Polyakov soldering and second order frames : the role of the Cartan connection

The so-called "soldering" procedure performed by A.M. Polyakov in [1] for a SL(2,R)-gauge theory is geometrically explained in terms of a Cartan connection on second order frames of the projective space RP^1. The relationship between a Cartan connection and the usual (Ehresmann) connection on a principal bundle allows to gain an appropriate insight into the derivation of the genuine " diffeomorphisms out of gauge transformations" given by Polyakov himself.Comment: Accept\'e pour publication dans Lett. Math. Phy

Atom efficient preparation of zinc selenates for the synthesis of selenoesters under “On Water” conditions

The use of PhSZnBr as sulfenylating agent in a solvent-free protocol to prepare in excellent yields thiol esters from acyl chlorides is here reported. Products were efficiently obtained by grinding the neat reagents for 5 min in a mortar. DFT calculations showed that the coordination of solvent molecules to the metal center of PhSZnBr results in the destabilization of the frontier MOs, thus reducing the reactivity towards the acyl chloride if compared to solvent-free conditions. A possible mechanism based on the coordination of the carbonyl group of the acyl chloride to the metal center of PhSZnBr is proposed

Attribuzione di elementi maggiori ed in traccia, contenuti nel particolato atmosferico, alle diverse sorgenti di emissione nell'area di Civitavecchia. Risultati preliminari

Consiglio Nazionale delle Ricerche (CNR). Biblioteca Centrale / CNR - Consiglio Nazionale delle RichercheSIGLEITItal

Reaction kinetics and targeting to cellular glutathione S-transferase of the glutathione peroxidase mimetic PhSeZnCl and its D,L-polylactide microparticle formulation

Catalytic properties and cellular effects of the glutathione peroxidase (GPx)-mimetic compound PhSeZnCl or its d,l-lactide polymer microencapsulation form (M-PhSeZnCl) were investigated and compared with the prototypical Se-organic compounds ebselen and diselenide (PhSe)2. PhSeZnCl was confirmed to catalyze the ping-pong reaction of GPx with higher Vmax than ebselen and (PhSe)2, but the catalytic efficiency calculated for the cosubstrates glutathione (GSH) and H2O2, and particularly the high reactivity against thiols (lowest KM for GSH in the series of test molecules), suggested poor biological applicability of PhSeZnCl as a GPx mimetic. Cytotoxicity of PhSeZnCl was demonstrated in various cancer cell lines via increased reactive oxygen species (ROS) generation, depletion of intracellular thiols, and induction of apoptosis. Experiments carried out in GSH S-transferase P (GSTP)-overexpressing K562 human erythroleukemia cells and in GSTP1-1-knockout murine embryonic fibroblasts (MEFs) demonstrated that this cytosolic enzyme represents a preferential target of the redox disturbances produced by this Se-compound with a key role in controlling H2O2 generation and the perturbation of stress/survival kinase signaling. Microencapsulation was adopted as a strategy to control the thiol reactivity and oxidative stress effects of PhSeZnCl, then assessing applications alternative to anticancer. The uptake of this "depowered" GPx-mimetic formulation, which occurred through an endocytosis-like mechanism, resulted in a marked reduction of cytotoxicity. In MCF-7 cells transfected with different allelic variants of GSTP, M-PhSeZnCl lowered the burst of cellular ROS induced by the exposure to extracellular H2O2, and the extent of this effect changed between the GSTP variants. Microencapsulation is a straightforward strategy to mitigate the toxicity of thiol-reactive Se-organic drugs that enhanced the antioxidant and cellular protective effects of PhSeZnCl. A mechanistic linkage of these effects with the expression pattern and signaling properties of GSTP . This has overcome the GPx-mimetic paradigm proposed for Se-organic drugs with a more pragmatic concept of GSTP signaling modulators