983 resultados para cation-radicals
Resumo:
The University of Barcelona is developing a pilot-scale hot wire chemical vapor deposition (HW-CVD) set up for the deposition of nano-crystalline silicon (nc-Si:H) on 10 cm × 10 cm glass substrate at high deposition rate. The system manages 12 thin wires of 0.15-0.2 mm diameter in a very dense configuration. This permits depositing very uniform films, with inhomogeneities lower than 2.5%, at high deposition rate (1.5-3 nm/s), and maintaining the substrate temperature relatively low (250 °C). The wire configuration design, based on radicals' diffusion simulation, is exposed and the predicted homogeneity is validated with optical transmission scanning measurements of the deposited samples. Different deposition series were carried out by varying the substrate temperature, the silane to hydrogen dilution and the deposition pressure. By means of Fourier transform infrared spectroscopy (FTIR), the evolution in time of the nc-Si:H vibrational modes was monitored. Particular importance has been given to the study of the material stability against post-deposition oxidation.
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Hypothermia is a condition in which core temperature drops below the level necessary to maintain bodily functions. The decrease in temperature may disrupt some physiological systems of the body, including alterations in microcirculation and reduction of oxygen supply to tissues. The lack of oxygen can induce the generation of reactive oxygen and nitrogen free radicals (RONS), followed by oxidative stress, and finally, apoptosis and/or necrosis. Furthermore, since the hypothermia is inevitably followed by a rewarming process, we should also consider its effects. Despite hypothermia and rewarming inducing injury, many benefits of hypothermia have been demonstrated when used to preserve brain, cardiac, hepatic, and intestinal function against ischemic injury. This review gives an overview of the effects of hypothermia and rewarming on the oxidant/antioxidant balance and provides hypothesis for the role of reactive oxygen species in therapeutic hypothermia.
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Comparative phylogeography seeks for commonalities in the spatial demographic history of sympatric organisms to characterize the mechanisms that shaped such patterns. The unveiling of incongruent phylogeographic patterns in co-occurring species, on the other hand, may hint to overlooked differences in their life histories or microhabitat preferences. The woodlouse-hunter spiders of the genus Dysdera have undergone a major diversi cation on the Canary Islands. The species pair Dysdera alegranzaensis and Dysdera nesiotes are endemic to the island of Lanzarote and nearby islets, where they co-occur at most of their known localities. The two species stand in sharp contrast to other sympatric endemic Dysdera in showing no evidence of somatic (non-genitalic) differentiation. Phylogenetic and population genetic analyses of mitochondrial cox1 sequences from an exhaustive sample of D. alegranzaensis and D. nesiotes specimens, and additional mitochondrial (16S, L1, nad1) and nuclear genes (28S, H3) were analysed to reveal their phylogeographic patterns and clarify their phylogenetic relationships. Relaxed molecular clock models using ve calibration points were further used to estimate divergence times between species and populations. Striking differences in phylogeography and population structure between the two species were observed. Dysdera nesiotes displayed a metapopulation-like structure, while D. alegranzaensis was characterized by a weaker geographical structure but greater genetic divergences among its main haplotype lineages, suggesting more complex population dynamics. Our study con rms that co-distributed sibling species may exhibit contrasting phylogeographic patterns in the absence of somatic differentiation. Further ecological studies, however, will be necessary to clarify whether the contrasting phylogeographies may hint at an overlooked niche partitioning between the two species. In addition, further comparisons with available phylogeographic data of other eastern Canarian Dysdera endemics con rm the key role of lava ows in structuring local populations in oceanic islands and identify localities that acted as refugia during volcanic eruptions
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The purpose of our project is to contribute to earlier diagnosis of AD and better estimates of its severity by using automatic analysis performed through new biomarkers extracted from non-invasive intelligent methods. The methods selected in this case are speech biomarkers oriented to Sponta-neous Speech and Emotional Response Analysis. Thus the main goal of the present work is feature search in Spontaneous Speech oriented to pre-clinical evaluation for the definition of test for AD diagnosis by One-class classifier. One-class classifi-cation problem differs from multi-class classifier in one essen-tial aspect. In one-class classification it is assumed that only information of one of the classes, the target class, is available. In this work we explore the problem of imbalanced datasets that is particularly crucial in applications where the goal is to maximize recognition of the minority class as in medical diag-nosis. The use of information about outlier and Fractal Dimen-sion features improves the system performance.
