Coarse-graining strategies in polymer solutions

We review a coarse-graining strategy (multiblob approach) for polymer solutions in which groups of monomers are mapped onto a single atom (a blob) and effective blob-blob interactions are obtained by requiring the coarse-grained model to reproduce some coarse-grained features of the zero-density isolated-chain structure. By tuning the level of coarse graining, i.e. the number of monomers to be mapped onto a single blob, the model should be adequate to explore the semidilute regime above the collapse transition, since in this case the monomer density is very small if chains are long enough. The implementation of these ideas has been previously based on a transferability hypothesis, which was not completely tested against full-monomer results (Pierleoni et al., J. Chem. Phys, 127, 171102 (2007)). We study different models proposed in the past and we compare their predictions to full-monomer results for the chain structure and the thermodynamics in the range of polymer volume fractions \Phi between 0 and 8. We find that the transferability assumption has a limited predictive power if a thermodynamically consistent model is required. We introduce a new tetramer model parametrized in such a way to reproduce not only zero-density intramolecular and intermolecular two-body probabilities, but also some intramolecular three-body and four-body distributions. We find that such a model correctly predicts three-chain effects, the structure and the thermodynamics up to \Phi ~ 2, a range considerably larger than that obtained with previous simpler models using zero-density potentials. Our results show the correctness of the ideas behind the multiblob approach but also that more work is needed to understand how to develop models with more effective monomers which would allow us to explore the semidilute regime at larger chain volume fractions.Comment: 33 pages, 19 figures, submitted to Soft Matte

Fractal aggregation of porcine fumarase induced by free radicals

The present study demonstrates that H2O2 and OH center dot cause fibril aggregation and catalytic inactivation of porcine fumarase. In the aggregated (oxidized) enzyme, modifications in both secondary and tertiary protein structure occur and the enzyme aggregation obeys to fractal geometry. We then collected information on the fractal dimension and on the size and shape of fumarase aggregates by using Synchrotron Radiation (SR) Small Angle X-ray Scattering (SAXS) analysis. The geometrical self-similarity assessment of aggregates has been revealed by both AFM and SEM measurements at different scale of magnification. Micrographs collected remarkably demonstrate that the oxidized enzyme shows dendn'tic fractal structure over a large range of sizes. (c) 2007 Published by Elsevier B.V

Effects of carotenoid supplementation on colour expression, oxidative stress and body mass in rehabilitated captive adult kestrels (Falco tinnunculus)

Carotenoids are considered a limited resource for animals because they are not synthesised by the body. Birds use carotenoids, mainly xanthophylls, for physiological functions, such as anti-oxidant activity, and for colour expression; hence, they need to shunt carotenoids between competitive demands. Recent studies suggest that the anti-oxidant role of xanthophylls might not be as important as previously thought and that at high concentrations they may, in fact, acquire pro-oxidant properties. In this work, we studied the effects of a moderate xanthophyll supplementation (115 mg of carotenoids/kg diet/day; 4 weeks) on serum carotenoids, serum concentration of reactive oxygen metabolites (ROMs), serum anti-oxidant capacity (OXY), the degree of oxidative stress (OS; ROMs/OXY x 1,000), body mass, and skin colour, in rehabilitated captive adult Eurasian kestrels (Falco tinnunculus). The supplementation caused increased levels of serum carotenoids (similar to 90%), ROMs (similar to 82%), OS (similar to 115%) and an immediate loss of body mass (similar to 6.2%), but it did not affect OXY and tarsi skin hue. The red (similar to 16%) and yellow (similar to 15%) colorimetric components were increased after the first week of supplementation and the effect persisted during the rest of the experiment. Two months after the end of supplementation, serum carotenoids, OS and ROMs returned to baseline levels, however the body mass did not. Our findings suggest that, above a certain physiological threshold, carotenoids can cause detrimental effects. This is relevant for the trade-off between expression of sexual signals and the costs of maintaining/producing them

Analysis of degraded papers by means of non-destructive spectroscopic techniques".

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ATRP synthesis and association properties of temperature responsive dextran copolymers grafted with poly(N-isopropylacrylamide)

Temperature responsive copolymers of dextran grafted with poly(N-isopropylacrylamide) (Dex-g-PNIPAAM) were prepared by atom transfer radical polymerization (ATRP) in homogeneous mild conditions without using protecting group chemistry. Dextran macroinitiator was synthesized by reaction of dextran with 2-chloropropionyl chloride at room temperature in DMF containing 2% LiCl. ATRP was carried out in DMF: water 50:50 (v/v) mixtures at room temperature with CuBr/Tris(2-dimethylaminoethyl)amine (Me(6)TREN) as catalyst. Several grafted copolymers with well defined number and length of low polydispersity grafted chains were prepared. Temperature induced association properties in aqueous solution were studied as a function of temperature and polymer concentration by dynamic light scattering, fluorescence spectroscopy and atomic force microscopy (AFM). LCST, ranging from 35 to 41 degrees C, was significantly affected by number and length of grafted chains. The fine tuning of LCST around body temperature is an important characteristic not obtainable by conventional radical grafting of PNIPAAM. Well defined spherical nanoparticles were formed above the LCST of PNIPAAM. Hydrodynamic diameter was in the range 73-98 nm. (C) 2009 Elsevier Ltd. All rights reserved