A single cation or anion dendrimer-based liquid electrolyte

We propose here a novel liquid dendrimer-based single ion conductor as a potential alternative to conventional molecular liquid solvent-salt solutions in rechargeable batteries, sensors and actuators. A specific change from ester (-COOR) to cyano (-CN) terminated peripheral groups in generation-one poly(propyl ether imine) (G1-PETIM)-lithium salt complexes results in a remarkable switchover from a high cation (tLi+ = 0.9 for -COOR) to a high anion (tPF6- = 0.8 for -CN) transference number. This observed switchover draws an interesting analogy with the concept of heterogeneous doping, applied successfully to account for similar changes in ionic conductivity arising out of dispersion of insulator particle inclusions in weak inorganic solid electrolytes. The change in peripheral group simultaneously affects the effective ionic conductivity, with the room temperature ionic conductivity of PETIM-CN (1.9 × 10-5 Ω-1 cm-1) being an order of magnitude higher than PETIM-COOR (1.9 × 10-6 Ω-1 cm-1). Notably, no significant changes are observed in the lithium mobility even following changes in viscosity due to the change in the peripheral group. Changes in the peripheral chemical functionality directly influence the anion mobility, being lower in PETIM-COOR than in PETIM-CN, which ultimately becomes the sole parameter controlling the effective transport and electrochemical properties of the dendrimer electrolytes.

An examination of the associations among multiple memory systems, past tense, and vocabulary in typically developing 5 year old children

Purpose: Considerable research has investigated the role of verbal working memory in language development in children with and without language problems. Much less is currently known about the relationship between language and the declarative and procedural memory systems. This study examined whether these 2 memory systems were related to typically developing children's past tense and lexical knowledge.

Method: Fifty-eight typically developing children approximately 5 years of age completed a battery of linguistic and nonlinguistic tasks, including tests of vocabulary, past tense production, and procedural and declarative memory.

Results: The results showed that declarative and procedural memory were not correlated with either regular or irregular past tense use. A significant correlation was observed between declarative memory and vocabulary.

Conclusions: The results of the study were not consistent with the view that the declarative and procedural memory systems support children's use of the regular and irregular past tense. However, evidence was found suggesting that declarative memory supports vocabulary in this age group.

Gelled ionic liquid sodium ion conductors for sodium batteries

Owing to the unique properties of certain Ionic liquids (ILs) as safe and green solvents, as well as the potential of sodium as an alternative to lithium as charge carriers, we investigate gel sodium electrolytes as safe, low cost and high performance materials with sufficient mechanical properties for application in sodium battery technologies. We investigate the effect of formation of two types of gel electrolytes on the properties of IL electrolytes known to support Na/Na⁺ electrochemistry. The ionic conductivity is only slightly decreased by 0.0005 and 0.0002 S cm^-1 in the case of 0.3 and 0.5 M NaNTf2 systems respectively as the physical properties transition from liquid to gel. We observed facile plating and stripping of Na metal around 0 V vs. Na/Na⁺ through the cyclic voltammetry. A wide-temperature range of the gelled IL state, of more than 100 K around room temperature, is achieved in the case of 0.3 and 0.5 M NaNTf2. We conclude that the formation of a gel does not significantly affect the liquid-like ion dynamics in these materials, as further evidenced by DSC and FTIR analysis.

Enhanced mechanical response of an ultrafine grained Ti-6Al-4V alloy produced through warm symmetric and asymmetric rolling

An equiaxed ultrafine-grained (UFG) microstructure was successfully produced in a Ti-6Al-4V alloy with an average grain size of 110-230. nm through symmetric and asymmetric warm rolling of a martensitic starting microstructure. The UFG material displayed a combination of ultrahigh strength and ductility at room temperature. Compared with the conventional symmetric rolling, the asymmetric rolling process led to a more pronounced effect of microstructure refinement and a higher tensile ductility. The optimum mechanical response was obtained though the asymmetric rolling at 70% reduction, offering an ultimate tensile strength of 1365. MPa and a total elongation of ~23%. Apart from the magnitude of grain refinement, the inclination of basal texture component from the normal towards the rolling direction during asymmetric rolling and possible strain induced β to martensite transformation may concurrently contribute to a remarkable tensile strength-ductility balance.

