906 resultados para Partition of unity implicits


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A variety of seemingly unrelated processes, such as core-mantle interaction, desulfurization, and direct precipitation from a silicate melt have been proposed to explain the formation of Ru-Os-Ir alloys (here referred to as osmiridiums) found in terrestrial mantle rocks. However, no consensus has yet been reached on how these important micrometer-sized phases form. In this paper we report the results of an experimental study on the solubilities of Ru, Os and Ir in sulfide melts (or mattes) as a function of alloy composition at 1300 degrees C. Considering the low solubilities of Ru, Os, and Ir in silicate melts, coupled with their high matte/silicate-melt partition coefficients, our results indicate that these elements concentrate initially at the ppm level in a matte phase in the mantle source region. During partial melting, the extraction of sulfur into silicate melt leads to a decrease in fS(2) that triggers the exsolution of osmiridiums from the refractory matte in the residue. The newly formed osmiridiums may persist in the terrestrial mantle for periods exceeding billions of years. (C) 2012 Elsevier Ltd. All rights reserved.

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This study shows that MP-1, a peptide from the venom of the Polybia paulista wasp, is more toxic to human leukemic T-lymphocytes than to human primary lymphocytes. By using model membranes and electrophysiology measurements to investigate the molecular mechanisms underlying this selective action, the porelike activity of MP-1 was identified with several bilayer compositions. The highest average conductance was found in bilayers formed by phosphatidylcholine or a mixture of phosphatidylcholine and phosphatidylserine (70:30). The presence of cholesterol or cardiolipin substantially decreases the MP-1 pore activity, suggesting that the membrane fluidity influences the mechanism of selective toxicity. The determination of partition coefficients from the anisotropy of Tip indicated higher coefficients for the anionic bilayers. The partition coefficients were found to be 1 order of magnitude smaller when the bilayers contain cholesterol or a mixture of cholesterol and sphingomyelin. The blue shift fluorescence, anisotropy values, and Stern-Volmer constants are indications of a deeper penetration of MP-1 into anionic bilayers than into zwitterionic bilayers. Our results indicate that MP-1 prefers to target leukemic cell membranes, and its toxicity is probably related to the induction of necrosis and not to DNA fragmentation. This mode of action can be interpreted considering a number of bilayer properties like fluidity, lipid charge, and domain formation. Cholesterol-containing bilayers are less fluid and less charged and have a tendency to form domains. In comparison to healthy cells, leukemic T-lymphocyte membranes are deprived of this lipid, resulting in decreased peptide binding and lower conductance. We showed that the higher content of anionic lipids increases the level of binding of the peptide to bilayers. Additionally, the absence of cholesterol resulted in enhanced pore activity. These findings may drive the selective toxicity of MP-1 to Jurkat cells.

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Photosensitizers (PS) photodynamic activities are regulated by their location in the biological target, which modulates their photophysical and photochemical features. In this work the PS partition for the Xanthene Dyes Fluorescein (FSC), Eosin Y(EOS), Erythrosin B (ERY) and Rose Bengal B (RBB) in biomimetic models (SDS, CTAB and Pluronic P-123 micelles) and the effects on their photophysical characteristics are evaluated. The hydrophobic and electrostatic forces that govern the PS-micelle interaction are analyzed. At physiological pH (7.25), the ability of the dianionic protolytic form of the dyes to be positioned into the micelle palisade and its micelle interaction depends not only on the hydrophobicity of the dye but also on the micellar surface charge. The Binding Constants obey exactly the same order of the Partition Coefficients for the dyes in P-123 and CTAB micelles. The Stern-Volmer treatment pointed out that dyes are located inside the micelle, especially ERY and RBB. The magnitude of the dye-micelle interaction increased from SDS, P-123 and finally CTAB micelles due to the charges between dye and micelle, and among the xanthenes, their hydrophobic characteristics. Within the micelle pseudo phase, ERY and RBB are still very efficient photosensitizers exhibiting high quantum yield of singlet oxygen, which turns them very attractive especially with P-123 polymeric system as drug delivery systems in photodynamic therapy. (C) 2012 Elsevier B.V. All rights reserved.

