NMR and Raman studies of a novel fast-ion-conducting polymer-in-salt electrolyte based on LiCF3SO3 and PAN

We report spectroscopic results from investigations of a novel solid polymeric fast-ion-conductor based on poly(acrylonitrile), (PAN, of repeat unit [CH₂CH(CN)]_n), and the salt LiCF₃SO3 . From NMR studies of the temperature and concentration dependencies of ⁷Li- and ^lH-NMR linewidths, we conclude that significant ionic motion occurs at temperatures close to the glass transition temperature of these polymer-in-salt electrolytes, in accordance with a recent report on the ionic conductivity. In the dilute salt-in-polymer regime, however, ionic motion appears mainly to be confined to local salt-rich domains, as determined from the dramatic composition dependence of the ionic conductivity. FT-Raman spectroscopy is used to directly probe the local chemical anionic environment, as well as the Li⁺–PAN interaction. The characteristic δ_s(CF₃) mode of the CF₃SO₃⁻ anion at _~750–780 cm^−l shows that the ionic substructure is highly complex. Notably, no spectroscopic evidence of free anions is found even at relatively salt-depleted compositions (e.g. N:Li_~60–10:1). A strong Li⁺–PAN interaction is manifested as a pronounced shift of the characteristic polymer C=N stretching mode, found at _~2244 cm^−l in pure PAN, to _~2275 cm^−l for Li⁺-coordinated C=N moieties. Our proton-NMR data suggest that upon complexation of PAN with LiCF3 SO₃, the glass transition occurs at progressively lower temperatures.

Developing fast ion conductors from nanostructured polymers

- Introduction
- Polymer electrolytes
- Composite electrolytes
- Conclusions
- References

Lithium doped N-methyl-N-ethylpyrrolidiniumbis(trifluoromethanesulfonyl)amide fast-ion conducting plastic crystals

The incorporation of dopant levels of lithium ions (0.5 to 9.3% by mole) in the N-methyl-N-ethylpyrrolidinium bis(trifluoromethanesulfonyl)amide (P₁₂TFSA) plastic crystalline phase results in increases in the solid state ionic conductivity of more than 3 orders of magnitude at 298 K. Conductivities as high as 10^−-4 S cm⁻¹ at 323 K have been measured in these doped plastic crystal phases. These materials can therefore be classified as fast-ion conductors. Higher levels of Li only marginally increase the conductivity, up to around 33 mol%, followed by a slight decrease to 50 mol%. Thermal analysis behaviour has allowed the partial development of the binary phase diagram for the LiTFSA–P₁₂TFSA system between 0–50 mol% LiTFSA, which suggests the presence of a solid solution single phase at concentrations less than 9.3 mol% LiTFSA. There is also strong evidence of eutectic behaviour in this system with a eutectic transition temperature around 308 K at 33 mol% LiTFSA. A model relating ionic conduction to phase behaviour in this system is presented. The increased conductivity upon doping has been associated with lithium ion motion via⁷Li solid state NMR linewidth measurements.

Fast ion conduction in an acid doped pentaglycerine plastic crystal

High proton conductivity has been achieved in the high temperature plastic crystal phase of pentaglycerine when doped with strong acids, including trifluoromethanesulfonic acid (triflic acid) and methanesulfonic acid. The solid–solid phase transition from the ordered to plastic phase in this material occurs at 86 °C and conductivities of 10^{− 3} S/cm were measured in the high temperature plastic phase on the addition of 1 mol% triflic acid. In the case of methanesulfonic acid, the conductivities showed a greater dependence on acid concentration and were lower than for triflic acid, as expected on the basis of acid strengths. Electrochemical characterisation shows a clear hydrogen reduction process indicating that the proton is the mobile species in the plastic phase.

Fast ion conduction in molecular plastic crystals

Doping of lithium salts and acids into the plastic crystal phase of succinonitrile has shown for the first time of the possibility of creating solid state electrolytes based on plastic crystalline solvents where the matrix itself is neutral and hence not intrinsically conductive. These materials illustrate the concept of a solid state electrolyte solvent. Room temperature conductivities up to 3.4×10⁻⁴ S cm⁻¹ were obtained with 5 wt.% lithium bis(trifluoromethanesulfonylamide) in succinonitrile. Pulsed field gradient NMR measurements indicate that both cation and anion are mobile in this lattice. Proton conductivity was also observed when methane sulfonic acid or glacial acetic acid was used as dopants, however, the conductivity in these systems is limited by the poor dissociating ability of these acids.

