239 research outputs found
New bryophyte taxon records for tropical countries 1
This is the first in a series of papers listing new records, which will be published whenever sufficient new records have been found. The taxa are arranged by countries for an easier evaluation, e.g. updates of checklists. The initials of the contributor for each record is shown in square brackets after the record, and these initials are interpreted at the end of the paper
The Critical Role of Water at the Gold-titania Interface in Catalytic CO Oxidation
We provide direct evidence of a water-mediated reaction mechanism for room-temperature CO oxidation over Au/TiO2 catalysts. A hydrogen/deuterium kinetic isotope effect of nearly 2 implicates O-H(D) bond breaking in the rate-determining step. Kinetics and in situ infrared spectroscopy experiments showed that the coverage of weakly adsorbed water on TiO2 largely determines catalyst activity by changing the number of active sites. Density functional theory calculations indicated that proton transfer at the metal-support interface facilitates O2 binding and activation; the resulting Au-OOH species readily reacts with adsorbed Au-CO, yielding Au-COOH. Au-COOH decomposition involves proton transfer to water and was suggested to be rate determining. These results provide a unified explanation to disparate literature results, clearly defining the mechanistic roles of water, support OH groups, and the metal-support interface
NaBr Poisoning of Au/TiO\u3csub\u3e2\u3c/sub\u3e Catalysts: Effects on Kinetics, Poisoning Mechanism, and Estimation of the Number of Catalytic Active Sites
Sodium bromide was used to intentionally poison a commercial Au/TiO2 catalyst with the goals of understanding the nature of halide poisoning and evaluating the number and nature of the catalytic active sites. A series of eight poisoned catalysts were prepared by impregnating the parent catalyst with methanolic solutions of NaBr. Each catalyst was tested with CO oxidation catalysis under differential reactor conditions; O2 reaction orders and Arrhenius activation energies were determined for each material. All of the kinetic data, including a Michaelis−Menten analysis, indicated that the primary effect of adding NaBr was to reduce the number of catalytically active sites. Density functional theory calculations, employed to evaluate likely binding sites for NaBr, showed that NaBr binds more strongly to Au corner and edge atoms than it does to the titania support or to exposed Au face atoms. Infrared spectroscopy of adsorbed CO, along with a Temkin analysis of the data, was also used to evaluate changes to the catalyst upon NaBr deposition. These studies suggested that NaBr addition induces some subtle changes in the coverage dependent properties of CO adsorption, but that these did not substantially impact the CO coverage of the CO binding sites. The experimental and computational results are discussed in terms of possible poisoning mechanisms (siteblocking vs off-site binding and modification); the nature and number of active sites are also discussed in the context of the results
CO Adsorption on Supported Gold Nanoparticle Catalysts: Application of the Temkin Model
The adsorption of CO on the supported gold nanoparticle catalysts Au/TiO2, Au/Fe2O3, and Au/ZrO2 was examined using infrared transmission spectroscopy to quantify the isobaric CO coverage as a function of temperature. The Temkin adsorbate interaction model was then applied to account for the adsorption behavior. To test the general applicability of the Temkin model, this treatment was also applied to three data sets from the literature. This included another real-world catalyst and two model catalysts. All data sets were accurately represented by the Temkin adsorbate interaction model. The resulting thermodynamic metrics are consistent with previous determinations and reflect a particle size-dependence. In particular, the intrinsic adsorption enthalpy at zero CO coverage varies almost linearly with Au particle size, and this trend appears to be correlated with the abundance of low-coordinate Au sites (cf., CN = 6 and 7 for corners and edges, respectively). For very small particles with mostly CN = 6 corner sites, the enthalpy reflects strong binding (cf., −ΔH0 ≈ 78 kJ/mol), while for large particles with mostly CN = 7 edge sites, the enthalpy reflects weaker binding (cf., −ΔH0 ≈ 63 kJ/mol). The results also suggest that these sites are coupled. This study demonstrates that the Temkin adsorbate interaction model accurately represents adsorption data, yields meaningful metrics that are useful for characterizing nanoparticle catalysts, and should be applicable to other adsorption data sets