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Parabens are antimicrobial preservatives widely used in pharmaceutical, cosmetic and food industries. The alkyl chain connected to the ester group defines some important physicochemical characteristics of these compounds, including the partition coefficient and redox properties. The voltammetric and computational analyses were carried out in order to evaluate the redox behavior of these compounds and other phenolic analogues. A strong correlation between chemical substituents inductive effects of parabens with redox potentials was observed. Using cyclic voltammetry and glassy carbon working electrode, only one irreversible anodic peak was observed around 0.8 V for methylparaben (MP), ethylparaben (EP), propylparaben (PP), butylparaben (BP), benzylparaben (BzP) and p-substituted phenolic analogues. The electrodonating inductive effect of alkyl groups was demonstrated by the anodic oxidation potential shift to lower values as the carbon number increases and, therefore the parabens (and other phenolic analogues) oxidation processes to the quinonoidic forms showed great dependence on the substituent pattern.

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Some cyanopolyynes, HCnN (n = 1, 3, ... , 17), are investigated by means of calculations at the MP2/cc-pVTZ and CCSD/cc-pVDZ levels. Although the MP2/cc-pVTZ results for geometries and molecular dipole moments are encouraging, the CCSD/cc-pVDZ level was superior for the study of infrared fundamental intensities. The main bands are also analyzed with a charge-charge flux-dipole flux (CCFDF) partition model based on quantities given by the Quantum Theory of Atoms in Molecules (QTAIM). The intensity of vibrations corresponding to the stretching of CH bonds (3471-3473 cm(-1)) increases in line with the number of carbon atoms (from 61 to 146 km mol(-1) between HCN and HC13N). This increase is due to the charge flux contribution while the other contributions remain roughly unaltered except for HCN. Moreover, the hydrogen atom loses an almost constant amount of electronic charge during the CH bond enlargement and a small fraction of this charge spreads to atoms farther and farther away from hydrogen as the molecule size increases. The band associated with the doubly degenerate CH bending vibrations (643-732 cm(-1)) presents approximately the same intensity in all the studied cyanopolyynes (from 67 to 76 km mol(-1)). The CCFDF/QTAIM contributions are also nearly the same for these bending modes in HC5N and larger systems. The intensity of the mode mostly identified as CN stretching (around 2378-2399 cm(-1) except for HCN) increases from HCN up to HC7N (from 0.3 to 83 km mol(-1)) and nearly stabilizes around 80-90 km mol(-1) for larger systems. The CCFDF/QTAIM contributions for this mode also change significantly up to HC7N and remain almost constant in larger systems. We also observed the appearing of a very relevant band between 2283 and 2342 cm(-1). This mode is mainly associated with the symmetric stretching of CC triple bonds near the molecule center and exhibits large charge fluxes while the other contributions are almost negligible in the largest cyanopolyynes. The two vibrational bands associated with the smallest frequencies are also studied and extrapolation equations are suggested to predict their positions in larger cyanopolyynes. (C) 2012 Elsevier B.V. All rights reserved.

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Parabens are antimicrobial preservatives widely used in pharmaceutical, cosmetic and food industries. The alkyl chain connected to the ester group defines some important physicochemical characteristics of these compounds, including the partition coefficient and redox properties. The voltammetric and computational analyses were carried out in order to evaluate the redox behavior of these compounds and other phenolic analogues. A strong correlation between chemical substituents inductive effects of parabens with redox potentials was observed. Using cyclic voltammetry and glassy carbon working electrode, only one irreversible anodic peak was observed around 0.8 V for methylparaben (MP), ethylparaben (EP), propylparaben (PP), butylparaben (BP), benzylparaben (BzP) and p-substituted phenolic analogues. The electrodonating inductive effect of alkyl groups was demonstrated by the anodic oxidation potential shift to lower values as the carbon number increases and, therefore the parabens (and other phenolic analogues) oxidation processes to the quinonoidic forms showed great dependence on the substituent pattern.

