925 resultados para support surface functional group influence
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We report on the bottom-up fabrication of BN-substituted heteroaromatic networks achieved by surface-assisted polymerization and subsequent cyclodehydrogenation of specifically designed BN-substituted precursor monomers based on a borazine core structural element. To get insight into the cyclodehydrogenation pathway and the influence of molecular flexibility on network quality, two closely related precursor monomers with different degrees of internal cyclodehydrogenation have been employed. Scanning tunneling microscopy shows that, for both monomers, surface-assisted cyclodehydrogenation allows for complete monomer cyclization and the formation of covalently interlinked BN-substituted polyaromatic hydrocarbon networks on the Ag(111) surface. In agreement with experimental observations, density functional theory calculations reveal a significantly lower energy barrier for the cyclodehydrogenation of the conformationally more rigid precursor monomer, which is also reflected in a higher degree of long-range order of the obtained heteroaromatic network. Our proof-of-concept study will allow for the fabrication of atomically precise substitution patterns within BNC heterostructures.
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Major depressive disorder (MDD) is associated with structural and functional alterations in the prefrontal cortex (PFC) and anterior cingulate cortex (ACC). Enhanced ACC activity at rest (measured using various imaging methodologies) is found in treatment-responsive patients and is hypothesized to bolster treatment response by fostering adaptive rumination. However, whether structural changes influence functional coupling between fronto-cingulate regions and ACC regional homogeneity (ReHo) and whether these functional changes are related to levels of adaptive rumination and treatment response is still unclear. Cortical thickness and ReHo maps were calculated in 21 unmedicated depressed patients and 35 healthy controls. Regions with reduced cortical thickness defined the seeds for the subsequent functional connectivity (FC) analyses. Patients completed the Response Style Questionnaire, which provided a measure of adaptive rumination associated with better response to psychotherapy. Compared with controls, depressed patients showed thinning of the right anterior PFC, increased prefrontal connectivity with the supragenual ACC (suACC), and higher ReHo in the suACC. The suACC clusters of increased ReHo and FC spatially overlapped. In depressed patients, suACC ReHo scores positively correlated with PFC thickness and with FC strength. Moreover, stronger fronto-cingulate connectivity was related to higher levels of adaptive rumination. Greater suACC ReHo and connectivity with the right anterior PFC seem to foster adaptive forms of self-referential processing associated with better response to psychotherapy, whereas prefrontal thinning impairs the ability of depressed patients to engage the suACC during a major depressive episode. Bolstering the function of the suACC may represent a potential target for treatment.
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We investigate the transition from unitary to dissipative dynamics in the relativistic O(N) vector model with the λ(φ2)2 interaction using the nonperturbative functional renormalization group in the real-time formalism. In thermal equilibrium, the theory is characterized by two scales, the interaction range for coherent scattering of particles and the mean free path determined by the rate of incoherent collisions with excitations in the thermal medium. Their competition determines the renormalization group flow and the effective dynamics of the model. Here we quantify the dynamic properties of the model in terms of the scale-dependent dynamic critical exponent z in the limit of large temperatures and in 2≤d≤4 spatial dimensions. We contrast our results to the behavior expected at vanishing temperature and address the question of the appropriate dynamic universality class for the given microscopic theory.
