Nano-electrochemical detection of hydrogen or protons using palladium nanoparticles: distinguishing surface and bulk hydrogen.

The benefits of using nanoparticle-modified electrodes are exemplified through the electrochemical detection of protons and/or hydrogen. It is shown that a palladium-nanoparticle-modified boron-doped diamond allows voltammetric information relating to the relative roles played by the surface and the bulk metal to be obtained for the proton-hydrogen system at palladium surfaces which is not accessible using palladium macroelectrodes or microelectrodes.     

Counting unrooted maps on the plane

A planar map is a 2-cell embedding of a connected planar graph, loops and parallel edges allowed, on the sphere. A plane map is a planar map with a distinguished outside (“infinite”) face. An unrooted map is an equivalence class of maps under orientation-preserving homeomorphism, and a rooted map is a map with a distinguished oriented edge. Previously we obtained formulae for the number of unrooted planar n-edge maps of various classes, including all maps, non-separable maps, eulerian maps and loopless maps. In this article, using the same technique we obtain closed formulae for counting unrooted plane maps of all these classes and their duals. The corresponding formulae for rooted maps are known to be all sum-free; the formulae that we obtain for unrooted maps contain only a sum over the divisors of n. We count also unrooted two-vertex plane maps.     

On worst-case aggregation analysis for network location problems

Network location problems occur when new facilities must be located on a network, and the network distances between new and existing facilities are important. In urban, regional, or geographic contexts, there may be hundreds of thousands (or more) of existing facilities, in which case it is common to aggregate existing facilities, e.g. represent all the existing facility locations in a zip code area by a centroid. This aggregation makes the size of the problem more manageable for data collection and data processing purposes, as well as for purposes of analysis; at the same time, it introduces errors, and results in an approximating location problem being solved. There seems to be relatively little theory for doing aggregation, or evaluating the results of aggregation; most approaches are based on experimentation or computational studies. We propose a theory that has the potential to improve the means available for doing aggregation.This research was supported in part by the National Science Foundation, Grant No. DDM-9023392.     

Synthesis of an asymmetric fullerene dimer via sequential cycloadditions

A single isomer of a monofunctionalised C₇₀ fullerene is isolated and characterised using variable temperature NMR spectroscopy. Pendant methylene bromide groups allow for further cycloaddition reactions and a C₆₀-C₇₀ asymmetric fullerene dimer is thus prepared.     

On a zero equation model of turbulence

In this paper we study a widely used zero equation model of turbulence. The governing equations are derived by applying to the incompressible Navier-Stokes equations the Reynolds time averaging procedure. We achieve closure by employing the eddy viscosity concept. Using the Implicit Function Theorem we obtain an existence and uniquencess result. We also discuss the existence of nonsingular solutions. Finally, we present an algorithm for solving the modeled equations.     

Properties of polystyrene-poly(methylmethacrylate) random and diblock copolymers in dilute and semidilute solutions

Solution properties for random and diblock copolymers of polystyrene (PS) and poly(methyl methacrylate) (PMMA) have been measured by dynamic and total intensity light scattering in solvents of differing quality. The results are compared with the corresponding properties for PS and PMMA homopolymers of similar molecular weight, in order to determine if interactions between unlike monomers are significant. The hydrodynamic radius (R_h) and diffusion second virial coefficient (k_d) for the random copolymer are found to be larger than the corresponding values for the homopolymers in a solvent which is near-theta for the two homopolymers, whereas no such effect is observed for the block copolymer. This suggests that most intrachain interactions occur a relatively short distance along the chain backbone. In a mutual good solvent R_h and k_d of the random copolymer are comparable to the average of the values for the homopolymers, indicating that in a good solvent monomer/solvent interactions dominate over monomer/monomer interactions. For an isolated diblock copolymer in a mutual good solvent, there is no evidence that interactions between unlike monomers lead to additional expansion of the entire molecule, as measured by R_h, nor expansion of the individual blocks as probed by light scattering with one block optically masked. However, at low but finite concentration there is evidence (the coefficients of the binary interaction terms in the viscosity and the mutual diffusion coefficient, and the second and third virial coefficients) that a weak ordering effect may exist in block copolymer solutions, far from the conditions where microphase separation occurs. Finally, measurements of ternary polymer-polymer-solvent solutions show no dependence on monomer composition or monomer distribution for the tracer diffusion of probe PS-PMMA copolymers in a PMMA/toluene matrix. This indicate that the frictional interaction is largely unaffected by interactions between unlike monomers. However, there is evidence that the thermodynamic interaction is more unfavorable between a random copolymer and the homopolymer matrix than between a diblock and the matrix. © 1994 John Wiley & Sons, Inc.     

Polynomial-time approximation schemes for packing and piercing fat objects

We consider two problems: given a collection of n fat objects in a fixed dimension, (1) ( packing) find the maximum subcollection of pairwise disjoint objects, and (2) ( piercing) find the minimum point set that intersects every object. Recently, Erlebach, Jansen, and Seidel gave a polynomial-time approximation scheme (PTAS) for the packing problem, based on a shifted hierarchical subdivision method. Using shifted quadtrees, we describe a similar algorithm for packing but with a smaller time bound. Erlebach et al.'s algorithm requires polynomial space. We describe a different algorithm, based on geometric separators, that requires only linear space. This algorithm can also be applied to piercing, yielding the first PTAS for that problem.     

Domain size equilibration in sphere‐forming block copolymers

The kinetics of domain size equilibration were studied for asymmetric poly(ethylene‐alt‐propylene)‐b‐poly(dimethyl siloxane) (EPDMS) and polyisoprene‐b‐poly(dimethyl siloxane) (IDMS) block copolymers in the body‐centered cubic ordered phase. Small‐angle X‐ray scattering measurements of the principal peak position (q*) were made as a function of time after temperature jumps within the ordered state. The equilibration times were remarkably long, especially on cooling and for temperatures below 100 °C. For example, after a quench to 40 °C, q* for EPDMS had not fully equilibrated even after several weeks of annealing; IDMS required several days to equilibrate at the same temperature. In contrast, a lamella‐forming EPDMS sample was able to adjust q* within the timescale of the measurements (i.e., minutes) with both heating and cooling over the same temperature range. Measurements of tracer diffusion indicated that chain mobility was not the rate‐limiting step, although differences in mobility did account for the differences between EPDMS and IDMS. Rather, the limiting step was the required reduction in the number density of spheres on cooling; the disappearance of spheres, either by evaporation or by fusion, provided a large kinetic barrier. Lamellae, however, could adjust domain dimensions simply by local displacements of individual chains. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 715–724, 2003