155 resultados para VALENCE CHANGE


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Recent studies have shown that changes in global mean precipitation are larger for solar forcing than for CO2 forcing of similar magnitude.In this paper, we use an atmospheric general circulation model to show that the differences originate from differing fast responses of the climate system. We estimate the adjusted radiative forcing and fast response using Hansen's ``fixed-SST forcing'' method.Total climate system response is calculated using mixed layer simulations using the same model. Our analysis shows that the fast response is almost 40% of the total response for few key variables like precipitation and evaporation. We further demonstrate that the hydrologic sensitivity, defined as the change in global mean precipitation per unit warming, is the same for the two forcings when the fast responses are excluded from the definition of hydrologic sensitivity, suggesting that the slow response (feedback) of the hydrological cycle is independent of the forcing mechanism. Based on our results, we recommend that the fast and slow response be compared separately in multi-model intercomparisons to discover and understand robust responses in hydrologic cycle. The significance of this study to geoengineering is discussed.

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The paper proposes two methodologies for damage identification from measured natural frequencies of a contiguously damaged reinforced concrete beam, idealised with distributed damage model. The first method identifies damage from Iso-Eigen-Value-Change contours, plotted between pairs of different frequencies. The performance of the method is checked for a wide variation of damage positions and extents. The method is also extended to a discrete structure in the form of a five-storied shear building and the simplicity of the method is demonstrated. The second method is through smeared damage model, where the damage is assumed constant for different segments of the beam and the lengths and centres of these segments are the known inputs. First-order perturbation method is used to derive the relevant expressions. Both these methods are based on distributed damage models and have been checked with experimental program on simply supported reinforced concrete beams, subjected to different stages of symmetric and un-symmetric damages. The results of the experiments are encouraging and show that both the methods can be adopted together in a damage identification scenario.

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Regional impacts of climate change remain subject to large uncertainties accumulating from various sources, including those due to choice of general circulation models (GCMs), scenarios, and downscaling methods. Objective constraints to reduce the uncertainty in regional predictions have proven elusive. In most studies to date the nature of the downscaling relationship (DSR) used for such regional predictions has been assumed to remain unchanged in a future climate. However,studies have shown that climate change may manifest in terms of changes in frequencies of occurrence of the leading modes of variability, and hence, stationarity of DSRs is not really a valid assumption in regional climate impact assessment. This work presents an uncertainty modeling framework where, in addition to GCM and scenario uncertainty, uncertainty in the nature of the DSR is explored by linking downscaling with changes in frequencies of such modes of natural variability. Future projections of the regional hydrologic variable obtained by training a conditional random field (CRF) model on each natural cluster are combined using the weighted Dempster-Shafer (D-S) theory of evidence combination. Each projection is weighted with the future projected frequency of occurrence of that cluster (''cluster linking'') and scaled by the GCM performance with respect to the associated cluster for the present period (''frequency scaling''). The D-S theory was chosen for its ability to express beliefs in some hypotheses, describe uncertainty and ignorance in the system, and give a quantitative measurement of belief and plausibility in results. The methodology is tested for predicting monsoon streamflow of the Mahanadi River at Hirakud Reservoir in Orissa, India. The results show an increasing probability of extreme, severe, and moderate droughts due to limate change. Significantly improved agreement between GCM predictions owing to cluster linking and frequency scaling is seen, suggesting that by linking regional impacts to natural regime frequencies, uncertainty in regional predictions can be realistically quantified. Additionally, by using a measure of GCM performance in simulating natural regimes, this uncertainty can be effectively constrained.

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We study the properties of single red blood cells (RBCs) held in an optical-tweezers trap. We observe a change in the spectrum of Brownian fluctuations between RBCs from normal and malaria-infected samples. The change, caused by infection-induced structural changes in the cell, appears as a statistical increase in the mean (by 25%) and standard deviation (by 200%) of the corner frequency measured over similar to 100 cells. The increase is observed even though the ensemble of cells being measured consists mostly of cells that do not actually host the parasite, but are from an infected pool. This bystander effect appears to vindicate other observations that infected cells can affect the biomechanical properties of uninfected cells. The change is also observed to be independent of the stage of infection and its duration, highlighting its potential for disease detection. (C) 2010 Society of Photo-Optical Instrumentation Engineers. [DOI: 10.1117/1.3427142].

