Redox-dependent activation of CO dehydrogenase from Rhodospirillum rubrum

Studies of initial activities of carbon monoxide dehydrogenase (CODH) from Rhodospirillum rubrum show that CODH is mostly inactive at redox potentials higher than −300 mV. Initial activities measured at a wide range of redox potentials (0–500 mV) fit a function corresponding to the Nernst equation with a midpoint potential of −316 mV. Previously, extensive EPR studies of CODH have suggested that CODH has three distinct redox states: (i) a spin-coupled state at −60 to −300 mV that gives rise to an EPR signal termed Cred1; (ii) uncoupled states at <−320 mV in the absence of CO2 referred to as Cunc; and (iii) another spin-coupled state at <−320 mV in the presence of CO2 that gives rise to an EPR signal termed Cred2B. Because there is no initial CODH activity at potentials that give rise to Cred1, the state (Cred1) is not involved in the catalytic mechanism of this enzyme. At potentials more positive than −380 mV, CODH recovers its full activity over time when incubated with CO. This reductant-dependent conversion of CODH from an inactive to an active form is referred to hereafter as “autocatalysis.” Analyses of the autocatalytic activation process of CODH suggest that the autocatalysis is initiated by a small fraction of activated CODH; the small fraction of active CODH catalyzes CO oxidation and consequently lowers the redox potential of the assay system. This process is accelerated with time because of accumulation of the active enzyme.

Evolução estrutural e performance catalítica de nanopartículas de AuPd de composição variável

Nanopartículas bimetálicas de AuPd têm mostrado excelente atividade catalítica em reações de oxidação. O entendimento dos efeitos da variação da composição e morfologia das nanopartículas bimetálicas em suas propriedades catalíticas é fundamental para a preparação de catalisadores cada vez mais ativos e seletivos. Neste trabalho foram estudadas nanopartículas bimetálicas de AuPd de composição variável suportadas sobre um suporte constituído por nanopartículas de magnetita revestidas por sílica. O efeito da calcinação e da redução com hidrogênio sobre a morfologia e composição das nanopartículas bimetálicas foi acompanhado pelas técnicas de TEM, XEDS, XAS, XRD e XPS. A correlação entre estrutura, composição e atividade catalítica dos catalisadores preparados foi estudada pelo acompanhamento de reações de oxidação de monóxido de carbono e de oxidação de álcool benzílico. As amostras não calcinadas apresentaram segregação metálica em todas as composições estudadas. Após a etapa de calcinação, maior segregação metálica foi encontrada, com a formação de óxido de paládio na superfície das nanopartículas, exceto na amostra mais rica em ouro. O tratamento das amostras oxidadas com hidrogênio foi capaz de reduzir os metais oxidados na superfície das nanopartículas, mas um enriquecimento em paládio na superfície e maior segregação entre ouro e paládio foram observados. Uma melhora na atividade catalítica na oxidação de monóxido de carbono foi observada juntamente com um aumento na composição de paládio, além disso, observou-se uma maior atividade catalítica em relação às nanopartículas não calcinadas para as amostras calcinadas e reduzidas. Para a oxidação de álcool benzílico um aumento na atividade catalítica de até cinco vezes foi observado após a calcinação dos catalisadores, com maior atividade para a amostra de composição Au1Pd2. A queda na atividade catalítica após a redução dos catalisadores mostrou que a presença de óxido de paládio na superfície das nanopartículas é fundamental para que seja observada uma maior atividade catalítica.

Synthesis of Robust Hierarchical Silica Monoliths by Surface-Mediated Solution/Precipitation Reactions over Different Scales: Designing Capillary Microreactors for Environmental Applications

A synthetic procedure to prepare novel materials (surface-mediated fillings) based on robust hierarchical monoliths is reported. The methodology includes the deposition of a (micro- or mesoporous) silica thin film on the support followed by growth of a porous monolithic SiO2 structure. It has been demonstrated that this synthesis is viable for supports of different chemical nature with different inner diameters without shrinkage of the silica filling. The formation mechanism of the surface-mediated fillings is based on a solution/precipitation process and the anchoring of the silica filling to the deposited thin film. The interaction between the two SiO2 structures (monolith and thin film) depends on the porosity of the thin film and yields composite materials with different mechanical stability. By this procedure, capillary microreactors have been prepared and have been proved to be highly active and selective in the total and preferential oxidation of carbon monoxide (TOxCO and PrOxCO).

