Amino,ammonio and aminioethenes: a theoretical study of their structure and energetics

We have performed high level ab initio quantum mechanical calculations for aminoethene and the three isomeric 1,1‐ (Z)‐ or (E)‐1,2‐diaminoethenes as well as their singly and doubly charged cations derived by loss of electrons and/or upon protonation. Gas phase molecular structures were computed at the MP2/6‐311 + G(3df,2p) level. Standard molar enthalpies of formation in the gas phase, at T = 298.15 K, were estimated using the G3 composite method and atomization, isodesmic and homodesmotic reactions. Other energetic parameters were also calculated at the G3 level: proton affinities, basicities and adiabatic ionization enthalpies. Theoretical and experimental data are compared. The reported experimental data refer only to aminoethene wherein the standard molar enthalpy of formation has a considerable uncertainty, although the molecular structure is well established. There are no such data, neither structural nor thermochemical, for any of the three isomeric diaminoethenes. Isoelectronic comparisons are made. For example, the diprotonated diaminoethenes are isoelectronic to isobutene and (Z)‐ and (E)‐butene, while the doubly ionized diaminoethenes are likewise related to trimethylenemethane and 1,3‐butadiene. Copyright © 2013 John Wiley & Sons, Ltd.     

Lower semicontinuity and relaxation of signed functionals with linear growth in the context of {\mathcal A}-quasiconvexity

A lower semicontinuity and relaxation result with respect to weak-* convergence of measures is derived for functionals of the form $$\mu \in \mathcal{M}(\Omega; \mathbb{R}^d) \to \int \limits_\Omega f(\mu^a(x))\,{\rm {d}}x +\int \limits_\Omega f^\infty \left( \frac{{\rm{d}}\mu^s}{d|\mu^s|}(x)\right) \, d| \mu^s|(x),$$ where admissible sequences {μ _n } are such that ${\{{\mathcal{A}}\mu_{n}\}}$ converges to zero strongly in ${W^{-1 q}_{\rm loc}(\Omega)}$ and ${\mathcal {A}}$ is a partial differential operator with constant rank. The integrand f has linear growth and L ^∞-bounds from below are not assumed.     

The effect of the lubricated revolute joint parameters and hydrodynamic force models on the dynamic response of planar multibody systems

In this work a comprehensive methodology for dynamic modeling and analysis of planar multibody systems with lubricated revolute joints is presented. In general, this type of mechanical systems includes journal-bearings in which the load varies in both magnitude and direction. The fundamental issues associated with the theory of lubrication for dynamically loaded journal-bearings are revisited that allow for the evaluation of the Reynolds equation for dynamic regime. This approach permits the derivation of the suitable hydrodynamic force laws that are embedded into the dynamics of multibody systems formulation. In this work, three different hydrodynamic force models are considered, namely the Pinkus and Sternlicht approach for long journal-bearings and the Frêne et al. models for both long and short journal-bearings. Results for a planar slider?Ccrank mechanism with a lubricated revolute joint between the connecting-rod and slider are presented and utilized to discuss the assumptions and procedures adopted throughout the present study. Different test scenarios are taken into account with the purpose of performing a comparative study for quantifying the effect of the clearance size, lubricant viscosity, input crank speed and hydrodynamic force model on the dynamic response of multibody systems with lubricated revolute joints. From the global results obtained from computational simulations, it can be concluded that the clearance size, the lubricant viscosity and the operating conditions play a key role in predicting the dynamic behavior of multibody systems.     

Supported TiO2 in Ceramic Materials for the Photocatalytic Degradation of Contaminants of Emerging Concern in Liquid Effluents: A Review

The application of TiO₂ as a slurry catalyst for the degradation of contaminants of emerging concern (CEC) in liquid effluents has some drawbacks due to the difficulties in the catalyst reutilization. Thus, sophisticated and expensive separation methods are required after the reaction step. Alternatively, several types of materials have been used to support powder catalysts, so that fixed or fluidized bed reactors may be used. In this context, the objective of this work is to systematize and analyze the results of research inherent to the application of ceramic materials as support of TiO₂ in the photocatalytic CEC removal from liquid effluents. Firstly, an overview is given about the treatment processes able to degrade CEC. In particular, the photocatalysts supported in ceramic materials are analyzed, namely the immobilization techniques applied to support TiO₂ in these materials. Finally, a critical review of the literature dedicated to photocatalysis with supported TiO₂ is presented, where the performance of the catalyst is considered as well as the main drivers and barriers for implementing this process. A focal point in the future is to investigate the possibility of depurating effluents and promote water reuse in safe conditions, and the supported TiO₂ in ceramic materials may play a role in this scope.     