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Climate change is one of the most important global environmental challenges, with implications for food production, water supply, health, energy, etc. Addressing climate change requires a good scientific understanding as well as coordinated action at national and global level. This paper addresses these challenges. Historically, the responsibility for greenhouse gas emissions' increase lies largely with the industrialized world, though the developing countries are likely to be the source of an increasing proportion of future emissions. The projected climate change under various scenarios is likely to have implications on food production, water supply, coastal settlements, forest ecosystems, health, energy security, etc. The adaptive capacity of communities likely to be impacted by climate change is low in developing countries. The efforts made by the UNFCCC and the Kyoto Protocol provisions are clearly inadequate to address the climate change challenge. The most effective way to address climate change is to adopt a sustainable development pathway by shifting to environmentally sustainable technologies and promotion of energy efficiency, renewable energy, forest conservation, reforestation, water conservation, etc. The issue of highest importance to developing countries is reducing the vulnerability of their natural and socio-economic systems to the projected climate change. India and other developing countries will face the challenge of promoting mitigation and adaptation strategies, bearing the cost of such an effort, and its implications for economic development.

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The possible role of double valence fluctuation in both lead and oxide ions with reference to metallization in oxides of lead is examined by x-ray-photoemission spectroscopy, ultraviolet-photoemission spectroscopy (UPS), and 207Pb NMR studies. The double valence fluctuations may be viewed as Pb4++2O2-⇄Pb2+O22-. While the insulating oxides PbO, Pb3O4, and Sr2PbO4 show a single oxide ion, O2- characterized by O(1s) at 529.7 eV, the insulating peroxide BaO2 is characterized by the ion O22- with a single O(1s) at 533 eV. The metallic PbO2, BaPbO3, BaBiPbO3, and SrPbO3 showed the occurrence of both O2- and O22- ions. The valence band in these compounds has also been studied by UPS, and clear evidence for the coexistence of O2- and O22- is seen in PbO2. A simultaneous study of 207Pb NMR suggests that the Pb ion could also exist in mixed-valence states. Qualitative arguments are presented to rationalize the existence of such mixed valences of the anion in metal oxides in general and their role in superconductivity.

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The ability of prolactin to influence the responsiveness of the lactating rat pituitary to luteinising hormone releasing hormone has been examinedin vitro. The pituitary responsivenessin vivo to luteinising hormone releasing hormone decreased as a function of increase in the lactational stimulus. Prolactin inhibited the spontaneousin vitro release of luteinising hormone and follicle stimulating hormone to a small extent, from the pituitary of lactating rats with the suckling stimulus. However, it significantly inhibited the release of these two hormones from luteinising hormone releasing hormone-stimulated pituitaries. The responsiveness of pituitaries of rats deprived of their litter 24 h earlier, to luteinising hormone releasing hormone was also inhibited by prolactin, although minimal. It was concluded that prolactin could be influencing the functioning of the pituitary of the lactating rat by (a) partially suppressing the spontaneous release of gonadotropin and (b) inhibiting the responsiveness of the pituitary to luteinising hormone releasing hormone.

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The low-lying singlets and triplets of biphenyl are obtained exactly within the PPP model using the diagrammatic valence bond method. The energy gaps within the singlet manifold as well as the lowest singlet-triplet gap are found to be in good agreement with experimental results. The two weak absorptions between 4·1 and 4·2 eV reported experimentally are attributed to the two states lying below the optical gap that become weakly allowed on breaking electron-hole and inversion symmetries. The observed blue shift of the spectral lines, attributed to a change in dihedral angle, on going from crystalline to solution to vapour phase is also well reproduced within the PPP model. The bond orders show that the ground singlet state is benzenoidal while the dipole excited state as well as the lowest triplet state are quinonoidal and planar. Comparison with the experimental spin densities and the fine structure constants D and E in the triplet state point to slightly weaker correlations than assumed by the PPP model. The introduction of a 1-8 bond to mimic poly(paraphenylene)s gives an optical gap that is in good agreement with experiment.

