Mechanism and model of the oscillatory electro-oxidation of methanol

A mechanism for the kinetic instabilities observed in the galvanostatic electro-oxidation of methanol is suggested and a model developed. The model is investigated using stoichiometric network analysis as well as concepts from algebraic geometry (polynomial rings and ideal theory) revealing the occurrence of a Hopf and a saddle-node bifurcation. These analytical solutions are confirmed by numerical integration of the system of differential equations. (C) 2010 American Institute of Physics

Excitation energies from ground-state density-functionals by means of generator coordinates

The generator-coordinate method is a flexible and powerful reformulation of the variational principle. Here we show that by introducing a generator coordinate in the Kohn-Sham equation of density-functional theory, excitation energies can be obtained from ground-state density functionals. As a viability test, the method is applied to ground-state energies and various types of excited-state energies of atoms and ions from the He and the Li isoelectronic series. Results are compared to a variety of alternative DFT-based approaches to excited states, in particular time-dependent density-functional theory with exact and approximate potentials.

Mechanistic studies of the 'blue' Cu enzyme, bilirubin oxidase, as a highly efficient electrocatalyst for the oxygen reduction reaction

The 'blue copper' enzyme bilirubin oxidase from Myrothecium verrucaria shows significantly enhanced adsorption on a pyrolytic graphite 'edge' (PGE) electrode that has been covalently modified with naphthyl-2-carboxylate functionalities by diazonium coupling. Modified electrodes coated with bilirubin oxidase show electrocatalytic voltammograms for the direct, four-electron reduction of O(2) by bilirubin oxidase with up to four times the current density of an unmodified PGE electrode. Electrocatalytic voltammograms measured with a rapidly rotating electrode (to remove effects of O(2) diffusion limitation) have a complex shape (an almost linear dependence of current on potential below pH 6) that is similar regardless of how PGE is chemically modified. Importantly, the same waveform is observed if bilirubin oxidase is adsorbed on Au(111) or Pt(111) single-crystal electrodes (at which activity is short-lived). The electrocatalytic behavior of bilirubin oxidase, including its enhanced response on chemically-modified PGE, therefore reflects inherent properties that do not depend on the electrode material. The variation of voltammetric waveshapes and potential-dependent (O(2)) Michaelis constants with pH and analysis in terms of the dispersion model are consistent with a change in rate-determining step over the pH range 5-8: at pH 5, the high activity is limited by the rate of interfacial redox cycling of the Type 1 copper whereas at pH 8 activity is much lower and a sigmoidal shape is approached, showing that interfacial electron transfer is no longer a limiting factor. The electrocatalytic activity of bilirubin oxidase on Pt(111) appears as a prominent pre-wave to electrocatalysis by Pt surface atoms, thus substantiating in a single, direct experiment that the minimum overpotential required for O(2) reduction by the enzyme is substantially smaller than required at Pt. At pH 8, the onset of O(2) reduction lies within 0.14 V of the four-electron O(2)/2H(2)O potential.

Response of oriental fruit moth, Grapholita molesta (Busck) (Lepidoptera: Tortricidae), eggs to gamma radiation

As insects increase in radiotolerance as they develop and usually several developmental stages of the pest may be present in the fresh shipped commodity, it is important to know the radiation susceptibility of the stages of the target insect before the establishment of ionizing radiation quarantine treatments. This study was performed to determine the radiotolerance of eggs of the oriental fruit moth, Grapholita molesta (Busck) (Lepidoptera: Tortricidae), to gamma radiation. This species is considered as one of the most serious worldwide pests for temperate fruits, especially peaches. Eggs (12 h old) were exposed to 0 (control), 25, 35, 50, 75, 100, 125 and 150 Gy of gamma radiation. Surviving larvae were allowed to feed on an artificial diet. Three days after irradiation, it was verified that larvae`s cephalic capsules were significantly affected by gamma radiation, and the estimated mean LD(90) and LD(99) were 66.3 Gy and 125.8 Gy, respectively. Oriental fruit moth eggs revealed to be quite radiosensitive and very low doses as 50 Gy were sufficient to disrupt G. molesta embryogenesis. At 25 Gy, only male adults originated from the surviving larvae and, after mating with untreated fertile females, shown to be sterile. (C) 2010 Elsevier Ltd. All rights reserved.

