Dynamics of the reaction between the free end of a tethered self-avoiding polymer and a flat penetrable surface: A renormalization group study

The average time tau(r) for one end of a long, self-avoiding polymer to interact for the first time with a flat penetrable surface to which it is attached at the other end is shown here to scale essentially as the square of the chain's contour length N. This result is obtained within the framework of the Wilemski-Fixman approximation to diffusion-limited reactions, in which the reaction time is expressed as a time correlation function of a ``sink'' term. In the present work, this sink-sink correlation function is calculated using perturbation expansions in the excluded volume and the polymer-surface interactions, with renormalization group methods being used to resum the expansion into a power law form. The quadratic dependence of tau(r) on N mirrors the behavior of the average time tau(c) of a free random walk to cyclize, but contrasts with the cyclization time of a free self-avoiding walk (SAW), for which tau(r) similar to N-2.2. A simulation study by Cheng and Makarov J. Phys. Chem. B 114, 3321 (2010)] of the chain-end reaction time of an SAW on a flat impenetrable surface leads to the same N-2.2 behavior, which is surprising given the reduced conformational space a tethered polymer has to explore in order to react. (C) 2014 AIP Publishing LLC.

Component Selection in the Self-Assembly of Palladium(II) Nanocages and Cage-to-Cage Transformations

Dynamic supramolecular systems involving a tetratopic palladium(II) acceptor and three different pyridine-and imidazole-based donors have been used for self-selection by a synergistic effect of morphological information and coordination ability of ligands through specific coordination interactions. Three different cages were first synthesized by two-component self-assembly of individual donor and acceptor. When all four components were allowed to interact in a reaction mixture, only one out of three cages was isolated. The preferential binding affinity towards a particular partner was also established by transforming a non-preferred cage into a preferred cage by interaction with the appropriate ligand. Computational studies further supported the fact that coordination interaction of imidazole moiety to Pd-II is enthalpically more preferred compared to pyridine, which drives the selection process. Analysis of crystal packing of both complexes indicated the presence of strong hydrogen bonds between nitrate and water molecules and also H-bonded 3D networks of water. Both complexes exhibit promising proton conductivity (10(-5) to ca. 10(-3) Scm(-1)) at ambient temperature under a relative humidity of circa 98% with low activation energy.

OPTIMALITY OF THE PRODUCT-MATRIX CONSTRUCTION FOR SECURE MSR REGENERATING CODES

In this paper, we consider the security of exact-repair regenerating codes operating at the minimum-storage-regenerating (MSR) point. The security requirement (introduced in Shah et. al.) is that no information about the stored data file must be leaked in the presence of an eavesdropper who has access to the contents of l(1) nodes as well as all the repair traffic entering a second disjoint set of l(2) nodes. We derive an upper bound on the size of a data file that can be securely stored that holds whenever l(2) <= d - k +1. This upper bound proves the optimality of the product-matrix-based construction of secure MSR regenerating codes by Shah et. al.

The Self-Association of Graphane Is Driven by London Dispersion and Enhanced Orbital Interactions

We investigated the nature of the cohesive energy between graphane sheets via multiple CH center dot center dot center dot HC interactions, using density functional theory (DFT) including dispersion correction (Grimmes D3 approach) computations of n]graphane sigma dimers (n = 6-73). For comparison, we also evaluated the binding between graphene sheets that display prototypical pi/pi interactions. The results were analyzed using the block-localized wave function (BLW) method, which is a variant of ab initio valence bond (VB) theory. BLW interprets the intermolecular interactions in terms of frozen interaction energy (Delta E-F) composed of electrostatic and Pauli repulsion interactions, polarization (Delta E-pol), charge-transfer interaction (Delta E-CT), and dispersion effects (Delta E-disp). The BLW analysis reveals that the cohesive energy between graphane sheets is dominated by two stabilizing effects, namely intermolecular London dispersion and two-way charge transfer energy due to the sigma CH -> sigma*(HC) interactions. The shift of the electron density around the nonpolar covalent C-H bonds involved in the intermolecular interaction decreases the C-H bond lengths uniformly by 0.001 angstrom. The Delta E-CT term, which accounts for similar to 15% of the total binding energy, results in the accumulation of electron density in the interface area between two layers. This accumulated electron density thus acts as an electronic glue for the graphane layers and constitutes an important driving force in the self-association and stability of graphane under ambient conditions. Similarly, the double faced adhesive tape style of charge transfer interactions was also observed among graphene sheets in which it accounts for similar to 18% of the total binding energy. The binding energy between graphane sheets is additive and can be expressed as a sum of CH center dot center dot center dot HC interactions, or as a function of the number of C-H bonds.

