Reaction mechanism of the direct gas phase synthesis of H2O2 catalyzed by Au3

The gas phase reaction of molecular oxygen and hydrogen catalyzed by a Au3cluster to yield H2O2 was investigated theoretically using second order Z-averaged perturbation theory, with the final energies obtained with the fully size extensive completely renormalized CR-CC(2,3) coupled clustertheory. The proposed reaction mechanism is initiated by adsorption and activation of O2 on the Au3cluster. Molecular hydrogen then binds to the Au3O2 global minimum without an energy barrier. The reaction between the activated oxygen and hydrogen molecules proceeds through formation of hydroperoxide (HO2) and a hydrogen atom, which subsequently react to form the product hydrogen peroxide. All reactants, intermediates, and product remain bound to the goldcluster throughout the course of the reaction. The steps in the proposed reaction mechanism have low activation energy barriers below 15kcal∕mol. The overall reaction is highly exothermic by ∼30kcal∕mol

Wild edible fruits as a potential source of phytochemicals with capacity to inhibit lipid peroxidation

The edible fruits of four wild small trees or shrubs (Arbutus unedo, Crataegus monogyna, Prunus spinosa and Rubus ulmifolius) traditionally consumed in the Iberian Peninsula were studied to evaluate their potential for human nutrition, considering their content in bioactive compounds. Lipophilic phytochemicals, such as fatty acids and tocopherols, as well as some hydrophilic antioxidants, such as vitamin C (ascorbic and dehydroascorbic acids), and organic acids, were analysed. In addition, the antioxidant activity, measured as lipid peroxidation inhibition (β-carotene/linoleate and TBARS assays), was evaluated in each fruit. As far as we know, this is the first report relating to bioactive compounds in wild fruits with relation to the lipid peroxidation inhibition. Data revealed that these wild edible fruits are good sources of bioactive compounds such as ascorbic acid, tocopherols and polyunsaturated fatty acids. They could be considered as functional foods or potential sources of lipidic bioactive compounds to be included as antioxidant food ingredients or in dietary supplements, mainly Rubus ulmifolius, due to its high content in tocopherols. This study provides useful and relevant information that justify tocopherols influence in the prevention of lipid peroxidation, due to the strong correlation observed (r > 0.95) between these lipophilic bioactive compounds and the antioxidant activity.ERDF and the Spanish Ministry of Education and Science (CGL2006-09546/BOS). The authors are also grateful to Fundação para a Ciência e a Tecnologia (FCT, Portugal) and COMPETE/QREN/EU for financial support to CIMO (strategic project PEst-OE/AGR/UI0690/2011). We also thank to María Molina, Laura Aceituno, Susana González, and Manuel Pardo de Santayana for their collaboration in the gathering and preparation of the samples

Sustainable Synthesis of Oxalic and Succinic Acid through Aerobic Oxidation of C6 Polyols Under Mild Conditions

The sustainable chemical industry encompasses a shift from the use of fossil carbon to renewable carbon. The synthesis of chemicals from nonedible biomass (cellulosic or oil) represents one of the key steps for "greening" the chemical industry. In this paper, we report the aerobic oxidative cleavage of C6 polyols (5-HMF, glucose, fructose and sucrose) to oxalic acid (OA) and succinic acid (SA) in water under mild conditions using M@CNT and M@NCNT (M=Fe, V; CNT=carbon nanotubes; NCNT=N-doped CNT), which, under suitable conditions, were recoverable and reusable without any loss of efficiency. The influence of the temperature, O2pressure (PO2 ), reaction time and stirring rate are discussed and the best reaction conditions are determined for an almost complete conversion of the starting material and a good OA yield of 48%. SA and formic acid were the only co-products. The former could be further converted into OA by oxidation in the presence of formic acid, resulting in an overall OA yield of >62%. This process was clean and did not produce organic waste nor gas emissions

Acute health effects after accidental exposure to styrene from drinking water in Spain

OBJECTIVES: We studied subjective health symptoms in a population accidentally exposed to high styrene concentrations in drinking tap water. The contamination occurred during the reparation of a water tank. METHODS: Residents of 27 apartments in two buildings using the contaminated water were contacted. A questionnaire on subjective symptoms was administered to 84 out of 93 persons living in the apartments at the time of the accident. Styrene concentration was measured in samples of water collected two days after the accident. The means of exposure associated with appearance of symptoms were examined through case-control analyses. RESULTS: Styrene in water reached concentrations up to 900 μg/L. Symptoms were reported by 46 persons (attack rate 55 %). The most frequent symptoms were irritation of the throat (26%), nose (19%), eyes (18%) and the skin (14%). General gastrointestinal symptoms were observed with 11% reporting abdominal pain and 7% diarrhea. The factors most strongly associated with symptoms were drinking tap water (OR = 7.8, 95% CI 1.3–48), exposure to vapors from the basement (OR = 10.4, 2.3–47) and eating foods prepared with tap water (OR = 8.6, 1.9–40). All residents in the ground floor reported symptoms. CONCLUSIONS: This accidental contamination led to very high styrene concentrations in water and was related to a high prevalence of subjective symptoms of the eyes, respiratory tract and skin. Similar exposures have been described in workers but not in subjects exposed at their residence. Various gastrointestinal symptoms were also observed in this population probably due to a local irritative effect

Continuous electrochemical reduction of carbon dioxide into formate using a tin cathode: comparison with lead cathode

Electrochemical reduction has been pointed out as a promising method for CO2valorisation into useful chemicals. This paper studies the influence of key variables on the performance of an experimental system for continuous electro-reduction of CO2 to formate, when a tin plate is used as working electrode. Particular emphasis is placed on comparing the performance of Sn and Pb as cathodes. As was previously found with Pb, the influence of current density (“j”) using Sn was particularly noteworthy, and when j was raised up to a limit value of 8.5 mA cm−2, important increases of the rate of formate production were observed at the expense of lowering the Faradaic efficiency. However, unlike what was found with Pb, the performance using Sn improved when the electrolyte flow rate/electrode area ratio was increased within the range studied (0.57–2.3 mL min−1 cm−2). In this way, the use of Sn as cathode allowed achieving rates of formate production that were 25% higher than the maximum rates obtained with Pb, together with Faradaic efficiencies close to 70%, which were 15 points higher than those with Pb. These results reinforce the interest in Sn as electrode material in the electro-reduction of CO2 to formate.This work was conducted under the framework of the Spanish Ministry of Science and Innovation Project ENE2010-14828