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Aims. Permittivity measurements on porous samples of volcanic origin have been performed in the 0.05-190 GHz range under laboratory conditions in support of the Rosetta mission to comet 67P/Churyumov-Gerasimenko, specifically with the MIRO radiometric experiment and CONSERT radar experiment. Methods. The samples were split into several subsamples with different size ranges covering a few mu m to 500 mu m. Bulk densities of the subsamples were estimated to be in the 800 to 1500 kg/m(3) range. The porosities were in the range of 48% to 65%. From 50 MHz to 6 GHz and at 190 GHz, permittivity has been determined with a coaxial cell and with a quasi-optical bench, respectively. Results. Without taking into account the volume-scattering effect at 190 GHz, the real part of the permittivity, normalized by the bulk density, is in the range of 2.1 to 2.6. The results suggest that the real part of the permittivity of an ice-free dust mantle covering the nucleus is in the 1.5-2.2 range at 190 GHz. From these values, a lower limit for the absorption length for the millimeter receiver of MIRO has been estimated to be between 0.6 and 2 cm, in agreement with results obtained from MIRO in September 2014. At frequencies of interest for CONSERT experiment, the real part of the permittivity of a suspected ice-free dust mantle should be below 2.2. It may be in the range of 1.2 to 1.7 for the nucleus, in agreement with first CONSERT results, taking into account a mean temperature of 110 K and different values for the dust-to-ice volumetric ratio. Estimations of contributions of the different parameters to the permittivity variation may indicate that the porosity is the main parameter.
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Abundance of the Ommastrephes bartramii winter-spring cohort fluctuated greatly from 1995 to 2004. To understand how abundance was influenced by sea surface conditions, we examined the variations in the proportion of thermal habitats with favourable sea surface temperature (SST). The SST data of both the spawning and feeding grounds were used to calculate the monthly proportion of favourable-SST areas (PFSSTA). Catch per fishing day per fishing boat (catch per unit effort, CPUE) of the Chinese mainland squid-jigging fleet was used as squid abundance index. The relationships between CPUE and monthly PFSSTA at spawning and feeding grounds were analyzed, and the relationship between CPUE and selected PFSSTA was quantified with a multiple linear regression model. Results showed that February PFSSTA at the spawning ground and August to November PFSSTA at the feeding ground could account for about 60% of the variability in O. bartramii abundance between 1995 and 2004, that February was the most important period influencing squid recruitment during the spawning season, and that feeding ground PFSSTA during the fishing season would influence CPUE by causing squid to aggregate. Our forecast model was found to perform well when we compared the model-predicted CPUEs and the average CPUEs observed during August to November in 2005 and 2006 from the Chinese squid-jigging fishery.
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The World Health Organization estimates there are about 585,000 maternal deaths each year, with 98% of the maternal deaths in developing countries. Access to family planning methods is one method to decrease maternal mortality and morbidity. ^ The U.S. was the leader in providing financial and technical assistance to developing countries to enable women to have this access. The election of Ronald Regan changed the course of U.S. support; abortion became a central factor in the political decision-making with regards to the financial support of international family planning. ^ One factor that may sway policy-makers' decisions is the influence of ideological interest groups, Political Action Committees funding of candidates in relation to votes on bills that impacted on financial support of international family planning and the amount spent by these groups on lobbyist was reviewed. Pro-choice funding of candidates was greater for the four of the fives votes supporting family planning. Pro-Choice lobbyist spending was $185,000 vs. $8,184,000 spent by Pro-Life ideological groups. ^
