Resveratrol (3,5,4'-trihydroxy-trans-stilbene, 3,5,4'-THS) is a well-known natural antioxidant and cancer chemopreventive agent that has attracted much interest in the past decade. To find a more active antioxidant and investigate the antioxidative mechanism with resveratrol as the lead compound, we synthesized 3,5-dihydroxy-trans-stilbene (3,5-DHS), 4-hydroxy-trans-stilbene (4-HS) 3,4-dihydroxy-trans-stilbene (3,4-DHS), 4,4'-dihydroxy-trans-stilbene (4,4'-DHS), 4-hydroxy-3-methoxy-trans-stilbene (3-MeO-4-HS), 4-hydroxy-4'-methoxy-trans-stilbene (4'-MeO-4-HS), 4-hydroxy-4'-methyl-trans-stilbene (4'-Me-4-HS), 4-hydroxy-4'-nitro-trans-stilbene (4'-NO(2)-4-HS), and 4-hydroxy-4'-trifluoromethyl-trans-stilbene (4'-CF(3)-4-HS). The radical-scavenging activity and detailed mechanism of resveratrol and its analogues (ArOHs) were investigated by the reaction kinetics with galvinoxyl (GO(*)) and 2,2-diphenyl-1-picrylhydrazyl (DPPH(*)) radicals in ethanol and ethyl acetate at 25 degrees C, using UV-vis spectroscopy. It was found that the reaction rates increase with increasing the electron-rich environment in the molecules, and the compound bearing o-dihydroxyl groups (3,4-DHS) is the most reactive one among the examined resveratrol analogues. The effect of added acetic acid on the measured rate constant for GO(*)-scavenging reaction reveals that in ethanol that supports ionization solvent besides hydrogen atom transfer (HAT), the kinetics of the process is partially governed by sequential proton loss electron transfer (SPLET). In contrast to GO(*), DPPH(*) has a relatively high reduction potential and therefore enhances the proportion of SPLET in ethanol. The relatively low rate constants for the reactions of ArOHs with GO(*) or DPPH(*) in ethyl acetate compared with the rate constants in ethanol prove that in ethyl acetate these reactions occur primarily by the HAT mechanism. The contribution of SPLET and HAT mechanism depends on the ability of the solvent to ionize ArOH and the reduction potential of the free radical involved. Furthermore, the fate of the ArOH-derived radicals, i.e., the phenoxyl radicals, was investigated by the oxidative product analysis of ArOHs and GO(*) in ethanol. The major products were dihydrofuran dimers in the case of resveratrol, 4,4'-DHS, and 4-HS and a dioxane-like dimer in the case of 3,4-DHS. It is suggested from the oxidative products of these ArOHs that the hydroxyl group at the 4-position is much easier to subject to oxidation than other hydroxyl groups, and the dioxane-like dimer is formed via an o-quinone intermediate.

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The competitive adsorption isotherms of rac-1-phenyl-1-propanol on cellulose tribenzoate were measured by competitive frontal analysis. The experimental data were fitted to four different isotherm models: Langmuir, Bilangmuir, Langmuir-Freundlich, and Tóth. The fittings of the experimental data to all four models were satisfactory. It was excellent in the case of the Langmuir-Freundlich and the Tóth models. Overloaded elution profiles calculated with the Tóth isotherm were in good agreement with the experimental profiles in all the different experimental conditions investigated. This work extends to the case of binary mixtures the equivalence between the general rate and the lumped pore diffusion models already demonstrated for pure compounds when the ratio between the Stanton and the Biot numbers exceeds 5. The adsorption energy distribution for the Tóth isotherm was also calculated.

The effect of pressure on the retention behavior of insulin variants in RPLC on a YMC-ODS C18 column was investigated under linear conditions. The retention factors of these variants increase nearly 2-fold when the average column pressure is increased from 55 to 250 bar while their separation factors remain nearly unchanged. This effect is explained by a change of the partial molar volume of the insulin variants associated with their adsorption that decreases from -99 to -80 mL/mol for mobile-phase concentrations of acetonitrile increasing from 29 to 33% (v/v). This volume change is much larger than the one observed with low molecular weight compounds. For the same pressure variation, the average number Z of acetonitrile molecules displaced from the protein and the stationary phase upon adsorption increases from 22 to 23.3. The pressure-induced relative increase of the term b[S]/[D0]z (which corresponds to the initial slope of the adsorption isotherm) is approximately twice as large for Lispro than for porcine insulin. Because the binding constant of insulin decreases with increasing pressure, this suggests that the number of binding sites on the stationary phase increases even faster. Finally, it was observed that the column efficiency at flow rates higher than 0.6 mL/min increases slightly with increasing pressure. It is suggested that these observations are also valid for other proteins analyzed in RPLC.