974 resultados para Excited electronic state


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In order for solar energy to serve as a primary energy source, it must be paired with energy storage on a massive scale. At this scale, solar fuels and energy storage in chemical bonds is the only practical approach. Solar fuels are produced in massive amounts by photosynthesis with the reduction of CO(2) by water to give carbohydrates but efficiencies are low. In photosystem II (PSII), the oxygen-producing site for photosynthesis, light absorption and sensitization trigger a cascade of coupled electron-proton transfer events with time scales ranging from picoseconds to microseconds. Oxidative equivalents are built up at the oxygen evolving complex (OEC) for water oxidation by the Kok cycle. A systematic approach to artificial photo synthesis is available based on a ""modular approach"" in which the separate functions of a final device are studied separately, maximized for rates and stability, and used as modules in constructing integrated devices based on molecular assemblies, nanoscale arrays, self-assembled monolayers, etc. Considerable simplification is available by adopting a ""dyesensitized photoelectrosynthesis cell"" (DSPEC) approach inspired by dye-sensitized solar cells (DSSCs). Water oxidation catalysis is a key feature, and significant progress has been made in developing a single-site solution and surface catalysts based on polypyridyl complexes of Ru. In this series, ligand variations can be used to tune redox potentials and reactivity over a wide range. Water oxidation electrocatalysis has been extended to chromophore-catalyst assemblies for both water oxidation and DSPEC applications.

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Extensive ab initio calculations using a complete active space second-order perturbation theory wavefunction, including scalar and spin-orbit relativistic effects with a quadruple-zeta quality basis set were used to construct an analytical potential energy surface (PES) of the ground state of the [H, O, I] system. A total of 5344 points were fit to a three-dimensional function of the internuclear distances, with a global root-mean-square error of 1.26 kcal mol(-1). The resulting PES describes accurately the main features of this system: the HOI and HIO isomers, the transition state between them, and all dissociation asymptotes. After a small adjustment, using a scaling factor on the internal coordinates of HOI, the frequencies calculated in this work agree with the experimental data available within 10 cm(-1). (C) 2011 American Institute of Physics. [doi: 10.1063/1.3615545]

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Anthocyanins, the major red, purple, and blue pigments of plants, absorb visible as well as UV radiation and are effective antioxidants and scavengers of active oxygen species. In plant leaves, one of the functional roles proposed for anthocyanins is protection of the photosynthetic apparatus from the effects of excess incident visible or UV-B radiation and photooxidative stress. In essence, a photoprotective role requires that the excited singlet states of both complexed and uncomplexed anthocyanins deactivate back to the ground state so quickly that intersystem crossing, photoreaction, and diffusion-controlled quenching processes cannot compete. Studies of the photochemical properties of synthetic analogs of anthocyanins and of several naturally occurring anthocyanins show that this is indeed the case, uncomplexed anthocyanins decaying back to the ground state via fast (subnanosecond) excited-state proton transfer (ESPT) and anthocyanin-copigment complexes by fast (sub-picosecond) charge-transfer-mediated internal conversion.

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The alternative low-spin states of Fe3+ and Fe2+ cytochrome c induced by SDS or AOT/hexane reverse micelles exhibited the heme group in a less rhombic symmetry and were characterized by electron paramagnetic resonance, UV-visible, CD, magnetic CD, fluorescence, and Raman resonance. Consistent with the replacement of Met 80 by another strong field ligand at the sixth heme iron coordination position, Fe3+ ALSScytc exhibited 1-nm Soret band blue shift and e enhancement accompanied by disappearance of the 695-nm charge transfer band. The Raman resonance, CD, and magnetic CD spectra of Fe3+ and Fe2+ ALSScytc exhibited significant changes suggestive of alterations in the heme iron microenvironment and conformation and should not be assigned to unfold because the Trp(59) fluorescence remained quenched by the neighboring heme group. ALSScytc was obtained with His(33) and His(26) carboxyethoxylated horse cytochrome c and with tuna cytochrome c (His(33) replaced by Asn) pointing out Lys(79) as the probable heme iron ligand. Fe3+ ALSScytc retained the capacity to cleave tert-butylhydroperoxide and to be reduced by dithiothreitol and diphenylacetaldehyde but not by ascorbate. Compatible with a more open heme crevice, ALSScytc exhibited a redox potential similar to 200 mV lower than the wild-type protein (1220 mV) and was more susceptible to the attack of free radicals.