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Atherosclerosis is widely accepted as a complex genetic phenotype and is the usual cause of cardiovascular disease, the world’s leading killer. Genetic factors have been proven to be important risk contributors for atherosclerosis and much work has been done to identify promising candidates that might play a role in the development of atherosclerosis. It is well known that many independent replications are needed to unequivocally establish a valid genotype-phenotype association across different populations before the findings are extended to clinical settings and to the expensive follow-up studies designed to identify causal genetic variants. Aiming to replicate the association with atherosclerosis in the Pathobiological Determinants of Atherosclerosis in Youth (PDAY) study, we assessed the relationship of 32 atherosclerosis candidate SNPs to atherosclerosis in the PDAY cohort, consisting of AA and EA young people aged 15-34 years who died of non-medical causes. Two association studies, a whole sample study and a 1:1 matched case control study were performed by use of multiple linear regression and logistic regression analyses, respectively. For the whole sample association study, 32 SNPs among 2,650 individuals (1,369 AA and 1,281 EA) were tested for the association with six early atherosclerosis phenotypes: abdominal aorta fatty streaks, abdominal aorta raised lesions, right coronary artery fatty streaks, right coronary artery raised lesions, thoracic aorta fatty streaks, and thoracic aorta raised lesions. For the matched case-control association study, 337 case-control paired samples were included; cases were chosen with the highest total raised lesion scores from the studied population, while controls were randomly selected from individuals that had no raised lesions and matched to cases by age, gender and race. Sixteen SNPs in 13 genes were found to be significantly associated with atherosclerosis in at least one of the PDAY association studies. Among these 16 findings: eight SNPs (rs9579646, rs6053733, rs3849150, rs10499903, rs2148079, rs5073691, rs10116277, and rs17228212) successfully replicated previous results, six SNPs (rs17222814, rs10811661, rs7028570, rs7291467, rs16996148 and rs10401969) were reported as new findings exclusive to our study, the last two of the 16 SNPs, rs501120 and rs6922269, showed either intriguing or conflicting result. SNP rs17222814 in ALOX5AP and SNP rs3849150 in LRRC18 were consistently associated with atherosclerosis in both prior and the two PDAY association studies. SNP rs3849150 was also identified to be highly correlated with a non-synonymous coding SNP, rs17772611, which may damage the protein (polyphen score = 0.996), suggesting that SNP rs17772611 may be the causal functional variant.^ In conclusion, our study added more support for the association of these candidate genes with atherosclerosis. SNPs rs3849150 and rs17772611 of LRRC18, as well as SNP rs17222814 of ALOX5AP, were the most significant findings from our study, and may be ranked among the best for further study.^
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The stomach is thought to be protected from luminal acid by a gastric mucosal barrier that restricts the diffusion of acid into tissue. This study tested the hypothesis that the hydrophobic luminal surface of canine gastric mucosa incubated in Ussing chambers, impedes the back-diffusion of luminal acid into the tissue. Isolated sheets of mucosa were treated with cimetidine to inhibit spontaneous acid secretion, and incubated under conditions that prevented significant secretion of luminal bicarbonate. By measuring acid loss from the luminal compartment using the pH-stat technique, acid back-diffusion was continuously monitored; potential difference (PD) was measured as an index of tissue viability. Tissue luminal surface hydrophobicity was estimated by contact angle analysis at the end of each experiment. Addition of 16,16-dimethyl prostaglandin E$\sb2$ to the nutrient compartment enhanced luminal surface hydrophobicity, but did not reduce acid back-diffusion in tissues that maintained a constant PD. 10 mM salicylate at pH 4.00 in the luminal compartment reduced surface hydrophobicity, but this decrease did not occur if 1 ug/ml prostaglandin was present in the nutrient solution. Despite possessing relatively hydrophilic and relatively hydrophobic surface properties, respectively, acid back-diffusion in the absence of salicylate was not significantly different between these two groups. Neither group maintained a PD after incubation with salicylate. Lastly, radiolabelled salicylate was used to calculate the free (non-salicylate associated) acid loss in tissues incubated with salicylate and/or prostaglandin. No significant correlation was found between free acid back-diffusion and luminal surface hydrophobicity. These data do not support the hypothesis that acid back-diffusion in impeded by the hydrophobic surface presented by isolated canine gastric mucosa. ^