Switch point finding using polynomial regression for fuzzy type reduction algorithms

Karnik-Mendel (KM) algorithm is the most widely used type reduction (TR) method in literature for the design of interval type-2 fuzzy logic systems (IT2FLS). Its iterative nature for finding left and right switch points is its Achilles heel. Despite a decade of research, none of the alternative TR methods offer uncertainty measures equivalent to KM algorithm. This paper takes a data-driven approach to tackle the computational burden of this algorithm while keeping its key features. We propose a regression method to approximate left and right switch points found by KM algorithm. Approximator only uses the firing intervals, rnles centroids, and FLS strnctural features as inputs. Once training is done, it can precisely approximate the left and right switch points through basic vector multiplications. Comprehensive simulation results demonstrate that the approximation accuracy for a wide variety of FLSs is 100%. Flexibility, ease of implementation, and speed are other features of the proposed method.

Synthetic hydrogels 2. Polymerization induced phase separation in acrylamide systems

Acrylamide hydrogels were synthesized in the presence of various non-solvents for linear polyacrylamide to examine phase separation during polymerization. The process was found to be dependent upon the segmental volume, the chemical structure, and the concentration of the non-solvent. The concept of conversion-phase diagram for linear polymer is introduced and used qualitatively to understand polymerization induced phase separation (PIPS), and to predict the onset of PIPS during hydrogel synthesis.

Embedding systemic science with FFSR and DPI, phase 2 : final project report

Systemic Science (systems thinking) provides a structured approach to better conceptualise and operationalise problems and to deal with complexity, uncertainty and risk. Systemic Science is different from traditional forms of scientific investigation because it focuses on 'the whole' rather than the component parts.

Systemic science is a skill that DPI generally lacks, although certain sections of the organisation do employ its principles with success. The objective of this project was to enhance DPI's existing systems thinking capability, with particular emphasis on FFSR, to develop the skills in more staff across the organisation, and to showcase the merits of the approach by applying the concepts on existing/planned projects. This report details ‘Phase 2’ (year 2) of the project and as such, outputs from the separate ‘Phase 1’ are not reported here.

Prevalence of the thioamide {···H-N-C=S}2 synthon-solid-state (X-ray crystallography), solution (NMR) and gas-phase (theoretical) structures of O-methyl-N-aryl-thiocarbamides

Structural investigations, i.e. solid-state (X-ray), solution (¹H NMR) and gas-phase (theoretical), on molecules with the general formula MeOC(S)N(H)C₆H₄-4-Y: Y = H (1), NO₂ (2), C(O)Me (3), Cl (4) have shown a general preference for the adoption of an E-conformation about the central C–N bond. Such a conformation allows for the formation of a dimeric hydrogen-bonded {H–N–C=S}₂ synthon as the building block. In the cases of 1–3, additional C–H^...O interactions give rise to the formation of tapes of varying topology. A theoretical analysis shows that the preference for the E-conformation is about the same as the crystal packing stabilisation energy and consistent with this, the compound with Y = C(O)OMe, (5), adopts a Z-conformation in the solid-state that facilitates the formation of N–H^...O, C–H^...O and C–H^...S interactions, leading to a layer structure. Global crystal packing considerations are shown to be imperative in dictating the conformational form of molecules 1–5.

Characterisation of nickel(II) extraction by 2-hydroxy-5-nonylacetophenone oxime (LIX 84) in a micellar phase

The properties of the nickel(II)/2-hydroxy-5-nonylacetophenone oxime (HNAPO), an active ingredient in LIX 84, extraction system were characterised in a micellar system. The extinction coefficient, λ_max of HNAPO (316 nm) and the Ni²⁺ complex (387 nm) in a neutral micellar system, poly dispersed octa-ethyleneglycol mono-n-dodecyl ether (G₁₂A₈) were determined as 3100 and 3500 M⁻¹ cm⁻¹, respectively. HNAPO was found to have a neutral micellar phase and bulk aqueous phase pK_a of 11.5 and 12.5, respectively. The extraction equilibrium constant, K_ex, was determined to be 10^−8.0, and the deviation from theory observed at high pH can be accounted for by consideration of the competition for nickel(II) ions by hydroxide ions and HNAPO. A micellar phase of octa-ethyleneglycol mono-n-dodecyl ether (C₁₂E₈) was determined to be an appropriate model of the free oil/water interface from the solubilised location of HNAPO. Utilising the interfacial probe, 4-heptadecyl-7-hydroxy coumarin (HHC) allowed the determination of the electrostatic surface potential of mixed micelles of G₁₂A₈ and sodium dodecyl sulphate (SDS) or dodecyl trimethyl ammonium chloride (DTAC). The electrostatic surface potential was a linear function of the number of additional surfactant monomers within the G₁₂A₈ micelle, for the concentration range studied. For G₁₂A₈/DTAC mixed micelles, the surface potential was given by +1.1 mV per DTAC molecule per micelle, and for G₁₂A₈/SDS mixed micelles the relationship was −1.4 mV per SDS molecule per micelle.