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We show both theoretical and experimental evidences of the appearance of ferromagnetism in MgO thin films. First-principles calculations allow predicting the possibility of the formation of a local moment in MgO, provided the existence of Mg vacancies which create holes on acceptor levels near the O 2p-dominated valence band. Magnetic measurements evidence of the existence of room-temperature ferromagnetism in MgO thin films. High-resolution transmission electron microscopy demonstrates the existence of cation vacancies in our samples. Finally, by applying the element specificity of the x-ray magnetic circular dichroism technique, we also demonstrate that the magnetic moments of the system arise from the spin polarization of the 2p electrons of oxygen atoms surrounding Mg vacancies.
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Single-stranded DNA (ssDNA) plays a major role in several biological processes. It is therefore of fundamental interest to understand how the elastic response and the formation of secondary structures are modulated by the interplay between base pairing and electrostatic interactions. Here we measure force-extension curves (FECs) of ssDNA molecules in optical tweezers set up over two orders of magnitude of monovalent and divalent salt conditions, and obtain its elastic parameters by fitting the FECs to semiflexible models of polymers. For both monovalent and divalent salts, we find that the electrostatic contribution to the persistence length is proportional to the Debye screening length, varying as the inverse of the square root of cation concentration. The intrinsic persistence length is equal to 0.7 nm for both types of salts, and the effectivity of divalent cations in screening electrostatic interactions appears to be 100-fold as compared with monovalent salt, in line with what has been recently reported for single-stranded RNA. Finally, we propose an analysis of the FECs using a model that accounts for the effective thickness of the filament at low salt condition and a simple phenomenological description that quantifies the formation of non-specific secondary structure at low forces.
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Neutral and selective processes c an drive repeated patterns of evolu tion in dif ferent groups of populationsexp eriencing similar ecol ogica l gradients. In this paper, we used a combinat ion of nucl ear and mitochondrialDNA markers, as well as geometric morphometrics, to investigate repeated patterns of morphological andgenetic divergence of E uropean minnows in two mountain ranges : the Pyrenees and the Al ps. Europeanminnows (Phoxinus phoxinus) are cyprinid fish i nha bitin g most freshwater bodies in Europe, including those indifferent mountain r anges that could act as major geographical barriers to gene flow. We explored patterns ofP. phoxinus phenotypic and genetic di versi fication along a gradi ent of alti tude common to the two mountainranges, and tested for isolation by distance (IBD), isolation by environment (IBE) and isolation by adaptation(IBA). The results indicated that populations from the Pyr enees a nd the Alps bel ong to two well differentiated,reciprocally monophyletic mt DNA lineages. Substantial genetic differentiation due to geographical isolationwithin and between populations from the Pyrenees and the Alps was also found using rapidly evolving AFLPsmarkers (isolation by distance or IBD), as well as morphological differences between mountain ranges. Als o,morphology varied strong ly with elevation and so did genetic differentiation to a lower extent. Despitemoderate evidence for IBE and IBA, and therefore of repeated evolution, substantial population heterogeneitywas found at the genetic level, suggesting that selection and population specific genetic drift act in concert toaffect genetic divergence.
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Store-operated Ca(2+) channels (SOCs) are voltage-independent Ca(2+) channels activated upon depletion of the endoplasmic reticulum Ca(2+) stores. Early studies suggest the contribution of such channels to Ca(2+) homeostasis in insulin-secreting pancreatic β-cells. However, their composition and contribution to glucose-stimulated insulin secretion (GSIS) remains unclear. In this study, endoplasmic reticulum Ca(2+) depletion triggered by acetylcholine (ACh) or thapsigargin stimulated the formation of a ternary complex composed of Orai1, TRPC1, and STIM1, the key proteins involved in the formation of SOCs. Ca(2+) imaging further revealed that Orai1 and TRPC1 are required to form functional SOCs and that these channels are activated by STIM1 in response to thapsigargin or ACh. Pharmacological SOCs inhibition or dominant negative blockade of Orai1 or TRPC1 using the specific pore mutants Orai1-E106D and TRPC1-F562A impaired GSIS in rat β-cells and fully blocked the potentiating effect of ACh on secretion. In contrast, pharmacological or dominant negative blockade of TRPC3 had no effect on extracellular Ca(2+) entry and GSIS. Finally, we observed that prolonged exposure to supraphysiological glucose concentration impaired SOCs function without altering the expression levels of STIM1, Orai1, and TRPC1. We conclude that Orai1 and TRPC1, which form SOCs regulated by STIM1, play a key role in the effect of ACh on GSIS, a process that may be impaired in type 2 diabetes.