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The tumor-suppressing function of p53 can be affected in a variety of manners. Here, we describe a novel mechanism of transformation by mutant p53. Previously, it had been believed that mutant p53 molecules transform cells by oligomerizing with wild-type p53 and inactivating it. However, we demonstrated that there exists an additional mechanism of inactivation of p53 available to p53 mutants. It involves sequestration of cofactors necessary to p53, and subsequent interruption of its transactivation and tumor suppression functions. The p53 amino or carboxyl termini, known to interact with a large number of cellular factors, can affect wild-type p53 in this manner. Although they are unable to oligomerize with wild-type p53, they transform cells containing p53, and inhibit its transactivation ability. In addition, they interrupt growth suppression by p53, but not RB, confirming that they specifically affect p53 function, rather than having a general growth-stimulatory phenomenon. Also, we have cloned a p53 tumor mutation which results in expression of the amino terminus of p53. This provides a means to study the factor-sequestration transforming mechanism in vivo. Additionally, we found that the published sequence of the mdm2 gene is in error. mdm2 is a gene intimately involved with p53, blocking its ability to transform cells. Finally, previous data had established the influence of cell-cycle status on p53 function. In growth-arrested cells, wild-type p53 expressed by a transgene cannot activate transcription, but if these cells are forced to cycle by addition of cyclin E, p53 once again becomes functional. In this study, we extend these findings by examining only those cells successfully transfected, using fluorescence-activated cell sorting. Our results support the previous data, that cyclin E pushes growth-arrested cells back into the cell cycle. In summary, we have demonstrated the potential importance of cofactor association and protein modification to the abilities of p53 to cause transcription activation and repression, inhibition of DNA replication and induction of DNA repair, and initiation of cell-cycle arrest and apoptosis. Further elucidation of these processes and their roles in tumor suppression will prove fascinating indeed. ^
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Pteropods are a group of holoplanktonic gastropods for which global biomass distribution patterns remain poorly resolved. The aim of this study was to collect and synthesize existing pteropod (Gymnosomata, Thecosomata and Pseudothecosomata) abundance and biomass data, in order to evaluate the global distribution of pteropod carbon biomass, with a particular emphasis on its seasonal, temporal and vertical patterns. We collected 25 902 data points from several online databases and a number of scientific articles. The biomass data has been gridded onto a 360 x 180° grid, with a vertical resolution of 33 WOA depth levels. Data has been converted to NetCDF format. Data were collected between 1951-2010, with sampling depths ranging from 0-1000 m. Pteropod biomass data was either extracted directly or derived through converting abundance to biomass with pteropod specific length to weight conversions. In the Northern Hemisphere (NH) the data were distributed evenly throughout the year, whereas sampling in the Southern Hemisphere was biased towards the austral summer months. 86% of all biomass values were located in the NH, most (42%) within the latitudinal band of 30-50° N. The range of global biomass values spanned over three orders of magnitude, with a mean and median biomass concentration of 8.2 mg C l-1 (SD = 61.4) and 0.25 mg C l-1, respectively for all data points, and with a mean of 9.1 mg C l-1 (SD = 64.8) and a median of 0.25 mg C l-1 for non-zero biomass values. The highest mean and median biomass concentrations were located in the NH between 40-50° S (mean biomass: 68.8 mg C l-1 (SD = 213.4) median biomass: 2.5 mg C l-1) while, in the SH, they were within the 70-80° S latitudinal band (mean: 10.5 mg C l-1 (SD = 38.8) and median: 0.2 mg C l-1). Biomass values were lowest in the equatorial regions. A broad range of biomass concentrations was observed at all depths, with the biomass peak located in the surface layer (0-25 m) and values generally decreasing with depth. However, biomass peaks were located at different depths in different ocean basins: 0-25 m depth in the N Atlantic, 50-100 m in the Pacific, 100-200 m in the Arctic, 200-500 m in the Brazilian region and >500 m in the Indo-Pacific region. Biomass in the NH was relatively invariant over the seasonal cycle, but more seasonally variable in the SH. The collected database provides a valuable tool for modellers for the study of ecosystem processes and global biogeochemical cycles.
