Neutral and Charged 1-Butyl-3-methylimidazolium Triflate Clusters: Equilibrium Concentration in the Vapor Phase and Thermal Properties of Nanometric Droplets

Ground state energy, structure, and harmonic vibrational modes of 1-butyl-3-methylimidazolium triflate ([bmim][Tf]) clusters have been computed using an all-atom empirical potential model. Neutral and charged species have been considered up to a size (30 [bmim][Tf] pairs) well into the nanometric range. Free energy computations and thermodynamic modeling have been used to predict the equilibrium composition of the vapor phase as a function of temperature and density. The results point to a nonnegligible concentration of very small charged species at pressures (P ~ 0.01 Pa) and temperatures (T 600 K) at the boundary of the stability range of [bmim][Tf]. Thermal properties of nanometric neutral droplets have been investigated in the 0 T 700 K range. A near-continuous transition between a liquidlike phase at high T and a solidlike phase at low T takes place at T ~ 190 K in close correspondence with the bulk glass point Tg ~ 200 K. Solidification is accompanied by a transition in the dielectric properties of the droplet, giving rise to a small permanent dipole embedded into the solid cluster. The simulation results highlight the molecular precursors of several macroscopic properties and phenomena and point to the close competition of Coulomb and dispersion forces as their common origin.

The challenge of patients’ unmet palliative care needs in the final stages of chronic illness.

Background: There is consensus in the literature that the end of life care for patients with chronic illness is suboptimal, but research on the specific needs of this population is limited. Aim: This study aimed to use a mixed methodology and case study approach to explore the palliative care needs of patients with a non-cancer diagnosis from the perspectives of the patient, their significant other and the clinical team responsible for their care. Patients (n 18) had a diagnosis of either end-stage heart failure, renal failure or respiratory disease. Methods: The Short Form 36 and Hospital and Anxiety and Depression Questionnaire were completed by all patients. Unstructured interviews were (n 35) were conducted separately with each patient and then their significant other. These were followed by a focus group discussion (n 18) with the multiprofessional clinical team. Quantitative data were analysed using simple descriptive statistics and simple descriptive statistics. All qualitative data were taped, transcribed and analysed using Colaizzi’s approach to qualitative analysis. Findings: Deteriorating health status was the central theme derived from this analysis. It led to decreased independence, social isolation and family burden. These problems were mitigated by the limited resources at the individual’s disposal and the availability of support from hospital and community services. Generally resources and support were perceived as lacking. All participants in this study expressed concerns regarding the patients’ future and some patients described feelings of depression or acceptance of the inevitability of imminent death. Conclusion: Patients dying from chronic illness in this study had many concerns and unmet clinical needs. Care teams were frustrated by the lack of resources available to them and admitted they were ill-equipped to provide for the individual’s holistic needs. Some clinicians described difficulty in talking openly with the patient and family regarding the palliative nature of their treatment. An earlier and more effective implementation of the palliative care approach is necessary if the needs of patients in the final stages of chronic illness are to be adequately addressed. Pa

Absolute Atomic Oxygen Density Distributions in the Effluent of a Micro Scale Atmospheric Pressure Plasma Jet

The coplanar microscale atmospheric pressure plasma jet (µ-APPJ) is a capacitively coupled radio frequency discharge (13.56 MHz, ~15W rf power) designed for optimized optical diagnostic access. It is operated in a homogeneous glow mode with a noble gas flow (1.4 slm He) containing a small admixture of molecular oxygen (~0.5%). Ground state atomic oxygen densities in the effluent up to 2 × 1014 cm-3 are measured by two-photon absorption laser-induced fluorescence spectroscopy (TALIF) providing space resolved density maps. The quantitative calibration of the TALIF setup is performed by comparative measurements with xenon. A maximum of the atomic oxygen density is observed for 0.6% molecular oxygen admixture. Furthermore, an increase in the rf power up to about 15W (depending on gas flow and mixture) leads to an increase in the effluent’s atomic oxygen density, then reaching a constant level for higher powers.

Absolute atomic oxygen density profiles in the discharge core of a microscale atmospheric pressure plasma jet

The micro atmospheric pressure plasma jet is an rf driven (13.56 MHz, ~20 W) capacitively coupled discharge producing a homogeneous plasma at ambient pressure when fed with a gas flow of helium (1.4 slm) containing small admixtures of oxygen (~0.5%). The design provides excellent optical access to the plasma core. Ground state atomic oxygen densities up to 3x1016 cm-3 are measured spatially resolved in the discharge core by absolutely calibrated two-photon absorption laser-induced fluorescence spectroscopy. The atomic oxygen density builds up over the first 8 mm of the discharge channel before saturating at a maximum level. The absolute value increases linearly with applied power.