Case studies on the formation of chalcogenide self-assembled monolayers on surfaces and dissociative processes

This report examines the assembly of chalcogenide organic molecules on various surfaces, focusing on cases when chemisorption is accompanied by carbon-chalcogen atom-bond scission. In the case of alkane and benzyl chalcogenides, this induces formation of a chalcogenized interface layer. This process can occur during the initial stages of adsorption and then, after passivation of the surface, molecular adsorption can proceed. The characteristics of the chalcogenized interface layer can be significantly different from the metal layer and can affect various properties such as electron conduction. For chalcogenophenes, the carbon-chalcogen atombond breaking can lead to opening of the ring and adsorption of an alkene chalcogenide. Such a disruption of the pi-electron system affects charge transport along the chains. Awareness about these effects is of importance from the point of view of molecular electronics. We discuss some recent studies based on X-ray photoelectron spectroscopy that shed light on these aspects for a series of such organic molecules.

The Metabolic Core and Catalytic Switches Are Fundamental Elements in the Self-Regulation of the Systemic Metabolic Structure of Cells

19 p.

Territorial Integrity and Self-Determination : The Approach of the International Court of Justice in the Advisory Opinion on Kosovo

[EN] On 17 February 2008 Kosovo approved its declaration of independence from Serbia. The declaration was raised as a unilateral secession, a category which to date is widely debated by the international community, but supported in that case by a respectable number of the United Nation member states. A great many legal issues have been raised by the International Court of Justice's Advisory Opinion on Kosovo. This opinion was eagerly awaited by legal scholars due to both its possible effects and the scope of its principles outside the context of decolonization in what it could constitute of new approach to the international scenario for the twenty-first century. The ICJ stated that the declaration of independence was in accordance with international law if it was not prohibited. The answer turned on whether or not international law prohibited the declaration of independence, without ever examining whether an entity seeking secession is entitled with a positive right to secede and if so, under which circumstances. The basic issue can be summarised as whether or not we are facing a new course in the interpretation of certain classical categories of international law: the principle of territorial integrity, statehood, sovereignty, recognition, the right to external self-determination, etc. In this study we shall analyse some of the aspects arising from the Advisory Opinion of the International Court of Justice on the Accordance with international law of the unilateral declaration of independence in respect of Kosovo focusing on the territorial issue. Firstly we shall analyse the scope of the principle of territorial integrity of States and how it operates ; secondly, we shall focus on the scope of that principle in relation to the interior of the State, and ask ourselves how international law operates in relation to declarations of independence. Lastly, we shall deal with the principle of respect for territorial integrity in the specific case of Serbia with respect to Kosovo, and then end with a series of general conclusions. This study aims, definitely, to contribute to the theoretical debate on the challenges to the traditional certainties of international law in this area.

Pre-construction coral survey of the M/V Wellwood Grounding Site: April 23-24, 2002

This report documents abundance and cover for selected elements of the benthic coral reef assemblage at the site of the 1984 grounding of the M/V Wellwood on Molasses Reef, Florida Keys. The purpose of the effort was to establish a pre-construction baseline before the installation of reef modules at the site. The installation process is intended to stabilize fractured substrates that were recently exposed by storm impacts, and to provide three-dimensional relief in order to enhance reef community recovery. It is hoped that the restoration effort will result in a biological assemblage with the character of the transition community that would exist there had the incident not occurred. To date, the assemblage has developed the character of a comparatively featureless hard ground similar in composition to hard ground areas and transition zones surrounding the grounding site. These data will allow scientists and resource managers to better track the trajectory of recovery following the installation of modules. Direct counts of scleractinian and gorgonian corals, hydrocorals of the genus Millepora, and zoanthids of the genus Palythoa were made in three areas within and around the grounding site. The site is poorly developed with respect to scleractinian colony size and cover compared to surrounding areas. Key scleractinian species necessary for the development of topographic relief in the area denuded by the grounding are not well represented in the current community. Though gorgonian cover and richness is similar in all study areas, gorgonian community recovery in the damaged area is not complete. Unlike surrounding areas, one species, Pseudopterogorgia americana, accounts for over half of all corals at the grounding site, over 80% of all gorgonians, and nearly all the coral cover. Based on these findings and other observations made in the 18 years since the grounding, recommendations are made that should be considered in the course of human intervention targeted at stabilizing and enhancing the site. (PDF contains 24 pages.)

Promotion of research expertise online: the self-assessment tool

Helping HEIs identify whether the way they use online channels to communicate information about the expertise of researchers within their institution meets the needs of: – Business and community users – Researchers themselves.