Lithium-doped plastic crystal electrolytes exhibiting fast ion conduction for secondary batteries

Rechargeable lithium batteries have long been considered an attractive alternative power source for a wide variety of applications. Safety and stability1 concerns associated with solvent-based electrolytes has necessitated the use of lithium intercalation materials (rather than lithium metal) as anodes, which decreases the energy storage capacity per unit mass. The use of solid lithium ion conductors - based on glasses, ceramics or polymers - as the electrolyte would potentially improve the stability of a lithium metal anode while alleviating the safety concerns. Glasses and ceramics conduct via a fast ion mechanism, in which the lithium ions move within an essentially static framework. In contrast, the motion of ions in polymer systems is similar to that in solvent-based electrolytes - motion is mediated by the dynamics of the host polymer, thereby restricting the conductivity to relatively low values. Moreover, in the polymer systems, the motion of the lithium ions provides only a small fraction of the overall conductivity2, which results in severe concentration gradients during cell operation, causing premature failure3. Here we describe a class of materials, prepared by doping lithium ions into a plastic crystalline matrix, that exhibit fast lithium ion motion due to rotational disorder and the existence of vacancies in the lattice. The combination of possible structural variations of the plastic crystal matrix and conductivities as high as 2 3 1024 S cm21 at 60 8C make these materials very attractive for secondary battery applications.

Effect of clinician designation on emergency department fast track performance

Objective To examine the effect of clinician designation on emergency department (ED) fast track performance.
Design and Setting A retrospective audit of patients managed in the fast track area of an ED in metropolitan Melbourne, Australia.
Participants Patients triaged to ED fast track from 1 January 2008 to 31 December 2008 (n=8714).
Main Outcome Measures Waiting times in relation to Australasian triage scale (ATS) recommendations and ED length of stay (LOS) for non-admitted patients were examined for each clinician group.
Results Compliance with ATS waiting time recommendations was highest (82.5%) for emergency nurse practitioners/candidates and lowest (48.2%) for junior medical officers. Median ED LOS was less than 3 h for non-admitted patients, and 85.8% of non-admitted fast track patients (n=6278) left the ED within 4 h. Patients managed by emergency nurse practitioners/ candidates had the shortest ED LOS (median 1.7 h) and patients managed by junior medical officers and locum medical officers the longest ED LOS (median 2.7 h) (x²=498.539, df=6, p<0.001).
Conclusions Clinician designation does impact on waiting times and, to a lesser extent, ED LOS for patients managed in ED fast track systems. Future research should focus on obtaining a better understanding of the relationship between clinician expertise, time-based performance measures and quality of care indicators.

Individual and area-level socioeconomic associations with fast food purchasing

Background It has been suggested that those with lower socioeconomic characteristics would be more likely to seek energy-dense food options such as fast food because of cheaper prices; however, to date the evidence has been inconsistent. This study examines both individual- and area-level socioeconomic characteristics and their independent associations with chain-brand fast food purchasing.

Methods Data from the 2003 Victorian Lifestyle and Neighbourhood Environments Study (VicLANES); a multilevel study of 2547 adults from 49 small-areas in Melbourne, Australia, were used. Multilevel multinomial models adjusted for confounders were used to assess associations between individual socioeconomic position (education, occupation and income) and area socioeconomic characteristics in relation to fast food purchasing from five major fast food chains with outcome categories: never, at least monthly and at least weekly. The study finally assessed whether any potential area-level associations were mediated by fast food access.

Results Increased fast food purchasing was independently associated with lower education, being a blue-collar employee and decreased household income. Results for area-level disadvantage were marginally insignificant after adjustment for individual-level characteristics, although they were suggestive that living in an area with greater levels of disadvantage increased an individual's odds of more frequent fast food purchasing. This effect was further attenuated when measures of fast food restaurant access were included in the models.

Conclusion Independent effects of lower individual-level socioeconomic characteristics and more frequent fast food purchasing for home consumption are demonstrated. Although evidence was suggestive of an independent association with area-level disadvantage this did not reach statistical significance.

Fast food restaurant locations : could they be 'supersizing' local communities?

This review examines the current state of knowledge related to the location of fast food restaurants. Previous studies have revealed some communities are more exposed to fast food restaurants. However, the influence of increased exposure to fast food on dietary behaviours remains unresolved. This is identified as an area of priority for future research.

