Asymptotic-preserving &; well-balanced schemes for radiative transfer and the Rosseland approximation

Summary. We are concerned with efficient numerical simulation of the radiative transfer equations. To this end, we follow the Well-Balanced approachs canvas and reformulate the relaxation term as a nonconservative product regularized by steady-state curves while keeping the velocity variable continuous. These steady-state equations are of Fredholm type. The resulting upwind schemes are proved to be stable under a reasonable parabolic CFL condition of the type tO(x²) among other desirable properties. Some numerical results demonstrate the realizability and the efficiency of this process.Mathematics Subject Classification (1991): 82C70, 65M06, 35B25Work partially supported by EEC network #HPRN-CT-2002-00282.Revised version received July 21, 2003     

Probing fragment complementation by rigid-body docking: in silico reconstitution of calbindin D9k

Fragment complementation is gaining an increasing impact as a nonperturbing method to probe noncovalent interactions within protein supersecondary structures. In this study, the fast Fourier transform rigid-body docking algorithm ZDOCK has been employed for in silico reconstitution of the calcium binding protein calbindin D9k, from its two EF-hands subdomains, namely, EF1 (residues 1-43) and EF2 (residues 44-75). The EF1 fragment has been used both in its wild type and in nine mutant forms, in line with in vitro experiments. Consistent with in vitro data, ZDOCK reconstituted the proper fold of wild-type and mutated calbindin, locating the nativelike structures (i.e., holding a root-mean-square deviation < 1 A with respect to the X-ray structure) among the first 10 top-scored solutions out of 4000. Moreover, the three independent in silico reconstitutions of wild-type calbindin ranked a nativelike structure at the top of the output list, that is, the best scored one. The algorithm has been also successfully challenged in reconstituting the EF2 homodimer from two identical copies of the monomer. Furthermore, quantitative models consisting of linear correlations between thermodynamic data and ZDOCK scores were built, providing a tested tool for very fast in silico predictions of the free energy of association of protein-protein complexes solved at the atomic level and known to not undergo significant conformational changes upon binding.     

A canonical treatment of nonautonomous systems of type\dot \upsilon = f(t) + c.

We solve by canonical methods, the Hamilton-Jacobi equation and the Poisson bracket technique, the special type of nonautonomous systems described by the equation . The general expressions so obtained are applied to the free rocket and the rocket in a uniform gravitational field, which serve as illustrations and test of the general results.     

Contouring of artwork surface by fringe projection and FFT analysis

In the present work, we propose a simple optical method to perform profilometry on works of art. The method is based on the projection of a Ronchi grating onto the surface to be analyzed. When viewed at an angle different from the projection angle, the grid pattern appears deformed by the surface shape. This pattern is digitized, by a high-resolution CCD camera, and then processed using a Fourier transform analysis. The technique is free from the errors caused by higher harmonic components of the grating pattern. Furthermore, the method relies on very simple equipment and it is therefore suitable for in situ measurements. Theoretical details and examples of the technique in operation are given.     

Mechanical Characterization of Angle-Ply Composite Laminates by Differential Moiré Method: The Influence of Specimens' Length-to-Width Ratio

The influence exerted by the specimen proportions on the measured performance of angle-ply [+45°/–45°]_s composite laminates is studied. Three kinds of specimens are considered, having different length-to-width ratios, made with glass/epoxy unidirectional or fabric laminae. The static tensile characteristics are measured by means of load cells, electric strain gauges and through the Moiré fringes method. The strain fields are analysed and the effects of stress concentration at the laminate-free edges are evaluated, as well as their influence on the strain distribution and the measured strength and stiffness. The results are summarized as diagrams of ultimate load and elastic modulus versus length-to-width ratio of the different specimens investigated. These diagrams allow the designer to evaluate the influence exerted by specimen proportions on the measured performance, as well as to compare characteristics which are heterogeneous, as obtained with different kinds of specimen.     

Carbynes phonons: a tight binding force field

Modeling the vibrational structure of linear carbon chains has proved to be a difficult task with present first-principles calculations. This limits their applicability for the interpretation of experimental data, such as Raman scattering experiments on linear carbon chains within nanotubes. These limitations can be overcome by means of a simple tight binding scheme for pi-electrons. In this work a force field for the calculation of longitudinal phonon dispersion branches is built on the basis of bond-bond polarizabilities and just three parameters. The so obtained phonon dispersion branches are in very good agreement with the experimental data on carbynes in different environments and polyynes of any length. The model is discussed in relation to the importance of long range vibrational interactions in carbynes. The physical phenomena affecting their vibrational properties (i.e., Kohn anomaly, electron-phonon coupling) can be accurately and analytically described by the present approach.     