Generation of Atomic Oxygen in the Effluent of an Atmospheric Pressure Plasma Jet

The planar 13.56MHz RF-excited low temperature atmospheric pressure plasma jet (APPJ) investigated in this study is operated with helium feed gas and a small molecular oxygen admixture. The effluent leaving the discharge through the jet’s nozzle contains very few charged particles and a high reactive oxygen species’ density. As its main reactive radical, essential for numerous applications, the ground state atomic oxygen density in the APPJ’s effluent is measured spatially resolved with two-photon absorption laser induced fluorescence spectroscopy. The atomic oxygen density at the nozzle reaches a value of ~1016 cm-3. Even at several centimetres distance still 1% of this initial atomic oxygen density can be detected. Optical emission spectroscopy (OES) reveals the presence of short living excited oxygen atoms up to 10 cm distance from the jet’s nozzle. The measured high ground state atomic oxygen density and the unaccounted for presence of excited atomic oxygen require further investigations on a possible energy transfer from the APPJ’s discharge region into the effluent: energetic vacuum ultraviolet radiation, measured by OES down to 110 nm, reaches far into the effluent where it is presumed to be responsible for the generation of atomic oxygen.

Geometric bonding effects in the X2A1, A2∑+u, and B2IIg states of Li2F

Published ab-initio and pseudopotential calculations for the dialkali halide systems suggest that the preferred co-linear geometry is for the metal to approach the metal end of the alkali halide. Here, ab-initio calculations on the Li2F system reveal that the well depth on the halide side in this radical is much deeper and is a local saddle-point associated with the ionic non-linear global minima. Although many features of the pseudopotential surfaces are confirmed, significant differences are apparent including the existence of a linear excited state instead of a triangular one, a considerably deeper global minimum some 50% lower in energy and a close approach between the X2A1 and the states, with the minimum 87 kJ mol-1 below the ground state asymptote. All the results can be rationalised as the avoided crossings between a long range, covalent potential dominant within the LiLiF geometry and an ionic state that forms the global minimum. Calculations on the 3rd 2A' potential indicate that even for Li + LiF collisions at ultracold temperatures the collision dynamics could involve as many as three electronic states.

Application to argon ions of a new technique to measure the two-electron contribution to the ground state energy of helium-like ions

We have measured the two-electron contribution of the ground state energy of helium-like argon ions using an electron beam ion trap (EBIT). A two-dimensional map was measured showing the intensity of x-rays from the trap passing through a krypton-filled absorption cell. The independent axes of this map were electron beam energy and x-ray energy. From this map, we deduced the two-electron contribution of the ground state of helium-like argon. This experimentally determined Value (312.4 +/- 9.5 eV) was found to be in good agreement with our calculated values (about 303.35 eV) and previous calculations of the same quantity. Based on these measurements, we have shown that a ten-day absorption spectroscopy run with a super-EBIT should be sufficient to provide a new benchmark value for the two-electron contribution to the ground state of helium-like krypton. Such a measurement would then constitute a test of quantum electrodynamics to second order.

Growth Coalitions and Rural Development Police in the EU and the US

A recent issue of EuroChoices (7:1) was devoted to a discussion of comparative US-EU rural development policies. This article discusses the concept of growth coalitions, well developed in urban literature but less so in rural literature. Some light is shed on the different positions of rural and environmental issues in EU and US policies. The agricultural lobby is the dominant actor in agricultural growth coalitions because it perceives land in terms of its exchange value. Environmental and rural development actors perceive land in terms of its use value and its contributions to quality of life: they form a rural development coalition, seeing the need to balance growth with quality of life, but they have less political power than the agricultural growth coalition. In the European context, rural and environmental agendas are linked to a multi-functional agricultural agenda allowing common ground between these two coalitions and greater visibility in the policy arena. In the US, rural interests and environmental groups are more often in opposition to agriculture. This reduces their political visibility and clout. The challenge is how to link the power of the agricultural growth coalitions with rural development coalitions to achieve a broader balance of concerns and a more effective rural development policy.

The use of cues for attention in ancient Greek art: aspects that influence concentration in the work of art and its elements

The goal of this study is to identify cues for the cognitive process of attention in ancient Greek art, aiming to find confirmation of its possible use by ancient Greek audiences and artists. Evidence of cues that trigger attention’s psychological dispositions was searched through content analysis of image reproductions of ancient Greek sculpture and fine vase painting from the archaic to the Hellenistic period - ca. 7th -1st cent. BC. Through this analysis, it was possible to observe the presence of cues that trigger orientation to the work of art (i.e. amplification, contrast, emotional salience, simplification, symmetry), of a cue that triggers a disseminate attention to the parts of the work (i.e. distribution of elements) and of cues that activate selective attention to specific elements in the work of art (i.e. contrast of elements, salient color, central positioning of elements, composition regarding the flow of elements and significant objects). Results support the universality of those dispositions, probably connected with basic competencies that are hard-wired in the nervous system and in the cognitive processes.

Do environmental and task characteristics matter in the control of externalized local public services? Unveiling the relevance of party characteristics and citizens’ offstage voice

Purpose: The purpose of this paper is to investigate the mechanisms adopted by cities to control the provision of externalized public services and to explore the determinants of such control choices.