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A saddle shaped tetracluster porphyrin species containing four [Ru(3)O(OAc)(6)(py)(2)](+) clusters coordinated to the N-pyridyl atoms of 5,10,15,20-tetra(3-pyridyl)porphyrin, H(2)(3-TCPyP), has been investigated in comparison with the planar tetra(4-pyridyl) porphyrin analogue H(2)(4-TCPyP). The steric effects from the bulky peripheral complexes play a critical role in the H(2)(3-TCPyP) species, determining a non-planar configuration around the porphyrin centre and precluding any significant pi-electronic coupling, in contrast with the less hindered H(2)(4-TCPyP) species. Both systems exhibit a photoelectrochemical response in the presence of nanocrystalline TiO(2) films, involving the porphyrin excitation around 450 nm. However, only in the H(2)(4-TCPyP) case do the cluster moieties also contribute to the photoinduced electron injection process at 670 nm, reflecting the relevance of the electronic coupling between the porphyrin centre and the peripheral complexes.

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Sedimentary organic matter is a good tool for environmental evaluation where the sediments are deposited. We determined the elemental and C- and N-isotopic compositions of 211 sub-surface sediment samples from 13 cores (ranging from 18 to 46cm), collected in the Cananeia-Iguape estuarine-lagoonal system. The aim of this research is to evaluate the environmental variations of this tropical coastal micro-tidal system over the last decades, through SOM distribution. The studied parameters show differences between the cores located in the northern (sandy-silt sediments) and southern (sand and silty-sand) portions. The whole area presents a mixed organic matter origin signature (local mangrove plants: < -25.6 parts per thousand PDB/ phytoplancton delta(13)C values: -19.4 parts per thousand PDB). The northern cores, which submitted higher sedimentation deposition (1.46cm year(-1)), are more homogenous, presenting lower delta(13)C (< -25.2 parts per thousand PDB) and higher C/N values (in general >14), directly related to the terrestrial input from Ribeira de Iguape River (24,000 km(2) basin). The southern portion presents lower sedimentation rates (0.38cm year(-1)) and is associated to a small river basin (1,340 km(2)), presenting values Of delta(13)C: -25.0 to 23.0 parts per thousand PDB and of C/N ratio: 11 to 15. In general, the elemental contents in the 15 cores may be considered from low to medium (< 2.0% C - < 0.1% N), compared to similar environments. Although a greater marine influence is observed in the southern system portion, the majority of the cores present an elevated increase of continental deposition, most likely related to the strong silting process that the area has been subjected to since the 1850s, when an artificial channel was built linking, directly, the Ribeira River to the estuarine-lagoonal system.

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Examination of the mechanisms involved in the construction of present-day vegetative deposits along coastal waterways has made it possible to establish depositional patterns that can be compared with those found in similar environments in geologic time. These patterns include not only the composition and transport of the debris but also an estimation of the time involved in its deposition. Six sites with active deposits of plant macrodebris in the coastal basin of the Itanhaem River, Sao Paulo State, Brazil, were used in the study. In the central portion of the basin, the interior coastal plain is covered with restinga forest (dense, wet tropical forest of low altitudes), while the lower portion consists of mangrove swamps. The coast reflects anthropogenic intervention, and only a few scattered remnants of precolonization dune vegetation remain. The results after three years of study suggest that the accumulation of plant macrodebris in the middle and lower portions of the basin is parautochthonous, since only the leaves of genera typical of the restinga forest and mangrove swamp, respectively, were found. Along the coast the accumulations involved a mixture of parautochthonous and allochthonous elements. On the levee of the Branco River and within the mangrove swamp, deposition was slow, and many of the elements decayed quickly; such accumulations show little potential for preservation and eventual fossilization. A different site, however, reveals the rapid deposition of thick layers of plant debris, presumably associated with storms, and these accumulations are preserved for long periods, constituting good candidates for possible fossilization.

