Beryllium compounds for the carbon-halogen bond activation of phenyl halides: the role of non-innocent ligands.

Beryllium is a metallomimetic main-group element, i.e., it behaves similarly to transition metals (TMs) in some bond activation processes. To investigate the ability of Be compounds to activate C-X bonds (X = F-I), we have computationally investigated, using DFT methods, the reaction of (CAAC)2Be (CAAC = 1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene) and a series of five-membered heterocyclic beryllium bidentate ligands with phenyl halides. We have analysed all plausible reaction mechanisms and our results show that, after the initial C-X oxidative addition, migration of the phenyl group occurs towards the less electronegative heteroatom. Our theoretical study highlights the important role of bidentate non-innocent ligands in providing the required electrons for the initial Ph-X oxidative addition. In contrast, the monodentate ligand, CAAC, does not favour this oxidative addition.

Design of Silica-Oligourethane-Collagen Membranes for Inflammatory Response Modulation: Characterization and Polarization of a Macrophage Cell Line.

The polarization of macrophages M0 to M1 or M2 using molecules embedded in matrices and hydrogels is an active field of study. The design of biomaterials capable of promoting polarization has become a paramount need nowadays, since in the healing process macrophages M1 and M2 modulate the inflammatory response. In this work, several immunocytochemistry and ELISA tests strongly suggest the achievement of polarization using collagen-based membranes crosslinked with tri-functionalized oligourethanes and coated with silica. Measuring the amount of TGF-ß1 secreted to culture media by macrophages growth on these materials, and quantifying the macrophage morphology, it is proved that it is possible to stimulate the anti-inflammatory pathway toward M2, having measurements with p ≤ 0.05 of statistical significance between the control and the collagen-based membranes. Furthermore, some physicochemical characteristics of the hybrid materials are tested envisaging future applications: collagenase degradation resistance, water uptake, collagen fiber diameter, and deformation resistance are increased for all the crosslinked biomaterials. It is considered that the biological and physicochemical properties make the material suitable for the modulation of the inflammatory response in the chronic wounds and promising for in vivo studies.

In vitro evaluation of apoptotic effect of bis(acetylacetonato-k2 O,O')(1,10-phenanthroline-k2 N,N')Zn(II) complex.

Phenanthroline derivatives have been reported as potential bioactive compounds because of their ability to interact with DNA. To evaluate the antiproliferative effect of bis(acetylacetonate-k2 O,O)(1,10-phenanthroline-k2 N,N)Zn(II) or Zn(acac)2 (phen) complex, the compound was obtained in a simple manner and further characterized to determine crystal structure, thermal behavior, morphology, and spectroscopic properties. The structure of the complex was confirmed by X-ray single structure as well as by 1H and 13C nuclear magnetic resonance (NMR) in dmso-d6 (dimethyl sulfoxide) solution and in the solid state by 13C CP/MAS. Although preparation of this compound has been described previously, there are no reports on its biological activity; here, we assessed its antiproliferative effect on fibroblasts, A253, FaDu, Cal-27, RH-30, RD, U-373, C6, A-549, MDA-MB-231, and MCF-7 cancer cell lines at different doses (50-100 and 150 µg/ml). The cell viability was determined by MTT assay and high activity was observed for the most of the cell lines, and TUNEL results showed the induction of apoptosis.

Hydrocortisone release from tablets based on bioresorbable poly(ether-ester-urethane)s

Abstract Bioresorbable linear poly(ether-ester-urethane)s with different hydrophilic characteristics were synthesized from triblock copolymers of poly(ε-caprolactone)-poly(ethylene oxide)-poly(ε-caprolactone) (PCL-PEO) as macrodiols, and L-lysine diisocyanate (LDI) or hexamethylenediisocyanate (HDI) were used as the required diisocyanates. Macrodiols were obtained by ring-opening polymerization (ROP) of ε-caprolactone (CL). Polyurethanes were synthesized by the reaction of the triblock copolymers with LDI or HDI in solution using stannous 2-ethylhexanoate as catalyst. Polyurethane tablets were fabricated and investigated as prospective drug delivery systems. The effect of the PEO content on the polymers' performance as drug carriers was evaluated. It was found that water provoked more swelling and erosion of polymers with higher contents of PEO. The hydrocortisone release profiles were analyzed using the Ritger-Peppas approximation. An anomalous release behaviour (values of n higher than 0.5) was found for most of the analyzed samples.

Quantum chemical characterization of zwitterionic structures: Supramolecular complexes for modifying the wettability of oil-water-limestone system.

In this work, we present a quantum chemical study pertaining to some supramolecular complexes acting as wettability modifiers of oil-water-limestone system. The complexes studied are derived from zwitterionic liquids of the types N'-alkyl-bis, N-alquenil, N-cycloalkyl, N-amyl-bis-beta amino acid or salts acting as sparkling agents. We studied two molecules of zwitterionic liquids (ZL10 and ZL13), HOMO and LUMO levels, and the energy gap between them, were calculated, as well as the electron affinity (EA) and ionization potential (IP), chemical potential, chemical hardness, chemical electrophilicity index and selectivity descriptors such Fukui indices. In this work, electrochemical comparison was realized with cocamidopropyl betaine (CPB), which is a structure zwitterionic liquid type, nowadays widely applied in enhanced recovery processes.