Application of Asymmetric Marcus-Hush Theory to Voltammetry in Room-Temperature Ionic Liquids

Asymmetric MarcusHush (AMH) theory is applied for the first time in ionic solvents to model the voltammetric reduction of oxygen in 1-butyl-1-methylpyrrolidinium bis-(trifluoromethylsulfonyl)-imide and of 2-nitrotoluene (2-NT), nitrocyclopentane (NCP), and 1-nitro-butane (BuN) in trihexyltetradecylphosphonium tris(pentafluoroethyl)trifluorophosphate on a gold microdisc electrode. An asymmetry parameter, gamma, was estimated for all systems as -0.4 for the reduction of oxygen and -0.05, 0.25, and 0 +/- 0.05 for the reductions of 2-NT, NCP, and BuN, respectively, which suggests equal force constants of reactants and products in the case of 2-NT and BuN and unequal force constants for oxygen and NCP where the force constants of the oxidized species are greater than the reduced species in the case of oxygen and less than the reduced species in the case of NCP. Previously measured values for a, the Butler-Volmer transfer coefficient, reflect this in each case. Where appreciable asymmetry occurs, AMH theory was seen to parametrize the experimental data better than either Butler-Volmer or symmetric Marcus-Hush theory, allowing additionally the extraction of reorganization energy. This is the first study to provide key physical insights into electrochemical systems in room-temperature ionic liquids using AMH theory, allowing elucidation of the reorganization energies and the relative force constants of the reactants and products in each reaction.

An in-situ surface electrochemistry approach toward whole-cell studies: Charge transfer between Geobacter sulfurreducens and electrified metal/electrolyte interfaces through linker molecules

Electrochemical reactivity and structure properties of electrogenic bacteria, Geobacter sulfurreducens (Gs) were studied to explore the heterogeneous electron transfer at the bacteria/electrode interface using electrochemical and in-situ spectroscopic techniques. The redox behavior of Gs adsorbed on a gold electrode, which is modified with a ω-functionalized self-assembled monolayer (SAM) of alkanethiols, depends strongly on the terminal group. The latter interacts directly with outermost cytochromes embedded into the outer membrane of the Gs cells. The redox potential of bacterial cells bound electrostatically to a carboxyl-terminated SAM is close to that observed for bacteria attached to a bare gold electrode, revealing a high electronic coupling at the cell/SAM interface. The redox potentials of bacterial cells adsorbed on amino- and pyridyl-terminated SAMs are significantly different suggesting that the outermost cytochromes changes their conformation upon adsorption on these SAMs. No redox activity of Gs was found with CH3-, N(CH3)3+- and OH-terminated SAMs. Complementary in-situ spectroscopic studies on bacteria/SAMs/Au electrode assemblies were carried out to monitor structure changes of the bacterial cells upon polarization. Spectro-electrochemical techniques revealed the electrochemical turnover of the oxidized and reduced states of outer membrane cytochromes (OMCs) in Gs, providing evidence that the OMCs are responsible for the direct electron transfer to metal electrodes, such as gold or silver, during the electricity production. Furthermore, we observed spectroscopic signatures of the native structure of the OMCs and no conformational change during the oxidation/reduction process of the microorganisms. These findings indicate that the carboxyl-anchoring group provides biocompatible conditions for the outermost cytochromes of the Gs, which facilitate the heterogeneous electron transfer at the microorganism/electrode interface.

An in situ surface electrochemistry approach towards whole-cell studies: the structure and reactivity of a Geobacter sulfurreducens submonolayer on electrified metal/electrolyte interfaces

A direct electron transfer process between bacterial cells of electrogenic species Geobacter sulfurreducens (Gs) and electrified electrode surfaces was studied to exploit the reactivity of Gs submonolayers on gold and silver surfaces. A submonolayer of Gs was prepared and studied to explore specifically the heterogeneous electron transfer properties at the bacteria/electrode interface. In situ microscopic techniques characterised the morphology of the Gs submonolayers under the operating conditions. In addition, complementary in situ spectroscopic techniques that allowed us to access in situ molecular information of the Gs with high surface selectivity and sensitivity were employed. The results provided clear evidence that the outermost cytochrome C in Gs is responsible for the heterogeneous electron transfer, which is in direct contact with the metal electrode. Feasibility of single cell in situ studies under operating conditions was demonstrated where the combination of surface-electrochemical tools at the nano- and micro-scale with microbiological approaches can offer unique opportunities for the emerging field of electro-microbiology to explore processes and interactions between microorganisms and electrical devices.