Who is eating where? Findings from the SESAW study

Objective: Foods prepared outside of the home have been linked to less-than-ideal nutrient profiles for health. We examine whether the locations where meals are prepared and consumed are associated with socio-economic predictors among women.
Design: A cross-sectional study using self-reported data. We examined multiple locations where meals are prepared and consumed: (i) at home; (ii) fast food eaten at home; (iii) fast food eaten at the restaurant; (iv) total fast food; (v) non-fast-food restaurant meals eaten at home; (vi) non-fast-food restaurant meals eaten at the restaurant; and (vii) all non-fast-food restaurant meals. Multilevel logistic regression was used to determine whether frequent consumption of meals from these sources varied by level of education, occupation, household income and area-level disadvantage.
Setting: Metropolitan Melbourne, Australia.
Subjects: A total of 1328 women from forty-five neighbourhoods randomly sampled for the SocioEconomic Status and Activity in Women study.
Results: Those with higher educational qualifications or who were not in the workforce (compared with those in professional employment) were more likely to report frequent consumption of meals prepared and consumed at home. High individual and area-level socio-economic characteristics were associated with a lower likelihood of frequent consumption of fast food and a higher likelihood of frequent consumption of meals from non-fast-food sources. The strength and significance of relationships varied by place of consumption.
Conclusions: The source of meal preparation and consumption varied by socioeconomic predictors. This has implications for policy makers who need to continue to campaign to make healthy alternatives available in out-of-home food sources.

Brand salience for fast-moving consumer goods : an empirically based model

Brand salience, or the prominence of a brand in memory, has been linked to brand choice and purchase by consumers. The research reported in this paper proposed and tested a model of brand salience for fast-moving consumer goods, which incorporates knowledge, media consumption, and brand image as antecedents. A quasi-experimental method was utilised, where 270 respondents undertook a free recall exercise using category cues, and then completed multiitem measures of brand knowledge, brand associations, and purchase likelihood. Analysis of the data using SEM found support for an empirical model of brand salience where there was a relationship between brand salience and purchase likelihood. The empirical evidence supports building a brand in a primary category, in order to build the depth and breadth of the brand’s associations in consumer memory.

Altered fast- and slow-twitch muscle fibre characteristics in female mice with a (S248F) knock-in mutation of the brain neuronal nicotinic acetylcholine receptor

We generated a mouse line with a missense mutation (S248F) in the gene (CHRNA4) encoding the α4 subunit of neuronal nicotinic acetylcholine receptor (nAChR). Mutant mice demonstrate brief nicotine induced dystonia that resembles the clinical events seen in patients with the same mutation. Drug-induced dystonia is more pronounced in female mice, thus our aim was to determine if the S248F mutation changed the properties of fast- and slow-twitch muscle fibres from female mutant mice. Reverse transcriptase-PCR confirmed CHRNA4 gene expression in the brain but not skeletal muscles in normal and mutant mice. Ca²⁺ and Sr²⁺ force activation curves were obtained using skinned muscle fibres prepared from slow-twitch (soleus) and fast-twitch (EDL) muscles. Two significant results were found: (1) the (pCa₅₀ - pSr₅₀) value from EDL fibres was smaller in mutant mice than in wild type (1.01 vs. 1.30), (2) the percentage force produced at pSr 5.5 was larger in mutants than in wild type (5.76 vs. 0.24%). Both results indicate a shift to slow-twitch characteristics in the mutant. This conclusion is supported by the identification of the myosin heavy chain (MHC) isoforms. Mutant EDL fibres expressed MHC I (usually only found in slow-twitch fibres) as well as MHC IIa. Despite the lack of spontaneous dystonic events, our findings suggest that mutant mice may be having subclinical events or the mutation results in a chronic alteration to muscle neural input.

Fast finite-time consensus of a class of high-order uncertain nonlinear systems

This paper poses and solves a new problem of consensus control where the task is to make the fixed-topology multi-agent network, with each agent described by an uncertain nonlinear system in chained form, to reach consensus in a fast finite time. Our development starts with a set of new sliding mode surfaces. It is proven that, on these sliding mode surfaces, consensus can be achieved if the communication graph has the proposed directed spanning tree. Next, we introduce the multi-surface sliding mode control to drive the sliding variables to the sliding mode surfaces in a fast finite time. The control Lyapunov function for fast finite time stability, motivated by the fast terminal sliding mode control, is used to prove the reachability of the sliding mode surface. A recursive design procedure is provided, which guarantees the boundedness of the control input.