Fuentescorcoran0646

A new nanocluster-based silver(i) tert-butylethynide compound, namely, (tBuC[triple bond, length as m-dash]CAg)2(Ag4SiW12O40)(DMSO)6 (HT-1), has been synthesized and structurally characterized by X-ray crystallography. The two kinds of nanocluster synthons (a silver aggregate named [(tBuC[triple bond, length as m-dash]C)2Ag6(DMSO)6] and a SiW12 polyoxoanion) are assembled into a three-dimensional coordination network, which has a non-centrosymmetric crystal lattice. Powder second-harmonic generation (SHG) measurements reveal that HT-1 belongs to the phase-matchable class with a moderately strong SHG response of about 3 times that of the KH2PO4 (KDP) sample. HT-1 represents the first example of a Ag(i) alkynyl cluster compound with a SHG response. The present study not only extends the application fields of Ag(i) alkynyl clusters but also demonstrates a new paradigm for understanding the Ag(i) alkynyl structural chemistry.A general and efficient strategy for the synthesis of protected α-amino acids is reported. The method uses malonate derivatives as the starting materials and Cs2CO3 as a base at 60 degrees, giving α-amino acid derivatives in moderate yields by releasing CO2. This methodology shows broad substrate scope (primary and secondary acids), excellent functional group tolerance and high efficiency to give the desired products under mild reaction conditions. It also allows the construction of β and γ-amino acids and other unnatural products.Porphyrin-based periodic mesoporous organosilica nanoparticles (PMO) synthesized from a large functional octatriethoxysilylated porphyrin precursor and allowing two-photon excitation photodynamic therapy (TPE-PDT) and NIR imaging were synthesized. These PMO were grafted with polyethylene glycol (PEG) moieties and an analogue of mannose 6-phosphate functionalized at the anomeric position (AMFA). AMFAs are known to efficiently target mannose 6-phosphate receptors (M6PRs) which are over-expressed in various cancers. Here, we demonstrated for the first time that M6PRs were over-expressed in rhabdomyosarcoma (RMS) cells and could be efficiently targeted with PMO-AMFA allowing TPE imaging and TPE-PDT of RMS cells. The comparison with healthy myoblasts demonstrated an absence of biological effects, suggesting a cancer cell specificity in the biomedical action observed.We report the first application of a rigid P2N3 pincer ligand in p-block chemistry by preparing its bismuth complex. We also report the first example of bismuth complexes featuring a flexible PNP pincer ligand, which shows phase-dependent structural dynamics. Highly electrophilic, albeit thermally unstable, Bi(iii) complexes of the PNP ligand were also prepared.An interface between poly(methyl-methacrylate) PMMA-supported phosphorene and layers of linear alkane chains has been studied computationally to reveal an efficient route to noncovalent passivation in terms of the effective coverage of surface area. The formation of strongly ordered compact planar aggregates of alkanes driven by the anisotropy of the phosphorene surface greatly improves the packing at the interface. Small mechanical deformations of the phosphorene structure induced by the interaction with PMMA substrate, a polymer dielectric material, do not alter substantially the mechanical, electronic properties of phosphorene. This indicates remarkable possibilities of using alkanes for prevention of phosphorene from surface degradation phenomena and suggests new technological routes for the fabrication of phosphorene-based electronic devices.In this study, anisotropic SmCo5 magnets were prepared by a distinctive method, which is the high-temperature reductive annealing of Co@Sm2O3 with a specially designed nanostructure. High resolution transmission electron microscopy and elemental mapping show that the precursor self-assembly is composed of hcp-structured Co nano-rods with a coherent crystallographic orientation. During high temperature reduction, the Sm2O3 shell preserves the original morphology and alignment of these anisotropic Co nano-arrays, providing a template for hcp-structured SmCo5 single crystal particle synthesis. The as-prepared SmCo5 magnets exhibit well-controlled size and morphology, and a high coercivity of 30.9 kOe at room temperature. No stabilizer coating is necessary to prevent the formation of polycrystals in this synthesis.Advanced glycation end products (AGEs) and their important intermediate products (α-dicarbonyl compounds) that are generated by the Maillard reaction are closely related to diabetes. Our study first investigated the mechanisms of the anti-glycation effects of epicatechin (EC), (-)-epicatechin gallate (ECG), (-)-epigallocatechin (EGC), and (-)-epigallocatechin gallate (EGCG) in an alcoholic environment. The results showed that catechins played an important role in the inhibition of AGE formation, and the effect of EC was the best. Their corresponding mechanisms included total antioxidant capacity (TAOC), 1,1-diphenyl-2-picrylhydrazyl (DPPH) scavenging ability, trapping of methylglyoxal (MGO), protection of the protein structure, and inhibition of the activities of α-amylase, α-glucosidase, and β-glucosidase, which were consistent with the study of molecular docking. This study will offer a theoretical basis for the applications of different types of catechins to alcoholic beverages as natural AGE formation inhibitors.We study the reactivity of Fe(iv)O moieties supported by a metal-organic framework (MOF-74) in the oxidation reaction of methane to methanol using all-electron, periodic density-functional theory calculations. We compare results concerning the electronic properties and reactivity obtained using two hybrid (B3LYP and sc-BLYP) and two standard generalised gradient corrected (PBE and BLYP) semi-local density functional approximations. The semi-local functionals are unable to reproduce the expected reaction profiles and yield a qualitatively incorrect representation of the reactivity. Non-local hybrid functionals provide a substantially more reliable description and predict relatively modest (ca. 60 kJ mol-1) reaction energy barriers for the H-atom abstraction reaction from CH4 molecules. see more We examine the origin of these differences and we highlight potential means to overcome the limitations of standard semi-local functionals in reactivity calculations in solid-state systems.