Reactions of naphthalene in N2O5?NO3?NO2? air mixtures

The reactions of naphthalene in N₂O₅? NO₃? NO₂? N₂? O₂ reactant mixtures have been investigated over the temperature range 272–297 K at ca. 745 torr total pressure and at 272 K and ca. 65 torr total pressure using long pathlength Fourier transform infrared absorption spectroscopy. 2,3-Dimethyl-2-butene was added to the reactant mixtures at 272 K to rapidly scavenge the NO₃ radicals both initially present in the added N₂O₅ and formed from the thermal decomposition of N₂O₅ during the reactions. The data obtained in the presence and absence of added 2,3-dimethyl-2-butene showed that napthalene undergoes initial reaction with the NO₃ radical to form an NO₃-naphthalene adduct, which either rapidly decomposes back to the reactants (at a rate of ca. 5 × 10⁵ s^?1 at 298 K) or reacts exclusively with NO₂ to form products. When NO₃ radicals, N₂O₅ and NO₂ are in equilibrium, this overall process is kinetically equivalent to reaction of naphthalene with N₂O₅, and previous kinetic and product studies have indeed assumed the reactions of naphthalene and alkyl-substituted naphthalenes in N₂O₅? NO₃? NO₂? air mixtures to be with N₂O₅, and not with NO₃ radicals.     

Extraction and analysis of ellagic acid from novel complex sources

Ellagic acid (EA) was quantified by reversed-phase high-performance liquid chromatography (RPHPLC) coupled with photodiode array detection (DAD) in five fine-powdered plants collected from the semiarid region of Mexico. Samples analysed included Jatropha dioica branches (Dragon’s blood), Euphorbia antisyphyllitica branches (Candelilla), Turnera diffusa Willd leaves (Damiana), Flourensia cernua leaves (hojasén) and Punica granatum husk (pomegranate) at two maturity stages (“turning” or intermediate and maturated fruit, considered as positive controls). The results demonstrated high EA concentrations in all tested samples which are novel sources of this natural antioxidant. The method developed for the EA analysis is fast and it showed an excellent linearity range, repeatability, intra-and inter-day precision and accuracy with respect to the methods reported for the EA analysis.     

Nanocomposites by melt intercalation based on polycaprolactone and organoclay

Nanocomposites based on biodegradable polycaprolactone (PCL) and organically modified layered silicates (organoclay) were prepared by melt mixing. Their structures and properties were characterized by wide‐angle X‐ray diffraction, thermal analysis, and rheological measurements. The exfoliation of the organoclay was achieved via a melt mixing process in an internal mixer and showed a dependence on the type of organic modifier, the organoclay contents, and the processing temperature. The addition of the organoclay to PCL increased the crystallization temperature of PCL, but a high content of the organoclay could show an inverse effect. The PCL/organoclay nanocomposites showed a significant enhancement in their mechanical properties and thermal stability due to the exfoliation of the organoclay. The nanocomposites showed a much higher complex viscosity than the neat PCL and significant shear‐thinning behavior in the low frequency range. The shear storage modulus and loss modulus of the nanocomposites also exhibited less frequency dependence than the pure PCL in the low frequency range, and this was caused by the strong interactions between the organoclay layers and PCL molecules and by the good dispersion of exfoliated organoclay platelets in the PCL. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 670–678, 2003     

Photoprotection in the brown alga Macrocystis pyrifera: evolutionary implications

The dissipation of energy as heat is essential for photosynthetic organisms to protect themselves against excess light. We compared Photosystem II florescence changes (non-photochemical quenching, NPQ) in the brown alga Macrocystis pyrifera with that of Ficus sp., a higher plant to examine if the mechanism of heat dissipation (energy-dependent quenching, qE) differs between these evolutionary distant groups of phototrophs. We discovered that M. pyrifera had a slower rise of NPQ upon illumination than the Ficus sp. Further, the NPQ relaxation phase that takes place in the first minutes after light to dark transition is absent in this brown alga. We found that the NPQ induction rate in this alga was 1.5 times faster in preilluminated samples than in dark-adapted samples; this was associated with an increase in the rate of accumulation of the carotenoid zeaxanthin. Therefore, we conclude that NPQ in M. pyrifera is associated only with the formation of zeaxanthin. These results indicate that M. pyrifera lacks the fast component of qE that is related to allosteric changes in the light harvesting complexes of Ficus sp., a representative of higher plants. Although the xanthophyll cycle of this brown alga is similar to that of Ficus sp., yet, the transthylakoid proton gradient (ΔpH) does not influence NPQ beyond the activation of the violaxanthin de-epoxidase enzyme. These findings suggest that NPQ control mechanisms are not universal and we suggest that it may have diverged early in the evolution of different groups of eukaryotic phototrophs.     

Structure and cytotoxicity of phidianidines A and B: first finding of 1,2,4-oxadiazole system in a marine natural product

Two indole alkaloids, phidianidines A (1) and B (2), exhibiting an uncommon 1,2,4-oxadiazole ring linked to the indole system, have been isolated from the marine opisthobranch mollusk Phidiana militaris. The structures of the two metabolites have been elucidated by spectroscopic techniques. Phidianidines exhibit high cytotoxicity against tumor and nontumor mammalian cell lines in in vitro assays.