Mechanism of Thyroxine Deiodination by Naphthyl‐Based Iodothyronine Deiodinase Mimics and the Halogen Bonding Role: A DFT Investigation

This paper deals with a systematic density functional theory (DFT) study aiming to unravel the mechanism of the thyroxine (T4) conversion into 3,3′,5‐triiodothyronine (rT3) by using different bio‐inspired naphthyl‐based models, which are able to reproduce the catalytic functions of the type‐3 deiodinase ID‐3. Such naphthalenes, having two selenols, two thiols, and a selenol–thiol pair in peri positions, which were previously synthesized and tested in their deiodinase activity, are able to remove iodine selectively from the inner ring of T4 to produce rT3. Calculations were performed including also an imidazole ring that, mimicking the role of the His residue, plays an essential role deprotonating the selenol/thiol moiety. For all the used complexes, the calculated potential energy surfaces show that the reaction proceeds via an intermediate, characterized by the presence of a X?I?C (X=Se, S) halogen bond, whose transformation into a subsequent intermediate in which the C?I bond is definitively cleaved and the incipient X?I bond is formed represents the rate‐determining step of the whole process. The calculated trend in the barrier heights of the corresponding transition states allows us to rationalize the experimentally observed superior deiodinase activity of the naphthyl‐based compound with two selenol groups. The role of the peri interactions between chalcogen atoms appears to be less prominent in determining the deiodination activity.     

Thermal Conductivity of Soils at Very Low Moisture Content and Moderate Temperatures

An analysis of soil thermal conductivity data shows that, at very low moisture content, this property first varies insignificantly and then begins to increase from a certain critical moisture content, whose value tends to depend on clay mass fraction. Two simple models evaluating the critical moisture content were developed; the first one is a fraction of the permanent wilting point; the second one is a simple linear function dependent on clay mass fraction. An insignificant variation of soil thermal conductivity is observed at 20°C, within a water pressure head ranging from 1×10³ to 1×10³m, while for higher temperatures (45–50°C) from 5000 to 100000m. Three extensions of the enhanced thermal conductivity model by Sundberg, namely SUN-1, SUN-2 and SUN-3, were proposed and tested. They produce an average root mean square error of 27%, 24% and 30%, respectively, with respect to experimental data. SUN-1and SUN-2 predictions could be further improved if better estimates of thermal conductivity at the dry state and the permanent wilting point were provided. SUN-3 is a simple model which does not require information about the PWP and critical moisture content. All SUN models have a potential for implementing the latent heat transfer component.     

The effect of velocity on rigid wheel performance

A simulation model to predict the effect of velocity on rigid-wheel performance for off-road terrain was examined. The soil–wheel simulation model is based on determining the forces acting on a wheel in steady state conditions. The stress distribution at the interface was analyzed from the instantaneous equilibrium between wheel and soil elements. The soil was presented by its reaction to penetration and shear. The simulation model describes the effect of wheel velocity on the soil–wheel interaction performances such as: wheel sinkage, wheel slip, net tractive ratio, gross traction ratio, tractive efficiency and motion resistance ratio. Simulation results from several soil-wheel configurations corroborate that the effect of velocity should be considered. It was found that wheel performance such as net tractive ratio and tractive efficiency, increases with increasing velocity. Both, relative wheel sinkage and relative free rolling wheel force ratio, decrease as velocity increases. The suggested model improves the performance prediction of off-road operating vehicles and can be used for applications such as controlling and improving off-road vehicle performance.     

Polymer contribution to the thermal conductivity and viscosity in a dilute solution (Fraenkel Dumbbell model)

The phase-space kinetic theory for polymeric liquid mixtures is used to obtain an expression for the polymer contribution to the thermal conductivity of a nonflowing, dilute solution of polymers, where the polymer molecules are modeled as Fraenkel dumbbells. This theory takes into account three mechanisms for the energy transport: diffusion of kinetic energy (including the Öttinger-Petrillo term), diffusion of intramolecular energy, and the work done against the intramolecular forces. This paper is an extension of previous developments for the Hookean dumbbell model and the finitely-extensible dumbbell model. A comparison among the dumbbell results suggests that the thermal conductivity increases with chain stiffness. In addition, the zero-shear-rate viscosity and first normal-stress coefficient are also given for the Fraenkel dumbbell model.Dedicated to Prof. John D. Ferry on the occasion of his 85th birthday.     