Hydrogen production from soft-drink wastewater in an upflow anaerobic packed-bed reactor

The production of hydrogen from soft-drink wastewater in two upflow anaerobic packed-bed reactors was evaluated. The results show that soft-drink wastewater is a good source for hydrogen generation. Data from both reactors indicate that the reactor without medium containing macro- and micronutrients (R2) provided a higher hydrogen yield (3.5 mol H(2) mol(-1) of sucrose) as compared to the reactor (R1) with a nutrient-containing medium (3.3 mol H(2) mol(-1) of sucrose). Reactor R2 continuously produced hydrogen, whereas reactor R1 exhibited a short period of production and produced lower amounts of hydrogen. Better hydrogen production rates and percentages of biogas were also observed for reactor R2, which produced 0.4 L h(-1) L(-1) and 15.8% of H(2), compared to reactor R1, which produced 0.2 L h(-1) L(-1) and 2.6% of H(2). The difference in performance between the reactors was likely due to changes in the metabolic pathway for hydrogen production and decreases in bed porosity as a result of excessive biomass growth in reactor R1. Molecular biological analyses of samples from reactors R1 and R2 indicated the presence of several microorganisms, including Clostridium (91% similarity), Enterobacter (93% similarity) and Klebsiella (97% similarity). Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Fermentative hydrogen production by microbial consortium

Heat pre-treatment of the inoculum associated to the pH control was applied to select hydrogen-producing bacteria and endospores-forming bacteria. The source of inoculum to the heat pre-treatment was from a UASB reactor used in the slaughterhouse waste treatment. The molecular biology analyses indicated that the microbial consortium presented microorganisms affiliated with Enterobacter cloacae (97% and 98%), Clostridium sp. (98%) and Clostridium acetobutyricum (96%), recognized as H, and volatile acids` producers. The following assays were carried out in batch reactors in order to verify the efficiencies of sucrose conversion to H-2 by the microbial consortium: (1) 630.0 mg sucrose/L, (2) 1184.0 mg sucrose/L, (3) 1816.0 mg sucrose/L and (4) 4128.0 mg sucrose/L. The subsequent yields were obtained as follows: 15% (1.2 mol H-2/mol sucrose), 20% (1.6 mol H-2/mol sucrose), 15% (1.2 mol H-2/mol sucrose) and 4% (0.3 mol H-2/mol sucrose), respectively. The intermediary products were acetic acid, butyric acid, methanol and ethanol in all of the anaerobic reactors. (C) 2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Application of an anaerobic packed-bed bioreactor for the production of hydrogen and organic acids

This study investigates the feasibility of an anaerobic bioreactor for treating low contents of organic matter to generate organic acids and hydrogen. The device employed for this purpose was a horizontal packed-bed bioreactor fed with glucose-based synthetic wastewater and operated with hydraulic retention times from 0.5 to 2 h. A microbial biofilm was developed without previous inoculation, using expanded clay beads (4.8-6.3 mm) as support material. Alkalinity was found to be the main parameter affecting the production of hydrogen and organic acids, and the system produced optimal output when operating without a buffer agent. The average hydrogen production was 2.48, 2.15 and 1.81 molH(2) mol(-1) of glucose for NaHCO3 influent concentrations of 0, 1000 and 2000 mg L-1, respectively. The operational regime of the bioreactor, the support material and the controlled alkalinity were effective in selecting and immobilizing microbial fermenting biofilms, which successfully produced hydrogen and organic acids throughout the operating period. Exploratory assays indicated the feasibility of organic acid extraction using an anionic polymeric resin. (C) 2007 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Biohydrogen production in anaerobic fluidized bed reactors: Effect of support material and hydraulic retention time

This study evaluated two different support materials (polystyrene and expanded clay) for biohydrogen production in an anaerobic fluidized bed reactor (AFBR) treating synthetic wastewater containing glucose (4000 mg L(-1)). The AFBRs contained either polystyrene (R1) or expanded clay (R2) as support materials were inoculated with thermally pre-treated anaerobic sludge and operated at a temperature of 30 degrees C and a pH of approximately 5.5. The AFBRs were operated with a range of hydraulic retention times (HRTs) between 1 and 8 h. For R1 with an HRT of 2 h, the maximum hydrogen yield (HY) was 1.90 mol H(2) mol(-1) glucose, with 0.805 mg of biomass (as total volatile solids, or TVS) attached to each g of polystyrene. For R2 operated at an HRT of 2 h, the maximum HY was 2.59 mol H(2) moll glucose, with 1.100 mg of attached biomass (as TVS) g(-1) expanded clay. The highest hydrogen production rates (HPR) were 0.95 and 1.21 L h(-1) L(-1) for R1 and R2, respectively, using an HRT of 1 h. The H(2) content increased from 16-47% for R1 and from 22-51% for R2. No methane was detected in the biogas produced throughout the period of AFBR operation. These results show that the values of HY, HPR, H(2) content, and g of attached biomass g(-1) support material were all higher for AFBRs containing expanded clay than for reactors containing polystyrene. (C) 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.