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Despite the great importance of soybeans in Brazil, there have been few applications of soybean crop modeling on Brazilian conditions. Thus, the objective of this study was to use modified crop models to estimate the depleted and potential soybean crop yield in Brazil. The climatic variable data used in the modified simulation of the soybean crop models were temperature, insolation and rainfall. The data set was taken from 33 counties (28 Sao Paulo state counties, and 5 counties from other states that neighbor São Paulo). Among the models, modifications in the estimation of the leaf area of the soybean crop, which includes corrections for the temperature, shading, senescence, CO2, and biomass partition were proposed; also, the methods of input for the model's simulation of the climatic variables were reconsidered. The depleted yields were estimated through a water balance, from which the depletion coefficient was estimated. It can be concluded that the adaptation soybean growth crop model might be used to predict the results of the depleted and potential yield of soybeans, and it can also be used to indicate better locations and periods of tillage.

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Although sex ratios close to unity are expected in dioecious species, biased sex ratios are common in nature. It is essential to understand causes of skewed sex ratios in situ, as they can lead to mate limitation and have implications for the success of natural populations. Female-skewed sex ratios are commonly observed in copepods in situ. Here we discuss the challenges of copepod sex ratio research and provide a critical review of factors determining copepod sex ratios, focusing on 2 main objectives. The first is a critique of the male predation theory, which is currently the main process thought to be responsible for female-skewed sex ratios. It assumes that males have higher mortality because of increased vulnerability to predation during their search for mates. We show that there is little support for the male predation theory, that sex ratios skewed toward females occur in the absence of predation, that sex ratios are not related to predation pressure, and that where sex-skewed predation does occur, it is biased toward females. Our second objective is to suggest alternative hypotheses regarding the determination of sex ratios. We demonstrate that environmental factors, environmental sex determination and sex change have strong effects on copepod sex ratios, and suggest that differential physiological longevity of males and females may be more important in determining sex ratios than previously thought. We suggest that copepod sex ratios are the result of a mixture of factors.

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The intensity of regional specialization in specific activities, and conversely, the level of industrial concentration in specific locations, has been used as a complementary evidence for the existence and significance of externalities. Additionally, economists have mainly focused the debate on disentangling the sources of specialization and concentration processes according to three vectors: natural advantages, internal, and external scale economies. The arbitrariness of partitions plays a key role in capturing these effects, while the selection of the partition would have to reflect the actual characteristics of the economy. Thus, the identification of spatial boundaries to measure specialization becomes critical, since most likely the model will be adapted to different scales of distance, and be influenced by different types of externalities or economies of agglomeration, which are based on the mechanisms of interaction with particular requirements of spatial proximity. This work is based on the analysis of the spatial aspect of economic specialization supported by the manufacturing industry case. The main objective is to propose, for discrete and continuous space: i) a measure of global specialization; ii) a local disaggregation of the global measure; and iii) a spatial clustering method for the identification of specialized agglomerations.

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The purpose of this Thesis is to develop a robust and powerful method to classify galaxies from large surveys, in order to establish and confirm the connections between the principal observational parameters of the galaxies (spectral features, colours, morphological indices), and help unveil the evolution of these parameters from $z \sim 1$ to the local Universe. Within the framework of zCOSMOS-bright survey, and making use of its large database of objects ($\sim 10\,000$ galaxies in the redshift range $0 < z \lesssim 1.2$) and its great reliability in redshift and spectral properties determinations, first we adopt and extend the \emph{classification cube method}, as developed by Mignoli et al. (2009), to exploit the bimodal properties of galaxies (spectral, photometric and morphologic) separately, and then combining together these three subclassifications. We use this classification method as a test for a newly devised statistical classification, based on Principal Component Analysis and Unsupervised Fuzzy Partition clustering method (PCA+UFP), which is able to define the galaxy population exploiting their natural global bimodality, considering simultaneously up to 8 different properties. The PCA+UFP analysis is a very powerful and robust tool to probe the nature and the evolution of galaxies in a survey. It allows to define with less uncertainties the classification of galaxies, adding the flexibility to be adapted to different parameters: being a fuzzy classification it avoids the problems due to a hard classification, such as the classification cube presented in the first part of the article. The PCA+UFP method can be easily applied to different datasets: it does not rely on the nature of the data and for this reason it can be successfully employed with others observables (magnitudes, colours) or derived properties (masses, luminosities, SFRs, etc.). The agreement between the two classification cluster definitions is very high. ``Early'' and ``late'' type galaxies are well defined by the spectral, photometric and morphological properties, both considering them in a separate way and then combining the classifications (classification cube) and treating them as a whole (PCA+UFP cluster analysis). Differences arise in the definition of outliers: the classification cube is much more sensitive to single measurement errors or misclassifications in one property than the PCA+UFP cluster analysis, in which errors are ``averaged out'' during the process. This method allowed us to behold the \emph{downsizing} effect taking place in the PC spaces: the migration between the blue cloud towards the red clump happens at higher redshifts for galaxies of larger mass. The determination of $M_{\mathrm{cross}}$ the transition mass is in significant agreement with others values in literature.

