New N,O-containing ligands for the biomimetic copper-catalyzed polymerization of 2,6-dimethylphenol

Poly(2,6-dimethyl-1,4-phenylene ether) (PPE), which is widely used in high-performance engineering plastics, is obtained by the copper-catalyzed oxidative coupling of 2,6-dimethylphenol. The oxidative polymerizations have been carried out in acetonitrile with structurally related [copper-(N,O-containing ligand)] complexes as the catalyst precursor compounds, which appeared to be of great interest for a better understanding of the factors influencing the catalytic activities. Steric effects (influence of a methyl group close to the metal center; ligands 4–7) or electronic effects (imino versus amino group; ligands 4, 5, 8 and 6, 7, 9, respectively) on the polymerization rates have been demonstrated. The use of mono- or dinucleating ligands has strengthened the proposed mechanism of the reaction involving dinuclear active species.     

Homogeneous versus heterogeneous catalytic reactions to eliminate organics from waste water using H2O2

Homogeneous (Cu²⁺ ions) and heterogeneous (Cu²⁺-pillared clay) Fenton-like catalysts have been compared in the conversion of p-coumaric acid. The performances of the two classes of catalysts are similar for an analogous amount of copper, but there are some relevant differences in terms of (i) the presence of an induction time, (ii) the turnover frequency, (iii) the efficiency in the use of H₂O₂, (iv) the initial attack of p-coumaric acid (hydroxylation on the aromatic ring or oxidative attack on the double bond of the lateral chain), and (v) the effect of dissolved oxygen on the removal of total organic carbon (TOC). These differences were interpreted in terms of reaction network of generation of radical oxygen species and of organics conversion. The possible formation of a surface peroxo adduct coordinated to a copper binulcear site was also evidenced for the solid heterogeneous catalyst.     

An ensemble evolutionary constraint-based approach to understand the emergence of metabolic phenotypes

Constraint-based modeling is largely used in computational studies of metabolism. We propose here a novel approach that aims to identify ensembles of flux distributions that comply with one or more target phenotype(s). The methodology has been tested on a small-scale model of yeast energy metabolism. The target phenotypes describe the differential pattern of ethanol production and O₂ consumption observed in “Crabtree-positive” and “Crabtree-negative” yeasts in changing environment (i.e., when the upper limit of glucose uptake is varied). The ensembles were obtained either by selection among sampled flux distributions or by means of a search heuristic (genetic algorithm). The former approach provided indication about the probability to observe a given phenotype, but the resulting ensembles could not be unambiguously partitioned into “Crabtree-positive” and “Crabtree-negative” clusters. On the contrary well-separated clusters were obtained with the latter method. The cluster analysis further allowed identification of distinct groups within each target phenotype. The method may thus prove useful in characterizing the design principles underlying metabolic plasticity arising from evolving physio-pathological or developmental constraints.     

Alder ene functionalization of polyisobutene oligomer and styrene-butadiene-styrene triblock copolymer

The Alder ene functionalization reaction of double bonds containing macromolecules such as polyisobutene oligomer (PIB) and a styrene-butadiene-styrene triblock copolymer (SBS) samples with maleic anhydride (MAH) or diethyl maleate (DEM) as enophiles is described. The analysis of the products by means of different techniques assesses the addition of the polar molecules to the reactive vinylidene units of the polymer with functional degrees (FD) depending on the type of enophile and polymer reactivity. The role of the reaction conditions and the use as Lewis acids as catalysts are discussed in terms of their influence on the addition reaction extent and on the polymer molecular weight.     

A bio-inspired predictive sensory-motor coordination scheme for robot reaching and preshaping

This paper presents a sensory-motor coordination scheme for a robot hand-arm-head system that provides the robot with the capability to reach an object while pre-shaping the fingers to the required grasp configuration and while predicting the tactile image that will be perceived after grasping. A model for sensory-motor coordination derived from studies in humans inspired the development of this scheme. A peculiar feature of this model is the prediction of the tactile image. The implementation of the proposed scheme is based on a neuro-fuzzy module that, after a learning phase, starting from visual data, calculates the position and orientation of the hand for reaching, selects the best-suited hand configuration, and predicts the tactile feedback. The implementation of the scheme on a humanoid robot allowed experimental validation of its effectiveness in robotics and provided perspectives on applications of sensory predictions in robot motor control.     

