Probing the internal environment of PVP networks generated by irradiation with different sources

Poly(N-vinyl-2-pyrrolidone) (PVP) hydrogels have been synthesised from the aqueous solutions of the same linear polymer by two different radiation sources: electron beams and UV rays. The present investigation couples conventional hydrogel characterisation techniques with the study of the partition equilibria, fluorescence behaviour and release of two different molecular probes, 1-anilino-8-naphthalene sulphonate (ANS) and Thioflavin T (ThT). The two probes have comparable molecular weight and different structural and optical properties. The ‘chemical’ networks produced upon irradiation in different experimental conditions presented quite distinctive mechanical spectra, yielded to different porous solids upon freeze-drying and showed specific rehydration ratios when ‘equilibrated’ in water. More interestingly, they offered ‘hydrophobic pockets’ to host the ANS molecules in a way that the probe is completely occluded from water, making it fluoresce. Conversely, the generated PVP networks did not show any specific affinity towards the hydrophilic ThT that was only barely untaken.     

Well-defined transition metal complexes with phosphorus and nitrogen ligands for 1,3-dienes polymerization

This article provides an overview on recent progress in the polymerization of 1,3-dienes catalyzed by transition metal complexes with phosphorus and nitrogen ligands. Polymers having different microstructures (cis-1,4; 1,2; mixed cis-1,4/1,2) and tacticity (iso- or syndiotactic) were obtained from various 1,3-dienes (1,3-butadiene, isoprene, 1,3-pentadienes, 1,3-hexadienes) depending on the catalyst used, clearly suggesting that the catalyst structure (i.e. metal nature, type of ligand) strongly affects the polymerization chemo- and stereoselectivity. However, as indicated by the results obtained in the polymerization of substituted butadienes, a fundamental role in determining the selectivity is also played by the type of monomer: polymers with different structure, some of them completely new, were obtained from different monomers with the same catalyst. All these observations permitted to confirm, and in some cases to improve, the knowledge on the diene polymerization mechanism.     

Antioxidant and spectroscopic studies of crosslinked polymers synthesized by grafting polymerization of ferulic acid

A novel, simple synthetic strategy for the preparation of crosslinked polymers with significant antioxidant properties is proposed. Ferulic acid (FA), a well‐known antioxidant compound, due to its reactivity toward free radical process, was inserted into a polymeric network with methacrylic acid (MAA) and ethylene glycole dimethacrylate acting as comonomer and crosslinker, respectively. All the reactants were simultaneously mixed in the polymerization feed and one‐pot radical reaction was carried out. Irregular microparticles were prepared by bulk polymerization and microspheres by precipitation polymerization. The materials were characterized by nuclear magnetic resonance–magic angle spinning (NMR‐MAS) studies, to verify effective FA insertion into polymeric networks, and by morphological, dimensional analyses, and water absorption measurement to study their superficial and swelling properties, respectively. Antioxidant properties of materials were evaluated by linoleic acid emulsion system–thiocyanate assay, determination of scavenging activity on DPPH radicals, determination of available phenolic groups in polymeric matrices, and determination of total antioxidant capacity. Copyright © 2009 John Wiley & Sons, Ltd.     

On the molecular origin of cold denaturation of globular proteins

A polypeptide chain can adopt very different conformations, a fundamental distinguishing feature of which is the water accessible surface area, WASA, that is a measure of the layer around the polypeptide chain where the center of water molecules cannot physically enter, generating a solvent-excluded volume effect. The large WASA decrease associated with the folding of a globular protein leads to a large decrease in the solvent-excluded volume, and so to a large increase in the configurational/translational freedom of water molecules. The latter is a quantity that depends upon temperature. Simple calculations over the -30 to 150 °C temperature range, where liquid water can exist at 1 atm, show that such a gain decreases significantly on lowering the temperature below 0 °C, paralleling the decrease in liquid water density. There will be a temperature where the destabilizing contribution of the polypeptide chain conformational entropy exactly matches the stabilizing contribution of the water configurational/translational entropy, leading to cold denaturation.     

Ground states of simple bodies that may undergo brittle fractures

Equilibrium states of elastic-brittle solids that may suffer nucleation of cracks in finite deformation setting are analyzed. Crack patterns are described in terms of appropriate Radon measures, namely curvature varifolds with boundary. A new form of the energy is presented: it includes terms associated with the curvature of margins and tips of possible cracks. Existence of minima of the energy is established in classes of pairs of deformation and families of varifolds. Configurational balances in weak form are determined with reference to generic curvature varifolds with boundary. They include non-standard terms associated with the curvatures involved in the energy. Pointwise balances of configurational actions are also evaluated in a special case: new pointwise balances at the tips and along the margins of the crack pattern emerge.     

Sequestration of some biogenic amines and poly(allyl)amine by high molecular weight polycarboxylic ligands in aqueous solution

The interactions of two high molecular weight polycarboxylic ligands [polyacrylic-co-maleic, MW = 70 kDa, and poly(methyl vinyl ether-co-maleic acid), MW = 15 kDa] with some polyamines [1,4-diaminobutane (or putrescine), histamine and poly(allyl)amine, MW = 15 kDa] were studied, at t = 25 °C and at low ionic strength (I = 0.015 mol L^? 1) by potentiometric measurements. For all investigated systems, the formation of (am)(L)H_i species was found (am = amine, L = polycarboxylic ligand, i = 1…4); the stability of polyammonium–polycarboxylate complexes is fairly high and the formation percentage of most species reaches ～ 90% in the experimental conditions (mmolar concentration of reactants). The dependence on temperature and ionic strength of the stability of polyamine–polycarboxylate species was studied using some semiempirical equations and enthalpy data for the protonation of both components. The sequestering ability of polyelectrolytes towards amines was modeled by a sigmoid Boltzman type equation and was defined by calculating the parameter pL₅₀ (the total ligand concentration, as ? log C_L, able to bind 50% of cation); this parameter gives an objective representation of this ability. The dependence of pL₅₀ on pH, ionic strength and temperature was studied too.     

A Density Functional Theory Study of Poly (vinyl chloride) (PVC) Free Radical Polymerization

Summary: Quantum chemistry was applied to the free radical polymerization of Vinyl Chloride with the aim of elucidating the reaction kinetics and especially the formation of structural defects and low molecular weight polymer. The radical reactions were studied using the Density Functional Theory. All calculations were performed with B3LYP functionals and in particular the 6-31G(d,p) basis set was selected to evaluate the exchange and correlation energies. The computational method was first validated by predicting the rate constant of the propagation step and comparing the calculated values to experimental ones. Then intramolecular chain transfer, β-scission and branching reactions were also investigated, due to their direct connection with the production of defects in the growing chains. A comparison of the evaluated kinetic constants of such secondary reactions with other computational evaluations and experimental data was finally made.     

The Gilbert equation with dry-friction-type damping

A modified Gilbert equation for micromagnetics is considered, obtained by augmenting the standard viscous-like dissipation with a rate-independent term. We prove existence of a weak solution both with and without viscous dissipation. By scaling time we show that, if the applied field varies very slowly, then gyromagnetic effects and viscous dissipation become negligible. In the infinitesimally-slow-loading limit, the system thus becomes fully rate-independent.