On the stereochemistry of photoaddition between α,β-unsaturated ketones and olefins. III.

The α,β-unsaturated ketone $\text{1}$ yields with allene the photocycloadduct $\text{3}$ predicted by our empirical photoaddition rule and the byproduct 7. The formation of this material may be rationalized by the sequence $\text{1}$ → $\text{4}$ → $\text{5}$ → $\text{6}$ → $\text{7}$. The isomeric ketone $\text{2}$ is unreactive under the same conditions, since α addition is prohibited by the rule and β addition is severely blocked.     

Rapid access to structured triacylglycerols acylated with n-3 polyunsaturated fatty acids for nutritional applications

In order to better understand the metabolic fate of n-3 polyunsaturated fatty acids (PUFAs), an efficient access to symmetrical and unsymmetrical triacylglycerols (TGs), esterified with PUFAs, with known high purity, is required. In this context, we optimized the esterification of a mixture of glycerols protected as dioxane and dioxolane with PUFAs. The kinetics of this reaction depends on various factors, such as the fatty acid chain length and the stereochemistry of the dioxane. Then, one-pot acetal hydrolysis and esterification of hydroxyl groups led to the desired structured TGs without either double bond isomerization or acyl migration (except when symmetrical TGs are acylated with long-chain saturated fatty acids in external positions). PUFAs location on the glycerol backbone was assayed by NMR, HPLC and pancreatic lipase hydrolysis.     

Synthesis and evaluation of an Iejimalide-archazolid chimera

Even though the macrolides of the iejimalide family are of marine origin, whereas those of the archazolid series derive from terrestrial myxobacteria, a comparison of their constitution, stereochemistry, and biological activity suggests that these natural products are close structural and functional relatives. Guided by this perception, compound 5 was prepared, which hybridizes the macrolactone core of iejimalide B (2) with the tail of archazolid A (3). The cytotoxicity profile of this chimera, as determined with a panel of 12 human cancer cell lines, corresponds to that of the parent compound 2, although its potency is lower. This outcome may be interpreted on the basis of molecular dynamics calculations, which suggest that the low energy conformations of 2 and 5 are similar but the energetic barriers between the relevant conformers are distinctly higher for the hybrid structure. The synthesis of 5 hinged on a regioselective functionalization of 2,4-dibromothiazole 6, a highly selective CBS-reduction of ketone 8, a Suzuki cross coupling of vinyl boronate 17 with the elaborate alkenyl iodide 16, and a productive closure of the macrocycle by RCM, which requires the selective activation of two out of eight double bonds present in the cyclization precursor 20 by the second-generation Grubbs catalyst 21.     

Combined analysis by GC (RI), GC-MS and 13C NMR of the supercritical fluid extract of Abies alba twigs

Two samples (leaves and twigs) of Abies alba Miller from Corsica were extracted using supercritical CO2 and their chemical compositions were compared with those of the essential oils obtained from the same batch of plant material. In total 45 components were identified using combined analysis by GC (RI), GC-MS and 13C NMR. It was observed that the contents of monoterpenes (mainly represented by limonene, alpha-pinene and camphene) were significantly lower in the supercritical fluid extract (SFE) than in the essential oil (EO). Conversely, the proportions of sesquiterpenes were much higher in CO2 extracts than in essential oils (around 30% vs 4%). Cis-abienol, a diterpene alcohol, was identified only in SFE, and the proportions of this constituent (7.5% and 17.3%) were determined using quantitative 13C NMR since it was under estimated using the standard conditions of GC.     

A life cycle framework for the investigation of environmentally benign nanoparticles and products

While significant advances in our understanding of the behavior of engineered nanoparticles in the environment continue, there remains a need to engage the nanoparticle research community directly in the development and evaluation of environmentally benign nanoparticles to ensure that nanomaterial‐based industries emerge as tools for sustainability rather than environmental liabilities. Current research efforts aimed at understanding the environmental implications of nanotechnology emphasize existing groups of nanoparticles and products already in commercial distribution. While this is clearly necessary, this approach fails to identify and address the many tradeoffs associated with product performance and environmental quality. We believe this to be a critical gap in the ongoing exploration of nanostructured materials and their properties and applications. We posit that a number of issues are not being holistically addressed, including resource availability and allocation, manufacturing energy requirements and embodied energy, material efficiency, environmental properties of nanomaterials and nanoproducts, and waste generation. An interdisciplinary approach to research, based on the life cycle paradigm and devoted to the identification, investigation, synthesis, testing, and analysis of groups of new, more environmentally conscious nanoparticles is needed. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)