounted for by non - MT bound copper. In sharp contrast, larger amounts of zinc in kidney cortex samples were in the MT pool, compared to those in the non-MT pool given that cadmium was found to explain 69% of total zinc variation whereas copper explained only 17% of kidney zinc variations. The levels of copper in liver were found to be increased by 45-50% in subjects with high cadmium exposure level, compared to subjects of similar ages with medium exposure level. The levels of zinc and copper in kidney cortex samples in the subjects with high cadmium exposure were both found to be significantly elevated compared to those found in the medium-exposure group whereas copper contents were about 19-23% greater than in medium- as well as low-exposure groups. Taken together these results indicate increased sequestration of zinc and copper in liver and kidney cortex samples. The increases in metal sequestrations were observed in liver samples having cadmium contents of greater than 1 mug/g wet weight and in kidney cortex having cadmium contents of greater than 26 mug/g wet weight. Zinc and copper contents in lung of this sample group, however, were not associated with cadmium due probably to lower exposure levels compared to those of liver and kidney.

Role of oxygen in the nitrous oxide/carbon reaction

An investigation of the role of oxygen in the nitrous oxide/carbon reaction was carried out on various carbon samples (both graphitic and nongraphitic) over a range of temperatures and partial pressures. Previous work reported that oxygen strongly inhibited the nitrous oxide/carbon reaction. Large ratios of O-2/N2O were used in all previous work. In this work, the O-2/N2O ratio was kept below 1, and we found that oxygen did not inhibit the rate of the C + N2O reaction. Instead, the rate of the reaction in the presence of oxygen was essentially that predicted by the two independent reactions, nitrous oxide/carbon and oxygen/carbon, occurring simultaneously. A simple theoretical explanation is given for the observations, both past and present, on the basis of competitive chemisorption of nitrous oxide and oxygen on active sites.

gamma-alumina nanofibers prepared from aluminum hydrate with poly(ethylene oxide) surfactant

Introducing poly(ethylene oxide) surfactant to aluminum hydrate colloids can effectively direct the crystal growth of boehmite and the crystal morphology of final gamma-alumina crystallites. Fibrous crystallites of gamma-alumina about 3-4 nm thick and 30-60 nm long are obtained. They stack randomly, resulting in a structure with a low contact area between the fibers but with a very large porosity. Such a structure exhibits strong resistance to sintering when heated to high temperatures. A sample retains a BET surface area of 68 m(2)/g, after being heated to 1473 K. The surfactant molecules form micelles that interact with the colloid particles of aluminum hydroxide through hydrogen bonding. This interaction is not sufficient to change the intrinsic crystal structure of boehmite, but induces profound changes in the morphology of boehmite crystallites and their growth. The surfactant-induced fiber formation (SIFF) process has distinct features from templated synthesis but shows similarities in some respects to biomineralization processes in which inorganic crystals with complex morphological shapes can be formed in biological systems. SIFF offers an effective approach to create new nanostructures of inorganic oxide from aqueous media.

Electrospun Polyaniline-Reduced Graphene Oxide Composite Nanofibers Based High Sensitive Ammonia Gas Sensor