The Kaipara story: a closer look at the benefits of working together, the evolution of a federation of aquaculture self-help groups and a one-stop aqua shop in rural West Bengal

What is special about Kaipara is that most recently, they have founded a federation of Self-Help Groups that work together to develop their own support network and to draw in the support of others. This is a sophisticated ‘home-grown’ support infrastructure that is the subject of this story. (Pdf contains 8 pages).

STM study on the self-assembly of oligothiophene-based organic semiconductors

The self-assembly properties of a series of functionalized regioregular oligo(3-alkylthiophenes) were investigated by using scanning tunneling microscopy (STM) at the liquid-solid interface under ambient conditions. The characteristics of the 2-D crystals formed on the (0001) plane of highly ordered pyrolitic graphite (HOPG) strongly depend on the length of the p-conjugated oligomer backbone, on the functional groups attached to it, and on the alkyl substitution pattern on the individual thiophene units. Theoretical calculations were performed to analyze the geometry and electronic density of the molecular orbitals as well as to analyze the intermolecular interactions, in order to obtain models of the 2-D molecular ordering on the substrate.

Global Self-Organization of the Cellular Metabolic Structure

Background: Over many years, it has been assumed that enzymes work either in an isolated way, or organized in small catalytic groups. Several studies performed using "metabolic networks models'' are helping to understand the degree of functional complexity that characterizes enzymatic dynamic systems. In a previous work, we used "dissipative metabolic networks'' (DMNs) to show that enzymes can present a self-organized global functional structure, in which several sets of enzymes are always in an active state, whereas the rest of molecular catalytic sets exhibit dynamics of on-off changing states. We suggested that this kind of global metabolic dynamics might be a genuine and universal functional configuration of the cellular metabolic structure, common to all living cells. Later, a different group has shown experimentally that this kind of functional structure does, indeed, exist in several microorganisms. Methodology/Principal Findings: Here we have analyzed around 2.500.000 different DMNs in order to investigate the underlying mechanism of this dynamic global configuration. The numerical analyses that we have performed show that this global configuration is an emergent property inherent to the cellular metabolic dynamics. Concretely, we have found that the existence of a high number of enzymatic subsystems belonging to the DMNs is the fundamental element for the spontaneous emergence of a functional reactive structure characterized by a metabolic core formed by several sets of enzymes always in an active state. Conclusions/Significance: This self-organized dynamic structure seems to be an intrinsic characteristic of metabolism, common to all living cellular organisms. To better understand cellular functionality, it will be crucial to structurally characterize these enzymatic self-organized global structures.

Effects of geometric shape on the hydrodynamics of a self-propelled flapping foil

The hydrodynamics of a free flapping foil is studied numerically. The foil undergoes a forced vertical oscillation and is free to move horizontally. The effect of chord-thickness ratio is investigated by varying this parameter while fixing other ones such as the Reynolds number, the density ratio, and the flapping amplitude. Three different flow regimes have been identified when we increase the chord-thickness ratio, i.e., left-right symmetry, back-and-forth chaotic motion, and unidirectional motion with staggered vortex street. It is observed that the chord-thickness ratio can affect the symmetry-breaking bifurcation, the arrangement of vortices in the wake, and the terminal velocity of the foil. The similarity in the symmetry-breaking bifurcation of the present problem to that of a flapping body under constraint is discussed. A comparison between the dynamic behaviors of an elliptic foil and a rectangular foil at various chord-thickness ratios is also presented.

Construction, extension and evaluation of the improved smoking kiln (Banda) in Kainji Lake area

Fish smoking, as a traditional occupation of fishermen and women in Kainji Lake Area (Nigeria) is done using simple traditional ovens called 'Banda', the fuel for the smoking being almost hundred percent dependent on wood. A simple modification was made to the traditional 'Banda' oven using a damper to prevent burning of the fish. A comparison of the improved and the traditional 'Banda' was made. The results indicate that fuel wood consumption was reduced 52 percent by using the improved 'Banda', which implied that 50 percent of fish processor's income could be saved through the adoption of this technology. The most important advantage of the improved kiln, fuel wood conservation, represents for fishers a problem of an economic importance. Whilst they are aware that it is becoming much more difficult to get the needed fuel wood, the children can still conveniently collect enough wood for both home use and processing activities. The cost of the components of the improved kiln, when compared with the traditional version may be considered quite significant, and hence the reluctance of the fish processors in constructing similar ones. Selected blacksmiths were trained to continue the fabrication of the kiln component. The training was carried out to assure that the improved kiln will be constructed even after the project will end to support the fabrication