Effect of counterion on the catalytic activity of NHC-gold(I) in A3 coupling reactions

Synthetic A3-coupling represents an efficient and environmentally convenient procedure for the production of propargylamines, relevant intermediates for the preparation of pharmacologically active substances. Gold(I) complexes of general formula NHC-Au-X have been synthesized, characterized, and tested in the A3-coupling reaction of benzaldehyde, piperidine and phenylacetylene on varying the anionic fragment X as halogenide (Cl, Br, I), acetate (OAc), hexafluorophosphate (PF6) or phenylacetylide (-C≡CPh), with 5-dichloro[N-methyl, N’(2-hydroxy-2-phenyl)ethyl imidazole-2-ylidene as NHC ligand. The kinetic profiles were interpreted with DFT (Density Functional Theory) studies on bond dissociation energies (BDE) of the counterion as well as on the relative stability of the neutral NHC-Au-X complexes with respect to their ionic forms [Au(NHC)2]+[AuX2]-

Per presentare una disciplina curiosa e uno studio stimolante, per potenziare passione e vivacita intellettuale

ItL'uso della matematica nella società è cambiato profondamente negli ultimi decenni. Ciò ha influito sul suo ruolo nel percorso educativo che ha anche perso, così, una visione organica. E' necessario che la scuola della progettualità e dell'autonomia recuperi l'unitarietà del sapere, e riconquisti una visione globale del processo educativo. Sin dalla scuola di base può essere stimolata la creatività di ogni studente, con una scuola che guidi l'alunno a ricercare la conoscenza non solo con la logica e il ragionamento, ma anche con l'intuito e la fantasia e con una scuola che stimoli la curiosità, che sia attenta ai bisogni degli studenti e che ne favorisca il protagonismo in un clima di collaborazione. Ovviamente non è facile abbandonare la comoda via dei programmi tradizionali,i consueti criteri di verifica e di valutazione. La via della sperimentazione è più complessa e rischiosa. Nel lavoro si presentano aspetti e spunti particolari di argomenti che rendono la matematica curiosa ed affascinante quali i bioritmi ed i frattali e stimolante quale la crittografia. Si discutono, quindi, celebrazioni di organizzazioni mondiali quale, l'UNESCO, e conquiste sociali e civili di grandi scienziati che suscitano forti passioni ed evidenziano profondo spirito critico. Infine si presentano argomenti ludici e divertenti che richiedono creatività e fantasia mostrando matematica che stimola vivacità di pensiero e potenzia le capacità intellettuali

Synthesis, characterization, and optical properties of ROMP copolymers with pendant carbazole and coumarin groups

Two series of random copolymers containing at the same time two fluorescent groups, carbazole and coumarin, linked to a poly(norbornene dicarboximide) backbone have been prepared by controlled ring-opening metathesis polymerization (ROMP), promoted by Grubbs’ third generation catalyst (G3). The relative amount of the two functionalities was systematically varied along the copolymer chain, and the high degree of structural control observed allowed also for the preparation of a block copolymer with an equimolar content of fluorophore groups. In comparison to the related homopolymers, all the random copolymers exhibited in solution typical photoluminescence due to the carbazole or coumarin moiety, together with fluorescence arising from the energy transfer from the donor carbazole groups to the acceptor coumarin groups. This energy transfer seems to occur through intramolecular interactions, as it is not observed in the block copolymer and in the 50/50 homopolymer blend. On the other hand, in the solid state also the energy transfer from carbazole to coumarin through interchain interactions can take place. Of note, moving from solution to solid state fluorescence analysis, a blue shift of the band related to the energy transfer phenomenon is observed. This finding could be related to a combined effect of energy and electron transfer from donor to acceptor

Coupling of Josephson flux-flow oscillators to an external RC load

We investigate by numerical simulations the behavior of the power dissipated in a resistive load capacitively coupled to a Josephson flux flow oscillator and compare the results to those obtained for a d.c. coupled purely resistive load. Assuming realistic values for the parameters R and C, both in the high- and in the low-Tc case the power is large enough to allow the operation of such a device in applications.Comment: uuencoded, gzipped tar archive containing 11 pages of REVTeX text + 4 PostScript figures. To appear in Supercond. Sci. Techno

New Antenna Deployment, Pointing and Supporting Mechanism

On ITALSAT Flight 2, the Italian telecommunications satellite, the two L-Ka antennas (Tx and Rx) use two large deployable reflectors (2000-mm diameter), whose deployment and fine pointing functions are accomplished by means of an innovative mechanism concept. The Antenna Deployment & Pointing Mechanism and Supporting Structure (ADPMSS) is based on a new configuration solution, where the reflector and mechanisms are conceived as an integrated, self-contained assembly. This approach is different from the traditional configuration solution. Typically, a rigid arm is used to deploy and then support the reflector in the operating position, and an Antenna Pointing Mechanism (APM) is normally interposed between the reflector and the arm for steering operation. The main characteristics of the ADPMSS are: combined implementation of deployment, pointing, and reflector support; optimum integration of active components and interface matching with the satellite platform; structural link distribution to avoid hyperstatic connections; very light weight and; high performance in terms of deployment torque margin and pointing range/accuracy. After having successfully been subjected to all component-level qualification and system-level acceptance tests, two flight ADPMSS mechanisms (one for each antenna) are now integrated on ITALSAT F2 and are ready for launch. This paper deals with the design concept, development, and testing program performed to qualify the ADPMSS mechanism

Altered Expression of Protamine-like and Their DNA Binding Induced by Cr(VI): A Possible Risk to Spermatogenesis?

Chromium (VI) is the most dangerous oxidation state among the stable forms of chromium. In this work, we evaluated the effect of exposing Mytilus galloprovincialis for 24 h to 1, 10, and 100 nM chromium (VI) on the properties of Protamine-like (PLs) and their gene levels in the gonads. Specifically, we analyzed, by AU-PAGE and SDS-PAGE, PLs extracted from unexposed and exposed mussels. In addition, via EMSA, we evaluated the ability of PLs to bind DNA and also verified their potential to protect DNA from oxidative damage. Finally, we assessed possible alterations in gonadal expression of mt10, hsp70, and genes encoding for PLs-II/PL-IV and PL-III. We found that for all experimental approaches the most relevant alterations occurred after exposure to 1 nM Cr(VI). In particular, a comigration of PL-II with PL-III was observed by SDS-PAGE; and a reduced ability of PLs to bind and protect DNA from oxidative damage was recorded. This dose of chromium (VI) exposure was also the one that produced the greatest alterations in the expression of both mt10 and PL-II/PL-IV encoding genes. All of these changes suggest that this dose of chromium (VI) exposure could affect the reproductive health of Mytilus galloprovincialis

Synthesis and complexing properties of cyclic benzylopeptoids-a new family of extended macrocyclic peptoids

An efficient protocol for the solid-phase synthesis of six members of a new class of extended macrocyclic peptoids (based on ortho-, meta- and para-N-(methoxyethyl)aminomethyl phenylacetyl units) is described. Theoretical (DFT) and experimental (NMR) studies on the free and Na+-complexed cyclic trimers (3\u20135) and tetramers (6\u20138) demonstrate that annulation of the rigidified peptoids can generate new hosts with the ability to sequestrate one or two sodium cations with the affinities and stoichiometries defined by the macrocycle morphology. Ion transport studies have been also performed in order to better appreciate the factors promoting transmembrane cation translocation