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Rare species are one of the principal components of the species richness and diversity encountered in Dense Ombrophilous Tropical Forests. This study sought to analyze the rare canopy species within the Atlantic Coastal Forest in Rio de Janeiro State, Brazil. Six different communities were examined: Dense Ombrophilous alluvial Forest; Dense sub-montane Ombrophilous Forest; Dense Montane Ombrophilous in Serra do Mar and Serra da Mantiqueira. In each area the vegetation was sampled within forty 10 x 25 m plots alternately distributed along a linear transect. All trees with DBH (1.3 m above ground level) a parts per thousand yen5 cm were sampled. The canopy was characterized using the allometric relationship between diameter and height, and included all trees with BDH a parts per thousand yen10 cm and height a parts per thousand yen10 m. A total of 64 families, 206 genera, and 542 species were sampled, of which 297 (54.8%) represented rare species (less than one individual per hectare). The percentage of rare species varied from 34 to 50% in each of the different communities sampled. A majority of these rare trees belonged to the Rosidae, and a smaller proportion to the Dilleniidae. It was concluded that there was no apparent pattern to rarity among families, that rarity was probably derived from a number of processes (such as gap formation), and that a great majority of the rare species sampled were consistently rare. This indicates that the restricted geographic distribution and high degree of endemism of many arboreal taxa justifies the conservation of even small fragments of Atlantic Forest.

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The large amount of information in electronic contracts hampers their establishment due to high complexity. An approach inspired in Software Product Line (PL) and based on feature modelling was proposed to make this process more systematic through information reuse and structuring. By assessing the feature-based approach in relation to a proposed set of requirements, it was showed that the approach does not allow the price of services and of Quality of Services (QoS) attributes to be considered in the negotiation and included in the electronic contract. Thus, this paper also presents an extension of such approach in which prices and price types associated to Web services and QoS levels are applied. An extended toolkit prototype is also presented as well as an experiment example of the proposed approach.

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Superficial bottom samples were collected near diffusers of domestic sewage submarine outfalls at Araca and Saco da Capela, Sao Sebastiao Channel, Brazil. The goal of this study was to investigate the distribution and composition of live benthic foraminifera assemblages and integrate the results obtained with geochemical analyses to assess human-induced changes. According to the results obtained no environmental stress was observed near the Saco da Capela submarine outfall diffusers. The foraminifera assemblage is characterised by species typical of highly hydrodynamic environments, with well-oxygenated bottom waters and low nutrient contents. In contrast, near Araca submarine outfall, organic enrichment was denoted by high phosphorus, sulphur and, to a lesser extent, total organic carbon content. Harmful influences on foraminifera could be identified by low richness and specific diversity, as well as the predominance of detritivore feeder species, which are associated with higher organic matter flux and low oxygen in the interstitial pore water. (C) 2009 Elsevier Ltd. All rights reserved.

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The ubiquitin-proteasome system governs the half-life of most cellular proteins. Calorie restriction (CR) extends the maximum life span of a variety of species and prevents oxidized protein accumulation. We studied the effects of CR on the ubiquitin-proteasome system and protein turnover in aging Saccharomyces cerevisiae. CR increased chronological life span as well as proteasome activity compared to control cells. The levels of protein carbonyls, a marker of protein oxidation, and those of polyubiquitinated proteins were modulated by CR. Controls, but not CR cells, exhibited a significant increase in oxidized proteins. In keeping with decreased proteasome activity, polyubiquitinated proteins were increased in young control cells compared to time-matched CR cells, but were profoundly decreased in aged control cells despite decreased proteasomal activity. This finding is related to a decreased polyubiquitination ability due to the impairment of the ubiquitin-activating enzyme in aged control cells, probably related to a more oxidative microenvironment. CR preserves the ubiquitin-proteasome system activity. Overall, we found that aging and CR modulate many aspects of protein modification and turnover. (C) 2011 Elsevier Inc. All rights reserved.

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The Brazilian Atlantic Rainforest is internationally recognised as one of the most biodiverse and threatened tropical forests in the world [Myers, N., Mittermeier, R.A., Mittermeier, C.G., da Fonseca, G.A.B., Kent, J., 2000. Biodiversity hotspots for conservation priorities. Nature 403, 853-858]. The Seasonal Semi-Deciduous Forest is among the most fragmented and threatened biomes of the Atlantic Rainforest Domain. The largest remnant of this biome (35,000 ha) is protected by the Morro do Diabo State Park (MDSP), situated in the area known as the Pontal do Paranapanema, in Sao Paulo State, Brazil. Despite its environmental importance, the park is under political, economic and demographic pressure. The main aim of our research was to estimate the population`s willingness to pay (WTP) for the conservation of MDSP and for the Atlantic Rainforest`s remnants in Sao Paulo State as a whole, by means of the contingent valuation method (CVM). The results featured a high incidence of null WTP and of protest votes. Nevertheless, the population is willing to pay US$ 2,113,548.00/year (R$ 7,080,385.00/year) for the conservation of the MDSP (use and existence values), or US$ 60.39 ha/year (R$ 202.30/ha/year). The results indicate that the preservation value is strongly associated to the population`s ability to pay, increasing with income levels. Qualitative research questions showed that the population considers protected areas to be very important. Still, the valuation of MDSP revealed a gap between the government budget allotted to the park and the value assigned to the area by the public. (C) 2007 Elsevier B.V. All rights reserved.

