Polar effects in free-radical reactions. A new type of homolytic aromatic alkylation by silver catalyzed oxidation of acetone by peroxydisulphate in the presence of olefins.

Silver catalyzed peroxydisulphate oxidation of acetone in the presence of olefins and protonated heteroaromatic bases leads to compound I via addition of acetonyl radical to the olefin and scavenging of the resulting radical adduct by the aromatic base.     

Stress-relaxation behavior of a physical gel: Evidence of co-occurrence of structural relaxation and water diffusion in ionic alginate gels

Stress relaxation measurements on ionically cross-linked alginate gels in an unconfined uniaxial compression are reported. Data are obtained as a function of ionic (divalent calcium) concentration and for various sample radii. Analysis of the results shows that such gels, at all investigated concentrations, relax the stress by two different concurring mechanisms: (a) an internal relaxation, most probably due to detachment and re-bonding of the cations along the alginate chains, and (b) the diffusion of water out of the gel.     

Effect of compatibilization on thermal degradation kinetics of HDPE-based composites containing cellulose reinforcements

Dynamic thermogravimetric analysis under nitrogen flow was used to investigate the thermal decomposition process of high-density poly(ethylene) (HDPE)-based composites reinforced with cellulose fibers obtained from the recycling of multilayer carton scraps, as a function of the cellulose content and the compatibilization. The Friedman, Flynn–Wall–Ozawa, and Coats–Redfern methods were used to determine the apparent activation energy (E _a) of the thermal degradation of the cellulose component into the composites. E _a has been found dependent on the cellulose amount and on the cellulose/polymer matrix interfacial adhesion. In particular, it has been evidenced an increase of the cellulose thermal stability as a consequence of the improved interfacial adhesion between the components in NFR composites.     

Nanoparticle microinjection and Raman spectroscopy as tools for nanotoxicology studies

Microinjection techniques and Raman spectroscopy have been combined to provide a new methodology to investigate the cytotoxic effects due to the interaction of nanomaterials with cells. In the present work, this novel technique has been used to investigate the effects of Ag and Fe(3)O(4) nanoparticles on Hela cells. The nanoparticles are microinjected inside the cells and these latter ones are probed by means of Raman spectroscopy after a short incubation time, in order to highlight the first and impulsive mechanisms developed by the cells to counteract the presence of the nanoparticles. The results put in evidence a different behaviour of the cells treated with nanoparticles in comparison with the control cells; these differences are supposed to be generated by an emerging oxidative stress due to the nanoparticles. The achieved results demonstrate the suitability of the proposed method as a new tool for nanotoxicity studies.     

Combining Spontaneous Polymerization and Click Reactions for the Synthesis of Polymer Brushes: A “Grafting Onto” Approach

Two novel benzofulvene monomers bearing propargyl or allyl groups have been synthesized by means of readily accessible reactions, and were found to polymerize spontaneously by solvent removal, in the apparent absence of catalysts or initiators, to give the corresponding polybenzofulvene derivatives bearing clickable propargyl or allyl moieties. The clickable propargyl and allyl groups were exploited in appropriate click reactions to develop a powerful and versatile “grafting onto” synthetic methodology for obtaining tailored polymer brushes.     

Resummation of Perturbation Series and Reducibility for Bryuno Skew-Product Flows

We consider skew-product systems on 핥^d ×l SL(2,ℝ) for Bryuno base flows close to constant coefficients, depending on a parameter, in any dimension d, and we prove reducibility for a large measure set of values of the parameter. The proof is based on a resummation procedure of the formal power series for the conjugation, and uses techniques of renormalisation group in quantum field theory.     

Structural stability in resonant penetrative convection in a Forchheimer porous material

Structural stability is studied in the problem of a fluid saturating a porous medium of Forchheimer type when the density of the fluid has a cubic temperature dependence. This problem allows the possibility of resonance between internal layers in thermal convection. In this paper we investigate continuous dependence on the heat source, this source being an important quantity in the resonance problem.     

KAM Theory in Configuration Space and Cancellations in the Lindstedt Series

The KAM theorem for analytic quasi-integrable anisochronous Hamiltonian systems yields that the perturbation expansion (Lindstedt series) for any quasi-periodic solution with Diophantine frequency vector converges. If one studies the Lindstedt series by following a perturbation theory approach, one finds that convergence is ultimately related to the presence of cancellations between contributions of the same perturbation order. In turn, this is due to symmetries in the problem. Such symmetries are easily visualised in action-angle coordinates, where the KAM theorem is usually formulated by exploiting the analogy between Lindstedt series and perturbation expansions in quantum field theory and, in particular, the possibility of expressing the solutions in terms of tree graphs, which are the analogue of Feynman diagrams. If the unperturbed system is isochronous, Moser’s modifying terms theorem ensures that an analytic quasi-periodic solution with the same Diophantine frequency vector as the unperturbed Hamiltonian exists for the system obtained by adding a suitable constant (counterterm) to the vector field. Also in this case, one can follow the alternative approach of studying the perturbation expansion for both the solution and the counterterm, and again convergence of the two series is obtained as a consequence of deep cancellations between contributions of the same order. In this paper, we revisit Moser’s theorem, by studying the perturbation expansion one obtains by working in Cartesian coordinates. We investigate the symmetries giving rise to the cancellations which makes possible the convergence of the series. We find that the cancellation mechanism works in a completely different way in Cartesian coordinates, and the interpretation of the underlying symmetries in terms of tree graphs is much more subtle than in the case of action-angle coordinates.