Current trends in the computational modelling of polyoxometalates

Computational chemistry applied to the study of polyoxometalates has achieved its maturity in the last years. During two decades, important advances have been made using theoretical tools in the comprehension and interpretation of many relevant issues. In the present mini-review, we want to stress that different techniques have been incorporated to the routine of computation: from the very first Hartree?CFock LCAO-SCF calculation on the decavanadate anion, followed by numerous density functional theory?Cbased studies on increasingly complex systems, also applying correlated ab initio techniques for magnetism and, more recently, using molecular dynamics to analyse properties in liquid media, the information provided by computational chemistry gets more and more relevant.     

DFT Mechanistic Study on Diene Metathesis Catalyzed by Ru‐Based Grubbs–Hoveyda‐Type Carbenes: The Key Role of π‐Electron Density Delocalization in the Hoveyda Ligand

The catalytic activity and catalyst recovery of two heterogenized ruthenium‐based precatalysts ( H and NO₂(4) ) in diene ring‐closing metathesis have been studied by means of density functional calculations at the B3LYP level of theory. For comparison and rationalization of the key factors that lead to higher activities and higher catalyst recoveries, four other Grubbs–Hoveyda complexes have also been investigated. The full catalytic cycle (catalyst formation, propagation, and precatalyst regeneration) has been considered. DFT calculations suggest that either for the homogeneous and heterogenized systems the activity of the catalysts mainly depends on the ability of the precursor to generate the propagating carbene. This ability does not correlate with the traditionally identified key factor, the Ru???O interaction strength. In contrast, precatalysts with lower alkoxy‐dissociation energy barriers and lower stabilities compared with the propagating carbene also present larger C1? C2 bond length (i.e., lower π character of the C? C bond that exists between the metal–carbene (Ru?C) and the phenyl ring of the Hoveyda ligand). Catalyst recovery, regardless of whether a release–return mechanism occurs or not, is also mainly determined by the π delocalization. Therefore, future Grubbs–Hoveyda‐type catalyst development should be based on fine‐tuning the π‐electron density of the phenyl moiety, with the subsequent effect on the metalloaromaticity of the ruthenafurane ring, rather than considering the modification of the Ru???O interaction.     

Analytical approach for CRLH-based antennas design

This paper presents an analytical model for CRLH (Composite Right-Left Handed) antennas preliminary design. The objective of this work is to develop a tool to estimate quickly the scattering and radiating characteristics of these CRLH-based structures. The analytical model provides thus a set of parameters which roughly fulfill desired requirements. Afterwards, the antenna designer can refine the CRLH-based antenna performances with full 3D electromagnetic simulation software.     

Hidrogeochemical study in South Amazon region using Photoacoustic Spectroscopy

In this study we demonstrate the usefulness of the Photoacoustic Spectroscopy (PAS) in the investigation of water collected from a natural site located within the Amazon region, Brazil, during the wet to dry seasons transition (May/2006). The water samples were collected from different stages along a hydrologic pathway including precipitation water (Prec), groundwater (GW), through flow water (TF), overland flow water (OF), and stream flow water (SW). The observed photoacoustic spectral features, in the 0.3 to 1.0 μm wavelength region, fall within three distinct bands (C, S, and L). We found band-C, band-S and band-L occurring in the spectral range of 0.30 to 0.40 μm, 0.40 to 0.45 μm and 0.45 to 1.0 μm regions, respectively. The photoacoustic features shift peak positions and change intensities for all samples investigated, thus supporting the proposal of PAS as a useful technique to investigate water samples from natural environments.     

Estimation de Yule–Walker d'un CAR(p) observé à temps discret

Let (X(lδ), l=0,n) be a discrete observation at mesh δ>0 of X, a CAR(p). Classical Yule–Walker estimation are biased and must be corrected. Resultant estimators converge if T=nδ→+∞, are asymptotically normal with rate , and efficient. The diffusion coefficient is also estimated, with rate .     

Estimation of the Density of Hypoelliptic Diffusion Processes with Application to an Extended Itô's Formula

We prove a uniform bound for the density, p _t (x), of the solution at time t(0, 1] of a 1-dimensional stochastic differential equation, under hypoellipticity conditions. A similar bound is obtained for an expression involving the distributional derivative (with respect to x) of p _t (x). These results are applied to extend the Itô formula to the composition of a function (satisfying slight regularity conditions) with a hypoelliptic diffusion process in the spirit of the work of Föllmer et al. ⁽⁵⁾     

The bromopentadienyl acrylate approach to himbacine

[reaction: see text] The syntheses of 4,4a-didehydrohimbacine and 4,4a-didehydrohimandravine are presented. Key steps include an intramolecular Diels-Alder reaction of a bromopentadienyl acrylate and Suzuki-Miyaura and Stille coupling reactions.     

Synthesis and general properties of silated-hydroxypropyl methylcellulose in prospect of biomedical use

Synthesis of grafting silane on a hydro soluble cellulose ether (HPMC) was described. In alkaline medium, this derivate is under gel form. With a decrease of the pH, a self-hardening occurs due to the silanol condensation. For potential biomedical use, we described the silated-HPMC synthesis, the gel behavior after steam sterilization and the parameters of the silanol condensation i.e. pH, silane percentage and temperature. Minimum kinetic of the condensation was observed for pH between 5.5 and 6.5. So temperature catalyzed the reaction and the self-hardening speed was increased by silane percentage.