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Abstract This dissertation investigates the notion of equivalence with particular reference to lexical cohesion in the translation of political speeches. Lexical cohesion poses a particular challenge to the translators of political speeches and thus preserving lexical cohesion elements as one of the major elements of cohesion is undoubtedly crucial to their translation equivalence. We rely on Halliday’s (1994) classification of lexical cohesion which comprises: repetition, synonymy, antonymy, meronymy and hyponymy. Other traditional models of lexical cohesion are examined. We include Grammatical Parallelism for its role in creating textual semantic unity which is what cohesion is all about. The study shed light on the function of lexical cohesion elements as rhetorical device. The study also deals with lexical problems resulting from the transfer of lexical cohesion elements from the SL into the TL, which is often beset by many problems that most often result from the differences between languages. Three key issues are identified as being fundamental to equivalence and lexical cohesion in the translation of political speeches: sociosemiotic approach, register analysis, rhetoric, and poetic function. The study also investigates the lexical cohesion elements in the translation of political speeches from English into Arabic, Italian and French in relation to ideology, and its control, through bias and distortion. The findings are discussed, implications examined and topics for further research suggested.

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In the last years, sustainable horticulture has been increasing; however, to be successful this practice needs an efficient soil fertility management to maintain a high productivity and fruit quality standards. For this purpose composted organic materials from agri-food industry and municipal solid waste has been used as a source to replace chemical fertilizers and increase soil organic matter. To better understand the influence of compost application on soil fertility and plant growth, we carried out a study comparing organic and mineral nitrogen (N) fertilization in micro propagated plants, potted trees and commercial peach orchard with these aims: 1. evaluation of tree development, CO2 fixation and carbon partition to the different organs of two-years-old potted peach trees. 2. Determination of soil N concentration and nitrate-N effect on plant growth and root oxidative stress of micro propagated plant after increasing rates of N applications. 3. Assessment of soil chemical and biological fertility, tree growth and yield and fruit quality in a commercial orchard. The addition of compost at high rate was effective in increasing CO2 fixation, promoting root growth, shoot and fruit biomass. Furthermore, organic fertilizers influenced C partitioning, favoring C accumulation in roots, wood and fruits. The higher CO2 fixation was the result of a larger tree leaf area, rather than an increase in leaf photosynthetic efficiency, showing a stimulation of plant growth by application of compost. High concentrations of compost increased total soil N concentration, but were not effective in increasing nitrate-N soil concentration; in contrast mineral-N applications increased linearly soil nitrate-N, even at the lowest rate tested. Soil nitrate-N concentration influenced positively plant growth at low rate (60- 80 mg kg-1), whereas at high concentrations showed negative effects. In this trial, the decrease of root growth, as a response to excessive nitrate-N soil concentration, was not anticipated by root oxidative stress. Continuous annual applications of compost for 10 years enhanced soil organic matter content and total soil N concentration. Additionally, high rate of compost application (10 t ha-1 year-1) enhanced microbial biomass. On the other hand, different fertilizers management did not modify tree yield, but influenced fruit size and precocity index. The present data support the idea that organic fertilizers can be used successfully as a substitute of mineral fertilizers in fruit tree nutrient management, since they promote an increase of soil chemical and biological fertility, prevent excessive nitrate-N soil concentration, promote plant growth and potentially C sequestration into the soil.

