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.     

Antioxidant activity of o-bisphenols: the role of intramolecular hydrogen bonding

A kinetic and thermodynamic investigation on the antioxidant activity of 2,2'-methylenebis(6-tert-butyl-4-methylphenol) (2), 2,2'-ethylidenebis(4,6-di-tert-butylphenol) (3), and 4,4'-methylenebis(2,6-di-tert-butylphenol) (4) are reported. EPR studies of the equilibration between 3 or 4 and a reference phenol, and the corresponding phenoxyl radicals, allowed us to determine the O-H bond dissociation enthalpy (BDE) of the O-H bond as 81.2 and 81.1 kcal/mol in 3 and 4, respectively. Despite this similarity, the absolute rate constants for the reaction with peroxyl radicals, determined by autoxidation studies under controlled conditions, indicate that the o-bisphenols 2 and 3 behave as excellent antioxidants while the p-bisphenol 4 is less effective by a factor of 64 and 22, respectively. FT-IR spectroscopy and product studies suggest that the very good antioxidant activity of the o-bisphenols largely arises from both the reduced steric crowding about the hydroxyl group and the stabilization of the aroxyl radical due to the formation of an intramolecular hydrogen bond between the residual OH and the oxygen radical center.     

Electron density investigation of a push-pull ethylene (C14H24N2O2.H2O) by X-ray diffraction at T = 21 K

The electron charge distribution in a strongly twisted push-pull ethylene [PPE, 3-(1,3-diisopropyl-2-imidazolidinylidene)-2,4-pentanedione] has been determined by low temperature (T = 21 K) single-crystal X-ray diffraction analysis. The derived electronic properties are consistent with a zwitterionic molecule, as indicated by a charge transfer of 0.82(16) e from the push to the pull moieties and a charge polarization of 0.29(7) e on the olefinic bond. A dipole moment of 12(3) D has been determined, which compares well with ab initio theoretical results in terms of both modulus and orientation. The second moments, which have also been obtained with good precision, characterize PPE as a highly quadrupolar molecule. The special electronic features of the molecule confer particular topological properties to the electron density distribution, as evidenced by comparison with "standard" organic molecules. The crystallographic asymmetric unit of the present system includes one water molecule, which is hydrogen bonded to PPE. Its topological properties have also been investigated, together with an analysis of the hydrogen bonds involved.     

Anchor chain length alters the apparent mechanism of chloride channel function in SCMTR derivatives

Two membrane-anchored heptapeptides have been prepared and their pore-formation behavior in phospholipid bilayer membranes has been found to differ profoundly as a result only of alkyl chain length.     

Variable selection for multivariate calibration using a genetic algorithm: prediction of additive concentrations in polymer films from Fourier transform-infrared spectral data

Variable selection using a genetic algorithm is combined with partial least squares (PLS) for the prediction of additive concentrations in polymer films using Fourier transform-infrared (FT-IR) spectral data. An approach using an iterative application of the genetic algorithm is proposed. This approach allows for all variables to be considered and at the same time minimizes the risk of overfitting. We demonstrate that the variables selected by the genetic algorithm are consistent with expert knowledge. This very exciting result is a convincing application that the algorithm can select correct variables in an automated fashion.     

Langmuir–Blodgett films of pyridinium-dicyanomethanide dyes mixtures with photobleachable absorption bands

We report on Langmuir-Blodgett (LB) films characterization of 4-[5-dicyanomethanido)thien-2-y1]-N-(n-hexadecyl)pyridinium (C₁₆H₃₃-PDCNT), and 1-(N-(n-hexadecy]-4-pyridinio)-2-[5-(dicyanomethanido)thien-2-yl]ethene (C₁₆H₃₃-PDCNTE); LB films of the pure compounds and of the mixtures of the two compounds were prepared at 291 K: UV-vis investigation revealed the presence of photobleachable absorption bands, the ones at about 530 nm and 640 nm were due to charge transfer transitions of the monomer of C16H33-PDCNT and C₁₆H₃₃-PDCNTE, respectively; the sharp, photobleachable ones shifted to shorter wavelengths were due to H-aggregates of the two compounds. By changing the molar ratios of the two compounds in the mixtures and in other cases by annealing the LB films, the absorption maxima of the sharp, photobleachable bands due to H-aggregates could be tuned in the range 415–467 nm. These LB films are thus very promising in view of optical data storage applications.     

Equidistribution of negative statistics and quotients of Coxeter groups of type B and D

We generalize some identities and q-identities previously known for the symmetric group to Coxeter groups of type B and D. The extended results include theorems of Foata and Schützenberger, Gessel, and Roselle on various distributions of statistics, like inversion number, major index, and descent number. In order to show our results we provide explicit characterizations of the systems of minimal coset representatives of Coxeter groups of type B and D.     

Gas-chromatography–mass spectrometry analysis of dimethyl fumarate in consumer products

Two methods for the analysis of dimethyl fumarate (DMF) on silica gel, leather and other similar products are presented. The methods are based on solvent extraction or head space solid phase microextraction coupled with gas-chromatography–mass spectrometry. The methods are developed in order to satisfy the mandatory requirements of the European Community and with the aim to have easy and reliable methods to provide rapid responses.