Production and Purification of a Solvent-Resistant Esterase from Bacillus licheniformis S-86

New thermophilic and organic-solvent-tolerant Bacillus licheniformis S-86 strain is able to produce two active and solvent-stable esterases. Production of type I and II esterases was substantially enhanced when oils and surfactants were supplied as carbon sources. Grape oil (0.1% v/v) and Tween 20 to 60 (0.1% v/v) had enhanced enzyme production between 1.6- and 2.2-folds. Type II esterase was purified to homogeneity in a five-step procedure. This esterase was purified 76.7-fold with a specific activity of 135 U mg(-1). Molecular mass of the enzyme was estimated to be 38.4 kDa by sodium dodecyl sulfate polyacrylamide gel electrophoresis. Type II esterase was active mostly on esters with short acyl chains, which allowed to classify the enzyme as a carboxylesterase with a K (m) of 80.2 mmol l(-1) and a V (max) of 256.4 micromol min(-1) mg(-1) for p-nitrophenyl acetate. Also, B. licheniformis S-86 type II esterase displayed activity in presence of water-miscible organic solvents at 50% concentration and stability after 1-h incubation.     

Development of Polar Order in the Liquid Crystal Phases of a 4‐Cyanoresorcinol‐Based Bent‐Core Mesogen with Fluorinated Azobenzene Wings

A bent‐core mesogen consisting of a 4‐cyanoresorcinol unit as the central core and laterally fluorinated azobenzene wings forms four different smectic LC phase structures in the sequence SmA–SmC_s–SmC_sP_AR–M, all involving polar SmC_sP_S domains with growing coherence length of tilt and polar order on decreasing temperature. The SmA phase is a cluster‐type de Vries phase with randomized tilt and polar direction; in the paraelectric SmC_s phase the tilt becomes uniform, although polar order is still short‐range. Increasing polar correlation leads to a new tilted and randomized polar smectic phase with antipolar correlation between the domains (SmC_sP_AR) which then transforms into a viscous polar mesophase M. As another interesting feature, spontaneous symmetry breaking by formation of a conglomerate of chiral domains is observed in the non‐polar paraelectric SmC_s phase.     

A primal-mixed formulation for the strong coupling of quasi-Newtonian fluids with porous media

In this work we analyze a primal-mixed finite element method for the coupling of quasi-Newtonian fluids with porous media in 2D and 3D. The flows are governed by a class of nonlinear Stokes and linear Darcy equations, respectively, and the transmission conditions on the interface between the fluid and the porous medium are given by mass conservation, balance of normal forces and the Beavers-Joseph-Saffman law. We apply a primal formulation in the Stokes domain and a mixed formulation in the Darcy formulation. The “strong coupling” concept means that the conservation of mass across the interface is introduced as an essential condition in the space where the velocity unknowns live. In this way, under some assumptions on the nonlinear kinematic viscosity, a generalization of the Babu?ka-Brezzi theory is utilized to show the well posedness of the primal-mixed formulation. Then, we introduce a Galerkin scheme in which the discrete conservation of mass is imposed approximately through an orthogonal projector. The unique solvability of this discrete system and its Strang-type error estimate follow from the generalized Babu?ka-Brezzi theory as well. In particular, the feasible finite element subspaces include Bernadi-Raugel elements for the Stokes flow, and either the Raviart-Thomas elements of lowest order or the Brezzi-Douglas-Marini elements of first order for the Darcy flow, which yield nonconforming and conforming Galerkin schemes, respectively. In turn, piecewise constant functions are employed to approximate in both cases the global pressure field in the Stokes and Darcy domain. Finally, several numerical results illustrating the good performance of both discrete methods and confirming the theoretical rates of convergence, are provided.     

New Insights into the Reactivity of Cisplatin with Free and Restrained Nucleophiles: Microsolvation Effects and Base Selectivity in Cisplatin–DNA Interactions

The reactivity of cisplatin towards different nucleophiles has been studied by using density functional theory (DFT). Water was considered first to analyze the factors that govern the transformation of cisplatin into more electrophilic aquated species by using an activation‐strain model. It was found that the selectivity and reactivity of cisplatin is a delicate trade‐off between strain and interaction energies and that the second chloride is a worse leaving group than the first. When similar studies were carried out with imidazole, guanine (G), and adenine (A), it was found that in general the second nucleophilic substitution reactions have lower activation barriers than the first ones. Finally, simulations of the structural restrictions imposed by the DNA scaffold in intra‐ and interstrand processes showed that the geometries of the reaction products are nonoptimal with respect to the unrestrained A and G nucleophiles, although the energetic cost is not considerable under physiological conditions, which thus permits nucleophilic substitution reactions that lead to highly distorted DNA.     

