Mechanisms of antioxidant action: The effect of thermal processing on the antioxidant activity of sulphur compounds

The nickel dithiophosphates and their corresponding disulphides are shown to be more effective uv stabilisers for LDPE than the closely related nickel xanthates and disulphides (dixanthogens). In general, the nickel complexes in both series are more effective uv stabilisers than the disulphides.Evidence is presented to show that the better performance of the dithiophosphates than the xanthates is associated with their higher solubility in the polymer. For the same reason, nickel dithiolates containing long alkyl substituents are more effective uv stabilisers than those containing shorter alkyl substituents.Thermal processing adversely affects the photo-stabilising performance of nickel dithiolates whereas the performance of the less efficient disulphides is enhanced under the same conditions. In the former case, the uv stability of the polymer is shown to be directly proportional to the amount of the nickel complex left after processing. In the case of the disulphides, on the other hand, the evidence suggests that increasing the severity of their processing increases the extent of oxidation to products which are more effective uv stabilisers than the parent disulphides.     

Calculation of skin permeability coefficient for ionized and unionized species of indomethacin.

The contribution of ionized and unionized species to the overall permeation of weak electrolytes through the skin was investigated to determine the effect of pH in the vehicle on the permeability of indomethacin (IDM), as a model drug, through hairless rat skin. The permeability of IDM through polydimethylsiloxane (silicone) and poly(2-hydroxyethyl methacrylate) (pHEMA) membranes which may reflect lipid and aqueous pathway, respectively, was also measured for comparison. As the pH in the vehicle increased, there was an exponential increase in the skin permeation rate of IDM. The permeation rate of IDM through the silicone membrane was constant independent of pH, whereas that through the pHEMA membrane increased with increasing pH, similar to the skin permeation. The permeability coefficients of ionized and unionized species through the skin estimated using the skin permeation rates and solubilities of IDM at various pHs were 1.50 x 10(-7) and 2.79 x 10(-5) cm/s, respectively. These results indicated that the permeation of ionized species greatly contributed to the total permeation of IDM at higher pH, and that the total permeation rate of IDM was determined by the permeation of unionized species at lower pH. These contributions depend on the pH and pKa values and the ratio of permeability coefficient of each species. It was also confirmed that the skin has at least two kinds of permeation pathways and these two species permeate through a different pathway.     

Photoreduction de la benzophenone par des phtalimidines et des dihydro isoquinolones: Etude chimique par RMN PNIC

Benzophenone is photoreduced by pthalimidines and dihydro isoquinolones. The hydrogen atom α to the nitrogen atom is abstracted and radical coupling leads to adducts. CIDNP studies of these adducts show inversion of polarisation for the adduct on the N-alkyl chain when the nitrogen is bound to a benzylic methylene. This inversion is explained by considering that the radical on the N-alkyl chain derives from the radical on the ring.     

Synthesis and Physicochemical Study of Solid Complexes of Ti(IV), Zr(IV), and Zn(II) with Chrysin

Previously unknown solid complexes of Ti(IV), Zr(IV), and Zn(II) with chrysin were isolated, identified, and studied by thermogravimetric analysis and by UV-Vis, IR, and NMR spectroscopy.     

Catalytic hydroamination of furfuryl and tetrahydrofurfuryl alcohols with nitriles

Reaction of furfuryl and tetrahydrofurfuryl alcohols with nitriles over copper oxide catalysts under a hydrogen pressure of 15 atm at a temperature of 230C gives N-alkylfurfuryl- (yield 46–50%) and N-alkyl-tetrahydrofurfurylamines (49–53%), and N-alkylpiperidines (28–41%). A reaction mechanism is proposed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 23–26, January, 1988.     

Etude photochimique des benzo(A)- et benzo(C)acridines par CIDNP

Photoreactions of benzo(a)- and benzo(c)acridines in protic solvents were studied by CIDNP. Two routes to adducts are possible: direct recombination in the first radical pair (S state) or recombination of radicals after diffusion. The relative importance of each route seems to be linked to the presence of the benzo group and to solvent reactivity.