Wave turbulence buildup in a vibrating plate

We report experimental and numerical results on the buildup of the energy spectrum in wave turbulence of a vibrating thin elastic plate. Three steps are observed: first a short linear stage, then the turbulent spectrum is constructed by the propagation of a front in wave number space and finally a long time saturation due to the action of dissipation. The propagation of a front at the second step is compatible with scaling predictions from the Weak Turbulence Theory.     

Experimental and theoretical study of N-hexylcytosine and N-hexylcytosinium nitrate: the crucial role of hydrophobic and anion–π interactions

We report the synthesis and X-ray characterization of N¹-hexylcytosine (1) and N¹-hexylcytosinium nitrate (2). N¹-hexylcytosine (1) does not follow the same behaviour previously described for N¹-hexylthymine and N¹-hexyluracil in the solid state. This different behavior has been analyzed by means of density functional theory (DFT) calculations including the latest available correction for dispersion (D3). In addition hydrophobic and anion–π noncovalent interactions play a key role in stabilizing the 3D architectures of the compounds, which have been energetically studied using theoretical calculations and compared with similar structures retrieved from the Cambridge Structural Database (CSD). The anion–π–anion binding mode observed for nitrate in compound 2 is also observed in several crystal structures involving cytosine ring coordinated to transition metals.     

The Mechanism of Stereospecific C?H Oxidation by Fe(Pytacn) Complexes: Bioinspired Non‐Heme Iron Catalysts Containing cis‐Labile Exchangeable Sites

A detailed mechanistic study of the hydroxylation of alkane C? H bonds using H₂O₂ by a family of mononuclear non heme iron catalysts with the formula [Fe^II(CF₃SO₃)₂(L)] is described, in which L is a tetradentate ligand containing a triazacyclononane tripod and a pyridine ring bearing different substituents at the α and γ positions, which tune the electronic or steric properties of the corresponding iron complexes. Two inequivalent cis‐labile exchangeable sites, occupied by triflate ions, complete the octahedral iron coordination sphere. The C? H hydroxylation mediated by this family of complexes takes place with retention of configuration. Oxygen atoms from water are incorporated into hydroxylated products and the extent of this incorporation depends in a systematic manner on the nature of the catalyst, and the substrate. Mechanistic probes and isotopic analyses, in combination with detailed density functional theory (DFT) calculations, provide strong evidence that C? H hydroxylation is performed by highly electrophilic [Fe^V(O)(OH)L] species through a concerted asynchronous mechanism, involving homolytic breakage of the C? H bond, followed by rebound of the hydroxyl ligand. The [Fe^V(O)(OH)L] species can exist in two tautomeric forms, differing in the position of oxo and hydroxide ligands. Isotopic‐labeling analysis shows that the relative reactivities of the two tautomeric forms are sensitively affected by the α substituent of the pyridine, and this reactivity behavior is rationalized by computational methods.     

Analysis of Chemical and Biological Features Yields Mechanistic Insights into Drug Side Effects

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Highlights? Biological and chemical traits are flagged in >1,000 drug side effects ? Mechanistic insights are gained for most of the phenotypes ? Chemical features can account for unspecific or intricate biological phenomena ? Blending chemistry and biology helps in anticipating adverse events     

Tribological evaluation of HVOF thermal‐spray coatings as a hard chrome replacement

Hard chrome plating has been used in several different applications in industries that require abrasive sliding wear resistance, such as hydraulic pistons, shafts or bearings. However, the increasing environmental and worker safety pressures on electrolytic hard chrome are leading companies to adopt alternatives. The improvements of the high‐velocity‐oxy‐fuel (HVOF) thermal spray process allow the chromium coating replacement with a comparable or superior surface treatment and are more environmentally friendly. This HVOF process, as a flexible dry‐coating technology, avoids high‐volume waste streams and enables a flexible choice of coating material for each application. The cobalt–chromium‐cemented tungsten carbides are some of the easiest materials to spray and the WC‐10Co‐4Cr coatings have demonstrated superior performance over hard chrome with regard to mechanical and tribological properties. In this work, this coating has been deposited with a Sulzer Metco WokaJet‐400 kerosene fuel spray gun, and the spray conditions have been optimized in order to ensure the best properties of the coatings. The mechanical and tribological properties have been evaluated in coatings sprayed with four deposition conditions that involve different gas flow rates. The most wear‐resistant coating is obtained with those HVOF parameters that prevent decarburization of WC particles and, at the same time, allow an adequate agglomerate melting giving a good intersplat adhesion. The results indicate that HVOF‐sprayed WC‐CoCr coatings are a reliable alternative to electrolytic hard chrome (EHC) in the aeronautical industry to coat landing gear components. In particular, in the dry wear tests, the WC‐CoCr coatings outperform hard chrome coatings in wear resistance. Copyright © 2010 John Wiley & Sons, Ltd.     

Performance of 3D‐space‐based atoms‐in‐molecules methods for electronic delocalization aromaticity indices

Several definitions of an atom in a molecule (AIM) in three‐dimensional (3D) space, including both fuzzy and disjoint domains, are used to calculate electron sharing indices (ESI) and related electronic aromaticity measures, namely, I_ring and multicenter indices (MCI), for a wide set of cyclic planar aromatic and nonaromatic molecules of different ring size. The results obtained using the recent iterative Hirshfeld scheme are compared with those derived from the classical Hirshfeld method and from Bader's quantum theory of atoms in molecules. For bonded atoms, all methods yield ESI values in very good agreement, especially for C–C interactions. In the case of nonbonded interactions, there are relevant deviations, particularly between fuzzy and QTAIM schemes. These discrepancies directly translate into significant differences in the values and the trends of the aromaticity indices. In particular, the chemically expected trends are more consistently found when using disjoint domains. Careful examination of the underlying effects reveals the different reasons why the aromaticity indices investigated give the expected results for binary divisions of 3D space. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2011.     

Routes of π-electron delocalization in 4-substituted-1,2-benzoquinones

The substituent effect in 4-substituted-1,2-benzoquinone is investigated by means of modeling using B3LYP hybrid functional in conjunction with the 6-311+G(d,p) basis set. The interrelation between different types of substituents, X = NO, NO(2), CN, CHO, H, Me, OMe, OH, NH(2), NHMe and N(Me)(2), and both CO groups has been characterized both qualitatively and then quantitatively by means of several measures of π-electron delocalization (HOMA, MCI, DI, FLU) based on structural and electronic properties of 4-substituted-1,2-benzoquinones chosen for analysis. Results of this analysis clearly show that only the meta-placed CO group is affected by substituents, whereas the para-placed CO group is rather insensitive to substitution. These observations may help to explain diversified chemical properties (including reactivity) of CO centers in o-benzoquinone derivatives. Among others, they may explain differences in proton-accepting properties of carbonyl O atoms, as it is shown for simple models in which carbonyl groups in o-benzoquinone act as proton acceptors in H-bonds of O···H-F type.