New antitumour active platinum compounds containing carboxylate ligands in trans geometry: synthesis, crystal structure and biological activity

New asymmetric trans-platinum(II) complexes, composed of an isopropylamine, an azole and two carboxylate leaving groups, are presented. The crystal and molecular structures of one of the complexes has been determined and the cytotoxicity and reactivity with 5'-guanosine monophosphate is reported. The complexes show a reduced reactivity, but no decrease in cytotoxic activity compared to their chloro-counterparts. Furthermore the complexes largely overcome cisplatin resistance, they therefore present an interesting class of antitumour active trans-platinum complexes.     

Electrochemistry of copper complexes with macrocyclic polyamines containing pyrazole units

The voltammetric behaviour of bi- and mono-nuclear complexes formed in solution by Cu(2+) with three polyazacyclophanes containing pyrazole units in aqueous solution is described. Cyclic and square wave voltammetric responses at glassy carbon electrodes indicate that the reduction of copper-macrocycle complexes in solution takes place in two successive one-electron per Cu transfer processes coupled with preorganization and protonation reactions that mimic the behaviour of superoxide dismutase. The electrochemistry of ternary Cu(2+)-receptor-dopamine complexes exhibits significant differences with respect to the protection of the neurotransmitter from post-electron transfer cyclization reactions.     

Isolation and structural determination of xerophytolic acid A, a 3-geranyl-4-hydroxybenzoate derivative from Xerophyta plicata

A novel compound of a rare class of secondary metabolites, 3-geranyl-4-hydroxybenzoic acid derivative, methyl xerophytolate A (2), was isolated from the crude extract of Xerophyta plicata (Velloziaceae) collected in Rio de Janeiro, Brazil. The structure of 2 was elucidated using spectroscopic methods.     

A trimetal chain cocooned by two heptadentate polypyridylamide ligands

Compounds of nickel in which a chain of three metal atoms is closely embraced by two interlocking heptadentate dianions derived from a chain of five pyridyl groups linked at the 2, or 2 and 6, positions by four amide nitrogen atoms are reported. This new type of extended metal atom chain (EMAC) compound differs from earlier ones in that ligand exchange at the axial positions cannot occur, because the axial ligands are part of the entire ligand. Four such compounds, all crystallographically characterized, are reported. This work is a proof-of-concept project that will be extended to other metals with these and other homologous ligands.     

Viscum album aqueous extract induces NOS-2 and NOS-3 overexpression in Guinea pig hearts

Viscum album L. aqueous extract, on the Langendorff isolated and perfused heart model, decreases coronary vascular resistance, when compared to control group (36.00 +/- 2.00 vs. 15.80 +/- 1.96 dyn s cm-5). Our data support the fact that this mechanism involves NOS-2 and NOS-3 overexpression (4.65 and 7.89 times over control, respectively), which is correlated with increases in NO (6.24 +/- 2.49 vs. 147.95 +/- 2.79 pmol) and cGMP production (43.94 +/- 2.00 vs. 74.81 +/- 1.96 pmol mg-1 of tissue), compared to control values. Such an effect is antagonized by gadolinium(III) chloride, L-NAME and ODQ. Therefore, coronary vasodilator effect elicited by V. album L. aqueous extract is mediated by the NO/sGC pathway.     

Study of weak molecular interactions through thermodynamic mixing properties

The electron donor-acceptor abilities of some cyclic ethers (tetrahydropyran or tetrahydrofuran), benzene, and halobenzenes (fluorobenzene or chlorobenzene) and the molecular interactions between these compounds have been investigated through a wide set of thermodynamic mixing properties of their mixtures. The mixing properties have been derived from experimental measurements of density, speed of sound, refractive index, surface tension, heat of mixing, and vapor-liquid equilibrium at the temperature of 298.15 K.     

