Mechanism and release rates of surface confined cyclodextrin guests

The dissociation of a cobalt bisdiphenylterpyridine, [Co(biptpy)(2)](2+), guest at mixed (γ-CD-(py)(2))-alkanethiol layers (where γ-CD-(py)(2) is di-6(A), 6(B)- deoxy-6-(4-pyridylmethyl)amino- γ-cyclodextrin) formed on platinum electrodes is reported. Cyclic voltammetry (CV) shows reversible one-electron surface confined waves consistent with the Co(2/3+) couple bound at the interface. The quantity of [Co(biptpy)(2)](3+) reduced is found to be dependent on the scan rate employed, with greater amounts at higher scan rates. This behavior is in contrast to the CD guest ferrocene, which upon oxidation to the ferrocenium ion shows little charge associated with reduction even at elevated scan rates. Chronocoulometry was conducted to systematically vary the time spent oxidizing [Co(biptpy)(2)](2+) and to measure the resulting charge associated with the reduction of [Co(biptpy)(2)](3+). It is determined experimentally that as the pulse width increases, i.e. greater time spent in the oxidizing region, the amount of charge needed to reduce [Co(biptpy)(2)](3+) decreases dramatically. This decrease, along with the CV data, suggests strongly that the [Co(biptpy)(2)](3+) dissociates from the cavity. Significantly, this dissociation of the interfacial host-guest complex occurs on a much longer timescale (the order of seconds) compared to the oxidation of [Co(biptpy)(2)](2+) to [Co(biptpy)(2)](3+), which has been measured using high speed chronoamperometry to occur with a rate contant, k(0), of approximately 10(3) s(-1). The comparison of the timescale for dissociation of the interfacial complex and for electron transfer signifies that the electron transfer step occurs before dissociation, i.e. dissociation via an EC mechanism. The dissociation mechanism of [Co(biptpy)(2)](3+) is contrasted with that of the ferrocene/ferrocenium couple.     

Architected porous metals in electrochemical energy storage

Porous metallic structures are regularly used in electrochemical energy storage (EES) devices as supports, current collectors, or active electrode materials. Bulk metal porosification, dealloying, welding, or chemical synthesis routes involving crystal growth or self-assembly, for example, can sometimes provide limited control of porous length scale, ordering, periodicity, reproducibility, porosity, and surface area. Additive manufacturing has shown the potential to revolutionize the fabrication of architected metals, allowing complex geometries not usually possible by traditional methods, by enabling complete design freedom of a porous metal based on the required physical or chemical property to be exploited. We discuss properties of porous metal structures in EES devices and provide some opinions on how architected metals may alleviate issues with electrochemically active porous metal current collectors, and provide opportunities for optimum design based on electrochemical characteristics required by batteries, supercapacitors or other electrochemical devices.     

Generalized voronoi diagrams for moving a ladder. I: Topological analysis

Given a bounded open subset Ω of the plane whose boundary is the union of finitely many polygons, and a real number d > 0, a manifold FP (the [free placements]) may be defined as the set of placements of a closed oriented line-segment B (a [ladder]) of length d inside Ω. FP is a three-dimensional manifold. A [Voronoi complex] in this manifold, a two-dimensional cell complex, is defined by analogy with the classical geometric construction in the plane; within this complex a one-dimensional subcomplex N, called the skeleton, is defined. It is shown that every component of FP contains a unique component of N, and canonical motions are given to move the ladder to placements within N. In this way, general motion planning is reduced to searching in a suitable representation of N as a (combinatorial) graph. Efficient construction of N is described in a companion paper.     

Electron impact ionization of the noble gases in coplanar symmetric geometry over the energy range 100 to 1000 eV

Distorted-wave Born approximation calculations are reported for electron impact ionization of He, Ne, Ar, Kr and Xe in coplanar symmetric geometry at energies of 100, 500 and 1000 eV. Of special interest is double scattering effect at large angles.     

Capillary ion chromatography of inorganic anions on octadecyl silica monolith modified with an amphoteric surfactant