Surfaces of general type with <Emphasis Type="Italic">p</Emphasis><Subscript><Emphasis Type="Italic">g</Emphasis></Subscript>=0, <Emphasis Type="Italic">K</Emphasis><Superscript>2</Superscript>=6 and non birational bicanonical map

Let S be a minimal surface of general type with p_g=0 and K²=6, such that its bicanonical map is not birational. The map is a morphism of degree 4 onto a surface. The case of deg = 4 is completely classified in [Topology, 40 (5) (2001), 977–991] and the present paper completes the characterization of these surfaces. It is proven that the degree of cannot be equal to 3, and the geometry of surfaces with deg = 2 is analysed in detail. The last section contains three examples of such surfaces, two of which appear to be new.Mathematics Subject Classification (2000): 14J29     

The Bicanonical Map of Surfaces with pg = 0 and K2 >= 7, II

Minimal complex surfaces of general type with p_g = 0 and K²= 7 or 8 whose bicanonical map is not birational are studied.It is shown that if S is such a surface, then the bicanonicalmap has degree 2 (see Bulletin of the London Mathematical Society33 (2001) 1–10) and there is a fibration f: S P¹ suchthat (i) the general fibre F of f is a genus 3 hyperellipticcurve; (ii) the involution induced by the bicanonical map ofS restricts to the hyperelliptic involution of F. Furthermore, if , then f isan isotrivial fibration with six double fibres, and if , then f has five double fibres andit has precisely one fibre with reducible support, consistingof two components. 2000 Mathematics Subject Classification 14J29.     

Thermochemistry of (E)- and (Z)-disubstituted alkene species: a combined experimental and theoretical investigation of isomeric dimethyl fumarate and dimethyl maleate

The first unequivocal thermochemical/calorimetric determination of the enthalpies of combustion, phase change, and formation of a pair of (E)- and (Z)-disubstituted olefins of the type XCH = CHX, where X is an electron withdrawing group, is reported in this paper for the isomeric species dimethyl fumarate and dimethyl maleate (X = COOCH3). The corresponding density functional calculations, corrected for vibrational and thermal effects, confirm that the former isomer is more stable by some 30 kJ mol-1.     

Are isatin and isatoic anhydride antiaromatic and aromatic respectively? A combined experimental and theoretical investigation

This paper reports the results of our thermochemical/calorimetric determination of the enthalpies of combustion, phase change, and formation of isatin, isatoic anhydride, and N-methylisatin. The density functional calculations accompanied by vibrational and thermal corrections were also performed for these compounds and N-methylisatoic anhydride. Through a combination of theoretical calculations and associated isodesmic reactions, we have deduced that isatin has some antiaromatic character and isatoic anhydride enjoys some aromatic stabilization.     

Recovery of cryopreserved embryogenic cultures of maritime pine--effect of cryoprotectant and suspension density

Embryogenic cultures were obtained from seeds of open-pollinated maritime pine trees representing part of a breeding population. The aim of the present study was to develop and optimize a protocol for cryopreservation of Pinus pinaster somatic embryogenic tissue. The density of the embryogenic suspension and the type of pre-treatment significantly affected the recovery of cryopreserved embryogenic cultures, as evaluated by their survival and regrowth rate. An initial density of the suspension culture of 250 mg/ml improved the regrowth rate of the embryogenic lines. Pre-treatment with maltose 0.4 M significantly increased the regrowth rate when compared to the other tested carbohydrates. Also, the addition of DMSO in a mixture of PEG 4000 and sucrose (PSD solution), instead of DMSO alone, at the same final concentration, was clearly beneficial for recovery of cryopreserved tissues. This improved method for the cryopreservation of P pinaster embryogenic of cultures allowed the successful recovery of 97 percent of the lines stored in liquid of nitrogen.     

Validation of an Augmented Lagrangian Algorithm with a Gauss-Newton Hessian Approximation Using a Set of Hard-Spheres Problems

An Augmented Lagrangian algorithm that uses Gauss-Newton approximations of the Hessian at each inner iteration is introduced and tested using a family of Hard-Spheres problems. The Gauss-Newton model convexifies the quadratic approximations of the Augmented Lagrangian function thus increasing the efficiency of the iterative quadratic solver. The resulting method is considerably more efficient than the corresponding algorithm that uses true Hessians. A comparative study using the well-known package LANCELOT is presented.