The unimolecular elimination kinetics of benzaldoxime in the gas phase

The kinetics of the gas‐phase elimination of benzaldoxime was determined in a static reaction system over the temperature and pressure range 350°C–400°C and 56–140 Torr, respectively. The products obtained were benzonitrile and water. The reaction was found to be homogeneous, unimolecular, and tend to obey a first‐order rate law. The observed rate coefficient is represented by the following Arrhenius equation: According to kinetic and thermodynamic parameters, the reaction proceeds through a concerted, semi‐polar, four‐membered cyclic transition state type of mechanism. © 2007 Wiley Periodicals, Inc. 39: 145–147, 2007     

Applications of the matrix-assisted pulsed laser evaporation method for the deposition of organic,biological and nanoparticle thin films: a review

The matrix-assisted pulsed laser evaporation (MAPLE) technique offers an efficient mechanism to transfer soft materials from the condensed to the vapor phase, preserving the versatility, ease of use and high deposition rates of the pulsed laser deposition (PLD) technique. The materials of interest (polymers, biological cells, proteins, …) are diluted in a volatile solvent. Then the solution is frozen and irradiated with a pulsed laser beam. Here, important results of MAPLE deposition of polymer, biomaterials and nanoparticle films are summarized. Finally, the MAPLE mechanism is discussed. A review of experimental and theoretical works points out that the simple model of individual molecule evaporation must be abandoned. Solute concentration, solubility, evaporation temperature of solvents, laser pulse power density and laser penetration depth emerge as important parameters to explain the morphology of the MAPLE-deposited films.     

An ellipsoidal frontier model: Allocating input via parametric DEA

This paper presents the ellipsoidal frontier model (EFM), a parametric data envelopment analysis (DEA) model for input allocation. EFM addresses the problem of distributing a single total fixed input by assuming the existence of a predefined locus of points that characterizes the DEA frontier. Numeric examples included in the paper show EFM’s capacity to allocate shares of the total fixed input to each DMU so that they will all become efficient. By varying the eccentricities, input distribution can be performed in infinite ways, gaining control over DEA weights assigned to the variables in the model. We also show that EFM assures strong efficiency and behaves coherently within the context of sensitivity analysis, two properties that are not observed in other models found in the technical literature.     

Unusual shift of a nitro group in a phenylhydrazo-β-diketone

A novel para to meta shift of a nitro group at the phenyl ring of 3-(2-hydroxy-4-nitrophenylhydrazo)pentane-2,4-dione (H(2)L(1), 1), with formation of the new 3-(2-hydroxy-3,5-dinitrophenylhydrazo)pentane-2,4-dione (H(2)L(2), 2), occurs upon nitration of 1 with an equimolar amount of NaNO(2), under basic conditions. 2 acts as a polydentate ligand for the synthesis of the polymeric potassium [K(μ(5)-HL(2))](n) (3) and monomeric nickel(II) [Ni(H(2)O)(3)(L(2))]·H(2)O (4) compounds. They have been fully characterized, including single crystal X-ray analysis, and the complexes feature metal-organic (in 3) or supramolecular (in 4) 3D networks. The topological analysis of 3 reveals a uninodal 5-connected underlying net with the point symbol of (4(6).6(4)) and a very rare 5/4/t5 topology, which had not yet been observed in coordination polymers.     

Unprecedented stereoselective synthesis of cyclopenta[b]benzofuran derivatives and their characterisation assisted by aligned media NMR and 13C chemical shift ab initio predictions

A new approach to the synthesis of cyclopenta[b]benzofuran derivatives via reaction of 1,3-dicarbonyl compounds with α,β,γ,δ-unsaturated aldehydes is described. The constitution and configuration of the new products have been firmly established by means of residual dipolar couplings (RDCs) and ab initio (13)C NMR chemical shift predictions.     