Ammonia is an important gas in many power plants and industrial processes so its detection is of extreme importance in environmental monitoring and process control due to its high toxicity. Ammonia’s threshold limit is 25 ppm and the exposure time limit is 8 h, however exposure to 35 ppm is only secure for 10 min. In this work a brief introduction to ammonia aspects are presented, like its physical and chemical properties, the dangers in its manipulation, its ways of production and its sources. The application areas in which ammonia gas detection is important and needed are also referred: environmental gas analysis (e.g. intense farming), automotive-, chemical- and medical industries. In order to monitor ammonia gas in these different areas there are some requirements that must be attended. These requirements determine the choice of sensor and, therefore, several types of sensors with different characteristics were developed, like metal oxides, surface acoustic wave-, catalytic-, and optical sensors, indirect gas analyzers, and conducting polymers. All the sensors types are described, but more attention will be given to polyaniline (PANI), particularly to its characteristics, syntheses, chemical doping processes, deposition methods, transduction modes, and its adhesion to inorganic materials. Besides this, short descriptions of PANI nanostructures, the use of electrospinning in the formation of nanofibers/microfibers, and graphene and its characteristics are included. The created sensor is an instrument that tries to achieve a goal of the medical community in the control of the breath’s ammonia levels being an easy and non-invasive method for diagnostic of kidney malfunction and/or gastric ulcers. For that the device should be capable to detect different levels of ammonia gas concentrations. So, in the present work an ammonia gas sensor was developed using a conductive polymer composite which was immobilized on a carbon transducer surface. The experiments were targeted to ammonia measurements at ppb level. Ammonia gas measurements were carried out in the concentration range from 1 ppb to 500 ppb. A commercial substrate was used; screen-printed carbon electrodes. After adequate surface pre-treatment of the substrate, its electrodes were covered by a nanofibrous polymeric composite. The conducting polyaniline doped with sulfuric acid (H2SO4) was blended with reduced graphene oxide (RGO) obtained by wet chemical synthesis. This composite formed the basis for the formation of nanofibers by electrospinning. Nanofibers will increase the sensitivity of the sensing material. The electrospun PANI-RGO fibers were placed on the substrate and then dried at ambient temperature. Amperometric measurements were performed at different ammonia gas concentrations (1 to 500 ppb). The I-V characteristics were registered and some interfering gases were studied (NO2, ethanol, and acetone). The gas samples were prepared in a custom setup and were diluted with dry nitrogen gas. Electrospun nanofibers of PANI-RGO composite demonstrated an enhancement in NH3 gas detection when comparing with only electrospun PANI nanofibers. Was visible higher range of resistance at concentrations from 1 to 500 ppb. It was also observed that the sensor had stable, reproducible and recoverable properties. Moreover, it had better response and recovery times. The new sensing material of the developed sensor demonstrated to be a good candidate for ammonia gas determination.

Characterization of Nitric Oxide Reductase (NOR) from pseudomonas nautica, a study on biologic nitric oxide reduction

Dissertation submitted to obtain the phD degree in Biochemistry, specialty in Physical- Biochemistry, by the Faculdade de Ciências e Tecnologia from the Universidade Nova de Lisboa

The electron transfer complex between nitrous oxide reductase and its electron donors

J Biol Inorg Chem (2011) 16:1241–1254 DOI 10.1007/s00775-011-0812-9

A new CuZ active form in the catalytic reduction of N2O by nitrous oxide reductase from Pseudomonas nautica

J Biol Inorg Chem (2010) 15:967–976 DOI 10.1007/s00775-010-0658-6

Electron transfer complex between nitrous oxide reductase and cytochrome c552 from Pseudomonas nautica: kinetic, nuclear magnetic resonance, and docking studies

Biochemistry. 2008 Oct 14;47(41):10852-62. doi: 10.1021/bi801375q

Activation of N2O reduction by the fully reduced micro4-sulfide bridged tetranuclear Cu Z cluster in nitrous oxide reductase

J. Am. Chem. Soc., 2003, 125 (51), pp 15708–15709 DOI: 10.1021/ja038344n

The effects of electron-hole separation on the photoconductivity of individual metal oxide nanowires

The responses of individual ZnO nanowires to UV light demonstrate that the persistent photoconductivity (PPC) state is directly related to the electron¿hole separation near the surface. Our results demonstrate that the electrical transport in these nanomaterials is influenced by the surface in two different ways. On the one hand, the effective mobility and the density of free carriers are determined by recombination mechanisms assisted by the oxidizing molecules in air. This phenomenon can also be blocked by surface passivation. On the other hand, the surface built-in potential separates the photogenerated electron¿hole pairs and accumulates holes at the surface. After illumination, the charge separation makes the electron¿hole recombination difficult and originates PPC. This effect is quickly reverted after increasing either the probing current (self-heating by Joule dissipation) or the oxygen content in air (favouring the surface recombination mechanisms). The model for PPC in individual nanowires presented here illustrates the intrinsic potential of metal oxide nanowires to develop optoelectronic devices or optochemical sensors with better and new performances.