Ricerc@Sapienza

Access to chiral calix[4]arenes can unlock novel supramolecular architectures for enantioselective catalysis and molecular recognition. However, accessibility to these structures has been significantly hindered so far. We report herein the synthesis and characterization of di- and trifunctionalized cone-calix[4]arenes featuring a lactone moiety spanning the distal positions at the upper rim. The lactones force the whole skeleton to assume pinched-cone conformations. The ring-closure is favored by the high conformational flexibility of the calixarene scaffold.

The oxidation of a series of aryl 1-methyl-1-phenylethyl sulfides with H2O2catalyzed by the two tetradentate nonheme-iron complexes [(PDP)FeII(SbF6)2] and [(BPMCN)FeII(OTf)2] occurs by an electron transfer-oxygen transfer (ET/OT) mechanism as supported by the observation of products deriving from fragmentation of the corresponding radical cations in association with S-oxidation products (sulfoxides). © 2017 Taylor & Francis Group, LLC.

A new on-line multidimensional system for sequential trapping and individual elution and separationof peptides based on their molecular weight is described. By sequentially using two chemically differenttrapping columns, a polymethacrylate monolith and a packed C18 one, peptides from complex samplescan be on-line trapped and divided into two fractions, containing respectively mainly medium-large pep-tides and smaller peptides. Then, by means of two switching valves working in parallel, the two fractionswere individually separated by reversed phase chromatography.

This Account describes from a personal point of view the possible strategies to tackle and optimize non-covalent organocatalyzed reactions. When chemical intermediates are covalently bound, predictive mechanicistic pictures can be depicted. In contrast, there are several organocatalyzed transformations (e.g. those employing Cinchona alkaloids) for which optimization is essentially based on a trial-and-error approach. The experience of authors is that these reactions can be tackled with a rational approach employing DoE, Design of Experiment.

Improving the efficacy of gene therapy vectors is still an important goal toward the development of safe and efficient gene therapy treatments. S/MAR (scaffold/matrix attached region)-based vectors are maintained extra-chromosomally in numerous cell types, which is similar to viral-based vectors. Additionally, when established as an episome, they show a very high mitotic stability.

The mechanisms by which microRNAs control pediatric high-grade gliomas (pHGGs) have
yet to be fully elucidated. Our studies of patient-derived pHGG tissues and of the pHGG cell line
KNS42 revealed down-regulation in these tumors of three microRNAs, specifically miR-107, miR-181c,
and miR-29a-3p. This down-regulation increases the proliferation of KNS42 cells by de-repressing
expression of the Notch2 receptor (Notch2), a validated target of miR-107 and miR-181c and a

In the field of restoration of cultural heritage, it has been developed coatings containing nanoparticles having multifunctional features, to protect stone materials against environmental degrading agents. Detecting such nanoparticle concentration within the coating, can represent a challenging issue because its monitoring over time can provide insights about the treatment durability. This paper deals with a theoretical basis to develop an instrumental method to fulfil this requirement.

By using molecular dynamics based on a custom polarizable force field, we have studied the solvation of La3+ in an equimolar mixture of dimethylsulfoxide (DMSO) with water. An extended structural analysis has been performed to provide a complete picture of the physical properties at the basis of the interaction of La3+ with both solvents. Through our simulations we found that, very likely, the first solvation shell in the mixture is not unlike the one found in pure water or pure DMSO and contains 9 solvent molecules.

Background: Epithelial ovarian cancer has a poor prognosis, mostly due to its late diagnosis and the development of drug resistance after a first platinum-based regimen. The presence of a specific population of “cancer stem cells” could be responsible of the relapse of the tumor and the development of resistance to therapy. For this reason, it would be important to specifically target this subpopulation of tumor cells in order to increase the response to therapy.

A straightforward one-pot approach to the synthesis of challenging 12-arylindolo[1,2-c]quinazolin-6(5H)-ones is described. Starting from readily available o-(o-aminophenylethynyl)trifluoroacetanilides, palladium-catalyzed aminoarylation of the triple bond with ArI, ArBr, and ArN2 +BF4 – is followed by cyclization of the resulting N-trifluoro­acetyl-2-(o-aminophenyl)-3-aryl indole. This sequential reaction provides the title compounds by means of a rare elimination of trifluoromethane.