Zinc(II) ortho-hydroxyphenylhydrazo-β-diketonate complexes and their catalytic ability towards diastereoselective nitroaldol (Henry) reaction

The zinc(II) complexes with ortho-hydroxy substituted arylhydrazo-β-diketonates [Zn(2)(CH(3)OH)(2)(μ-L(1))(2)] (5), [Zn{(CH(3))(2)SO}(H(2)O)(L(2))] (6), [Zn(2)(H(2)O)(2)(μ-L(3))(2)] (7) and [Zn(H(2)O)(2)(L(4))]·H(2)O (8) were synthesized by reaction of a zinc(II) salt with the appropriate hydrazo-β-diketone, HO-2-C(6)H(4)-NHN=C{C(=O)CH(3)}(2) (H(2)L(1), 1), HO-2-O(2)N-4-C(6)H(3)-NHN=C{C(=O)CH(3)}(2) (H(2)L(2), 2), HO-2-C(6)H(4)-NHN=CC(=O)CH(2)C(CH(3))(2)CH(2)C(=O) (H(2)L(3), 3) or HO-2-O(2)N-4-C(6)H(3)-NHN=[CC(=O)CH(2)C(CH(3))(2)CH(2)C(=O) (H(2)L(4), 4). They were fully characterized, namely by X-ray diffraction analysis that disclosed the formation of extensive H-bonds leading to 1D chains (5 and 6), 2D layers (7) or 3D networks (8). The thermodynamic parameters of the Zn(II) reaction with H(2)L(2) in solution, as well as of the thermal decomposition of 1-8 were determined. Complexes 5-8 act as diastereoselective catalysts for the nitroaldol (Henry) reaction. The threo/erythro diastereoselectivity of the β-nitroalkanol products ranges from 8:1 to 1:10 with typical yields of 80-99%, depending on the catalyst and substrate used.     

New insights into the mechanism of activation of atom transfer radical polymerization by Cu(I) complexes

The kinetics of activation of RX by a Cu(I) complex has been investigated in MeCN both in the absence and presence of halide ions. The system Cu(I)/L/X(-) (L = Me(6)TREN) is mainly composed of Cu(I)L(+), XCu(I)L and Cu(I)X(2)(-), but only Cu(I)L(+) is found to be an active catalyst reacting with RX.     

A different way to verify the violation of the WWŻB inequality

The solution to Bell theorem for N-qubits was widely studied in [M. ?ukowski, ?. Brukner, Phys. Rev. Lett. 88, 210401 (2002)]. Here we present a different way to obtain the solution of that theorem for the dichotomic experiment. In order to obtain a solution for the Werner-Wolf-?ukowski-Brukner WW?B inequality a new correlation function is proposed. This new correlation function expresses directly the constraints imposed by local theories. We use the general Greenberger-Horne-Zeilinger (GHZ) state, whereof, as it is well known, emerges a family of entangled states that do not violate the WW?B inequality [M. ?ukowski, ?. Brukner, W. Laskowski, M. Wie?niak, Phys. Rev. Lett. 88, 210402 (2002)], i.e. it can be described by a local realistic theory, to illustrate our results.     

Stochastic equilibrium assignment with variable demand: Theoretical and implementation issues

Recently, it has been pointed out that transport models should reflect all significant traveler choice behavior. In particular, trip generation, trip distribution, modal split as well as route choice should be modeled in a consistent process based on the equilibrium between transport supply and travel demand. In this paper a general fixed-point approach that allows dealing with multi-user stochastic equilibrium assignment with variable demand is presented. The main focus was on investigating the effectiveness of internal and external approaches and of different algorithmic specifications based on the method of successive averages within the internal approach. The vector demand function was assumed non-separable, non-symmetric cost functions were adopted and implementation issues, such updating step and convergence criterion, were investigated. In particular the aim was threefold: (i) compare the internal and the external approaches; (ii) investigate the effectiveness of different algorithmic specifications to solve the variable demand equilibrium assignment problem through the internal approach; (iii) investigate the incidence of the number of the links with non-separable and/or asymmetrical cost functions. The proposed analyses were carried out with respect to two real-scale urban networks regarding medium-size urban contexts in Italy.     

Quality and comparability of measurement of potentially toxic elements in urban soils by a group of European laboratories

A study has been conducted to assess the quality and comparability of measurement of aqua-regia-soluble cadmium, chromium, copper, iron, manganese, nickel, lead, and zinc in urban soils within a small cohort of European research laboratories specializing in soil science or environmental analytical chemistry. An initial survey indicated that highly variable levels of analytical quality control (e.g. use of certified reference materials) were routinely implemented in participant laboratories. When a set of soil samples—differing in metal contents and in characteristics such as pH and organic-matter content—were exchanged and analysed, approximately 20% of results differed from target values by more than 25%. A principal-component analysis was applied to data for chromium, copper, nickel, lead, and zinc, and proved successful in assessing overall laboratory performance. The study indicates that greater prominence needs to be given to quality assurance and control if comparable data are to be generated in international, collaborative research projects.