Invariant Forms and Automorphisms of Locally Homogeneous Multisymplectic Manifolds
It is shown that the geometry of locally homogeneous multisymplectic
manifolds (that is, smooth manifolds equipped with a closed nondegenerate form
of degree > 1, which is locally homogeneous of degree k with respect to a local
Euler field) is characterized by their automorphisms. Thus, locally homogeneous
multisymplectic manifolds extend the family of classical geometries possessing
a similar property: symplectic, volume and contact. The proof of the first
result relies on the characterization of invariant differential forms with
respect to the graded Lie algebra of infinitesimal automorphisms, and on the
study of the local properties of Hamiltonian vector fields on locally
multisymplectic manifolds. In particular it is proved that the group of
multisymplectic diffeomorphisms acts (strongly locally) transitively on the
manifold. It is also shown that the graded Lie algebra of infinitesimal
automorphisms of a locally homogeneous multisymplectic manifold characterizes
their multisymplectic diffeomorphisms.Comment: 25 p.; LaTeX file. The paper has been partially rewritten. Some
terminology has been changed. The proof of some theorems and lemmas have been
revised. The title and the abstract are slightly modified. An appendix is
added. The bibliography is update
Pathogenesis of aerosolized Eastern Equine Encephalitis virus infection in guinea pigs
Mice and guinea pigs were experimentally exposed to aerosols containing regionally-distinct strains (NJ1959 or ArgM) of eastern equine encephalitis virus (EEEV) at two exclusive particle size distributions. Mice were more susceptible to either strain of aerosolized EEEV than were guinea pigs; however, clinical signs indicating encephalitis were more readily observed in the guinea pigs. Lower lethality was observed in both species when EEEV was presented at the larger aerosol distribution (> 6 μm), although the differences in the median lethal dose (LD50) were not significant. Virus isolation and immunohistochemistry indicated that virus invaded the brains of guinea pigs within one day postexposure, regardless of viral strain or particle size distribution. Immunohistochemistry further demonstrated that neuroinvasion occurred through the olfactory system, followed by transneuronal spread to all regions of the brain. Olfactory bipolar neurons and neurons throughout the brain were the key viral targets. The main microscopic lesions in infected guinea pigs were neuronal necrosis, inflammation of the meninges and neuropil of the brain, and vasculitis in the brain. These results indicate that guinea pigs experimentally infected by aerosolized EEEV recapitulate several key features of fatal human infection and thus should serve as a suitable animal model for aerosol exposure to EEEV
Effects of Pd on Catalysis by Au: CO Adsorption, CO Oxidation, and Cyclohexene Hydrogenation by Supported Au and Pd−Au Catalysts
Incorporating small amounts of Pd into supported Au catalysts has been shown to have beneficial effects on selective hydrogenation reactions, particularly 1,3-butadiene hydrogenation and the hydrogenation of nitroaromatics, especially p-chloronitrobenzene. Appropriate Pd incorporation enhances hydrogenation activity while maintaining the desirable high selectivity of supported Au catalysts. To better understand this phenomenon, a series of alumina- and titania-supported Au and dilute Pd–Au catalysts were prepared via urea deposition–precipitation. The catalysts were studied with infrared spectroscopy of CO adsorption, CO oxidation catalysis, and cyclohexene hydrogenation catalysis with the goal of understanding how Pd affects the catalytic properties of Au. CO adsorption experiments indicated a substantial amount of surface Pd when the catalyst was under CO. Adsorption experiments at various CO pressures were used to determine CO coverage; application of the Temkin adsorbate interaction model allowed for the determination of adsorption enthalpy metrics for CO adsorption on Au. These experiments showed that Pd induces an electronic effect on Au, affecting both the nascent adsorption enthalpy (ΔH0) and the change in enthalpy with increasing coverage. This electronic modification had little effect on CO oxidation catalysis. Michaelis–Menten kinetics parameters showed essentially the same oxygen reactivity on all the catalysts; the primary differences were in the number of active sites. The bimetallic catalysts were poor cyclohexene hydrogenation catalysts, indicating that there is relatively little exposed Pd when the catalyst is under hydrogen. The results, which are discussed in the context of the literature, indicate that a combination of surface composition and Pd-induced electronic effects on Au appear to increase hydrogen chemisorption and hydrogenation activity while largely maintaining the selectivities associated with catalysis by Au