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This PhD thesis concerns geochemical constraints on recycling and partial melting of Archean continental crust. A natural example of such processes was found in the Iisalmi area of Central Finland. The rocks from this area are Middle to Late Archean in age and experienced metamorphism and partial melting between 2.7-2.63 Ga. The work is based on extensive field work. It is furthermore founded on bulk rock geochemical data as well as in-situ analyses of minerals. All geochemical data were obtained at the Institute of Geosciences, University of Mainz using X-ray fluorescence, solution ICP-MS and laser ablation-ICP-MS for bulk rock geochemical analyses. Mineral analyses were accomplished by electron microprobe and laser ablation ICP-MS. Fluid inclusions were studied by microscope on a heating-freezing-stage at the Geoscience Center, University Göttingen. Part I focuses on the development of a new analytical method for bulk rock trace element determination by laser ablation-ICP-MS using homogeneous glasses fused from rock powder on an Iridium strip heater. This method is applicable for mafic rock samples whose melts have low viscosities and homogenize quickly at temperatures of ~1200°C. Highly viscous melts of felsic samples prevent melting and homogenization at comparable temperatures. Fusion of felsic samples can be enabled by addition of MgO to the rock powder and adjustment of melting temperature and melting duration to the rock composition. Advantages of the fusion method are low detection limits compared to XRF analyses and avoidance of wet-chemical processing and use of strong acids as in solution ICP-MS as well as smaller sample volumes compared to the other methods. Part II of the thesis uses bulk rock geochemical data and results from fluid inclusion studies for discrimination of melting processes observed in different rock types. Fluid inclusion studies demonstrate a major change in fluid composition from CO2-dominated fluids in granulites to aqueous fluids in TTG gneisses and amphibolites. Partial melts were generated in the dry, CO2-rich environment by dehydration melting reactions of amphibole which in addition to tonalitic melts produced the anhydrous mineral assemblages of granulites (grt + cpx + pl ± amph or opx + cpx + pl + amph). Trace element modeling showed that mafic granulites are residues of 10-30 % melt extraction from amphibolitic precursor rocks. The maximum degree of melting in intermediate granulites was ~10 % as inferred from modal abundances of amphibole, clinopyroxene and orthopyroxene. Carbonic inclusions are absent in upper-amphibolite facies migmatites whereas aqueous inclusion with up to 20 wt% NaCl are abundant. This suggests that melting within TTG gneisses and amphibolites took place in the presence of an aqueous fluid phase that enabled melting at the wet solidus at temperatures of 700-750°C. The strong disruption of pre-metamorphic structures in some outcrops suggests that the maximum amount of melt in TTG gneisses was ~25 vol%. The presence of leucosomes in all rock types is taken as the principle evidence for melt formation. However, mineralogical appearance as well as major and trace element composition of many leucosomes imply that leucosomes seldom represent frozen in-situ melts. They are better considered as remnants of the melt channel network, e.g. ways on which melts escaped from the system. Part III of the thesis describes how analyses of minerals from a specific rock type (granulite) can be used to determine partition coefficients between different minerals and between minerals and melt suitable for lower crustal conditions. The trace element analyses by laser ablation-ICP-MS show coherent distribution among the principal mineral phases independent of rock composition. REE contents in amphibole are about 3 times higher than REE contents in clinopyroxene from the same sample. This consistency has to be taken into consideration in models of lower crustal melting where amphibole is replaced by clinopyroxene in the course of melting. A lack of equilibrium is observed between matrix clinopyroxene / amphibole and garnet porphyroblasts which suggests a late stage growth of garnet and slow diffusion and equilibration of the REE during metamorphism. The data provide a first set of distribution coefficients of the transition metals (Sc, V, Cr, Ni) in the lower crust. In addition, analyses of ilmenite and apatite demonstrate the strong influence of accessory phases on trace element distribution. Apatite contains high amounts of REE and Sr while ilmenite incorporates about 20-30 times higher amounts of Nb and Ta than amphibole. Furthermore, trace element mineral analyses provide evidence for magmatic processes such as melt depletion, melt segregation, accumulation and fractionation as well as metasomatism having operated in this high-grade anatectic area.

