Semigroups of Composition Operators in BMOA and the Extension of a Theorem of Sarason

In this paper we deal with the maximal subspace in BMOA where a general semigroup of analytic functions on the unit disk generates a strongly continuous semigroup of composition operators. Particular cases of this question are related to a well-known theorem of Sarason about VMOA. Our results describe analytically that maximal subspace and provide a condition which is sufficient for the maximal subspace to be exactly VMOA. A related necessary condition is also proved in the case when the semigroup has an inner Denjoy-Wolff point. As a byproduct we provide a generalization of the theorem of Sarason. This research has been partially supported by the Ministerio de Educación y Ciencia projects n. MTM2006-14449-C02-01 and MTM2005-08350-C03-03 and by La Consejería de Educación y Ciencia de la Junta de Andalucía.     

Solvent effects on oxygen-17 chemical shifts in methyl formate: linear solvation shift relationships

A multiple linear regression analysis has been carried out using the Kamlet-Abboud-Taft solvatochromic parameters in order to quantify the solvent effects on the (17)O chemical shifts of methyl formate (MF). The influence of the solvents upon the carbonyl oxygen chemical shifts is smaller for MF than for N-methylformamide (NMF). The influence (in parts per million) of the solvent polarity-polarizability reduces from -21.9pi* in amides to -9.6pi* in MF. The influence of the solvent hydrogen-bond-donor acidities reduces from -42.0alpha in formamides to -16.9alpha in MF. The solvent effects upon the dicoordinated oxygen chemical shifts of MF are smaller in magnitude and opposite in direction, i.e., 4.8pi* and 2.6alpha, than those for the carbonyl oxygen. (17)O hydration shifts have been calculated for the NMF + (H(2)O)(6) and MF + (H(2)O)(5) complexes by the ab initio GIAO method at the 6-311 + G** level. The hydration shifts calculated for the carbonyl oxygens of NMF and MF and for the dicoordinated oxygen of MF, -102.4, -64.7, and 17.6 ppm, respectively, show the same trend as the corresponding empirical hydration shifts, -101.7, -42.0, and 14.2 ppm.     

Solvent effects in ionic liquids: empirical linear energy-density relationships

Multiparameter linear energy-density relationships to model solvent effects in room temperature ionic liquids (RTILs) are introduced and tested. The model incorporates two solvent dependent and two specific solute-solvent parameters represented by a set of electronic indexes derived from the conceptual density functional theory. The specific solute-solvent interactions are described in terms of the electronic chemical potential for proton migration between the anion or cation and the transition state structure of a specific reaction. These indexes provide a quantitative estimation of the hydrogen bond (HB) acceptor basicity and the hydrogen bond donor acidity of the ionic solvent, respectively. A sound quantitative scale of HB strength is thereby obtained. The solvent dependent contributions are described by the global electrophilicity of the cation and nucleophilicity of the anion forming the ionic liquid. The model is illustrated for the kinetics of cycloaddition of cyclopentadiene towards acrolein. In general, cation HB acidity outweighs the remaining parameters for this reaction.     

Optimizing the rank position of the DMU as secondary goal in DEA cross-evaluation

Cross-efficiency evaluation is an extension of Data Envelopment Analysis (DEA) that permits not only the determination of a ranking of Decision Making Units (DMUs) but also the elimination of unrealistic weighting schemes, thereby rescinding the necessity for the inclusion of individual judgements in the models. The main deficiency of the procedure is the non-uniqueness of the optimal weights, which results in the peer evaluations dependences, for instance, on the software used to determine DMU’s efficiencies. This shortfall justifies the inclusion of secondary goals in order to determine cross-efficiency values. In this paper a new proposal of a secondary goal is studied. The idea is related with that proposed in Wu et al. (2009), in which the objective is the optimization of the rank position of the DMU under evaluation. In the procedure proposed here, an incentive to break level-pegging ties between alternatives is introduced by considering that efficiency scores induce a weak order of alternatives. The model is illustrated with a preference-aggregation application.     

Predicting the reaction mechanism of nucleophilic substitutions at carbonyl and thiocarbonyl centres of esters and thioesters

In nucleophilic substitution reactions at carbonyl centres, there are two possible channels. The first one occurs when the attack of nucleophilic agents takes place simultaneously with the departure of the nucleofuge. This process is named as concerted. The second possibility is the formation of a reaction intermediate, typically a tetrahedral intermediate from which the nucleofuge departs after passing through a second transition state. This second mechanism is defined as stepwise. Whether a concerted or stepwise mechanism is to be expected for a given reaction depends on several factors. Among these determinants are the nucleophilicity of the attacking group, the leaving group ability of the nucleofuge, and the solvent, which affects both the stability of the intermediate or the transition states involved. The role of the electrophilic centre can however become an important factor that can determine the reaction mechanism. In this work we show that the group nucleophilic Fukui function model may be used to rationalize and to predict the reaction mechanism of the title compounds towards alicyclic amines. In general, when the electrophilic carbon centre is attached to the soft sulfur atom, the reaction mechanism is predicted to follow a stepwise route. When the electrophilic carbon atom is attached to a harder oxygen centre, the reaction mechanism is determined by chemical substitution at the nucleofuge moiety. Experimental verification for a set of four substrates is presented. Copyright © 2012 John Wiley & Sons, Ltd.     

Temperature effect on electrochemical properties of lithium manganese phosphate with carbon coating and decorating with MWCNT for lithium-ion battery

Journal of Solid State Electrochemistry - The increasing demands for higher energy density and higher power capacity of Li-ion secondary batteries have led to a search for electrode materials whose...     

Etch features in bismuth germanate (Bi4Ge3O12) single crystal

The three component mixture of HCl: HNO₃: CH₃COOH in the volumetric proportion of 3: 1: 4 was found to be a satisfactory etchant for various surfaces of Bi₄Ge₃O₁₂. The correlation between etch pits and dislocations was established by means of repeated etching and optical observations.     

NMR study of the coordinating behavior of 2,6‐bis(benzimidazol‐2′‐yl)pyridine

The coordination sites of 2,6‐bis(benzimidazol‐2′‐yl)pyridine ( 1 ) toward protons and the diamagnetic metal ions Li⁺, Na⁺, and Co³⁺ were investigated by NMR spectroscopy. Variable temperature ¹H and ¹³C NMR experiments were performed on 1 in order to evaluate the tautomeric equilibrium and hydrogen bonding. Imidazole dicoordinated aromatic nitrogen atoms were protonated by trichloroacetic acid and the three N‐dicoordinated atoms by fuming H₂SO₄. Reactions of the ligand 1 and benzimidazole 2 with metallic sodium or LiH afforded anionic species; the alkali metal ions appeared solvated by THF, but not by the ligands 1 or 2 . In contrast, reaction of 1 with Co(III) produces the stable cation [Co( 1 ‐H)₂]⁺ with cobalt ion coordinated by two molecules of the monodeprotonated ligand. © 2000 John Wiley & Sons, Inc. Heteroatom Chem 11:392–398, 2000