Investigating nano-structured domains within ionic liquids: the effect of cation change on thermal equilibrium and relaxation of spiropyran and spirooxazine.

The established belief that ionic liquids (ILs) behave as homogenous solvents such as that observed in molecular solvents has been challenged.1, 2 Previous use of solvatochromic probe dyes has allowed for the traditional parameter of ‘polarity’ to be determined.3 These values were compared to the kinetics of the photochromic spirocyclic compounds spirooxazine (SO) and spiropyran (SP). The nature of SO substituents limit the ability of hydrogen bond formation and so relies primarily on electrostatic interactions with the solvent system. Such an increase in solute freedom would be expected to increase the ability of the molecules to dissociate and migrate within the solvent system. A polarity-kinetic relationship for spirocyclic compounds has been established in molecular solvents with increasing polarity exhibiting decreased rates of thermal relaxation from the coloured merocyanine (MC) form to the spiro (SO/SP) form.4 However, thermal relaxation of SO in ionic liquids fails to present a correlation between polarity and kinetics. Kinetic studies were further enhanced by analysis of the relaxation process using thermodynamic parameters of activation. Previous studies have (primarily molecular modelling) proposed that ionic liquids possess a structured in-homogenous structure containing distinct areas of polar and non-polar regions.5 The probe dyes used to examine parameters such as hydrogen bonding (Kamlet-Taft) and polarity (ET30) may only examine a particular region in the solvent. This means that the probe molecules may solvate in one region while compounds such as SO may interact in another region completely and therefore not allow for correlation of polarity to thermal relaxation rates observed. The closed form is a neutral compound exhibiting non-polar characteristics. MC, due to its zwitterionic nature, is in contrast highly polar. We believe that the size and ratio of polar to non-polar regions may be a critical factor in the process of SO thermal relaxation. Increasing non-polar regions may encourage the SO form by shifting equilibrium and encouraging migration and facilitate enhanced closure of MC within the solvent system. Thermal relaxation of SO may therefore allow for confirmation of the theory of IL structuring. Due to the large range of ILs possible, a correlation in structural effects and a quantifiable change may aid in a more detailed understanding of ILs and facilitate customisability of the liquids to meet specific polarity/solvation requirements

Physico-chemical properties of ionic-liquid water mixtures

In order for Ionic Liquids (ILs) to be utilized to their full potential, it is necessary to have a complete understanding of their physical properties, including phase transitions temperatures1. We have previously reported into the extent of structuring of ILs using photochromic molecular probes, and investigated the appropriate IL water content to yield hydrated IL systems for analysis of polarity and to create environments suitable for effective enzyme activity 1,2,3. In this study we investigated interactions in hydrated ILs containing variable hydrophobic and hydrophilic regions through optical and thermal analysis. The enthalpies and phase transitions of the systems were compared, between the temperature range -50°C to +30°C for the ILs with varying degrees of hydration. Reichardtʼs dye was used as a molecular probe to monitor changes in interactions in the ILs as a function of temperature. Comparisons were made between ILs and for ILs with varying degrees of hydration. Spectroscopic studies were performed using Perkin Elmer UV-Visible Spectrometer and phase transitions monitored using a Perkin Elmer Differential Scanning Calorimeter. The ILs examined are; Trihexyltetradecylphosphonium Chloride [P6,6,6,14 Cl] Tributyl-tetradecylphosphonium Chloride, [P4,4,4,14 Cl], 1-Ethyl-methyl-3-imidazolium-ethyl Sulfate [Emim][EtSO4] and Trihexyltetradecylphosphonium Dicyanamide [P6,6,6,14 DCA]. 1. Robert Byrne, Simon Coleman, Simon Gallagher, and Dermot Diamond. Designer Molecular Probes for Phosphonium Ionic Liquids. Physical Chemistry Chemical Physics, 2010. 2. Kyoko Fujita, Douglas R. MacFarlane, Maria Forsyth, Masahiro Yoshizawa-Fujita, Kenichi Murata,† Nobuhumi Nakamura, and Hiroyuki Ohno*,Solubility and Stability of Cytochrome c in Hydrated Ionic Liquids: Effect of Oxo Acid Residues and Kosmotropicity, 2007. 3. SergeiV.DzyubaandRichardA.Bartsch,Expandingthepolarityrange of ionic liquids, Tetrehedron Letters, 2002

Next generation analytical platforms for environmental sensing: new technologies for old problems

