956 resultados para quaternary structure changes


Relevância:

40.00% 40.00%

Publicador:

Resumo:

Department of Marine Geology & Geophysics, Cochin University of Science and Technology

Relevância:

40.00% 40.00%

Publicador:

Resumo:

Globally, plant-pollinator communities are subject to a diverse array of perturbations and in many temperate and semi-arid systems fire is a dominant structuring force. We present a novel and highly integrated approach, which quantifies, in parallel, the response to fire of pollinator communities, floral communities and floral reward structure. Mt Carmel, Israel is a recognised bee-flower biodiversity hotspot, and using a chronosequence of habitats with differing post-fire ages, we follow the changes in plant-pollinator community organisation from immediately following a burn until full regeneration of vegetation. Initially, fire has a catastrophic effect on these communities, however, recovery is rapid with a peak in diversity of both flowers and bees in the first 2 years post-fire, followed by a steady decline over the next 50 years. The regeneration of floral communities is closely matched by that of their principal pollinators. At the community level we quantify, per unit area of habitat, key parameters of nectar and pollen forage known to be of importance in structuring pollinator communities. Nectar Volume, nectar water content, nectar concentration and the diversity of nectar foraging niches are all greatest immediately following fire with a steady decrease as regeneration proceeds. Temporal changes in energy availability for nectar, pollen, total energy (nectar + pollen) and relative importance of pollen to nectar energy show a similar general decline with site age, however, the pattern is less clear owing to the highly patchy distribution of floral resources. Changes in floral reward structure reflect the general shift from annuals (generally low-reward open access flowers) to perennials (mostly high-reward and restricted access flowers) as post-fire regeneration ensues. The impact of fire on floral communities and their associated rewards have clear implications for pollinator community structure and we discuss this and the role of other disturbance factors on these systems.

Relevância:

40.00% 40.00%

Publicador:

Resumo:

The degradation of bisphenol A and nonylphenol involves the unusual rearrangement of stable carboncarbon bonds. Some nonylphenol isomers and bisphenol A possess a quaternary alpha-carbon atom as a common structural feature. The degradation of nonylphenol in Sphingomonas sp. strain TTNP3 occurs via a type II ipso substitution with the presence of a quaternary alpha-carbon as a prerequisite. We report here a new degradation pathway of bisphenol A. Consequent to the hydroxylation at position C-4, according to a type 11 ipso substitution mechanism, the C-C bond between the phenolic moiety and the isopropyl group of bisphenol A is broken. Besides the formation of hydroquinone and 4-(2-hydroxypropan-2-yl) phenol as the main metabolites, further compounds resulting from molecular rearrangements consistent with a carbocationic intermediate were identified. Assays with resting cells or cell extracts of Sphingomonas sp. strain TTNP3 under an 18 02 atmosphere were performed. One atom of 180, was present in hydroquinone, resulting from the monooxygenation of bisphenol A and nonylphenol. The monooxygenase activity was dependent on both NADPH and flavin adenine dinucleotide. Various cytochrome P450 inhibitors had identical inhibition effects on the conversion of both xenobiotics. Using a mutant of Sphingomonas sp. strain TTNP3, which is defective for growth on nonylphenol, we demonstrated that the reaction is catalyzed by the same enzymatic system. In conclusion, the degradation of bisphenol A and nonylphenol is initiated by the same monooxygenase, which may also lead to ipso substitution in other xenobiotics containing phenol with a quaternary a-carbon.

Relevância:

40.00% 40.00%

Publicador:

Resumo:

[VIVO(acac)(2)] reacts with an equimolar amount of benzoyl hydrazone of 2-hydroxyacetophenone (H2L1) or 5-chloro-2-hydroxyacetophenone (H2L2) in the presence of excess pyridine (py) in methanol to produce the quaternary [(VO)-O-V(L-1)(OCH3)(py)] (1) and [(VO)-O-V(L-2)(OCH3)(py)] (2) complexes, respectively, while under similar condition, the benzoyl hydrazones of 2-hydroxy-5-methylacetophenone (H2L3) and 2-hydroxy-5-methoxyacetophenone (H2L4) afforded only the methoxy bridged dimeric [(VO)-O-V(L-3/L-4)(OCH3)](2) complexes. The X-ray structural analysis of 1 and 2 indicates that the geometry around the metal is distorted octahedral where the three equatorial positions are occupied by the phenolate-O, enolate-O and the imine-N of the fully deprotonated hydrazone ligand in its enolic form and the fourth one by a methoxide-O atom. An oxo-O and a pyridine-N atom occupy two axial positions. Quaternary complexes exhibit one quasi-reversible one-electron reduction peak near 0.25 V versus SCE in CH2Cl2 and they decompose appreciably to the corresponding methoxy bridged dimeric complex in CDCl3 solution as indicated by their H-1 NMR spectra. These quaternary VO3+ complexes are converted to the corresponding V2O34+-complexes simply on refluxing them in acetone and to the VO2+-complexes on reaction with KOH in methanol. An equimolar amount of 8-hydroxyquinoline (Hhq) converts these quaternary complexes to the ternary [(VO)-O-V(L)(hq)] complexes in CHCl3. (C) 2009 Elsevier B. V. All rights reserved.

