5 resultados para Population Synthesis

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


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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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This work demonstrates, for the first time. a time-resolved electron paramagnetic resonance (EPR) monitoring of a chemical reaction occurring in a polymeric structure. The progress of the coupling of a N-alpha-tert-butyloxycarbonyl-2.2.6.6-tetramethylpiperidine-1-oxyl-4-amino-4-carboxylic acid (Boc-TOAC) spin probe to a model peptide-resin was followed through EPR spectra. Progressive line broadening of EPR peaks was observed, indicative of an increased population of immobilized spin probe molecules attached to the solid support. The time for spectral stabilization of this process coincided with that determined in a previous Coupling study. thereby validating this in situ quantitative monitoring of the reaction. In addition, the influence of polymer swelling degree and solvent viscosity, as well as of the steric hindrance within beads. on the rate of coupling reaction was also addressed. A deeper evaluation of the latter effect was possible by determining unusual polymer parameters such as the average site-site distance and site-concentration within resin beads in each solvent system. (c) 2006 Elsevier Ltd. All rights reserved.

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Population parameters of the shrimp Xiphopenaeus kroyeri (Heller, 1862) (sex ratio, length-frequency distributions (carapace length, CL), growth, lifespan, size of sexual maturity, spawning and recruitment) were analyzed in a long-term study from January 1998 through June 2003. The data on these parameters were collected and analyzed to test the hypothesis that the main period of juvenile recruitment in the bay coincides with the period of fishery closures currently designated by the Brazilian Institute of Environment and Renewable Natural Resources. Monthly collections were conducted along the southeastern Brazilian coast, using a shrimp fishing boat with “double-rig” nets sampling at stations up to 40 m depth. Sex ratios were female-biased only in zones with high reproductive activity such as in stations deeper than 15 m (χ2 test, p<0.05). The mean size of males and females was 15.3 ± 3.1 mm CL and 16.2 ± 4.7 mm CL, respectively, with size at sexual maturity estimates (CL50) of 14.8 mm for males and 15.5 mm for females. Mean growth curves provided estimates of CL∞ = 29.31 mm, k = 0.009/day, t0=−0.25 and CL∞ = 35.33 mm, k = 0.006/day, t0=−0.23 for males and females, respectively, and average lifespans of 1.35 for males and 2.12 years for females. Recruitment and abundances of reproductive females were highly correlated with the environmental factors such as higher water temperature and finer-grained bottom sediment (canonical correlation, r=0.63, p<0.001). The reproductive peaks in February-April 1998, March-May 1999 and February-May 2002 were followed by recruitment peaks in May-July 1998, July-September 1999 and April-June 2002, respectively. Thus, the proposed period of fisheries closure (March to May) does not coincide with the main recruitment periods observed for X. kroyeri.

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