Existing platforms for monitoring of nutrient levels (phosphates, nitrates etc) and pathogens (E. coli) in water bodies are often prohibitively expensive (>€20k) due to the use of conventional sample/liquid handling which results in bulky and labour intensive (servicing and maintenance) devices. As a consequence, this results in monitoring strategies that suffer from a lack of sampling frequency and deployment scale. With outbreaks of waterborne illnesses are still commonly reported in Europe e.g Cryptosporidium, Galway, Ireland, 2008 and the need for the development of real-time monitoring platforms for early warning of potential health risks from waterborne pathogens, particularly in the food industry e.g water as a potential source of E. coli contamination in Germany and Europe, 2011, there is a clear need for advancement of available technologies. To address these challenges, the NAPES project proposes the development of low cost, autonomous system for environmental sensing in the aqueous environment. This project will investigate ways to deliver revolutionary advances in liquid/sample handling combined with new approaches to performing sensitive in-situ analytical measurements. The goal is to drive down the unit cost of these instruments by orders of magnitude to levels that can create a tipping point, at which the technology becomes ubiquitous. The project brings together a team of 8 participants; Dublin City University (IE), Eindhoven University of Technology (NL), Curie Institute (FR), CIC Microgune (ES), T.E Laboratories (IE), Williams Industrial services Ltd (UK), University of Milan (IT) and Aquila Biosciences Ltd (IE) and will integrate several innovative methods of fluid handling (microfluidic channels incorporating light actuated valves), pre-concentration (functionalised magnetic beads) and detection (phantom surfaces and lectin functionalised surfaces) to produce the next generation in water quality assessment. It is hoped that these new technologies will help produce affordable and fully deployable platforms that will increase sampling frequency and potentially the accuracy of detection through increased sample volume throughput and sensitive detection systems. The drive towards more effective water treatment will result in a demand for more strenuous measurement of key quality parameters, such as concentrations of key contaminants, to monitor improvements in treatment processes. This necessitates the development of reliable measurement systems to determine such parameters as a means of gauging the success of optimisation of these processes and highlighting areas where improvements may be required. The following talk will introduce the NAPES project, its consortium, the project’s objectives and summarise initial data from each of the on-going research streams that showcase the latest technologies begin developed within the project to achieve this goal. As part of the Nano4water cluster, NAPES hopes to contribute to increased citizen awareness and a contribution to increasing standards in water quality assessment within the EU

(Re-)Placing Pentecostalism: Swedish Mission and the idea of the Baltic

I draw on fieldwork based in the Word of Life Ministry, Sweden, to consider how these neo-Pentecostals have constructed the Baltic as a landscape of both action and imagination. One part of my argument states that we must see the ministry’s attitudes to Sweden and the wider Baltic region in terms of its desire to situate itself within Swedish revivalist history. I also argue, however, that we can fruitfully draw on Bakhtin’s notion of the ‘chronotope’ to trace how the Baltic constitutes a potent spatio-temporal context for the construction of a narrative which encourages Word of Life members to see their missionary role as being contained within, but also looking far beyond, the Baltic Sea region

Itinerant Ferromagnetism in an Atom Trap

We propose an experiment to explore the magnetic phase transitions in interacting fermionic Hubbard systems, and describe how to obtain the ferromagnetic phase diagram of itinerant electron systems from these observations. In addition signatures of ferromagnetic correlations in the observed ground states are found: for large trap radii (trap radius $R_T > 4$, in units of coherence length $\xi$), ground states are topological in nature -- a "skyrmion" in 2D, and a "hedgehog" in 3D.Comment: Final Published version. References adde

Are the Ultra-Faint Dwarf Galaxies Just Cusps?

We develop a technique to investigate the possibility that some of the recently discovered ultra-faint dwarf satellites of the Milky Way might be cusp caustics rather than gravitationally self-bound systems. Such cusps can form when a stream of stars folds, creating a region where the projected 2-D surface density is enhanced. In this work, we construct a Poisson maximum likelihood test to compare the cusp and exponential models of any substructure on an equal footing. We apply the test to the Hercules dwarf (d ~ 113 kpc, M_V ~ -6.2, e ~ 0.67). The flattened exponential model is strongly favored over the cusp model in the case of Hercules, ruling out at high confidence that Hercules is a cusp catastrophe. This test can be applied to any of the Milky Way dwarfs, and more generally to the entire stellar halo population, to search for the cusp catastrophes that might be expected in an accreted stellar halo.Comment: Accepted for publication in ApJ Letters. Minor revisions from version

Use of an audio-paced incremental swimming test in young national-level swimmers

Purpose:To evaluate the reliability and sensitivity to training of an audio-paced incremental swimming test.Methods:Eight young national-level male swimmers (age 15 ± 1 year) performed a 7 × 200-m incremental swimming test (velocities 1.19, 1.24, 1.28, 1.33, 1.39, and 1.45 m/s and maximal sprint pace) using an audio-pacing device. The same test was performed 4 times by each participant, 1 wk apart to assess reliability (WK1, WK2) and after 9 and 20 wk of training (WK9, WK20). Blood lactate concentration ([La−]) and heart rate (HR) were recorded after each stage. Outcome measures were the velocity (v) and HR at lactate markers of 2 mM, 4 mM, and Δ1 mM.Results:Velocities at the lactate markers proved to be more reliable than HR, with typical errors ranging from 0.66% to 2.30% and 1.28% to 4.50%, respectively (shifts in mean ranged –0.91% to 0.73% and –0.84% to 1.79%, respectively). Across WK1, WK9, and WK20 there were significant improvements in peak velocity (P &lt; .001) and each of the velocities associated with the lactate markers (P &lt; .05), whereas only HR at Δ1 mM improved (P &lt; .05).Conclusions:This article demonstrates that an audio-paced incremental swimming test is reliable for use with junior swimmers and is sensitive to changes observed after training. The postswimming measurement of HR in the pool was comparatively less reliable.</jats:sec

TACTICAL APPLICATION OF BIOMECHANICS TO VOLLEYBALL USING INTERACTIVE COMPUTER SOFTWARE

Biomechanics of the techniques of volleyball players have been studied in several research papers (Coleman et aI, 1993, Huang et ai, 1998), but the application of fluid dynamics to the behaviour of volleyballs after spiking impact has only been investigated in one study (Kao et ai, 1994). The tactical uses of information on the flight of volleyballs were considered briefly in Kao et al.'s paper, but there were some omissions and errors concerning players' tactical capabilities. It was therefore the aim of this study to design and construct computer software which would allow coaching staff (or their support teams) to make objective decisions about defensive and offensive tactics in volleyball