Design/methodology/approach: The paper presents the results of a multiple case study based on the experiences of three cities and three public services (transport, solid waste collection and home care services for the elderly), where control mechanisms and their possible antecedents were analyzed.

Findings: The results show that the control models found in the cases analyzed do not correspond to the "pure" patterns described in the private sector literature and that the factors identified by management control contributions do not seem to be exhaustive in explaining the configuration of control systems in the public sector. While environmental and task characteristics only partially explain the adoption of certain configurations of control, the features of the control systems seem to be rather influenced by variables that are related to party characteristics.

Originality/value: The paper shows that the combinations of control mechanisms are more multifaceted than those presented in the literature, and that the factors identified in the private sector literature do not seem to explain comprehensively the configuration of control systems in the public sector. © Emerald Group Publishing Limited.

Three dimensional number density mapping in the plume of a low temperature laser ablated magnesium plasma

Simultaneous optical absorption and laser-induced fluorescence measurements have been used to map the three-dimensional number densities of ground-state ions and neutrals within a low-temperature KrF laser-produced magnesium plasma expanding into vacuum. Data is reported for the symmetry plane of the plasma, which includes the laser interaction point at a delay of 1 μs after the ∼30 ns KrF laser ablation pulse and for a laser fluence of 2 J cm−2 on target. The number density distributions of ion and neutral species within this plane indicate that two distinct regions exist within the plume; one is a fast component containing ions and neutrals at maximum densities of ∼3×1013 cm−3 and ∼4×1012 cm−3, respectively and the second is a high-density region containing slow neutral species, at densities up to ∼1×1015 cm−3.

FMRFamide-like peptides (FLPs) enhance voltage-gated calcium currents to elicit muscle contraction in the human parasite Schistosoma mansoni.

Schistosomes are amongst the most important and neglected pathogens in the world, and schistosomiasis control relies almost exclusively on a single drug. The neuromuscular system of schistosomes is fertile ground for therapeutic intervention, yet the details of physiological events involved in neuromuscular function remain largely unknown. Short amidated neuropeptides, FMRFamide-like peptides (FLPs), are distributed abundantly throughout the nervous system of every flatworm examined and they produce potent myoexcitation. Our goal here was to determine the mechanism by which FLPs elicit contractions of schistosome muscle fibers. Contraction studies showed that the FLP Tyr-Ile-Arg-Phe-amide (YIRFamide) contracts the muscle fibers through a mechanism that requires Ca2+ influx through sarcolemmal voltage operated Ca2+ channels (VOCCs), as the contractions are inhibited by classical VOCC blockers nicardipine, verapamil and methoxyverapamil. Whole-cell patch-clamp experiments revealed that inward currents through VOCCs are significantly and reversibly enhanced by the application of 1 µM YIRFamide; the sustained inward currents were increased to 190% of controls and the peak currents were increased to 180%. In order to examine the biochemical link between the FLP receptor and the VOCCs, PKC inhibitors calphostin C, RO 31–8220 and chelerythrine were tested and all produced concentration dependent block of the contractions elicited by 1 µM YIRFamide. Taken together, the data show that FLPs elicit contractions by enhancing Ca2+ influx through VOCC currents using a PKC-dependent pathway.

Lateralized behaviour in the domestic cat, Felis silvestris catus

Lateralized behaviour in the felids has been subject to little investigation. We examined the paw use of 42 domestic cats on three tasks designed to determine whether the animals performed asymmetrical motor behaviour. The influence of the cats' sex and age on their paw preferences was also explored. The distribution of the cats' paw preferences differed significantly between the three tasks. Task 1, the most complex exercise involving retrieval of a food treat from an empty jar, encouraged the most apparent display of lateralized behaviour, with all but one animal showing a strong preference to use either their left or right paw consistently. Tasks 2 (an exercise involving reaching for a toy suspended overhead) and 3 (a challenge involving reaching for a toy moving along the ground) encouraged ambilateral motor performance. Lateralized behaviour was strongly sex related. Male and female cats showed paw preferences at the level of the population, but in opposite directions. Females had a greater preference for using their right paw; males were more inclined to adopt their left paw. Feline age was unrelated to either strength or direction of preferred paw use. Overall, the findings suggest that there are two distinct populations of paw preference in the cat that cluster strongly around the animals' sex. The results also point to a relationship between lateralized behaviour and task complexity. More apparent patterns of lateralized behaviour were evident on more complex manipulatory tasks, hinting at functional brain specialization in this species. © 2009 The Association for the Study of Animal Behaviour.

Increasing entanglement through engineered disorder in the random Ising chain

The ground-state entanglement entropy between block of sites in the random Ising chain is studied by means of the Von Neumann entropy. We show that in presence of strong correlations between the disordered couplings and local magnetic fields the entanglement increases and becomes larger than in the ordered case. The different behavior with respect to the uncorrelated disordered model is due to the drastic change of the ground state properties. The same result holds also for the random three-state quantum Potts model.