A 1:1.5 complex of 5,7-dioxo-1,4,8,11-tetraazacyclotetradecane and 2,6-dihydoxyanthraquinone

A complex of 5,7-dioxo-1,4,8,11-tetraazacyclotetradecane (dioxocyclam) and 2,6-dihydoxyanthraquinone (anthraflavic acid) has been obtained. The complex (crystals grown from water-ethanol solution) has a stoichiometry dioxocyclam-anthraflavic acid 1:1:5. C₃₁H₃₂N₄O₈, chemical formula weight 588.61, triclinic, P – 1, a = 10.542(3) Å, b = 11.936(2) Å, c = 12.206(2) Å, = 104.00(1)°, = 92.68(2)°, = 103.64(2)°, V = 1439.4 (5) ų, Z = 2, D_x = 1.358 g cm^–3. Only one of the two amine N-atoms of the macrocycle is protonated due to very weak acidic properties of 2,6-dihydoxyanthraquinone. Due to the rather poor quality of the crystals and structure refinement, reliable determination of H-bonds is complicated. Nevertheless, several types of H-bonding responsible for the formation of a developed supramolecular network can be suggested: between the protonated amino groups and macrocycle's C=O moieties; between non-protonated amino groups and macrocycle's C=O moieties; between protonated and non-protonated amino groups; between the amide NH and C=O groups of anthraflavic acid; and between protonated and deprotonated hydroxy groups of the acid. Two types of anthraflavic components can be distinguished in the lattice: those having a parallel orientation with respect to the macrocyclic fragments and forming hydrogen bonds with the latter, and those lying in an approximately perpendicular plane and not involved in H-bonding with the macrocycles.     

Mössbauer effect phase determination in iron oxide–polyaniline nanocomposites

Mössbauer effect spectroscopy and thermal analysis techniques were applied to characterize polyaniline composites successfully synthesized by embedding Fe oxide nanoparticles (about 10–13 nm) in a polymeric matrix in the presence of dodecyl benzene sulfonic acid and HCl (dopant). Thermal techniques provided quantitative information on iron oxide content and on polyaniline stability and transformations. Mössbauer results indicated that for the whole studied composition range, 3.4 to 100 iron oxide wt.%, composites hold maghemite particles. A preliminary study of the conductivity of the nanocomposites was performed. The largest conductivity was observed for a 8 wt.% maghemite composite where all particles are magnetically unblocked at room temperature within the Mössbauer time window.     

Nafion/tetraruthenated porphyrin glassy carbon-modified electrode: characterization and voltammetric studies of sulfite oxidation in water–ethanol solutions

In this work, the modification of a glassy carbon electrode with tetraruthenated porphyrins electrostatically assembled onto a Nafion film, previously adsorbed on the electrode surface, is reported. This modified electrode was characterized by scanning electron microscopy–energy-dispersive X-ray, Raman spectroscopy, UV-Vis spectroelectrochemistry, and cyclic voltammetry. The Nafion film onto the glassy carbon electrode shows a smooth disposition; when the tetraruthenated porphyrin is incorporated on the Nafion film, the complex is adsorbed in a homogeneous way. The modified electrode catalyzes HSO₃⁻ oxidation in water–ethanol solutions and shows an enhanced stability compared with the electrode modified with the dip coating method. Rotating disk electrode experiments showed a kinetic limitation to the electron transfer controlled by charge propagation in the film. I/E curves show a Tafel slope of 120 mV/decade corresponding to a first electron-transfer reaction, depending on the potential, as the determining step. Spectroelectrochemical experiments demonstrated that Ru(II) is the active site for the electrocatalysis.     

Synthesis and characterization of new complexes of the type [Ru(CO)2Cl2 (2‐phenyl‐1,8‐naphthyridine‐kN) (2‐phenyl‐1,8‐naphthyridine‐kN′)]. Preliminary applications in homogeneous catalysis

Novel ruthenium (II) complexes were prepared containing 2‐phenyl‐1,8‐naphthyridine derivatives. The coordination modes of these ligands were modified by addition of coordinating solvents such as water into the ethanolic reaction media. Under these conditions 1,8‐naphthyridine (napy) moieties act as monodentade ligands forming unusual [Ru(CO)₂Cl₂(η¹‐2‐phenyl‐1,8‐naphthyridine‐ kN )(η¹‐2‐phenyl‐1,8‐naphthyridine‐kN′)] complexes. The reaction was reproducible when different 2‐phenyl‐1,8‐naphthyridine derivatives were used. On the other hand, when dry ethanol was used as the solvent we obtained complexes with napy moieties acting as a chelating ligand. The structures proposed for these complexes were supported by NMR spectra, and the presence of two ligands in the [Ru(CO)₂Cl₂(η¹‐2‐phenyl‐1,8‐naphthyridine‐ kN )(η¹‐2‐phenyl‐1,8‐naphthyridine‐kN′)] type complexes was confirmed using elemental analysis. All complexes were tested as catalysts in the hydroformylation of styrene showing moderate activity in N,N′‐dimethylformamide. Copyright © 2008 John Wiley & Sons, Ltd.     

Struggle for space: viral extinction through competition for cells

The design of protocols to suppress the propagation of viral infections is an enduring enterprise, especially hindered by limited knowledge of the mechanisms leading to viral extinction. Here we report on infection extinction due to intraspecific competition to infect susceptible hosts. Beneficial mutations increase the production of viral progeny, while the host cell may develop defenses against infection. For an unlimited number of host cells, a feedback runaway coevolution between host resistance and progeny production occurs. However, physical space limits the advantage that the virus obtains from increasing offspring numbers; thus, infection clearance may result from an increase in host defenses beyond a finite threshold. Our results might be relevant to devise improved control strategies in environments with mobility constraints or different geometrical properties.     

Electromagnetic properties of manganese-zinc ferrite with lithium substitution

Polycrystalline manganese-zinc ferrite with lithium substitution of composition Li_0.5xMn_0.4Zn_0.6−xFe_2+0.5xO₄ (0.0≤x≤0.4) was prepared by the usual ceramic method. X-ray diffraction analysis confirmed that the samples have a spinel structure and are of single phase for some values of Li content. Lithium doping considerably modifies saturation magnetization since its value increases from 57.5 emu/g for x=0.0 to 82.9 emu/g for x=0.4. Lithium inclusion increases the real permeability (over 1 MHz) while the natural resonance frequency shifts to lower values as the fraction of Li increases. These ferrites show good electromagnetic properties as absorbers in the microwave range of 1 MHz - 1 GHz.     

Hermite pseudospectral approximations. An error estimate

We find an error bound for the pseudospectral approximation of a function in terms of Hermite functions, hn(x)=e−x²Hn(x), in certain weighted Sobolev spaces. We use properties of Hermite polynomials, as well as an asymptotic expression for their largest zeroes to achieve the mentioned estimate.     

Presmoothing the transition probabilities in the illness-death model

One major goal in clinical applications of multi-state models is the estimation of transition probabilities. In a recent paper, Meira-Machado et al. (2006) introduce a substitute for the Aalen-Johansen estimator in the case of a non-Markov illness-death model. The idea behind their estimator is to weight the data by the Kaplan-Meier weights pertaining to the distribution of the total survival time of the process. In this paper we propose a modification of Meira-Machado et al. (2006) estimator based on presmoothing. Consistency is established. We investigate the finite sample performance of the new estimator through simulations. Data from a study on colon cancer are used for illustration purposes.