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Governmental programmes should be developed to collect and analyse data on healthcare associated infections (HAIs). This study describes the healthcare setting and both the implementation and preliminary results of the Programme for Surveillance of Healthcare Associated Infections in the State of Sao Paulo (PSHAISP), Brazil, from 2004 to 2006. Characterisation of the healthcare settings was carried out using a national database. The PSHAISP was implemented using components for acute care hospitals (ACH) or long term care facilities (LTCF). The components for surveillance in ACHs were surgical unit, intensive care unit and high risk nursery. The infections included in the surveillance were surgical site infection in clean surgery, pneumonia, urinary tract infection and device-associated bloodstream infections. Regarding the LTCF component, pneumonia, scabies and gastroenteritis in all inpatients were reported. In the first year of the programme there were 457 participating healthcare settings, representing 51.1% of the hospitals registered in the national database. Data obtained in this study are the initial results and have already been used for education in both surveillance and the prevention of HAI. The results of the PSHAISP show that it is feasible to collect data from a large number of hospitals. This will assist the State of Sao Paulo in assessing the impact of interventions and in resource allocation. (C) 2010 The Hospital Infection Society. Published by Elsevier Ltd. All rights reserved.

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OBJECTIVE: The goal was to review published studies of analgesic effects of sweet solutions, to ascertain areas with sufficient evidence of effectiveness and areas of uncertainty. METHODS: Databases searched included Medline, Embase, the Cumulative Index to Nursing and Allied Health Literature database, and PsycINFO, using the terms pain*, infant*, neonat*, newborn*, sucrose, glucose, and alternative sugars. Publications were sorted according to type, year, painful procedure studied, placebo/no-treatment groups, population studied, and country of publication. RESULTS: A total of 298 relevant unique publications involving human infants were identified; 125 (42%) were primary research studies, of which 116 (93%) were randomized controlled trials. Healthy preterm or term newborns were included in 82 studies (65%), and sick or very low birth weight infants were included in 22 (18%). Most studies included single episodes of painful procedures, with only 3 (2%) conducted over long periods. Procedures investigated most frequently were heel lance (49%), venipuncture (14%), and intramuscular injection (14%). Placebo or no-treatment groups were included in 111 studies (89%); in 103 (93%) of those studies, sweet solutions reduced behavioral responses, compared with placebo/no treatment. CONCLUSION: Clinical equipoise relating to analgesic effects of sweet solutions no longer exists for single episodes of procedures for healthy preterm and term newborn infants. Uncertainties include outcomes after prolonged use of sweet solutions, concomitant use of other analgesics, and effectiveness beyond the newborn period. Future research should focus on addressing these knowledge and research gaps. Pediatrics 2010;126:894-902

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The aim of the present study was to compare and correlate training impulse (TRIMP) estimates proposed by Banister (TRIMP(Banister)), Stagno (TRIMP(Stagno)) and Manzi (TRIMP(Manzi)). The subjects were submitted to an incremental test on cycle ergometer with heart rate and blood lactate concentration measurements. In the second occasion, they performed 30 min. of exercise at the intensity corresponding to maximal lactate steady state, and TRIMP(Banister), TRIMP(Stagno) and TRIMP(Manzi) were calculated. The mean values of TRIMP(Banister) (56.5 +/- 8.2 u.a.) and TRIMP(Stagno) (51.2 +/- 12.4 u.a.) were not different (P > 0.05) and were highly correlated (r = 0.90). Besides this, they presented a good agreement level, which means low bias and relatively narrow limits of agreement. On the other hand, despite highly correlated (r = 0.93), TRIMP(Stagno) and TRIMP(Manzi) (73.4 +/- 17.6 u.a.) were different (P < 0.05), with low agreement level. The TRIMP(Banister) e TRIMP(Manzi) estimates were not different (P = 0.06) and were highly correlated (r = 0.82), but showed low agreement level. Thus, we concluded that the investigated TRIMP methods are not equivalent. In practical terms, it seems prudent monitor the training process assuming only one of the estimates.