Synthesis and inverse virtual screening of new bi-cyclic structures towards cancer-relevant cellular targets

Structural Chemistry - We report here synthetic approaches to access new classes of small molecules based on three heterocyclic scaffolds, i.e. 3,7-dihydropyrimido[4,5-d]pyridazine-4,8-dione,...     

Mild Friedel–Crafts Reactions inside a Hexameric Resorcinarene Capsule: C−Cl Bond Activation through Hydrogen Bonding to Bridging Water Molecules

A novel catalytic feature of a hexameric resorcinarene capsule is highlighted. The self‐assembled cage was exploited to promote the Friedel–Crafts benzylation of several arenes and heteroarenes with benzyl chloride under mild conditions. Calculations showed that there are catalytically relevant hydrogen‐bonding interactions between the bridging water molecules of the capsule and benzyl chloride, which is fundamental for the activation of the C?Cl bond. The capsule controls the reaction outcome. Inside the inner cavity of the capsule, N‐methylpyrrole is preferentially benzylated in the unusual β‐position while mesitylene reacts faster than 1,3‐dimethoxybenzene despite the greater π‐nucleophilicity of the latter compound.     

Synergic Interplay Between Halogen Bonding and Hydrogen Bonding in the Activation of a Neutral Substrate in a Nanoconfined Space

The principle of amplified halogen bonding (XB) in a small space is exploited as a catalytic tool for the activation of an XB acceptor substrate in a nanoconfined environment. The inner cavity of the resorcinarene capsule has been equipped with an XB catalyst bearing an ammonium unit acting as a Trojan horse to drive the catalyst inside the capsule. In the presence of a specific XB catalyst, the capsule is able to catalyze a Michael reaction between N‐methylpyrrole and methyl vinyl ketone. In the bulk medium in absence of the resorcinarene capsule, the XB catalyst is catalytically ineffective. Quantum‐mechanical investigations highlight that the Michael reaction proceeds through the activation of the carbonyl group by synergistically enhanced halogen/hydrogen‐bonding interactions and takes place in an open pentameric capsule.     

Oxidation states of iron as an indicator of the techniques used to burn clays and handcraft archaeological Tupiguarani ceramics by ancient human groups in Minas Gerais, Brazil

Ceramics of the Tupiguarani Tradition typically have in common the burning characteristics, their forms and decoration motifs. Dating such ceramic pieces with the radiocarbon method indicate that these artifacts were probably handcrafted between 1,500 and 500 years before the present. Fragments ceramic utensils were collected in the archaeological site of Beltrão, in the municipality of Corinto, state of Minas Gerais, Brazil. A fragment of about 50 mm in diameter and 15 mm thick, with a color gradation across the ceramic wall ranging from red, on one side, grayish, in the middle, and orange, on the opposite side, was selected for a more detailed examination. The fragment was transversely cut and a series of subsamples were separated from different points along the piece wall, in layer segments of ~3 mm. All subsamples were analyzed with Mössbauer spectroscopy at room temperature and 80 K. Results reveal that hematite is the magnetically ordered phase. A Fe^2?+? component (relative spectral area, 50 %) appears for the grayish subsample. According to these first results, the red subsample seems to be the side that had direct contact with fire used to burn the precursor clay in air. The grayish middle layer is probably due to the clay mixed with some ashes. Mössbauer data reveal that the orange layer, corresponding to the opposite side of the ceramic relatively to the direct fire, does contain about the same Fe^2?+?:Fe^3?+? ratio but much lower proportion of α-Fe₂O₃ than the red layer.