DEA with non-monotonic variables. Application to EU governments’ macroeconomic efficiency

Conventional Data Envelopment Analysis (DEA) considers monotonic variables, ie the lower the inputs and the larger the outputs, the better. There are, however, occasions when the monotonicity of a variable with respect to efficiency depends on the value of the variable, that is in a certain range of values an increase in the variable is desirable, while in another range it is a decrease of the variable that is desirable. In this paper, a DEA model that solves problems considering non-monotonic variables is proposed. An application to assess the macroeconomic efficiency of European Union Member States, as regards taxation, gross debt, GDP growth and employment is presented.     

The Use of In-line Quantitative Analysis to Follow Polymer Processing

In this work it is presented three applications of real time analysis during extrusion process using an optical device developed by our research group, which applies the concepts of light extinction. Monitoring of polymer blends morphology takes place to infer data concerned to dispersed phase size and concentration. The detector also enables information about melting temperature of polymer during extrusion and the level of viscous heating, and the exfoliation step during processing of a polymer-clay nanocomposite.     

Electron transfer in supercritical carbon dioxide: ultraexothermic charge recombination at the end of the "inverted region"

Charge-recombination rates in contact radical-ion pairs, formed between aromatic hydrocarbons and nitriles in supercritical CO(2) and heptane, decrease with the exothermicity of the reactions until they reach -70 kcal mol(-1), but from there on an increase is observed. The first decrease in rate is typical of the "inverted region" of electron-transfer reactions. The change to an increase in the rate for ultra-exothermic electron transfer indicates a new free-energy relationship. We show that the resulting "double-inverted region" is not due to a change in mechanism. It is an intrinsic property of electron-transfer reactions, and it is due to the increase of the reorganisation energy with the reaction exothermicity.     

Frustrated structure of an anticlinic-like smectic-C phase

We present a polarising optical microscopy study of the low-temperature anticlinic-like tilted mesophase of the liquid-crystal compound octylphenyl-2-chloro-4-(p-cyano-benzoyloxy) (DB₈Cl). This mesophase has been described as a bilayer smectic structure in which the molecules within each layer are organised in an anticlinic way. The optical textures observed in samples with planar orientation show a double stripe pattern, with the lines aligned parallel to the rubbing direction, characteristic of a double periodic modulation of the refractive index of the material. The long-period modulation is temperature dependent and disappears for thin sample cells (< 5μm). The short-period modulation is nearly independent of the thickness of the cells. The experimental results are analysed in terms of a model which considers that there is a special distribution of the principal optical axis which may be in or out of the polariser-analyser plane. The observed periodic variation of the principal optical axis could not be interpreted in terms of the original structure proposed for this phase. DB₈Cl presents a structure formed by dimers that can be viewed as flexible bent-core-like molecules, showing similarities with phases found in banana-like systems, but exhibiting a much more complex structure.     

Comparison between computational fluid dynamics,fluid–structure interaction and computational structural dynamics predictions of flow-induced wall mechanics in an anatomically realistic cerebral aneurysm model

Haemodynamically induced stress plays an important role in the progression and rupture of cerebral aneurysms. The current work describes computational fluid dynamics (CFD), fluid–structure interaction (FSI) and computational structural dynamics (CSD) simulations in an anatomically realistic model of a carotid artery with two saccular cerebral aneurysms in the ophthalmic region. The model was obtained from three-dimensional (3D) rotational angiographic imaging data. CFD and FSI were studied under a physiologically representative waveform of inflow. The arterial wall was assumed elastic or hyperelastic, as a 3D solid or as a shell depending on the type of modelling used. The flow was assumed to be laminar, non-Newtonian and incompressible. The CFD, FSI and CSD models were solved with the finite elements package ADINA. Predictions of velocity field and wall shear stress (WSS) on the aneurysms made using CFD and FSI were compared. The CSD model of the aneurysms using complete geometry was compared with isolated aneurysm models. Additionally, the effects of hypertensive pressure on CSD aneurysm models are also reported. The vortex structure, WSS, effective stress, strain and displacement of the aneurysm walls showed differences, depending on the type of modelling used.     

Computer reconstruction of pine growth rings using MRI

This work explores the use of magnetic resonance imaging (MRI) for nondestructive determination of wood characteristics and for 3D wood modeling. In this context, one of the applications under development is the automatic recognition and reconstruction of rings from transversal images obtained from MRI scanners. The algorithm analyzes a set of transversal MRI images, detecting and reconstructing growth ring edges. The information generated is then interpolated in order to obtain an accurate 3D picture of the log and its fundamental constituents (individual rings, knots, defects, etc). Results also show that the technique has potential for defect recognition, providing a powerful tool for future developments in wood analysis. The results are encouraging and further research is needed to develop automatic detection not only of rings, but also of different types of defects that are of paramount importance in the sawmill and plywood industries.