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Quantitative coccolithophore analyses were performed in core MD01-2446, located in the mid-latitude North Atlantic, to reconstruct climatically induced sea-surface water conditions throughout Marine Isotope Stages (MIS) 14-9. The data are compared to new and available paleoenvironmental proxies from the same site as well as other nearby North Atlantic records that support the coccolithophore signature at glacial-interglacial to millennial climate scale. Total coccolithophore absolute abundance increases during interglacials but abruptly drops during the colder glacial phases and deglaciations. Coccolithophore warm-water taxa (wwt) indicate that MIS11c and MIS9e experienced warmer and more stable conditions throughout the whole photic zone compared to MIS13. MIS11 was a long-lasting warmer and stable interglacial characterized by a climate optimum during MIS11c when a more prominent influence of the subtropical front at the site is inferred. The wwt pattern also suggests distinct interstadial and stadial events lasting about 4-10 kyr. The glacial increases of Gephyrocapsa margereli-G. muellerae 3-4 µm along with higher values of Corg, additionally supported by the total alkenone abundance at Site U1313, indicate more productive surface waters, likely reflecting the migration of the polar front into the mid-latitude North Atlantic. Distinctive peaks of G. margereli-muellerae (> 4 µm), C. pelagicus pelagicus, Neogloboquadrina pachyderma left coiling, and reworked nannofossils, combined with minima in total nannofossil accumulation rate, are tracers of Heinrich-type events during MIS12 and MIS10. Additional Heinrich-type events are suggested during MIS12 and MIS14 based on biotic proxies, and we discuss possible iceberg sources at these times. Our results improve the understanding of mid-Brunhes paleoclimate and the impact on phytoplankton diversity in the mid-latitude North Atlantic region.
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The first appearance of skeletal metazoans in the late Ediacaran (~550 million years ago; Ma) has been linked to the widespread development of oxygenated oceanic conditions, but a precise spatial and temporal reconstruction of their evolution has not been resolved. Here we consider the evolution of ocean chemistry from ~550 to ~541 Ma across shelf-to-basin transects in the Zaris and Witputs Sub-Basins of the Nama Group, Namibia. New carbon isotope data capture the final stages of the Shuram/Wonoka deep negative C-isotope excursion, and these are complemented with a reconstruction of water column redox dynamics utilising Fe-S-C systematics and the distribution of skeletal and soft-bodied metazoans. Combined, these inter-basinal datasets provide insight into the potential role of ocean redox chemistry during this pivotal interval of major biological innovation. The strongly negative d13C values in the lower parts of the sections reflect both a secular, global change in the C-isotopic composition of Ediacaran seawater, as well as the influence of 'local' basinal effects as shown by the most negative d13C values occurring in the transition from distal to proximal ramp settings. Critical, though, is that the transition to positive d13C values postdates the appearance of calcified metazoans, indicating that the onset of biomineralization did not occur under post-excursion conditions. Significantly, we find that anoxic and ferruginous deeper water column conditions were prevalent during and after the transition to positive d13C that marks the end of the Shuram/Wonoka excursion. Thus, if the C isotope trend reflects the transition to global-scale oxygenation in the aftermath of the oxidation of a large-scale, isotopically light organic carbon pool, it was not sufficient to fully oxygenate the deep ocean. Both sub-basins reveal highly dynamic redox structures, where shallow, inner ramp settings experienced transient oxygenation. Anoxic conditions were caused either by episodic upwelling of deeper anoxic waters or higher rates of productivity. These settings supported short-lived and monospecific skeletal metazoan communities. By contrast, microbial (thrombolite) reefs, found in deeper inner- and mid-ramp settings, supported more biodiverse communities with complex ecologies and large skeletal metazoans. These long-lived reef communities, as well as Ediacaran soft-bodied biotas, are found particularly within transgressive systems, where oxygenation was persistent. We suggest that a mid-ramp position enabled physical ventilation mechanisms for shallow water column oxygenation to operate during flooding and transgressive sea-level rise. Our data support a prominent role for oxygen, and for stable oxygenated conditions in particular, in controlling both the distribution and ecology of Ediacaran skeletal metazoan communities.