Structural characterization and oxidative dehydrogenation activity of V2O5/Ce(x)Zr(1-x)O2/SiO2 catalysts

The thermal stability of a nanosized Ce(x)Zr(1-x)O2 solid solution on a silica surface and the dispersion behavior of V2O5 over Ce(x)Zr(1-x)O2/SiO2 have been investigated using XRD, Raman spectroscopy, XPS, HREM, and BET surface area techniques. Oxidative dehydrogenation of ethylbenzene to styrene was performed as a test reaction to assess the usefulness of the VOx/Ce(x)Zr(1-x)O2/SiO2 catalyst. Ce(x)Zr(1-x)O2/SiO2 (1:1:2 mol ratio based on oxides) was synthesized through a soft-chemical route from ultrahigh dilute solutions by adopting a deposition coprecipitation technique. A theoretical monolayer equivalent to 10 wt % V2O5 was impregnated over the calcined Ce(x)Zr(1-x)O2/SiO2 sample (773 K) by an aqueous wet impregnation technique. The prepared V2O5/Ce(x)Zr(1-x)O2/SiO2 sample was subjected to thermal treatments from 773 to 1073 K. The XRD measurements indicate the presence of cubic Ce0.75Zr0.25O2 in the case of Ce(x)Zr(1-x)O2/SiO2, while cubic Ce0.5Zr0.5O2 and tetragonal Ce0.16Zr0.84O2 in the case of V2O5/Ce(x)Zr(1-x)O2/SiO2 when calcined at various temperatures. Dispersed vanadium oxide induces more incorporation of zirconium into the ceria lattice, thereby decreasing its lattice size and also accelerating the crystallization of Ce-Zr-O solid solutions at higher calcination temperatures. Further, it interacts selectively with the ceria portion of the composite oxide to form CeVO4. The RS measurements provide good evidence about the dispersed form of vanadium oxide and the CeVO4 compound. The HREM studies show the presence of small Ce-Zr-oxide particles of approximately 5 nm size over the surface of amorphous silica and corroborate with the results obtained from other techniques. The catalytic activity studies reveal the ability of vanadium oxide supported on Ce(x)Zr(1-x)O2/SiO2 to efficiently catalyze the ODH of ethylbenzene at normal atmospheric pressure. The remarkable ability of Ce(x)Zr(1-x)O2 to prevent the deactivation of supported vanadium oxide leading to stable activity in the time-on-stream experiments and high selectivity to styrene are other important observations.     

Nb2O5 "pathway effect" on hydrogen sorption in Mg

In the present work we investigate the hydrogen sorption mechanism in a MgH(2)/Nb(2)O(5) composite and analyze why Nb(2)O(5) could strongly improve hydrogen sorption kinetics in magnesium. Hereby we make use of the fact that Nb(2)O(5) nanoparticles are able to reduce the milling time significantly with the achievement of excellent sorption kinetics, and can so exclude effects occurring at long-term milling that make difficult the study of the mechanism. On the basis of extensive chemical, crystalline, and microstructural characterization of the MgH(2)/Nb(2)O(5) nanopowder system, a "pathway model" is proposed, which explains the kinetic hydrogen sorption improvement by a formation of pathways of niobium oxide species with lower oxidation state that facilitate the hydrogen transport into the sample. This mechanism is shown to be supported by additional oxidation experiments, which indicate increased oxygen diffusion through these pathways.     

Fourier multipliers and periodic solutions of delay equations in Banach spaces

In this paper we characterize the existence and uniqueness of periodic solutions of inhomogeneous abstract delay equations and establish maximal regularity results for strong solutions. The conditions are obtained in terms of R-boundedness of linear operators determined by the equations and Lp- Fourier multipliers. Periodic mild solutions are also studied and characterized.     

Invariants of 2 × 2 matrices, irreducible {\hbox{SL}(2, \mathbb{C})} characters and the Magnus trace map

We obtain an explicit characterization of the stable points of the action of on the cartesian product G  ^{× n} by simultaneous conjugation on each factor in terms of the corresponding invariant functions. From this, a simple criterion for the irreducibility of representations of finitely generated groups into G is derived. We also obtain analogous results for the action of on the vector space of n-tuples of 2 × 2 complex matrices. For a free group F _n of rank n, we show how to generically reconstruct the 2 ^n-2 conjugacy classes of representations F _n → G from their values under the map considered in Magnus [Math. Zeit. 170, 91–103 (1980)], defined by certain 3n − 3 traces of words of length one and two.