Long-term stability of hydrogen and organic acids production in an anaerobic fluidized-bed reactor using heat treated anaerobic sludge inoculum

This study evaluates the stability of hydrogen and organic acids production in an anaerobic fluidized-bed reactor (AFBR) that contains expanded clay (2.8-3.35 mm in diameter) as a support medium and is operated on a long-term basis. The reactor was inoculated with thermally pre-treated anaerobic sludge and operated with decreasing hydraulic retention time (HRT), from 8 h to 1 h, at a controlled temperature of 30 degrees C and a pH of about 3.8. Glucose (2000 mg L(-1)) was used as the substrate, generating conversion rates of 92-98%. Decreasing the HRT from 8 h to 1 h led to an increase in average hydrogen-production rates, with a maximum value of 1.28 L h(-1) L(-1) for an HRT of 1 h. In general, hydrogen yield production increased as HRT decreased, reaching 2.29 mol of H(2)/mol glucose at an HRT of 2 h and yielding a maximum hydrogen content of 37% in the biogas. No methane was detected in the biogas throughout the period of operation. The main soluble metabolites (SMP) were acetic acid (46.94-53.84% of SMP) and butyric acid (34.51-42.16% of SMP), with less than 15.49% ethanol. The steady performance of the AFBR may be attributed to adequate thermal treatment of the inoculum, the selection of a suitable support medium for microbial adhesion, and the choice of satisfactory environmental conditions imposed on the system. The results show that stable hydrogen production and organic acids production were maintained in the AFBR over a period of 178 days. (C) 2009 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Anaerobic fluidized bed reactor with expanded clay as support for hydrogen production through dark fermentation of glucose

This study evaluated hydrogen production in an anaerobic fluidized bed reactor (AFBR) fed with glucose-based synthetic wastewater. Particles of expanded clay (2.8-3.35 mm) were used as a support material for biomass immobilization. The reactor was operated with hydraulic retention times (HRT) ranging from 8 to 1 h. The hydrogen yield production increased from 1.41 to 2.49 mol H(2) Mol(-1) glucose as HRT decreased from 8 to 2 h. However, when HRT was 1 h, there was a slight decrease to 2.41 mol H(2) Mol(-1) glucose. The biogas produced was composed of H(2) and CO(2), and the H(2) content increased from 8% to 35% as HRT decreased. The major soluble metabolites during H(2) fermentation were acetic acid (HAc) and butyric acid (HBu), accounting for 36.1-53.3% and 37.7-44.9% of total soluble metabolites, respectively. Overall, the results demonstrate the potential of using expanded clay as support material for hydrogen production in AFBRs. (c) 2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Evaluation of gamma-radiation on green tea odor volatiles

The aim of this study was to evaluate the gamma radiation effects on green tea odor volatiles in green tea at doses of 0, 5, 10, 15 and 20 kGy. The volatile organic compounds were extracted by hydrodistillation and analyzed by GC/MS. The green tea had a large influence on radiation effects, increasing the identified volatiles in relation to control samples. The dose of 10 kGy was responsible to form the majority of new odor compounds following by 5 and 20 kGy. However, the dose of 5 kGy was the dose that degraded the majority of volatiles in non-irradiated samples, following by 20 kGy. The dose of 15 kGy showed has no effect on odor volatiles. The gamma radiation, at dose up to 20 kGy, showed statistically no difference between irradiated and non irradiated green tea on odors compounds. (C) 2010 Elsevier Ltd. All rights reserved.