Middle atmopsheric cabon monoxide above Kiruna, Sweden, 2008-2015

This data set contains profiles of atmospheric carbon monoxide (CO) concentrations retrieved from measurements made by the Kiruna Microwave Radiometer (KIMRA), housed at the Swedish Institute for Space Physics, Kiruna. The data is retrieved on a standard pressure grid that is 62 layers, spaced approximately equally in altitude between 2 km and 124 km. The current time range of the data is December 2008 to May 2015, with data gaps corresponding to Summer periods when the CO concentrations in the middle atmosphere drop to very low values, or to non-operation of the instrument. The profile information is considered useful between approximately 48 km and 86 km, specifically where the measurement response is above 0.8. If the CO profiles are being compared to another data set with significantly higher altitude resolution, the averaging kernel matrix should be used to smooth the higher resolution data. The error in the profile from statistical noise on the measured spectrum is also provided. This work has been funded by the German Federal Ministry of Education and Research through the research project: Role Of the Middle atmosphere in Climate (ROMIC, https://romic.iap-kborn.de).

An Evaluation of Carbon Concentrations Associted with Biodiesel Particulate Matter in an Underground Metal Mine

Exposure to diesel particulate matter from diesel exhaust has been shown to have adverse health effects in humans. In 2012 The International Agency for Research on Cancer classified diesel exhaust as a group 1 know human carcinogen. Because of the associated health effects, there has been a strong push to reduce the amount of diesel exhaust present in the mining industry. Biodiesel is one to the more common and promising control options used to reduce the amount of diesel particulate matter that is generated during fuel combustion. The use of biodiesel over petroleum diesel has been shown to reduce not only particulate matter, but hydro carbon and carbon monoxide mass emissions as well. Personal and area samples were collected at an underground metal mine in the northwestern United States to evaluate the current blend of B70 biodiesel. The objective of this research was to evaluate the carbon levels associated with diesel particulate matter generated from the combustion of a B70 biodiesel. Data was also compared to past studies on which diesel particulate matter from petroleum diesel was evaluated. Samples were taken on four separate four day campaigns between March and October of 2014. Area samples were taken from 7 different areas in the mine and personal samples were taken from a 20 person cohort. The equipment used for sampling was compliant with the NIOSH 5040 method. Statistical analysis of the results was done using Minitab 17 software. The statistical analysis showed that the total carbon concentrations from biodiesel were well below the MSHA exposure limit. Results also showed that organic/elemental carbon ratios were consistent with past studies as the concentrations of organic carbon were significantly higher than those of elemental carbon.

Ambiência aérea em alojamento de frangos de corte: poeira e gases

Air quality in animal production environment has been refereed as an interesting point for studies in environmental control systems with the focus both to the animal health which live in total confinement, as to the workers. The objective of this research was to determine the variation on the aerial environmental quality in two types of broiler housing: conventional (Gc) and tunnel type (Gt). The total dust values in both houses offered adequate rearing conditions to the birds; however, regarding the inhale dust in the air was above the limits recommended for humans. Carbon monoxide concentration in the heating phase during the evaluated period was above the 10 ppm maximum recommended, and it was higher during the cold season in Gt house (30 ppm) when compared to the Gc house (18 ppm). Ammonia concentration peaks in the air were above the 20 ppm recommended from the 20th day of production in both houses and in daily average, for a period higher in Gt (4h30) when compared to Gt (2h45). Only traces of nitrate oxide and methane were found while carbonic dioxide gas concentration evaluated during daytime met the limits allowed for both birds and labor.

The Coupled Aerosol and Tracer Transport model to the Brazilian developments on the Regional Atmospheric Modeling System (CATT-BRAMS) - Part 1: Model description and evaluation

We introduce the Coupled Aerosol and Tracer Transport model to the Brazilian developments on the Regional Atmospheric Modeling System (CATT-BRAMS). CATT-BRAMS is an on-line transport model fully consistent with the simulated atmospheric dynamics. Emission sources from biomass burning and urban-industrial-vehicular activities for trace gases and from biomass burning aerosol particles are obtained from several published datasets and remote sensing information. The tracer and aerosol mass concentration prognostics include the effects of sub-grid scale turbulence in the planetary boundary layer, convective transport by shallow and deep moist convection, wet and dry deposition, and plume rise associated with vegetation fires in addition to the grid scale transport. The radiation parameterization takes into account the interaction between the simulated biomass burning aerosol particles and short and long wave radiation. The atmospheric model BRAMS is based on the Regional Atmospheric Modeling System (RAMS), with several improvements associated with cumulus convection representation, soil moisture initialization and surface scheme tuned for the tropics, among others. In this paper the CATT-BRAMS model is used to simulate carbon monoxide and particulate material (PM(2.5)) surface fluxes and atmospheric transport during the 2002 LBA field campaigns, conducted during the transition from the dry to wet season in the southwest Amazon Basin. Model evaluation is addressed with comparisons between model results and near surface, radiosondes and airborne measurements performed during the field campaign, as well as remote sensing derived products. We show the matching of emissions strengths to observed carbon monoxide in the LBA campaign. A relatively good comparison to the MOPITT data, in spite of the fact that MOPITT a priori assumptions imply several difficulties, is also obtained.