17 resultados para Monatomic chains

em Repositório Institucional UNESP - Universidade Estadual Paulista "Julio de Mesquita Filho"


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In order to help elucidate the evolution of alpha-globins, the complete cDNA and amino acid sequences of Geochelone carbonaria and Geochelone denticulata land turtles alpha-D chains have been described. In G. carbonaria, the cDNA is 539 bp with ATG start codon located at position 46, TGA stop codon at position 469 and AATAAA polyadenylation signal at position 520. In G. denticulata, the cDNA is 536 bp with ATG start codon located at position 46, TGA stop codon at position 469 and AATAAA polyadenylation signal at position 517. Both cDNAs codify 141 amino acid residues, differing from each other in only four amino acid residues. When comparing with human Hb alpha-chain, alterations in important regions can be noted: alpha110 Ala-Gly, alpha114 Pro-Gly, alpha117 Phe-Tyr and alpha122 His-Gln. There is a high homology between the amino acids of these turtles when compared with chicken alpha-D chains, progressively decreasing when compared with human, crocodile, snake, frog and fish alpha-chains. Phylogenetic analysis of alpha-D chains shows that those of turtles are closer to those of birds than to snakes and lizards. (C) 2002 Elsevier B.V. All rights reserved.

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Meiosis and (or) mitosis of males and females of Cryptotermes brevis, Eucryptotermes wheeleri, and Neotermes fulvescens, all of them from the neotropical region, were analyzed. Cryptotermes brevis showed a similar karyotype to that obtained by other authors for specimens of the neartic and Australian regions (2n = 36 for females and 2n = 37 for males, with XX and XYY sex mechanisms, respectively). Eucryptotermes wheeleri, the only species that has been described in this genus, showed the lowest number of chromosomes reported for Isoptera (2n = 22) until now. The male meiosis of this species presents a linear chain of six sex chromosomes, three of them being X and three of them Y chromosomes. Neotermes fulvescens showed a diploid number of 40 for males and 42 for females and, in the first male meiosis, two linear chains of chromosomes, both related to sex. One of the chains, named A, presented nine chromosomes and the other, named B, seven chromosomes. Hypotheses to explain these mechanisms are formulated in this paper and putative ancestral relationships with other species of Kalotermitidae are presented.

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Resin solvation properties affect the efficiency of the coupling reactions in solid-phase peptide synthesis. Here we report a novel approach to evaluate resin solvation properties, making use of spin label electron paramagnetic resonance (EPR) spectroscopy. The aggregating VVLGAAIV and ING sequences were assembled in benzhydrylamine-resin with different amino group contents (up to 2.6 mmol/g) to examine the extent of chain association within the beads. These model peptidyl-resins were first labeled at their N-terminus with the amino acid spin label 2,2,6,6-tetramethylpiperidine-N-oxyl-4-amino-4-carboxylic acid (Toac). Their solvation properties in different solvents were estimated, either by bead swelling measurement or by assessing the dynamics of their polymeric matrixes through the analysis of Toac EPR spectra, and were correlated with the yield of the acylation reaction. In most cases the coupling rate was found to depend on bead swelling. Comparatively, the EPR approach was more effective. Line shape analysis allowed the detection of more than one peptide chain population, which influenced the reaction. The results demonstrated the unique potential of EPR spectroscopy not only for improving the yield of peptide synthesis, even in challenging conditions, but also for other relevant polymer-supported methodologies in chemistry and biology.

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We solve the spectrum of the closed Temperley-Lieb quantum spin chains using the coordinate Bethe ansatz. These models are invariant under the quantum group U-q[sl(2)].

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We solve the spectrum of quantum spin chains based on representations of the Temperley-Lieb algebra associated with the quantum groups U-q(X-n) for X-n = A(1), B-n, C-n and D-n. The tool is a modified version of the coordinate Bethe ansatz through a suitable choice of the Bethe states which give to all models the same status relative to their diagonalization. All these models have equivalent spectra up to degeneracies and the spectra of the lower-dimensional representations are contained in the higher-dimensional ones. Periodic boundary conditions, free boundary conditions and closed nonlocal boundary conditions are considered. Periodic boundary conditions, unlike free boundary conditions, bleak quantum group invariance. For closed nonlocal cases the models are quantum group invariant as well as periodic in a certain sense.

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Polyampholyte copolymers containing both positive and negative monomers regularly dispersed along the chain were studied. The Monte Carlo method was used to simulate chains with charged monomers interacting by screened Coulomb potential. The neutral polyampholyte chains collapse due to the attractive electrostatic interactions. The nonneutral chains are in extended conformations due to the repulsive polyelectrolyte effects that dominate the attractive polyampholyte interactions. The results are in good agreement with experiment.