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The distribution of calcareous dinoflagellate cysts in surface sediments from the Mediterranean Sea was quantitatively analysed. The samples contain 11 cyst species and the vegetative coccoid Thoracosphaera heimii. Cyst abundance increases towards the deeper parts of the basins and is generally higher in the eastern Mediterranean Sea. Three major distribution characteristics exist: (1) different assemblages in oceanic and neritic regions, (2) little agreement with the associations of areas studied so far like the Atlantic Ocean, and (3) a unique oceanic assemblage in the eastern Mediterranean Sea. A gradual change in cyst assemblages from the western to the eastern Mediterranean Sea was observed and statistically compared with the main environmental gradients in the upper water column. Temperature, nitrate concentration and possibly salinity appear to be the most important factors controlling cyst production. Three groups containing cysts with similar environmental preferences can be distinguished: (1) an eastern Mediterranean group related to relatively high temperature and salinity but low nitrate concentration, (2) a group of more or less consistently abundant cosmopolitan species tolerating or even preferring relatively low temperature and salinity but high nitrate concentration, and (3) a group containing species that are possibly adapted to neritic environments and have probably been transported from coastal areas into the studied regions. In contrast to other calcareous plankton, calcareous dinoflagellate cysts correlate strongly with the main environmental gradients in the Mediterranean Sea, bearing a high potential for palaeoenvironmental reconstructions.
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Coccolithophores, a key phytoplankton group, are one of the most studied organisms regarding their physiological response to ocean acidification/carbonation. The biogenic production of calcareous coccoliths has made coccolithophores a promising group for paleoceanographic research aiming to reconstruct past environmental conditions. Recently, geochemical and morphological analyses of fossil coccoliths have gained increased interest in regard to changes in seawater carbonate chemistry. The cosmopolitan coccolithophore Emiliania huxleyi (Lohm.) Hay and Mohler was cultured over a range of pCO2 levels in controlled laboratory experiments under nutrient replete and nitrogen limited conditions. Measurements of photosynthesis and calcification revealed, as previously published, an increase in particulate organic carbon production and a moderate decrease in calcification from ambient to elevated pCO2. The enhancement in particulate organic carbon production was accompanied by an increase in cell diameter. Changes in coccolith volume were best correlated with the coccosphere/cell diameter and no significant correlation was found between the coccolith volume and the particulate inorganic carbon production. The conducted experiments revealed that the coccolith volume of E. huxleyi is variable with aquatic CO2 concentration but its sensitivity is rather small in comparison with its sensitivity to nitrogen limitation. Comparing coccolith morphological and geometrical parameters like volume, mass and size to physiological parameters under controlled laboratory conditions is an important step to understand variations in fossil coccolith geometry.
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Background: Octopods have successfully colonised the world's oceans from the tropics to the poles. Yet, successful persistence in these habitats has required adaptations of their advanced physiological apparatus to compensate impaired oxygen supply. Their oxygen transporter haemocyanin plays a major role in cold tolerance and accordingly has undergone functional modifications to sustain oxygen release at sub-zero temperatures. However, it remains unknown how molecular properties evolved to explain the observed functional adaptations. We thus aimed to assess whether natural selection affected molecular and structural properties of haemocyanin that explains temperature adaptation in octopods. Results: Analysis of 239 partial sequences of the haemocyanin functional units (FU) f and g of 28 octopod species of polar, temperate, subtropical and tropical origin revealed natural selection was acting primarily on charge properties of surface residues. Polar octopods contained haemocyanins with higher net surface charge due to decreased glutamic acid content and higher numbers of basic amino acids. Within the analysed partial sequences, positive selection was present at site 2545, positioned between the active copper binding centre and the FU g surface. At this site, methionine was the dominant amino acid in polar octopods and leucine was dominant in tropical octopods. Sites directly involved in oxygen binding or quaternary interactions were highly conserved within the analysed sequence. Conclusions: This study has provided the first insight into molecular and structural mechanisms that have enabled octopods to sustain oxygen supply from polar to tropical conditions. Our findings imply modulation of oxygen binding via charge-charge interaction at the protein surface, which stabilize quaternary interactions among functional units to reduce detrimental effects of high pH on venous oxygen release. Of the observed partial haemocyanin sequence, residue 2545 formed a close link between the FU g surface and the active centre, suggesting a role as allosteric binding site. The prevalence of methionine at this site in polar octopods, implies regulation of oxygen affinity via increased sensitivity to allosteric metal binding. High sequence conservation of sites directly involved in oxygen binding indicates that functional modifications of octopod haemocyanin rather occur via more subtle mechanisms, as observed in this study.