Smart hydrogels for Novel Optical Functions

Nanocomposites of inherently conductive polyaniline (PANI) within a highly hydrophilic polyvinyl alcohol (PVA) based hydrogel have been produced by coupling a conventional dispersion chemical oxidative polymerization to a subsequent high energy irradiation step, in order to convert the polymer stabilizing the aqueous dispersion, namely the PVA, into a highly water swollen hydrogel incorporating the PANI particles. The incorporation of the electroactive and “pH-sensitive” polymer into a transparent and highly permeable hydrogel matrix has been pursued as a route to the development of a novel class of potentially biocompatible, smart hydrogels that can respond to changes of the surrounding environment with measurable changes in their optical properties. Absorption spectra show that the optical absorption bands typical of PANI, known to be reversibly affected by changes of the polymer oxidation state or pH or both, are well preserved in the PVA hydrogels. Even more interestingly, fluorescence is observed from the nanoparticles of PANI in its inherently conductive form, whose intensity is strongly affected by changes of pH. This has enhanced the importance of this material to a large extent from both a scientific and a practical point of view.     

Mauro Picone,Sandro Faedo,and the numerical solution of partial differential equations in Italy (1928–1953)

In this paper we revisit the pioneering work on the numerical analysis of partial differential equations (PDEs) by two Italian mathematicians, Mauro Picone (1885–1977) and Sandro Faedo (1913–2001). We argue that while the development of constructive methods for the solution of PDEs was central to Picone’s vision of applied mathematics, his own work in this area had relatively little direct influence on the emerging field of modern numerical analysis. We contrast this with Picone’s influence through his students and collaborators, in particular on the work of Faedo which, while not the result of immediate applied concerns, turned out to be of lasting importance for the numerical analysis of time-dependentPDEs.     

Population dynamics in compressible flows

Organisms often grow, migrate and compete in liquid environments, as well as on solid surfaces. However, relatively little is known about what happens when competing species are mixed and compressed by fluid turbulence. In these lectures we review our recent work on population dynamics and population genetics in compressible velocity fields of one and two dimensions. We discuss why compressible turbulence is relevant for population dynamics in the ocean and we consider cases both where the velocity field is turbulent and when it is static. Furthermore, we investigate populations in terms of a continuos density field and when the populations are treated via discrete particles. In the last case we focus on the competition and fixation of one species compared to another.     

Modified augmented Lagrangian preconditioners for the incompressible Navier–Stokes equations

We study different variants of the augmented Lagrangian (AL)‐based block‐triangular preconditioner introduced by the first two authors in [SIAM J. Sci. Comput. 2006; 28 : 2095–2113]. The preconditioners are used to accelerate the convergence of the Generalized Minimal Residual method (GMRES) applied to various finite element and Marker‐and‐Cell discretizations of the Oseen problem in two and three space dimensions. Both steady and unsteady problems are considered. Numerical experiments show the effectiveness of the proposed preconditioners for a wide range of problem parameters. Implementation on parallel architectures is also considered. The AL‐based approach is further generalized to deal with linear systems from stabilized finite element discretizations. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis and characterization of Si/Ga Eni Carbon Silicates

Phenylene-gallosilicates were prepared with the same crystalline structure as their aluminum ana-logues. The new Ga-Eni Carbon Silicates (Ga-ECS) phases were investigated by X-ray diffraction, scanning electron microscopy, nuclear magnetic resonance and thermogravimetric analysis, which demonstrated that gallium isomorphously replaced aluminum in the framework of the organ-ic-inorganic hybrids similar to the case of classical zeolites. Hybrid ECS materials were obtained with different types of bridged silsesquioxane precursors that maintained the aluminum-silicate nature of the inorganic moiety. This work confirms a new level of crystal chemistry versatility for this class of materials, and demonstrates the possibility to tailor also the inorganic part of the framework by changing the nature of the trivalent heteroatom.     

Tyrosine or Tryptophan? Modifying a Metalloradical Catalytic Site by Removal of the Cys–Tyr Cross-Link in the Galactose 6-Oxidase Homologue GlxA

The concerted redox action of a metal ion and an organic cofactor is a unique way to maximize the catalytic power of an enzyme. An example of such synergy is the fungal galactose 6-oxidase, which has inspired the creation of biomimetic copper oxidation catalysts. Galactose 6-oxidase and its bacterial homologue, GlxA, possess a metalloradical catalytic site that contains a free radical on a covalently linked Cys–Tyr and a copper atom. Such a catalytic site enables for the two-electron oxidation of alcohols to aldehydes. When the ability to form the Cys–Tyr in GlxA is disrupted, a radical can still be formed. Surprisingly, the radical species is not the Tyr residue but rather a copper second-coordination sphere Trp residue. This is demonstrated through the introduction of a new algorithm for Trp-radical EPR spectra simulation. Our findings suggest a new mechanism of free-radical transfer between aromatic residues and that the Cys–Tyr cross-link prevents radical migration away from the catalytic site.     

The physics of communicability in complex networks

A fundamental problem in the study of complex networks is to provide quantitative measures of correlation and information flow between different parts of a system. To this end, several notions of communicability have been introduced and applied to a wide variety of real-world networks in recent years. Several such communicability functions are reviewed in this paper. It is emphasized that communication and correlation in networks can take place through many more routes than the shortest paths, a fact that may not have been sufficiently appreciated in previously proposed correlation measures. In contrast to these, the communicability measures reviewed in this paper are defined by taking into account all possible routes between two nodes, assigning smaller weights to longer ones. This point of view naturally leads to the definition of communicability in terms of matrix functions, such as the exponential, resolvent, and hyperbolic functions, in which the matrix argument is either the adjacency matrix or the graph Laplacian associated with the network.     

Investigation of the Hydrate Plugging and Non-Plugging Properties of Oils

Three laboratories (Norwegian Institute of Science and Technology [NTNU], Institut Français du Pétrole [IFP], and the Colorado School of Mines [CSM]) determined hydrate plug formation characteristics in three oils, each in three conditions: (1) in their natural state, (2) with asphaltenes removed, and (3) with naturally occurring acids removed from the oil. The objective was to determine the major variables that affect hydrate plugging tendencies in oil-dominated systems, to enable the flow assurance engineer to qualitatively assess the tendency of an oil to plug with hydrates. In the past, it was indicated that chemical effects, for example, water-in-oil/hydrate-in-oil (emulsion/dispersion) stability, prevented hydrate plugs. For example, deasphalted oils provided low emulsion/dispersion stability and thus hydrate particles aggregated. In contrast pH 14-extracted oils were reported to remove stabilizing naphthenic acids, causing asphaltene precipitation on water/hydrate droplets, stabilizing the emulsion/dispersion to prevent aggregation and pluggage. This work suggests that in addition to chemistry, shear can enable plug-free operation in the hydrate region. High shear can prevent hydrate particle aggregation, while low shear encourages particle aggregation and plugging. As a result, flow assurance engineers may be able to forecast hydrate plug liability of an oil by a combination of chemistry and flow variables, such as: a) measurements of live oil emulsion stability, b) predictions of flow line shear, and c) knowledge of water cut. Plug formation qualitative trends are provided for the above three variables. Implications for flow assurance are given.