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Representation and quantification of uncertainty in climate change impact studies are a difficult task. Several sources of uncertainty arise in studies of hydrologic impacts of climate change, such as those due to choice of general circulation models (GCMs), scenarios and downscaling methods. Recently, much work has focused on uncertainty quantification and modeling in regional climate change impacts. In this paper, an uncertainty modeling framework is evaluated, which uses a generalized uncertainty measure to combine GCM, scenario and downscaling uncertainties. The Dempster-Shafer (D-S) evidence theory is used for representing and combining uncertainty from various sources. A significant advantage of the D-S framework over the traditional probabilistic approach is that it allows for the allocation of a probability mass to sets or intervals, and can hence handle both aleatory or stochastic uncertainty, and epistemic or subjective uncertainty. This paper shows how the D-S theory can be used to represent beliefs in some hypotheses such as hydrologic drought or wet conditions, describe uncertainty and ignorance in the system, and give a quantitative measurement of belief and plausibility in results. The D-S approach has been used in this work for information synthesis using various evidence combination rules having different conflict modeling approaches. A case study is presented for hydrologic drought prediction using downscaled streamflow in the Mahanadi River at Hirakud in Orissa, India. Projections of n most likely monsoon streamflow sequences are obtained from a conditional random field (CRF) downscaling model, using an ensemble of three GCMs for three scenarios, which are converted to monsoon standardized streamflow index (SSFI-4) series. This range is used to specify the basic probability assignment (bpa) for a Dempster-Shafer structure, which represents uncertainty associated with each of the SSFI-4 classifications. These uncertainties are then combined across GCMs and scenarios using various evidence combination rules given by the D-S theory. A Bayesian approach is also presented for this case study, which models the uncertainty in projected frequencies of SSFI-4 classifications by deriving a posterior distribution for the frequency of each classification, using an ensemble of GCMs and scenarios. Results from the D-S and Bayesian approaches are compared, and relative merits of each approach are discussed. Both approaches show an increasing probability of extreme, severe and moderate droughts and decreasing probability of normal and wet conditions in Orissa as a result of climate change. (C) 2010 Elsevier Ltd. All rights reserved.

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Analytical short time solution of moving boundary in heat conduction in a cylindrical mould under prescribed flux boundary condition has been studied in this paper. Partial differential equations are converted to integro-differential equations. These integro-differential equations which are coupled have been solved analytically for short time by choosing suitable series expansions for the unknown quantitities.

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Crystals of dl-arginine hemisuccinate dihydrate (I)(monoclinic; P21/c; a = 5.292, b = 16.296, c = 15.203 Å; α= 92.89°; Z = 4) and l-arginine hemisuccinate hemisuccinic acid monohydrate (II) (triclinic; P1; a = 5.099; b = 10.222, c = 14.626 Å; α= 77.31, β= 89.46, γ= 78.42°; Z = 2) were grown under identical conditions from aqueous solutions of the components in molar proportions. The structures were solved by direct methods and refined to R = 0.068 for 2585 observed reflections in the case of (I) and R = 0.036 for 2154 observed reflections in the case of (11). Two of the three crystallographically independent arginine molecules in the complexes have conformations different from those observed so far in the crystal structures containing arginine. The succinic acid molecules and the succinate ions in the structures are centrosymmetric and planar. The crystal structure of (II) is highly pseudosymmetric. Arginine-succinate interactions in both the complexes involve specific guanidyl-carboxylate interactions. The basic elements of aggregation in both the structures are ribbons made up of alternating arginine dimers and succinate ions. However, the ribbons pack in different ways in the two structures. (II) presents an interesting case in which two ionisation states of the same molecule coexist in a crystal. The two complexes provide a good example of the effect of change in chirality on stoichiometry, conformation, aggregation, and ionisation state in the solid state.

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Infrared spectroscopy provides a valuable tool to investigate the spin-state transition in Fe(II) complexes of the type Fe(Phen)2(NCS)2. With progressive substitution of Fe by Mn, the first-order transition changes over to a second-order transition, with a high residual population of the high-spin state even at very low temperatures