Relevância:

40.00% 40.00%

Publicador:

Resumo:

Changes in texture, microstructure, colour and protein solubility of Thai indigenous and broiler chicken Pectoralis muscle stripes cooked at different temperatures were evaluated. The change in shear value of both chicken muscles was a significant increase from 50 to 80 degrees C but no change from 80 to 100 degrees C. A significant decrease in fibre diameter was obtained in samples heated to an internal temperature of 60 degrees C and the greatest shrinkage of sarcomeres was observed with internal temperatures of 70-100 and 80-100 C for broiler and indigenous chicken muscles, respectively (P < 0.05). Cooking losses of indigenous chicken muscles increased markedly in the temperature range 80-100 C and were significantly higher than those of the broiler (P < 0.001). With increasing temperature, from 50 to 70 degrees C, cooked chicken muscle became lighter and yellower. Relationships between changes in sarcomere length, fibre diameter, shear value, cooking loss and solubility of muscle proteins were evaluated. It was found that the solubility of muscle protein was very highly correlated with the texture of cooked broiler muscle while sarcomere length changes and collagen solubility were important factors influencing the cooking loss and texture of cooked indigenous chicken muscle. (c) 2004 Elsevier Ltd. All rights reserved.

Relevância:

40.00% 40.00%

Publicador:

Resumo:

Much of the ongoing discussion regarding synchrony or bipolar asynchrony of paleoclimate events has centered on the timing and structure of the last glacial termination in the southern mid- latitudes, in particular the southwestern Patagonian region (50�e55�S). Its location adjacent to the Drake Passage andnear the southern margin of the southern westerly winds (SWW) allows examining the postulated links between the Southern Oceane SWW coupled system and tmospheric CO2 variations through the last glacial termination. Results from two sites located in the Última Esperanza area (52�S) allow us to infer SWW-driven changes in hydrologic balance during this critical time interval. These findings indicate peatland development under temperate/wet conditions between 14,600 and 14,900 cal yr BP, followed by cooling and a lake transgressive phase that led to a shallow lake during the early part of the Antarctic Cold Reversal (ACR, 13,600-14,600 cal yr BP), followed in turn by a deeper lake and modest warming during Younger Dryas time (YD, 11,800-13,000 cal yr BP), superseded by terrestrialization and forest expansion at the beginning of the Holocene. We propose that the SWW (i) strengthened and shifted northward during ACR time causing a precipitation rise in northwestern and southwestern Patagonia coeval with mid- and high-latitude cooling and a halt in the deglacial atmospheric CO2 rise; (ii) shifted southward during YD time causing a precipitation decline/increase in NW/SW Patagonia, respectively, high-latitude warming, and invigorated CO2 release from the Southern Ocean; (iii) became weaker between 10,000 and 11,500 cal yr BP causing a precipitation decline throughout Patagonia, concurrent with peak mid- and high-latitude temperatures and atmospheric CO2 concentrations.

Relevância:

40.00% 40.00%

Publicador:

Resumo:

Human nerve growth factor-induced B (NGFI-B) is a member of the NR4A subfamily of orphan nuclear receptors (NRs). Lacking identified ligands, orphan NRs show particular co-regulator proteins binding properties, different from other NRs, and they might have a non-classical quaternary organization. A body of evidence suggests that NRs recognition of and binding to ligands, DNA, homo- and heterodimerization partners and co-regulator proteins involve significant conformational changes of the NR ligand-binding domains (LBDs). To shed light on largely unknown biophysical properties of NGFI-B, here we studied structural organization and unfolding properties of NGFI-B ligand (like)-binding domain induced by chemical perturbation. Our results show that NGFI-B LBD undergoes a two-state guanidine hydrochloride (GndHCl) induced denaturation, as judged by changes in the a-helical content of the protein monitored by circular dichroism spectroscopy (CD). In contrast, changes in the tertiary structure of NGFI-B LBD, reported by intrinsic fluorescence, reveal a clear intermediate state. Additionally, SAXS results demonstrate that the intermediate observed by intrinsic fluorescence is a partially folded homodimeric structure, which further unfolds without dissociation at higher GndHCl concentrations. This partially unfolded dimeric assembly of NGFI-B LBD might resemble an intermediate that this domain access momentarily in the native state upon interactions with functional partners. (C) 2008 Elsevier B.V. All rights reserved.

