Antioxidant activity of hydroxystilbene derivatives in homogeneous solution

The antioxidant activity of the cis and trans isomers of several analogues of resveratrol and pterostilbene has been investigated, especially with regard to the effect of the stereochemistry about the olefinic double bond. The antioxidant power of these compounds was estimated by measuring the rate constants for their reactions with peroxyl radicals and, with two of them, the bond dissociation enthalpy (BDE) of the phenolic O-H bond which is cleaved in the inhibition reaction. The present data show that in homogeneous solution the various hydroxystilbenes investigated behave as mild antioxidants with the notable exceptions of the trans isomer of 4 and 6, whose activities are only slightly lower than that of alpha-tocopherol (vitamin E). The rate constants of the inhibition reaction show that the antioxidant activity of the cis-hydroxystilbene is in all the examined cases worse, by a factor ranging between 2 and 6, than that of the corresponding trans isomers. This lower reactivity depends on enthalpy factors as it can be inferred by the experimental values of the O-H bond dissociation enthalpy in the two geometric isomers of 3',5'-di-tert-butyl-4'-hydroxy-3,5-dimethoxystilbene showing that the strength of the O-H bond in the cis isomer is larger by 1.8 kcal/mol. DFT calculations provide a rationalization of this result, indicating that, although the cis geometry implies a destabilization with respect to the trans species of both phenoxyl radical and parent hydroxystilbene, the destabilization of the radical is larger because the folding of the structure strongly reduces the delocalization of the unpaired electron on the styryl group. A comparison of these results with previously reported data on the proapoptotic activity of these stilbenoids suggests that these two properties are not correlated.     

Properties of the silica layer during the formation of MCM-41 studied by EPR of a silica-bound spin probe

The properties of the silica layer during the formation of the mesoporous material MCM-41 were investigated by electron paramagnetic resonance (EPR) experiments carried out on a specifically designed, organo(trialkoxy)silane spin probe, SL1SiEt. Minute amounts of the spin probe were co-condensed with the silica source, tetraethyl orthosilicate (TEOS), in the synthesis of MCM-41 with cetyltrimethylammonium bromide (CTAB) under basic conditions. The mobility and location of the spin probe were followed in the CTAB micellar solution before the reaction, in the reaction mixture and in the final ordered material. It was found that the EPR spectra of hydrolyzed SL1SiEt throughout the room temperature part of the reaction are characteristic of a fast tumbling species, indicating that the silica is highly fluid prior to drying. After filtering, a slow motion type spectrum was observed, showing that the spin-label experiences considerable motional hindrance. The liquidlike behavior could be restored upon stirring the material in water. When the reaction is performed with a hydrothermal stage, the spectrum of SL1SiEt in the final product is the same as that of the room temperature synthesized material, but the addition of water did not restore the high mobility, due to a higher degree of silica cross-linking. The location of SL1SiEt throughout the formation process was obtained from electron spin-echo envelope modulation (ESEEM) measurements on MCM-41 prepared with CTAB deuterated either at the N-methyl or the alpha position and in a reaction carried out in D2O. Comparing the deuterium modulation depth, k(2H), induced by CTAB-alpha-d2, CTAB-d9, or D2O in CTAB micellar solutions of a number of reference spin probes with those of SL1SiEt revealed that the hydrolyzed SL1SiEt is located near the polar heads of the surfactant in the absence of base and TEOS. This supports the postulation of charge matching at the interface as a driving force for the formation of the mesostructure. Similar experiments carried out on reaction mixtures containing SL1SiEt showed a decrease of k(2H) from CTAB-alpha-d2 and CTAB-d9 compared to the micellar solution, exhibiting practically no time dependence. This indicates that the spin probe is pulled away from the micelle-water interface into the loosely linked, forming silica network. After drying, the modulation depth induced by CTAB-alpha-d2 and CTAB-d9 increases, showing that, once the water is removed, the silica walls contract around the micelles, pushing the silica-linked spin probe into the organic phase within the mesopores.     

A Note on Local Asymptotics of Solutions to Singular Elliptic Equations via Monotonicity Methods

This paper concerns the asymptotic behavior of solutions and their gradients to linear and nonlinear elliptic equations with singular coefficients of fuchsian type.     

Photothermal and photocatalytic processes on TiO2 based materials prepared by sol-gel method

In the present work, Fe³⁺ doped TiO₂ coatings on glass substrates were prepared by dip-coating from a sol-gel solution. The influence of the dopant concentration on the structure, optical, photocatalytic and photothermal properties of the films was studied. The results obtained have shown a strong correlation between the catalytic properties and the amount of iron dopant and the temperature of the thermal treatment.     

On the weak IFR aging of bivariate lifetime distributions

A new notion of bivariate aging in a competitive risk framework is introduced. Aging properties of bivariate distributions are defined by aging properties of a series system with possibly dependent components. A case of exponential marginals is considered. Sufficient conditions for a weak IFR aging (weak DFR negative aging) are derived and a number of simple examples are considered. Copyright © 2005 John Wiley & Sons, Ltd.     

Urea-Formaldehyde Microcapsules Containing an Epoxy Resin: Influence of Reaction Parameters on the Encapsulation Yield

In this work urea-formaldehyde microcapsules containing an epoxy resin are prepared by in situ polymerization of monomers in an oil-in-water emulsion. Scanning electronic microscopy (SEM) was performed to investigate on microcapsule size and surface morphology. Calorimetric and spectroscopic analyses were carried out with the aim of evaluate the encapsulation yield and the shell features. Factors determining the microencapsulability of the core material were described. In particular, our interest was devoted to a better understanding of the influence of the reaction parameters on the microcapsule properties. It was found that the encapsulation yield as well as the extent of urea-formaldehyde polymerization depends on the reaction temperature and the stirring speed.     

NMR study of the adsorption-desorption kinetics of dissolved tetraalanine in MCM-41 mesoporous material

In this study we show how deuterium magic-angle spinning NMR spectroscopy can be used to investigate the adsorption-desorption kinetics of molecules in solution at surface-liquid interfaces. An aqueous solution of deuterium-labeled tetraalanine is inserted in the pores of MCM-41 mesoporous material, and its 2H MAS NMR spectrum is measured as a function of temperature and fraction of filling of the pores. Prior to this study, the different types of water in MCM-41 are characterized as a function of water loading of the pores. Analysis of 2H MAS sideband line shapes enabled the determination of the adsorption and desorption rates and the activation energies of desorption.