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BACKGROUND & AIMS: The prognostic value of the different causes of renal failure in cirrhosis is not well established. This study investigated the predictive value of the cause of renal failure in cirrhosis. METHODS: Five hundred sixty-two consecutive patients with cirrhosis and renal failure (as defined by serum creatinine 1.5 mg/dL on 2 successive determinations within 48 hours) hospitalized over a 6-year period in a single institution were included in a prospective study. The cause of renal failure was classified into 4 groups: renal failure associated with bacterial infections, renal failure associated with volume depletion, hepatorenal syndrome (HRS), and parenchymal nephropathy. The primary end point was survival at 3 months. RESULTS: Four hundred sixty-three patients (82.4%) had renal failure that could be classified in 1 of 4 groups. The most frequent was renal failure associated with infections (213 cases; 46%), followed by hypovolemia-associated renal failure (149; 32%), HRS (60; 13%), and parenchymal nephropathy (41; 9%). The remaining patients had a combination of causes or miscellaneous conditions. Prognosis was markedly different according to cause of renal failure, 3-month probability of survival being 73% for parenchymal nephropathy, 46% for hypovolemia-associated renal failure, 31% for renal failure associated with infections, and 15% for HRS (P .0005). In a multivariate analysis adjusted for potentially confounding variables, cause of renal failure was independently associated with prognosis, together with MELD score, serum sodium, and hepatic encephalopathy at time of diagnosis of renal failure. CONCLUSIONS: A simple classification of patients with cirrhosis according to cause of renal failure is useful in assessment of prognosis and may help in decision making in liver transplantation.
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Several methodologies for the generation of oxyallyl cations from polybromoketones and other substrates are discussed. The mechanistic aspect of the [3+4] cycloaddition reaction between these cations and dienes leading to the formation of seven membered ring carbocyclic compounds is presented. Finally, some synthetic applications of the [3+4] cycloaddition are shown.
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Carotenoid polyenes play a wide role in nature and their photophysical properties make of these pigments a focus of research in photochemistry, photobiology and photomedicine. Some aspects of the singlet and triplet states and, their interaction with molecular and singlet oxygen and free radicals are briefly reviewed in this article.
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The physical and chemical characterization of vermicompost from bovine manure has been studied. It was examined the pH and cation exchangeable capacity (CEC), organic matter content, electric conductivity and elementary and XRD analyses, among other characteristics. The vermicompost was then applied to the retention and competition of metal micronutrients and pollutants (Cu and Zn) from metal nitrate solutions. The retention was affected by both the pH and adsorption time, while the competitive character of these metals for the substrate was relevant to each pH examined.
Resumo:
The initiation step of the light-induced polymerization kinetics of vinyl monomers using dye-sensitized photoinitiators to generate active radicals is discussed. The photoredox processes of basic dyes with amines and sulfinates are described as photochemical systems capable of starting free-radical polymerization of vinyl monomers in homogeneous and microheterogeneous media. Photophysical techniques like laser flash photolysis and time-correlated single photon counting are used to investigate the excited-state kinetics of the dyes.
Resumo:
Laser excitation of 0.01 M solutions of 1-indanone (Ia), 1-tetralone (Ib), 1-benzosuberone (Ic), and their a,a -dimethyl derivatives IIa-c, respectively, in benzene, produced transients with maximum absorption at 425 nm, and lifetimes ranging from 62 ns (IIa) to 5.5ms (Ic). Quenching studies using well known triplet quenchers such as 1,3-cyclohexadiene and oxygen demonstrated the triplet nature of these transients. In the presence of hydrogen donors, such as 2-propanol, the triplet state decay of the ketones Ia-c leads to the formation of the corresponding ketyl radicals, i.e. IIIa-c, which show absorption spectra very similar to the parent ketone, with lmax at 430 nm and lifetime in excess of 20 ms. Steady state irradiations show that the a,a -dimethyl ketones IIa and IIc form ortho-alkyl benzaldehydes probably derived from an initial a-cleavage of the corresponding triplet excited states.