Robust output feedback learning control for induction motor servo drives

This paper addresses the output feedback tracking control problem for induction motor servo drives with mechanical uncertainties: rotor angle, rotor speed and stator currents are assumed to be available for feedback. A robust adaptive learning control is designed under the assumption that the reference profile for the rotor angle is periodic with known period: it ‘learns’ the periodic disturbance signal by identifying the Fourier coefficients of any truncated approximation; ??₂ and ??_∞ transient performances are guaranteed in the ‘learning phase’. It is shown that, for any motor initial condition belonging to an arbitrary given compact set, by properly setting the control parameters: (i) the rotor position and flux modulus tracking errors exponentially converge to residual sets, which may be arbitrarily reduced by increasing the number of terms in the truncated Fourier series; (ii) when the unknown periodic disturbance can be represented by a finite Fourier series, the rotor position and flux modulus tracking errors exponentially converge to zero. As in field oriented‐control, the control algorithm generates references for the magnetizing flux component and for the torque component of the stator current leading to significant simplifications for current‐fed motors. Copyright © 2008 John Wiley & Sons, Ltd.     

Fibroblast protein profile analysis highlights the role of oxidative stress and vitamin K recycling in the pathogenesis of pseudoxanthoma elasticum

Pseudoxanthoma elasticum (PXE) is a genetic disorder associated to mutations in the ABCC6 gene; however, the pathogenetic mechanisms leading to elastic fibre calcifications and to clinical manifestations are still unknown. Dermal fibroblasts, directly involved in the production of the extracellular milieu, have been isolated from healthy subjects and from patients affected by PXE, cultured in vitro and characterized for their ability to produce reactive oxygen species, for structural and functional properties of their cell membranes, for changes in their protein profile. Data demonstrate that oxidative stress has profound and endurable consequences on PXE fibroblast phenotype being responsible for: reduced levels of global DNA methylation, increased amount of carbonylated proteins and of lipid peroxidation products, altered structural properties of cell membranes, modified protein expression. Data shed new light on the pathogenetic pathways in PXE, by identifying a network of proteins affecting elastic fibre calcification through inefficient vitamin K recycling, and highlight the role of differentially expressed proteins as targets for validating the efficacy of future therapeutic strategies aiming to delay and/or revert the pathologic phenotype of PXE fibroblasts. Moreover, data open new perspectives for investigating PXE-like phenotypes in the absence of ABCC6 mutations.     

Secondary bioreceptivity of granite: effect of salt weathering on subaerial biofilm growth

Salt crystallisation is a very common and powerful weathering agent that can modify the petrophysical properties of building stone such as granite. In addition, the weathering can affect the susceptibility of the stone to biological colonisation. The aims of the present study were to examine the properties of a granite weathered by sodium chloride crystallisation and to evaluate the effects of the weathering on the secondary bioreceptivity of the stone to subaerial phototrophic biofilms. For this purpose, granite samples were subjected to a laboratory-based accelerated salt weathering test, and changes in weight, open porosity, bulk density, capillary water content, abrasion pH and surface roughness of the samples were determined. Samples of both weathered and non-weathered granite were then inoculated with a multi-species phototrophic culture derived from a natural subaerial biofilm and incubated under standardised laboratory conditions for 3 months. The weight loss produced by the weathering process was consistent with significant changes in abrasion pH and surface roughness. The bioreceptivity of the stone was also altered. According to the bioreceptivity index, the granite under study was characterised by ‘mild primary bioreceptivity’, but ‘high secondary bioreceptivity’ after the salt weathering process. Study of the secondary bioreceptivity of stone materials can provide very useful information about response to weathering effects, and the findings can be used to improve the selection of materials for building purposes.     

A model checking-based approach for security policy verification of mobile systems

This article describes an approach for the automated verification of mobile systems. Mobile systems are characterized by the explicit notion of location (e.g., sites where they run) and the ability to execute at different locations, yielding a number of security issues. To this aim, we formalize mobile systems as Labeled Kripke Structures, encapsulating the notion of location net that describes the hierarchical nesting of the threads constituting the system. Then, we formalize a generic security-policy specification language that includes rules for expressing and manipulating the code location. In contrast to many other approaches, our technique supports both access control and information flow specification. We developed a prototype framework for model checking of mobile systems. It works directly on the program code (in contrast to most traditional process-algebraic approaches that can model only limited details of mobile systems) and uses abstraction-refinement techniques, based also on location abstractions, to manage the program state space. We experimented with a number of mobile code benchmarks by verifying various security policies. The experimental results demonstrate the validity of the proposed mobile system modeling and policy specification formalisms and highlight the advantages of the model checking-based approach, which combines the validation of security properties with other checks, such as the validation of buffer overflows.