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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Infrared and photoluminescence spectroscopies have been used to investigate the local environment of the Eu3+ ions in luminescent sol-gel derived materials-di-ureasils-based on a hybrid framework represented by U(600). This host is composed of a siliceous backbone grafted, through urea cross-links, to both ends of polymer segments incorporating 8.5 oxyethylene repeat units. The active centers have been introduced as europium perchlorate, Eu(ClO4)3. Samples with compositions n = 232, 62, 23, 12, and 6 (where n denotes the ratio of (OCH2CH2) moieties per lanthanide ion) have been examined. The combination of the information retrieved from the analysis of characteristic bands of the FTIR spectra-the perchlorate and the Amide I/Amide II features-with that obtained from the photoluminescence data demonstrates that at compositions n = 232 and 62 the anions are free, whereas the Eu3+ ions are complexed by the heteroatoms of the polyether chains. At higher salt concentration, the cations are bonded, not only to the ClO4 - ions, but also to the ether oxygen atoms of the organic segments and to the carbonyl oxygen atoms of the urea linkages. The dual behavior of U(600) with respect to cation coordination has been attributed to the presence in this nanohybrid of strong hydrogen-bonded urea-urea structures, which, at low salt content, cannot be disrupted, thus inhibiting the formation of Eu3+-O=C(urea) contacts and promoting the interaction between the lanthanide ions and the (OCH2CH2) moieties. The present work substantiates the claim that the activation of the coordinating sites of the di-ureasil framework can be tuned by varying either the guest salt concentration at constant chain length or the length of the.organic segments at constant salt concentration. This relevant property opens challenging new prospects in the fields of application of this class of hybrids. © 2001 American Chemical Society.

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Poly(p-phenylene vinylene) (PPV) derivatives are well known for their applications in polymer light emitting diodes (PLEDs). These derivatives are highly susceptible to photooxidation though, which is mainly caused by the scission of the vinyl double bond on the polymer backbone. In this work, we show that Langmuir-Blodgett (LB) films are less degraded than cast films of a PPV derivative (OC1OC6-PPV). Both films had similar thickness (∼50 nm) to allow for a more realistic comparison. Photodegradation experiments were carried out by illuminating the films with white light from a halogen lamp (50W, 12 V), placed at a fixed dstance from the sample. The decay was monitored by UV-Vis and FTIR spectroscopies. The results showed that cast films are completely degraded in ca. 300 min, while LB took longer times, ca. 1000 min, i.e. 3 times the values for the cast films. The degradation process occurs in at least two stages, the rates of which were calculated assuming that the reaction follows a first order kinetics. The characteristic times for the first stage were 3.6×10-2 and 1.3×10-3 min-1 for cast and LB films, respectively. For the second stage the characteristic times were 5.6×10-2 and 5.0×10 -3 min-1. The differences can be attributed to the more compact morphology in the LB than in the cast films. With a compact morphology the diffusion of oxygen in the LB film is hampered and this causes a delay in the degradation process.

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Introduction: Elastomeric materials are considered important sources of orthodontic forces. Objective: To assess force degradation over time of four commercially available orthodontic elastomeric chains (Morelli, Ormco, TP and Unitek). Methods: The synthetic elastics were submerged in 37 oC synthetic saliva and stretched by a force of 150 g (15 mm - Morelli and TP; 16mm - Unitek and Ormco). With a dynamometer, the delivered force was evaluated at different intervals: 30 minutes, 7 days, 14 days and 21 days. The results were subjected to ANOVA and Tukey's test. Results: There was a force decay between 19% to 26.67% after 30 minutes, and 36.67% to 57% after 21 days of activation. Conclusions: TP elastomeric chains exhibited the smallest percentage of force decay, with greater stability at all time intervals tested. Meanwhile, the Unitek chains displayed the highest percentage of force degradation, and no statically significant difference was found in force decay between Ormco and Morelli elastomeric chains during the study period.

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Modelling polymers with side chains is always a challenge once the degrees of freedom are very high. In this study, we present a successful methodology to model poly[2-methoxy-5-(2′-ethyl-hexyloxy)-p-phenylenevinylene] (MEH-PPV) and poly[3-hexylthiophene] (P3HT) in solutions, taking into account the influence of side chains on the polymer conformation. Molecular dynamics and semi-empirical quantum mechanical methods were used for structure optimisation and evaluation of optical properties. The methodology allows to describe structural and optical characteristics of the polymers in a satisfactory way, as well as to evaluate some usual simplifications adopted for modelling these systems. Effective conjugation lengths of 8-14.6 and 21 monomers were obtained for MEH-PPV and P3HT, respectively, in accordance with experimental findings. In addition, anti/syn conformations of these polymers could be predicted based on intrinsic interactions of the lateral branches. © 2013 Copyright Taylor and Francis Group, LLC.

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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)