Polarization Relaxation in an Ionic Liquid Confined between Electrified Walls

The response of a room temperature molten salt to an external electric field when it is confined to a nanoslit is studied by molecular dynamics simulations. The fluid is confined between two parallel and oppositely charged walls, emulating two electrified solid-liquid interfaces. Attention is focused on structural, electrostatic, and dynamical properties, which are compared with those of the nonpolarized fluid. It is found that the relaxation of the electrostatic potential, after switching the electric field off, occurs in two stages. A first, subpicosecond process accounts for 80% of the decay and is followed by a second subdiffusive process with a time constant of 8 ps. Diffusion is not involved in the relaxation, which is mostly driven by small anion translations. The relaxation of the polarization in the confined system is discussed in terms of the spectrum of charge density fluctuations in the bulk.

Tangible interfaces to explain Gaudi's use of ruled-surface geometries

This paper summarises the development of a machine-readable model series for explaining Gaudi's use of ruled surface geometry in the Sagrada Familia in Barcelona, Spain. The first part discusses the modeling methods underlying the columns of the cathedral and the techniques required to translate them into built structures. The second part discusses the design and development of a tangible machine-readable model to explain column-modeling methods interactively in educational contexts such as art exhibitions. It is designed to explain the principles underlying the column design by means of physical interaction without using mathematical terms or language.

Movements in gesture interfaces

There is a mismatch between the kinds of movements used in gesture interfaces and our existing theoretical understandings of gesture. We need to re-examine the assumptions of gesture research and develop theory more suited to gesture interface design. In addition to improved theory, we need to develop ways for participants in the process of design to adapt, extend and develop theory for their own design contexts. Gesture interface designers should approach theory as a contingent resource for design actions that is responsive to the needs of the design process.

Airports in their urban settings : towards a conceptual model of interfaces in the Australian context

In Australia, airports have emerged as important sub-regional activity centres and now pose challenges for both airport operation and planning in the surrounding urban and regional environment. The changing nature of airports in their metropolitan context and the emergence of new pressures and problems require the introduction of a fresh conceptual framework to assist the better understanding of these complex roles and spatial interactions. The approach draws upon the meta-concept of interfaces of an ‘airport metropolis’ as an organising device consisting of four main domains: economic development, land use,infrastructure, and governance. The paper uses the framework to further discuss airport and regional interactions and highlights the use of sustainability criteria to operationalise the model. The approach aims to move research and practice beyond the traditionally compartmentalised analysis of airport issues and policy-making by highlighting interdependencies between airports and regions.

Accident prediction model for railway-highway interfaces

Considerable past research has explored relationships between vehicle accidents and geometric design and operation of road sections, but relatively little research has examined factors that contribute to accidents at railway-highway crossings. Between 1998 and 2002 in Korea, about 95% of railway accidents occurred at highway-rail grade crossings, resulting in 402 accidents, of which about 20% resulted in fatalities. These statistics suggest that efforts to reduce crashes at these locations may significantly reduce crash costs. The objective of this paper is to examine factors associated with railroad crossing crashes. Various statistical models are used to examine the relationships between crossing accidents and features of crossings. The paper also compares accident models developed in the United States and the safety effects of crossing elements obtained using Korea data. Crashes were observed to increase with total traffic volume and average daily train volumes. The proximity of crossings to commercial areas and the distance of the train detector from crossings are associated with larger numbers of accidents, as is the time duration between the activation of warning signals and gates. The unique contributions of the paper are the application of the gamma probability model to deal with underdispersion and the insights obtained regarding railroad crossing related vehicle crashes. Considerable past research has explored relationships between vehicle accidents and geometric design and operation of road sections, but relatively little research has examined factors that contribute to accidents at railway-highway crossings. Between 1998 and 2002 in Korea, about 95% of railway accidents occurred at highway-rail grade crossings, resulting in 402 accidents, of which about 20% resulted in fatalities. These statistics suggest that efforts to reduce crashes at these locations may significantly reduce crash costs. The objective of this paper is to examine factors associated with railroad crossing crashes. Various statistical models are used to examine the relationships between crossing accidents and features of crossings. The paper also compares accident models developed in the United States and the safety effects of crossing elements obtained using Korea data. Crashes were observed to increase with total traffic volume and average daily train volumes. The proximity of crossings to commercial areas and the distance of the train detector from crossings are associated with larger numbers of accidents, as is the time duration between the activation of warning signals and gates. The unique contributions of the paper are the application of the gamma probability model to deal with underdispersion and the insights obtained regarding railroad crossing related vehicle crashes.