Relevância:

40.00% 40.00%

Publicador:

Resumo:

The stratigraphic subdivision and correlation of dune deposits is difficult, especially when age datings are not available. A better understanding of the controls on texture and composition of eolian sands is necessary to interpret ancient eolian sediments. The Imbituba-Jaguaruna coastal zone (Southern Brazil, 28 degrees-29 degrees S) stands out due to its four well-preserved Late Pleistocene (eolian generation 1) to Holocene eolian units (eolian generations 2, 3, and 4). In this study, we evaluate the grain-size and heavy-mineral characteristics of the Imbituba-Jaguartma eolian units through statistical analysis of hundreds of sediment samples. Grain-size parameters and heavy-mineral content allow us to distinguish the Pleistocene from the Holocene units. The grain size displays a pattern of fining and better sorting from generation 1 (older) to 4 (younger), whereas the content of mechanically stable (dense and hard) heavy minerals decreases from eolian generation 1 to 4. The variation in grain size and heavy-mineral content records shifts in the origin and balance (input versus output) of eolian sediment supply attributable mainly to relative sea-level changes. Dunefields submitted to relative sea-level lowstand conditions (eolian generation 1) are characterized by lower accumulation rates and intense post-depositional dissection by fluvial incision. Low accumulation rates favor deflation in the eolian system, which promotes concentration of denser and stable heavy minerals (increase of ZTR index) as well as coarsening of eolian sands. Dissection involves the selective removal of finer sediments and less dense heavy minerals to the coastal source area. Under a high rate of relative sea-level rise and transgression (eolian generation 2), coastal erosion prevents deflation through high input of sediments to the coastal eolian source. This condition favors dunefield growth. Coastal erosion feeds sand from local sources to the eolian system. including sands from previous dunefields (eolian generation 1) and from drowned incised valleys. Therefore, dunefields corresponding to transgressive phases inherit the grain-size and heavy-mineral characteristics of previous dunefields, leading to selective enrichment of finer sands and lighter minerals. Eolian generations 3 and 4 developed during a regressive-progradational phase (Holocene relative sea level highstand). The high rate of sediment supply during the highstand phase prevents deflation. The lack of coastal erosion favors sediment supply from distal sources (fluvial sediments rich in unstable heavy minerals). Thus, dunefields of transgressive and highstand systems tracts may be distinguished from dunefields of the lowstand systems tract through high rates of accumulation (low deflation) in the former. The sediment source of the transgressive dunefields (high input of previously deposited coastal sands) differs from that of the highstand dunefields (high input of fluvial distal sands). Based on this case study, we propose a general framework for the relation between relative sea level, sediment supply and the texture and mineralogy of eolian sediments deposited in siliciclastic wet coastal zones similar to the Imbituba-Jaguaruna coast (C) 2009 Elsevier B.V. All rights reserved.

Relevância:

40.00% 40.00%

Publicador:

Resumo:

Hybrid films from poly (methylmethacrylate) (PMMA) and dioctadecyldimethylammonium bromide (DODAB), cetyltrimethylammonium bromide (CTAB), or tetrapropylammonium bromide (TPAB) were characterized by determination of wettability, ellipsometry, atomic force microscopy, active compounds diffusion to water, X-ray photoelectron spectroscopy (XPS) with determination of atomic composition on the films surface, and biocidal activity against Pseudomonas aeruginosa or Staphylococcus aureus. QAC mobility in the films increased from DODAB to CTAB to TPAB. Diffusion and optimal hydrophobic hydrophilic balance imparted the highest bioactivity to CTAB. DODAB sustained immobilization at the film surface killed bacteria upon contact. TPAB ability to diffuse was useless because of its unfavorable hydrophobic hydrophilic balance for bioactivity.

Relevância:

40.00% 40.00%

Publicador:

Resumo:

Sabatini (2002) and Roberts and Wibbles (1999) Pointed Out That Voters in Latin American Countries are no Longer Choosing According to Their Ideological Preferences. Ashworth and Heyndels (2002) Showed That the Tax Choice In Oecd Countries Does not Follow the Ideological Pattern of Party Preferences. the Most Robust Result of This Work Shows That the Tax Choice in Latin American Countries Still Depends on This Ideological Preference. We Also Verified That Changes in the Tax Structure Depend on Changes Both in the Tax Burden and the Openness of the Economy

Relevância:

40.00% 40.00%

Publicador:

Resumo:

This paper argues that changes in the returns to occupational tasks have contributed to changes in the wage distribution over the last three decades. Using Current Population Survey (CPS) data, we first show that the 1990s polarization of wages is explained by changes in wage setting between and within occupations, which are well captured by tasks measures linked to technological change and offshorability. Using a decomposition based on Firpo, Fortin, and Lemieux (2009), we find that technological change and deunionization played a central role in the 1980s and 1990s, while offshorability became an important factor from the 1990s onwards.

Relevância:

40.00% 40.00%

Publicador:

Resumo:

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)