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Studies of organic fluorescent dyes are experiencing a renaissance related to the increasing demands posed by new microscopy techniques for high resolution and high sensitivity. While in the last decade single molecule equipment and methodology has significantly advanced and in some cases reached theoretical limits (e.g. detectors approaching unity quantum yields) unstable emission from chromophores and photobleaching become more and more the bottleneck of the advancement and spreading of single-molecule fluorescence studies. The main goal of this work was the synthesis of fluorophores that are water-soluble, highly fluorescent in an aqueous environment, have a reactive group for attachment to a biomolecule and posses exceptional photostability. An approach towards highly fluorescent, water-soluble and monofunctional perylene-3,4,9,10-tetracarboxdiimide and terrylene-3,4:11,12-tetra carboxidiimide chromophores was presented. A new synthetic strategy for the desymmetrization of perylenetetracarboximides was elaborated; water-solubility was accomplished by introducing sulfonyl substituents in the phenoxy ring. Two strategies have been followed relying on either non-specific or site specific labeling. For this purpose a series of new water-soluble monofunctional perylene and terrylene dyes, bearing amine or carboxy group were prepared. The reactivity and photophysical properties of these new chromophores were studied in aqueous medium. The most suitable chromophores were further derivatized with amine or thiol reactive groups, suitable for chemical modification of proteins. The performance of the new fluorescent probes was assessed by single molecule enzyme tracking, in this case phospholipase acting on phospholipid supported layers. Phospholipase-1 (PLA-1) was labeled with N-hydroxysuccinimide ester functionalized perylene and terrylene derivatives. The purification of the conjugates was accomplished by novel convenient procedure for the removal of unreacted dye from labeled enzymes, which involves capturing excess dye with a solid support. This novel strategy for purification of bioconjugates allows convenient and fast separation of labeled proteins without the need for performing time consuming chromatographic or electrophoretic purification steps. The outstanding photostability of the dyes and, associated therewith, the extended survival times under strong illumination conditions allow a complete characterization of enzyme action on its natural substrates and even connecting enzyme mobility to catalytic activity. For site-specific attachment of the rylene dyes to proteins the chromophores were functionalized with thioesters or nitrilotriacetic acid groups. This allowed attachment of the emitters to the N-terminus of proteins by native chemical ligation or complexation with His-tagged polypeptides at the N- or C-termini, respectively. The synthesis of a water-soluble perylenebis (dicarboximide) functionalized with a thioester group was presented. This chromophore exhibits an exceptional photostability and a functional unit for site-specific labeling of proteins. The suitability of the fluorophore as a covalent label was demonstrated via native chemical ligation with protein containing N-terminal cystein residue. We exploited also oligohisitidine sequences as recognition elements for site-selective labeling. The synthesis of a new water-soluble perylene chromophore, containing a nitrilotriacetic acid functional group was demonstrated, using solution-phase and solid-phase approaches. This chromophore combines the exceptional photophysical properties of the rylene dyes and a recognition unit for site-specific labeling of proteins. An important feature of the label is the unchanged emission of the dye upon complexation with nickel ions.

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Der vorliegende Artikel beschäftigt sich mit der performativen Aushandlung nationaler Kultur auf dem National Festival of Arts and Culture, das 2006 in Wa, Nordwestghana, stattfand. Die Autorin nahm an der Vorbereitung und Planung des Festivals in lokalen staatlichen Kulturinstitutionen teil, und beobachtete die Diskussionen um die Repräsentation einer (imaginierten) spezifischen Kultur des Nordens in scharfer Abgrenzung zu der des als dominant und diskriminierend empfundenen Südens. In diesem Zusammenhang werden Fragen der Authentizität und Authentifizierung, wie sie in der Planung und Rezeption diskutiert wurden, aufgegriffen und mit der Konzeption des Festivals als gleichzeitig einheitsstiftendes Vehikel für nationale Identität und als Austragungsort eines Wettbewerbs der Regionen um Anerkennung und Ressourcen in Verbindung gesetzt. Das Festival, so die Argumentation, ist eine cultural performance, die das Wesen einer „Kultur“ nicht nur abbildet, sondern auch die Möglichkeit des Wandels und der Subversion birgt. Performance meint hier also gleichzeitig die Aufführung und das Skript der Diskurse, die der Aufführung Bedeutung zuschreiben. Diesen doppelten Ansatz verfolgt der Artikel durch die Verknüpfung von Festivalbeobachtungen und Komiteesitzungsmitschriften im Rahmen der Vorbereitung.