Performance of Indian Manufacturing in the Post Reform Period
Many emerging countries in recent decades have relied on a development strategy that focused primarily on promoting the manufacturing sector and the exports of manufactured goods. However, an acceleration of growth of output and employment in manufacturing has eluded India. This is despite the fact that the central focus of the reforms in the 1980s and 1990s was to unshackle the manufacturing sector. Instead it is the services sector which has grown rapidly, contributing about two-third of GDP growth in recent years. This paper discusses the reasons behind the modest performance of the manufacturing sector in India post reforms. It argues that there are many factors that have inhibited the growth of industrial sector in India. One major factor is the rigid and strict labor laws which have affected the industrial performance in a number of ways, by keeping the size of the establishments small, by not encouraging the production of labor intensive goods, by pushing activities to the unorganized sector, and by keeping the Indian industry uncompetitive. Besides the labor laws other factors that are responsible for the modest performance of the manufacturing sector include difficulty in the acquisition of land for industrial use, inadequate financing and infrastructure, and cumbersome business climate. The paper presents arguments and evidence which shows the importance of these factors
Before and after study of bar workers' perceptions of the impact of smoke-free workplace legislation in the Republic of Ireland
<p>Abstract</p> <p>Background</p> <p><it>Objectives</it>: To compare support for, and perceptions of, the impacts of smoke-free workplace legislation among bar workers in the Republic of Ireland (ROI) pre- and post-implementation, and to identify predictors of support for the legislation.</p> <p>Methods</p> <p><it>Setting</it>: Public houses (pubs) in three areas of the ROI.</p> <p><it>Design</it>: Comparisons pre- and post-implementation of smoke-free workplace legislation.</p> <p><it>Participants</it>: From a largely non-random selection, 288 bar workers volunteered for the baseline survey; 220 were followed up one year later (76.4%).</p> <p><it>Outcome measures: </it>Level of support for the legislation, attitude statements concerning potential impacts of the law and modelled predictors of support for the legislation.</p> <p>Results</p> <p>Pre-implementation 59.5% of participants supported the legislation, increasing to 76.8% post-implementation. Support increased among smokers by 27.3 percentage points from 39.4% to 66.7% (p < 0.001) and among non-smokers by 12.4% percentage points from 68.8% to 81.2% (p = 0.003).</p> <p>Pre-legislation three-quarters of participants agreed that the legislation would make bars more comfortable and was needed to protect workers' health. Post-legislation these proportions increased to over 90% (p < 0.001). However, negative perceptions also increased, particularly for perceptions that the legislation has a negative impact on business (from 50.9% to 62.7%, p = 0.008) and that fewer people would visit pubs (41.8% to 62.7%, p < 0.001). After adjusting for relevant covariates, including responses to the attitude statements, support for the ban increased two to three-fold post-implementation. Regardless of their views on the economic impact, most participants agreed, both pre- and post-implementation, that the legislation was needed to protect bar workers' health.</p> <p>Conclusion</p> <p>Smoke-free legislation had the support of three-quarters of a large sample of bar workers in the ROI. However, this group holds complex sets of both positive and negative perspectives on the legislation. Of particular importance is that negative economic perceptions did not diminish the widely held perception that the ban is needed to protect workers' health.</p
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