Metallic nanoparticles affect uptake of polycyclic aromatic hydrocarbons and impacts in the Mediterranean mussels Mytilus galloprovincialis.

The impact of metallic nanoparticles (NPs) on the uptake and toxicity of persistent organic pollutants by marine bivalves was assessed through a comparative laboratory study by exposing mussels to polycyclic aromatic hydrocarbon (PAHs), in the presence and absence of ZnO and TiO2 NPs. PAHs and NPs concentration was analyzed after 14 days of exposure in mussels by GC/MS and ICP/AES. Furthermore, impact on the physiology and neurotoxicity of PAHs and NPs acting alone or in mixtures were also determined. Our results confirmed the bio-uptake of PAHs and NPs by mussels. In addition, the exposure NPs-PAHs resulted in different bio-uptake profile to that of PAHs alone. The NPs and accumulation of PAHs led to disturbance of essential metals concentration and to different impact profiles in the filtration and respiration capacities as well as in the acetylcholinesterase activity. Antagonist interactions between NPs and PAHs could occur after exposure.

Photoreduction of triplet thioxanthone derivative by azolium tetraphenylborate: a way to photogenerate N-heterocyclic carbenes.

Although N-heterocyclic carbenes (NHCs) have brought profound changes in catalytic organic synthesis, their generation generally requires an inert atmosphere and harsh conditions. To overcome these limitations, an air-stable NHC photogenerator has been developed involving two mild components: 1,3-bis(mesityl)imidazolium tetraphenylborate (IMesH+BPh4-) and electronically excited isopropylthioxanthone (ITX). In this study, the photochemical mechanism is investigated via the accurate identification of the transient species and photoproducts. Electron transfer reaction between the excited triplet state of ITX and BPh4- is demonstrated as being the primary photochemical step. Nanosecond laser spectroscopy shows an efficient quenching and the formation of the expected ITX radical anion. The oxidized borane species is not observed, suggesting that this short-lived species could dissociate very rapidly to give the phenyl radical - successfully identified using electron paramagnetic resonance - and triphenylborane. As regards the final photoproducts, 1H and 13C NMR spectroscopies support the formation of the targeted NHC, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes), suggesting the occurrence of a subsequent proton transfer reaction between ITX radical anion and imidazolium cation (IMesH+). Gas chromatography-mass spectrometry reveals three other products: biphenyl, isopropylthioxanthene and ITX. Their formation can be reconciled with a 2-step mechanism of photoinduced electron/proton transfer reactions. 11B NMR spectroscopy demonstrates that the main organoboron photoproduct is diphenylborinic acid formed by oxidation of BPh3. Due to its Lewis acidity, Ph2BOH can react with IMes to yield an NHC-boron adduct.

Changes in Plant Metabolism and Accumulation of Fungal Metabolites in Response to Esca Proper and Apoplexy Expression in the Whole Grapevine.

Trunk diseases have become among the most important grapevine diseases worldwide. They are caused by fungal pathogens that attack the permanent woody structure of the vines and cause various symptoms in woody and annual organs. This study examined modifications of plant responses in green stem, cordon, and trunk of grapevines expressing Esca proper (E) or apoplexy (A) event, which are the most frequent grapevine trunk disease symptoms observed in Europe. Transcript expression of a set of plant defense- and stress-related genes was monitored by quantitative reverse-transcription polymerase chain reaction while plant phytoalexins and fungal metabolites were quantified by high-performance liquid chromatography-mass spectrometry in order to characterize the interaction between the grapevine and trunk disease agents. Expression of genes encoding enzymes of the phenylpropanoid pathway and trans-resveratrol content were altered in the three organs of diseased plants, especially in the young tissues of A plants. Pathogenesis-related proteins and the antioxidant system were severely modulated in A plants, which indicates a drastic stress effect. In the meantime, fungal polyketides 6-MSA, (R)-mellein, and (3R,4R)-4-hydroxymellein, were accumulated in A plants, which suggests their potential effect on plant metabolism during the appearance of foliar symptoms.

Enantioselective synthesis of iclaprim enantiomers--a versatile approach to 2-substituted chiral chromenes.

Both enantiomers of the DHFR inhibitor iclaprim (R)-1 and (S)-1 were synthesized from the cyclopropyl homoallyl alcohols (R)-6 and (S)-6, respectively. As key steps these transformations include a Mitsunobu reaction and the formation of the diaminopyrimidine unit prior to a novel cyclization procedure to obtain the desired chromene heterocycle. The moderate enantioselectivity of the products (R)-1 and (S)-1 is related to the Mitsunobu reaction, which unfortunately did not proceed with complete inversion of configuration.

Influence of the temperature and the growth phase on the hopanoids and fatty acids content of Frateuria aurantia (DSMZ 6220).

The main lipids isolated from Frateuria aurantia (DSMZ 6220) are iso-branched fatty acids and triterpenoids of the hopane family like bacteriohopanetetrol and derived hopanoids, beside trace amounts of diploptene and rearranged compounds like fern-7-ene. The impact of the growth temperature and the growth phase in which cells were harvested on this lipid fingerprint was investigated. As expected, an increase of saturated compounds with temperature is the essential modification in the fatty acid composition. The fatty acid composition also varies significantly during the growth. Global lipid fingerprints, including at least PLFA and triterpenoids are suggested to be a tool for measuring the stress state of bacterial cells. Increasing amounts of C-31 hydroxylated hopanoids with a temperature increase is novel information which deserves attention and further investigation for a better comprehension of the physiological significance of modifications conditioned obviously by environmental changes.