Near-Wall Modification of an Explicit Algebraic Reynolds Stress Model Using Elliptic Blending

The elliptic blending approach is used in order to modify an Explicit Algebraic Reynolds Stress Model so as to reproduce the correct near wall behaviour of the turbulent stresses. The anisotropy stress tensor is expressed as a linear combination of tensor bases whose coefficients are sensitised to the non-local wall-blocking effect through the elliptic blending parameter γ. This parameter is obtained from a separate elliptic equation. The model does not use the distance from the wall thus it can be easily applied to complex geometries. It is validated against detailed DNS data for mean and turbulence quantities for the case of flow and heat transfer between parallel flat plates at three Reynolds numbers as well as against experimental data for the flow in a backward facing step at Re _H = 28,000. The comparison with DNS results or experiments is quite satisfactory and shows the validity of the approach.     

Synthesis of voiced sounds using low-dimensional models of the vocal cords and time-varying subglottal pressure

The vocal cords play an important role on voice production. Air coming from the lungs is forced through the narrow space between the two vocal cords that are set in motion in a frequency that is governed by the tension of the attached muscles. The motion of the vocal cords changes the type of flow, that comes from the lungs, to pulses of air, and as the flow passes through the oral and nasal cavities, it is amplified and further modified until it is radiated from the mouth. This complex process can be modeled by a system of integral-differential equations. This paper considers two mechanical models previously used for explaining the dynamics of the vocal cords. It shows that the level of naturalness of the sound generated by these models is rather poor, and it proposes temporal variations of the parameters of the models to increase such level. Examples of synthetic vowels and diphthongs are given to assess the models. In general, the results show that, although the system of voice production is complex, we can achieve satisfactory results with relatively simple low-dimensional models, by suitable temporal variations of the aerodynamic parameters.     

Approximate inertial manifolds for reaction-diffusion equations in high space dimension

The concept of approximate inertial manifolds was introduced by Foiaset al. (1987) in the case of the two-dimensional Navier-Stokes equations. These manifolds are finite dimensional smooth manifolds such that the orbits enter a very thin neighborhood of the manifold after a transient time; this concept replaces the one of inertial manifold when either an inertial manifold does not exist or its existence is not known. Our aim in this paper is to prove that approximate inertial manifolds exist for reaction-diffusion equations in high space dimension by opposition with exact inertial manifolds whose existence has only been proved in low dimension and for which nonexistence results have been obtained in space dimensionn=4.     

热轧产品微观组织和力学性能的数学模拟

 热轧产品的微观组织和力学性能的计算机预报涉及到塑性变形 力学、传热学、金属学、冶金学、实验技术等多个学科，是近年来迅 速发展的具有广泛应用前景的应用技术. 本文综述了作为该技术基础 的力学、传热学数值分析方法和微观组织、力学性能的预报模型.     

Impact of Turbulent Flow and Mean Mixture Fraction Results on Mixing Model Behavior in Transported Scalar PDF Simulations of Turbulent Non-premixed Bluff Body Flames

Numerical simulation results are presented for three turbulent jet diffusion flames, stabilized behind a bluff body (Sydney Flames HM1-3). Interaction between turbulence and combustion is modeled with the transported joint-scalar PDF approach. The focus of the study is on the impact of the quality of simulation results in physical space on the behavior of two micro-mixing models in composition space: the Euclidean Minimum Spanning Tree (‘EMST’) model and the modified Curl coalescence dispersion (‘CD’) model. Profiles of conditional means and variances of thermo-chemical quantities, conditioned on the mixture fraction, are discussed in the recirculation region and in the neck zone behind. The impact of the flow and mixing fields in physical space on the mixing model behavior in composition space is strong for the CD model and increases as the turbulence – chemistry interaction becomes stronger. The EMST conditional profiles, on the contrary, are hardly affected.