Determination of volatiles produced during radiation processing in Laurus cinnamomum

In order to protect food from pathogenic microorganisms as well as increase its shelf-life, while keeping sensorial properties (e.g., odor and taste), which are important properties required by spice buyers, it is necessary to analyze volatile formation from irradiation of medicinal and food herbs. Possible changes in the odor of these herbs are evaluated by characterizing different radiation doses and effects on sensorial properties, in order to allow better application of the irradiation technology. The aim of the present study was to analyze volatile formation on cinnamon (Laurus cinnamomum) samples after gamma irradiation. These samples were irradiated into plastic packages using a (60)Co facility. Radiation doses applied were 0, 5, 10, 15, 20 and 25 kGy. For the analysis of the samples, solid-phase microextraction (SPME) was applied, while for the analysis of volatile compounds, CG/MS. Spice irradiation showed the highest decrease in volatile compounds. For L. cinnamomum, the irradiation decreased volatile compounds by nearly 56% and 89.5%, respectively, comparing to volatile from a sample which had not been previously irradiated. Crown Copyright (C) 2009 Published by Elsevier Ltd. All rights reserved.

Consumer`s evaluation of the effects of gamma irradiation and natural antioxidants on general acceptance of frozen beef burger

The effect of addition of rosemary and oregano extracts on the sensory quality of irradiated beef burger was investigated. Batches of beef burgers were prepared with 400 ppm of rosemary or oregano extract and a group prepared with 200 ppm of synthetic butyl-hydroxytoluene (BHT)/butyl-hydroxy-anisol (BHA) was used as a control. Half of each formulation was irradiated at the maximum dose allowed for frozen meat (7 kGy). Samples were kept under frozen conditions (-20 degrees C) during the whole storage period, including during irradiation. Two analyses were performed after 20 and 90 days to verify the influence of the addition of the different types of antioxidants and the effect of irradiation and storage time on the acceptance of the product. Thirty-three and thirty-four untrained panelists were invited to participate in the first and second test, respectively. A structured hedonic scale ranging from 1 to 9 points was used in both analyses. BHT/BHA formulation obtained the highest score (6.73) and regarding the natural antioxidants, oregano received better acceptance (6.36). Irradiated samples formulated with oregano received a lower score, 6.03 in the first test and 5.06 in the second one, compared to the non-irradiated sample (6.36 and 5.79). In the second test (90 days), the sample formulated with BHT/BHA and which was irradiated received a higher score (6.59) when compared to the non-irradiated one (5.85). In both tests, the irradiated samples formulated with rosemary extract obtained a better score compared to the non-irradiated one, the scores being 5.00-3.82 and 5.00-3.76 in the first and second test, respectively. Our results allowed us to conclude that the natural antioxidants, rosemary and oregano extracts, present a good alternative for replacing synthetic additives in food industries, and that the irradiation process, in some cases, may help to enhance the sensory quality of food. (C) 2008 Elsevier Ltd. All rights reserved.

Acceptability of minimally processed and irradiated pineapple and watermelon among Brazilian consumers

This study aimed at evaluating the acceptance of MP watermelon and pineapple exposed to 1.0 and 2.5kGy compared to non-irradiated samples. No significant differences were observed in liking between irradiated and non-irradiated samples, and also between doses of 1.0 and 2.5 kGy. significant differences in sourness (pineapple) or sweetness (watermelon) and between intention of purchase of irradiated and non-irradiated fruits were riot observed as well. Results showed that MP watermelon and pineapple could be irradiated with doses up to 2.5 kGy without significant changes in acceptability. (C) 2008 Elsevier Ltd. All rights reserved.

Influence of gamma radiation onto polymeric matrix with papain

Papain is a proteolytic enzyme that has been widely used as debridement agent for scars and wound healing treatment. However, papain presents low stability, which limits its use to extemporaneous or short shelf-life formulations. The purpose of this study was to entrap papain into a polymeric matrix in order to obtain a drug delivery system that could be used as medical device. Since these systems must be sterile, gamma radiation is an interesting option and presents advantages in relation to conventional agents: no radioactive residues are formed: the product can be sterilized inside the final packaging and has an excellent reliability. The normative reference for the establishment of the sterilizing dose determines 25 kGy as the inactivation dose for viable microorganisms. A silicone dispersion was selected to prepare membranes containing 2% (w/w) papain. Irradiated and non-irradiated membranes were simultaneously assessed in order to verify whether gamma radiation interferes with the drug-releasing profile. Results showed that irradiation does not affect significantly papain release and its activity. Therefore papain shows radioresistance in the irradiation conditions applied. In conclusion, gamma radiation can be easily used as sterilizing agent without affecting the papain release profile and its activity onto the biocompatible device is studied. (C) 2009 Elsevier Ltd. All rights reserved.