A quantitative approach to the recycling of alpha-tocopherol by coantioxidants

A systematic investigation is reported on the regeneration of alpha-tocopherol (alpha-TOH) in homogeneous solution by coantioxidants in order to better understand the mechanism and the factors responsible for the effectiveness of this process. The current availability of thermochemical data concerning the reactants involved in the regeneration reactions, as well as a large number of the kinetic constants for the various reactions involved, allowed us to rationalize the experimental observations collected so far. Three limiting cases have been considered. The first case is that of a coantioxidant irreversibly regenerating alpha-TOH, where the effectiveness of the recycling process depends on the magnitude of the rate constant k(r). The second case is that of a coantioxidant reversibly recycling alpha-TOH, where regeneration can only be observed if the bond dissociation enthalpy value of the coantioxidant is lower or at least close to that of the O-H bond of alpha-tocopherol. The third case is that of a catechol derivative (chosen as a model compound for polyphenolic antioxidants), where recycling of alpha-TOH is feasible even though the BDE value is significantly higher than that of vitamin E. In this case, the driving force for the recycling process is the removal of the semiquinone radical from the catechol derivative by the alpha-tocopheroxyl radical, which makes the regeneration of alpha-TOH practically irreversible.     

Corrosion behavior in artificial seawater of thermal-sprayed WC-CoCr coatings on mild steel by electrochemical impedance spectroscopy

The corrosion behavior in artificial seawater of different as-sprayed ceramic-metallic (cermet) coatings applied on low-alloy steel was studied. Five conditions, associated to modifications of the composition of the powder or deposition parameters were evaluated. The degradation mechanisms were studied during extended immersion tests using conventional electrochemical measurement and electrochemical impedance spectroscopy. The extended immersion tests reveal that these as-thermal-sprayed coatings present a cathodic behavior compared with steel. During the first hours of immersion, the electrolyte infiltrates the defects of the coatings, which then result to the local degradation of the substrate accelerated by the galvanic coupling with the cermet coating. Optical observations and Raman analyses reveal the formation of calcium carbonates like aragonite on the cermet surface, very close to the appearance of local anodic sites. The cross-sectioned views reveal the infiltration of the corrosive solution, and the depth penetration of the degradation of steel substrate probably due to the acidification of the anodic sites.     

Modeling the co-antioxidant behavior of monofunctional phenols. Applications to some relevant compounds

A study on the regeneration of alpha-tocopherol (vitamin E) by phenolic co-antioxidants in homogeneous hydrocarbon solution is reported. The behavior of some relevant phenols such as BHA, BHT, and trans-resveratrol appears to be nicely predicted by a model based on the knowledge of kinetic and thermochemical data concerning the various reactants. Despite its good reputation as an antioxidant, trans-resveratrol was found only moderately effective (k(inh) = 2.0 x 10(5) M(-1) s(-1) in chlorobenzene at 303 K) and unable to recycle vitamin E.     

Limit of hanger linearity in suspension footbridge dynamics: A new section model

The mechanical behaviour of suspension bridges is characterised by nonlinearities due to the main cables geometric effects and to the inability of the hangers to sustain compressive loads. The nonlinear effects due to hanger slackening are expected to increase in suspension footbridges due to lightweight decks, that is, low dead to live load ratio, and to shallow plate-girder decks with very low flexural and torsional stiffness. In this paper a new section model is proposed to study the limit of hanger linearity in lightweight suspension footbridges. The model is inspired to a four degrees-of-freedom model already proposed in the literature, but is expressed with a new formalism that allows some interesting properties to be outlined. Specifically, the expression of a particular frequency, herein called relative antiresonance frequency, as a function of the model generalised properties is derived: if the system is loaded with a harmonic force having that frequency, the linear behaviour of the hangers is assured for every value of the force amplitude. The proposed section model is applied to a footbridge benchmark subject to the pedestrian harmonic load and results are compared with those obtained through a nonlinear dynamic analysis on a 3D Finite Element model of the bridge.     

Some asymptotic limits of reaction–diffusion systems appearing in reversible chemistry

This paper concerns reaction–diffusion systems consisting of three or four equations, which come out of reversible chemistry. We introduce different scalings for those systems, which make sense in various situations (species with very different concentrations or very different diffusion rates, chemical reactions with very different rates, etc.). We show how recently introduced mathematical tools allow to prove that the formal asymptotics associated to those scalings indeed hold at the rigorous level.     

Analysis of steady combustion processes in a recombination reaction

In the present paper, the combustion processes, represented by steady deflagration or detonation waves, are studied for a set of balance laws in the framework of Navier–Stokes reactive equations related to a diatomic recombination reaction. Moreover, a systematic analysis of the combustion solutions is carried out, investigating the influence of all the physical parameters present in the hydrodynamical equations: the Mach number of the gas mixture in the unburned state, the chemical link energy of the diatomic molecule and the activation energy of the reaction. Results are discussed according to several numerical experiments.     

Convex Polytopes and Quasilattices from the Symplectic Viewpoint

We construct, for each convex polytope, possibly nonrational and nonsimple, a family of compact spaces that are stratified by quasifolds, i.e. each of these spaces is a collection of quasifolds glued together in an suitable way. A quasifold is a space locally modelled on modulo the action of a discrete, possibly infinite, group. The way strata are glued to each other also involves the action of an (infinite) discrete group. Each stratified space is endowed with a symplectic structure and a moment mapping having the property that its image gives the original polytope back. These spaces may be viewed as a natural generalization of symplectic toric varieties to the nonrational setting.Partially supported by GNSAGA (CNR).     

N‐Arylated 3,5‐Dihydro‐4H‐dinaphtho[2,1‐c:1′,2′‐e]azepines: Axially Chiral Donors with High Helical Twisting Powers for Nonplanar Push–Pull Chromophores

Axially chiral, N‐arylated 3,5‐dihydro‐4H‐dinaphtho[2,1‐c:1′,2′‐e]azepines have been prepared by short synthetic protocols from enantiopure 1,1′‐bi(2,2′‐naphthol) (BINOL) and anilines. Alkynes substituted with two N‐phenyldinaphthazepine donors readily undergo a formal [2+2] cycloaddition, followed by retro‐electrocyclization, with tetracyanoethene (TCNE) to yield donor‐substituted 1,1,4,4‐tetracyanobuta‐1,3‐dienes (TCBDs) featuring intense intramolecular charge‐transfer (CT) interactions. A dicyanovinyl derivative substituted with one N‐phenyldinaphthazepine donor was obtained by a “one‐pot” oxidation/Knoevenagel condensation from the corresponding propargylic alcohol. Comparative electrochemical, X‐ray crystallographic, and UV/Vis studies show that the electron‐donor qualities of N‐phenyldinaphthazepine are similar to those of N,N‐dimethylanilino residues. The circular dichroism (CD) spectrum of a push–pull chromophore incorporating the chiral donor moiety features Cotton effects of exceptional intensity. With their elongated shape and the rigidity of the chiral N‐aryldinaphthazepine donors, these chromophores are effective inducers of twist distortion in nematic liquid crystals (LCs). Thus, a series of the dinaphthazepine derivatives was used as dopants in the nematic LC E7 (Merck) and high helical twisting powers (β) of the order of hundreds of μm^?1 were measured. Theoretical calculations were employed to elucidate the relation between the structure of the dopants and their helical twisting power. For the derivatives with two dinaphthazepine moieties, a strong dependence of the β‐values on the structure and conformation of the linker between them was found.