Structural studies on Ba(II) adducts of the cytosine nucleobase and its derivative 1-Methylcytosine*

Abstract

The use of the cytosine nucleobase or its 1-Methylcytosine derivative as ligands toward barium(II) cations led to the formation of three compounds, {[Ba(1-Mecyt)(H₂O)X₂]}_n [X=Cl (1), Br (2)], and {[Ba(cyt)₂(H₂O)(ClO₄)₂]}_n (3). Depending on the ligand and the counterion employed, 1–3 exhibit different architectures, which serve as a playground to study how the methyl substitution, together with the nature of the counterion are both significant in the self-assembling process of such species. The effect of the nature and size of the alkaline-earth metal ion on the final structural motif is also evident when comparing these structures with parent complexes of the Ca(II) ion.     

The flow over a thin airfoil subjected to elevated levels of freestream turbulence at low Reynolds numbers

Micro Air Vehicles (MAVs) can be difficult to control in the outdoor environment as they fly at relatively low speeds and are of low mass, yet exposed to high levels of freestream turbulence present within the Atmospheric Boundary Layer. In order to examine transient flow phenomena, two turbulence conditions of nominally the same longitudinal integral length scale (Lxx/c?=?1) but with significantly different intensities (Ti?=?7.2?% and 12.3?%) were generated within a wind tunnel; time-varying surface pressure measurements, smoke flow visualization, and wake velocity measurements were made on a thin flat plate airfoil. Rapid changes in oncoming flow pitch angle resulted in the shear layer to separate from the leading edge of the airfoil even at lower geometric angles of attack. At higher geometric angles of attack, massive flow separation occurred at the leading edge followed by enhanced roll up of the shear layer. This lead to the formation of large Leading Edge Vortices (LEVs) that advected at a rate much lower than the mean flow speed while imparting high pressure fluctuations over the airfoil. The rate of LEV formation was dependent on the angle of attack until 10° and it was independent of the turbulence properties tested. The fluctuations in surface pressures and consequently aerodynamic loads were considerably limited on the airfoil bottom surface due to the favorable pressure gradient.     

Nanoparticle debonding strength: A comprehensive study on interfacial effects

The most appealing feature of nanofilled polymers is the perspective of obtaining surprisingly high mechanical properties at low nanofiller volume fractions. The knowledge of nanostructure–property relationships is however essential for the design of these materials.In the present work, a model for the critical hydrostatic tension related to nanoparticle debonding is presented. The model accounts for some important issues inherently related to the nanoscale with particular reference to surface elastic stresses on the nanoparticle periphery and the emergence of a zone of altered chemistry surrounding the nanoparticle. The analytical solution suggests that the range of nanoparticle radii where interfacial effects do affect the solution is limited to the nanometer scale. In more details, considering the interphase and surface elastic properties used in the analysis, it has been found that for stiff particles with radius between 10 nm and 100 nm (silica, alumina and other metal oxide nanoparticles) the prominent role is played by the interphase elastic properties. Surface elastic constants were found to have, instead, only a negligible effect.     

Pyrrole-Annulated Heterocyclic Systems. Synthesis of 2H-Pyrrolo[3,4-b][1,5]benzothiazepine 4,4-Dioxide Derivatives

Condensation of 2-nitrothiophenol with ethyl propiolate afforded 3-(2-nitrophenylthio)propenoate. Oxidation of sulfur atom to sulfone group gave ethyl 3-(2-nitrophenylsulfonyl)propenoate, which underwent condensation with tosyl methylisocyanide (TosMIC) to yield ethyl 4-(2-nitrophenylsulfonyl)pyrrole-3-carboxylate. Reduction of nitro group afforded ethyl 4-(2-aminophenylsulfonyl)-1H-pyrrole-3-carboxylate, which was cyclized to 2H-pyrrolo[3,4-b][1,5] benzothiazepin-10(9H)-one 4,4-dioxide. Similar procedure was used for the synthesis of 9,10-dihydro-10-methyl-2H-pyrrolo[3,4-b][1,5]benzothiazepine 4,4-dioxide.     

Microwave-assisted oxidation of silibinin: a simple and preparative method for the synthesis of improved radical scavengers

A new and preparative oxidation of silibinin has been developed to give access to two different silibinin derivatives known for their enhanced antioxidant properties. Conventional heating methods were compared with results obtained from microwave (MW) heating. The base-catalysed oxidation of silibinin under MW heating is a very efficient method for the preparation of 2,3-dehydrosilybin and a related silybin rearrangement product. This latter compound shows enhanced radical scavenging properties. Optimised conditions were used to prepare 2,3-dehydrosilybins A and B from optically pure silybins A and B. An efficient, preparative purification method was also developed to enable isolation of different products in high purity.     

TiCl4-promoted addition of nucleophiles to open chain α-amidoalkylphenyl sulfones

Linear α-amidoalkylphenyl sulfones are converted into the corresponding N-acyliminium ions by treatment with TiCl₄ at low temperature and then made to react with different nucleophiles such as allyltrimethylsilane, silyl ketene acetal, anisole and thiophene.     

Synthesis,Characterization, and Biological Evaluation of a Dual-Action Ligand Targeting αvβ3 Integrin and VEGF Receptors

A dual-action ligand targeting both integrin α_Vβ₃ and vascular endothelial growth factor receptors (VEGFRs), was synthesized via conjugation of a cyclic peptidomimetic α_Vβ₃ Arg-Gly-Asp (RGD) ligand with a decapentapeptide. The latter was obtained from a known VEGFR antagonist by acetylation at the Lys13 side chain. Functionalization of the precursor ligands was carried out in solution and in the solid phase, affording two fragments: an alkyne VEGFR ligand and the azide integrin α_Vβ₃ ligand, which were conjugated by click chemistry. Circular dichroism studies confirmed that both the RGD and VEGFR ligand portions of the dual-action compound substantially adopt the biologically active conformation. In vitro binding assays on isolated integrin α_Vβ₃ and VEGFR-1 showed that the dual-action conjugate retains a good level of affinity for both its target receptors, although with one order of magnitude (10/20 times) decrease in potency. The dual-action ligand strongly inhibited the VEGF-induced morphogenesis in Human Umbilical Vein Endothelial Cells (HUVECs). Remarkably, its efficiency in preventing the formation of new blood vessels was similar to that of the original individual ligands, despite the worse affinity towards integrin α_Vβ₃ and VEGFR-1.