Synthesis, X-ray diffraction and computational study of the crystal packing of polycyclic hydrocarbons featuring aromatic and perfluoroaromatic rings condensed in the same molecule: 1,2,3,4-tetrafluoronaphthalene, -anthracene and -phenanthrene

We have synthesised some planar polycyclic compounds, in which unsubstituted aromatic rings are condensed with perfluorinated aromatic rings, and have carried out a combined X-ray diffraction and computational study to analyse their self-recognition behaviour in crystalline phases. We compare our results with the parent hydrocarbons and with other compounds that have a variable degree of fluorination. Whereas the molecular planes in crystals of hydrocarbons with mono- or difluorinated aromatic rings or of perfluorinated compounds arrange themselves in V-shaped configurations, our present results show that perfluorinated rings tend to stack over unsubstituted rings even when these two moieties coexist in a condensed system, producing crystalline materials with parallel molecular layers with the arene-perfluoroarene recognition pattern. Our analysis shows that the packing energy of all these crystals is dispersion-dominated and that coulombic terms are selective rather than quantitatively predominant in crystals with arene-perfluoroarene interactions. No compelling proof of a special role of C-H...F interactions has been found.     

Insights into the mechanism of electrocatalytic hydrogen evolution mediated by Fe2(S2C3H6)(CO)6: the simplest functional model of the Fe-hydrogenase active site

The di-iron complex Fe2(S2C3H6)(CO)6 (a), one of the simplest functional models of the Fe-hydrogenases active site, is able to electrocatalyze proton reduction. In the present study, the H2 evolving path catalyzed by a has been characterized using density functional theory. It is showed that, in the early stages of the catalytic cycle, a neutral mu-H adduct is formed; monoelectron reduction and subsequent protonation can give rise to a diprotonated neutral species (a-muH-SH), which is characterized by a mu-H group, a protonated sulfur atom, and a CO group bridging the two iron centers, in agreement with experimental IR data indicating the formation of a long-lived mu7-CO species. H2 release from a-muH-SH, and its less stable isomer a-H2 is kinetically unfavorable, while the corresponding monoanionic compounds (a-muH-SH- and a-H2-) are more reactive in terms of dihydrogen evolution, in agreement with experimental data. The key species involved in electrocatalysis have structural features different from the hypothetical intermediates recently proposed to be involved in the enzymatic process, an observation that is possibly correlated with the reduced catalytic efficiency of the biomimetic di-iron assembly.     

Site-directed conjugation of "clicked" glycopolymers to form glycoprotein mimics: binding to mammalian lectin and induction of immunological function

Synthesis of well-defined neoglycopolymer-protein biohybrid materials and a preliminary study focused on their ability of binding mammalian lectins and inducing immunological function is reported. Crucial intermediates for their preparation are well-defined maleimide-terminated neoglycopolymers (M(n) = 8-30 kDa; M(w)/M(n) = 1.20-1.28) presenting multiple copies of mannose epitope units, obtained by combination of transition-metal-mediated living radical polymerization (TMM LRP) and Huisgen [2+3] cycloaddition. Bovine serum albumin (BSA) was employed as single thiol-containing model protein, and the resulting bioconjugates were purified following two independent protocols and characterized by circular dichroism (CD) spectroscopy, SDS PAGE, and SEC HPLC. The versatility of the synthetic strategy presented in this work was demonstrated by preparing a small library of conjugating glycopolymers that only differ from each other for their relative epitope density were prepared by coclicking of appropriate mixtures of mannopyranoside and galactopyranoside azides to the same polyalkyne scaffold intermediate. Surface plasmon resonance binding studies carried out using recombinant rat mannose-binding lectin (MBL) showed clear and dose-dependent MBL binding to glycopolymer-conjugated BSA. In addition, enzyme-linked immunosorbent assay (ELISA) revealed that the neoglycopolymer-protein materials described in this work possess significantly enhanced capacity to activate complement via the lectin pathway when compared with native unmodified BSA.     

Experimental test of two-way quantum key distribution in the presence of controlled noise

We describe the experimental test of a quantum key distribution performed with a two-way protocol without using entanglement. An individual incoherent eavesdropping is simulated and induces a variable amount of noise on the communication channel. This allows a direct verification of the agreement between theory and practice.