A reversed-phase monolithic silica based capillary column (Onyx C(18), 150 mm x 0.1 mm) was modified with the amphoteric surfactant, N-dodecyl-N,N-(dimethylammonio)undecanoate (DDMAU) and evaluated for the separation and determination of inorganic anions using on-column capacitively coupled contactless conductivity detection (C(4)D). The chromatographic performance of the column was evaluated and under optimal conditions separation efficiencies of 56,200 plates per meter or 7025 plates per column (at detection point) were observed (for iodide). Direct plumbing of the capillary column to the micro-injector and on-column detection eliminated extra-column band broadening, thus allowing accurate analysis of van Deemter curves obtained for the monolithic capillary column. The calculated value for the C-term in the obtained van Deemter curve was between 3 and 4 ms for inorganic anions, allowing for the utilisation of relatively high flow rates without significant losses in efficiency. The performance of the C(4)D detector was investigated and compared for detection on an open tubular capillary column and on the modified monolithic silica capillary column. The on-column detection approach did not result in any significant decrease in peak sensitivity for the monolith compared to responses recorded for open tubular capillary columns, and in addition meant the system could be applied to rapid separations by simple variation in apparent column length. The proposed chromatographic system allowed for detection of common anions at sub-ppm level with a 10 nL injection volume. Additionally, on-column detection allowed visualisation of the development of the separation at any point in time and evaluation of the longitudinal uniformity of the ion-exchange coating.     

Constant flux relation for driven dissipative systems

Conservation laws constrain the stationary state statistics of driven dissipative systems because the average flux of a conserved quantity between driving and dissipation scales should be constant. This requirement leads to a universal scaling law for flux-measuring correlation functions, which generalizes the 4/5th law of Navier-Stokes turbulence. We demonstrate the utility of this simple idea by deriving new exact scaling relations for models of aggregating particle systems in the fluctuation-dominated regime and for energy and wave action cascades in models of strong wave turbulence.     

Fidelity enhancement by logical qubit encoding

We demonstrate coherent control of two logical qubits encoded in a decoherence free subspace (DFS) of four dipolar-coupled protons in an NMR quantum information processor. A pseudopure fiducial state is created in the DFS, and a unitary logical qubit entangling operator evolves the system to a logical Bell state. The four-spin molecule is partially aligned by a liquid crystal solvent, which introduces strong dipolar couplings among the spins. Although the system Hamiltonian is never fully specified, we demonstrate high fidelity control over the logical degrees of freedom. In fact, the DFS encoding leads to higher fidelity control than is available in the full four-spin Hilbert space.     

The coupled dynamics of two particles with different limit sets

We consider a system of two coupled particles evolving in a periodic and spatially symmetric potential under the influence of external driving and damping. The particles are driven individually in such a way that in the uncoupled regime, one particle evolves on a chaotic attractor, while the other evolves on regular periodic attractors. Notably, only the latter supports coherent particle transport. The influence of the coupling between the particles is explored, and in particular how it relates to the emergence of a directed current. We show that increasing the (weak) coupling strength subdues the current in a process, which in phase-space, is related to a merging crisis of attractors forming one large chaotic attractor in phase-space. Further, we demonstrate that complete current suppression coincides with a chaos-hyperchaos transition.     

A study of the contribution of doubly excited ionic states to the properties of hot dense high-Z plasmas

The role of two-electron processes, i.e. dielectronic recombination and autoionization, in the ionization balance and X-ray emission of hot dense plasmas composed of various high-Z materials is explored. Tungsten, gold, lead and uranium are considered. It is shown that the average ion charge and the high-energy emissivity are both sensitive to the dielectronic recombination rate. A systematic study demonstrates the degree of this sensitivity. It is found that the complete neglect of these 2-electron processes introduces a large error but once included, the key physical properties are quite insensitive to the rate over the important 2–3 keV temperature range. The high-energy emissivity depends strongly on temperature, peaking at conditions corresponding to a closed shell system, and on the square of the electron density, as for a coronal system.     

The morphology and structure of PS‐b‐P4VP block copolymer films by solvent annealing: effect of the solvent parameter

Lamellae (symmetric) forming polystyrene‐b‐poly(4‐vinylpyridine) (PS‐b‐P4VP) block copolymers (BCPs) were used to produce nanostructured thin films by solvent (toluene) casting (spin‐coating) onto silicon substrates. As expected, strong micellization of PS‐P4VP in toluene results in poorly ordered hexagonally structures films. Following deposition the films were solvent annealed in various solvents and mixtures thereof. A range of both morphologies including micelle and microphase separated structures were observed. It was found that nanostructures typical of films of regular thickness (across the substrate) and demonstrating microphase separation occurred only for relatively few solvents and mixtures. The data demonstrate that simple models of solvent annealing based on swelling of the polymer promoting higher polymer chain mobility are not appropriate and more careful rationalization is required to understand these data. Analysis suggests that regular phase separated films can only be achieved when the copolymer Hildebrand solubility parameter is very similar to the value of the solvent. It is suggested that the solvent anneal method used is best considered as a liquid phase technique rather than a vapor phase method. The results show that solvent annealing methods can be a very powerful means to control structure and in some circumstances dominate other factors such as surface chemistry and surface energies. Copyright © 2009 John Wiley & Sons, Ltd.