Second-degree Painlevé equations and their contiguity relations

We study second-order, second-degree systems related to the Painlevé equations which possess one and two parameters. In every case we show that by introducing a quantity related to the canonical Hamiltonian variables it is possible to derive such a second-degree equation. We investigate also the contiguity relations of the solutions of these higher-degree equations. In most cases these relations have the form of correspondences, which would make them non-integrable in general. However, as we show, in our case these contiguity relations are indeed integrable mappings, with a single ambiguity in their evolution (due to the sign of a square root).     

Mechanisms of antioxidant action: Antioxidant behaviour of nickel complex u.v. stabilisers

The antioxidant mechanisms involved in the u.v. stabilising activity of two nickel complexes, nickel dibutyl dithiocarbamate (NiDBC) and nickel acetophenone oxime (NiOx), have been investigated both by oxygen absorption measurements and in peroxide decomposition studies. NiDBC gives rise to a powerful catalyst for non-radical hydroperoxide decomposition; the rate of the reaction is faster in the presence than in the absence of light although the overall mechanisms appear to be very similar. NiOx is decomposed by hydroperoxides in a series of stoichiometric reactions which involve the consumption of at least six molecules of hydroperoxide per molecule of NiOx. Again the reaction is catalysed by light but the mechanism, which does not involve free-radical formation, is the same in the presence and absence of light. NiOx also appears to have weak radical trapping properties. Attempts to show that NiDBC and NiOx might interact sacrificially with photo-excited states of molecules (triplet carbonyl and singlet oxygen) were unsuccessful; the rates of photo-destruction of both complexes were unaffected by the presence of ketones both in the presence and absence of oxygen. This work confirms earlier conclusions that the nickel complex u.v. stabilisers function by auto-synergistic mechanisms involving u.v. screening and conventional chain-breaking and preventive antioxidant processes which operate during thermal processing operations as well as during environmental exposure. Although excited state quenching processes may occur, they appear to be less important in the overall scheme than the well established antioxidant mechanism.     

Biodegradable compositions by reactive processing of aliphatic polyester/polysaccharide blends

Commercially available biodegradable aliphatic polyesters, i.e., high molecular weight poly(ϵ-caprolactone) (PCL) and polylactide (PLA), were melt blended with a well-known natural and biodegradable polysaccharide: starch either as corn starch granules or as thermoplastic corn starch after plasticization with glycerol. Conventional melt blending yielded compositions with poor mechanical performances as a result of lack of interfacial adhesion between the rather hydrophobic polyester matrix and the highly hydrophilic and moisture sensitive starch phase. Interface compatibilization was achieved via two different strategies depending on the nature of the polyester chains. In case of PLA/starch compositions, PLA chains were grafted with maleic anhydride through a free radical reaction conducted by reactive extrusion. The maleic anhydride-grafted PLA chains (MAG-PLA) allowed for reinforcing the interfacial adhesion with granular starch as attested by TEM of cryofracture surface. As far as PCL/starch blends were concerned, the compatibilization was achieved via the interfacial localization of amphiphilic graft copolymers formed by grafting of PCL chains onto a polysaccharide backbone such as dextran. The PCL-grafted polysaccharide copolymers were synthesized by controlled ring-opening polymerization of ϵ-caprolactone proceeding via a coordination-insertion mechanism. These compatibilized PCL/starch compositions displayed much improved mechanical properties as determined by tensile testing as well as a much more rapid biodegradation as measured by composting testing.