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-bipyridines containing halogens as substituents, were enantioseparated by high-performance liquid chromatography in order to obtain pure enantiomer pairs. All stereoisomers were tested against the amyloid fibril formation (FF) of wild type (WT)-TTR and two mutant variants, V30M and Y78F, in acid mediated aggregation experiments. Among the 4,4&prime -bipyridine derivatives into the TTR. The gained results point out the importance of the right combination of H-bond sites and the presence of iodine as halogen-bond donor. Both experimental and theoretical evidences pave the way for the utilization of the iodinated 4,4&prime - bipyridines were rationally designed and prepared from a simple trihalopyridine in three steps, including a Cu-catalysed Finkelstein reaction to introduce iodine atoms on the heteroaromatic scaffold, and a Pd-catalysed coupling reaction to install the 2&prime -bipyridine structure is proposed as a novel chemical scaffold for the design of new transthyretin (TTR) fibrillogenesis inhibitors. In the frame of a proof-of-principle exploration, four chiral 3,3&prime -bipyridine. In silico docking studies were carried out in order to explore possible binding modes of the 4,4&prime -bipyridine derivatives, interesting inhibition activity was obtained for both enantiomers of the 3,3&prime -bipyridine core as template to design new promising inhibitors of TTR amyloidogenesis. -substituent. The corresponding racemates, along with other five chiral 4,4&prime -(4-hydroxyphenyl)-2-iodo-4,4&prime -tetrachloro-2-iodo-4,4&prime -tetrachloro-2-iodo-2&prime -substituted-4,4&prime -tetrachloro-2&prime The 3,3&prime ,5,5&prime

We determined the specific biomass burning biomarker levoglucosan in an ice core from the TALos Dome Ice CorE drilling project (TALDICE) during the mid- to late Holocene (6000–750 BP). The levoglucosan record is characterized by a long-term increase with higher rates starting at ∼ 4000 BP and peaks between 2500 and 1500 BP. The anomalous increase in levoglucosan centered at ∼ 2000 BP is consistent with other Antarctic biomass burning records. Multiple atmospheric phenomena affect the coastal Antarctic Talos Dome drilling site, where the Southern Annular Mode (SAM) is the most prominent as the Southern Annular Mode Index (SAMA) correlates with stable isotopes in precipitation throughout the most recent 1000 years of the ice core. If this connection remains throughout the mid- to late Holocene, then our results demonstrate that changes in biomass burning, rather than changes in atmospheric transport, are the major influence on the TALDICE levoglucosan record. Comparisons with charcoal syntheses help evaluate fire sources, showing a greater contribution from southern South American fires than from Australian biomass burning. The levoglucosan peak centered at ∼ 2000 BP occurs during a cool period throughout the Southern Hemisphere, yet during a time of increased fire activity in both northern and southern Patagonia. This peak in biomass burning is influenced by increased vegetation in southern South America from a preceding humid period, in which the vegetation desiccated during the following cool, dry period. The Talos Dome ice core record from 6000 to ∼ 750 BP currently does not provide clear evidence that the fire record may be strongly affected by anthropogenic activities during the mid- to late Holocene, although we cannot exclude at least a partial influence.

The reactivity of beta-aminocarbonates as anisotropic electrophiles has been investigated with several phenols. Products distribution shows that the regioselectivity of the anchimerically driven alkylation reaction depends on the nucleophiles. The results suggest that in the presence of nucleophiles that are also good leaving groups, the reaction takes place under thermodynamic control favoring the attack on the most sterically hindered carbon of the cyclic aziridinium intermediate. Furthermore, when an enantiomerically pure pyrrolidine-based carbonate was used, the reaction with phenols proceeds via a bicyclic aziridinium intermediate leading to the stereoselective synthesis of optically active 3-substituted piperidines via ring expansion reaction. These results were confirmed both by NMR spectroscopy and X-ray diffraction analysis.