Dynamic pacing strategies during the cycle phase of an ironman triathlon

Introduction: A nonlinear dynamic systems model has previously been proposed to explain pacing strategies employed during exercise.

Purpose: This study was conducted to examine the pacing strategies used under varying conditions during the cycle phase of an Ironman triathlon.

Methods: The bicycles of six well-trained male triathletes were equipped with SRM power meters set to record power output, cadence, speed, and heart rate. The flat, three-lap, out-and-back cycle course, coupled with relatively consistent wind conditions (17-30 km·h-1), enabled comparisons to be made between three consecutive 60-km laps and relative wind direction (headwind vs tailwind).

Results: Participants finished the cycle phase (180 km) with consistently fast performance times (5 h, 11 ± 2 min; top 10% of all finishers). Average power output (239 ± 25 to 203 ± 20 W), cadence (89 ± 6 to 82 ± 8 rpm), and speed (36.5 ± 0.8 to 33.1 ± 0.8 km·h-1) all significantly decreased with increasing number of laps (P < 0.05). These variables, however, were not significantly different between headwind and tailwind sections. The deviation (SD) in power output and cadence did not change with increasing number of laps; however, the deviations in torque (6.8 ± 1.6 and 5.8 ± 1.3 N·m) and speed (2.1 ± 0.5 and 1.6 ± 0.3 km·h-1) were significantly greater under headwind compared with tailwind conditions, respectively. The median power frequency tended to be lower in headwind (0.0480 ± 0.0083) compared with tailwind (0.0531 ± 0.0101) sections.

Conclusion: These data show evidence that a nonlinear dynamic pacing strategy is used by well-trained triathletes throughout various segments and conditions of the Ironman cycle phase. Moreover, an increased variation in torque and speed was found in the headwind versus the tailwind condition.

Solid state ion transport and phase behaviour in composites of N,N-methyl propylpyrrolidinium tetrafluoroborate and amorphous polyethylene oxide

The binary and ternary addition of 2 wt.% LiBF₄ and 2 wt.% amorphous polyethylene oxide (aPEO) respectively to the plastic crystal forming salt P₁₃BF₄ (where P₁₃⁺=methylpropyl pyrrolidinium cation) was investigated with specific focus on the phase behaviour and evaluation of transport characteristics. Differential scanning calorimetry (DSC), optical thermomicroscopy, solid state nuclear magnetic resonance (NMR), and AC impedance spectroscopy were used to develop an understanding of the conduction process in the pure and mixed systems. The morphology of the ternary compound appeared as hexagonal spherulites upon solidification. Multinuclear NMR Pulsed Field Gradient measurements (¹H,¹⁹F,⁷Li) to probe both cation and anion diffusion coefficients are reported. The anion is shown to be the most diffusive (at 320 K:¹⁹F=2.5×10⁻¹¹ m² s⁻¹; 1H: 1.8×10⁻¹¹ m² s⁻¹; ⁷Li: 1.1×10⁻¹¹ m² s⁻¹) in the ternary compound, with enhanced conductivity (2.7×10⁻⁵ S cm⁻¹ at 310 K) just below the melt.

Comparison of automated candidate gene prediction systems using genes implicated in type 2 diabetes by genome-wide association studies

Background
Automated candidate gene prediction systems allow geneticists to hone in on disease genes more rapidly by identifying the most probable candidate genes linked to the disease phenotypes under investigation. Here we assessed the ability of eight different candidate gene prediction systems to predict disease genes in intervals previously associated with type 2 diabetes by benchmarking their performance against genes implicated by recent genome-wide association studies.

Results
Using a search space of 9556 genes, all but one of the systems pruned the genome in favour of genes associated with moderate to highly significant SNPs. Of the 11 genes associated with highly significant SNPs identified by the genome-wide association studies, eight were flagged as likely candidates by at least one of the prediction systems. A list of candidates produced by a previous consensus approach did not match any of the genes implicated by 706 moderate to highly significant SNPs flagged by the genome-wide association studies. We prioritized genes associated with medium significance SNPs.

Conclusion
The study appraises the relative success of several candidate gene prediction systems against independent genetic data. Even when confronted with challengingly large intervals, the candidate gene prediction systems can successfully select likely disease genes. Furthermore, they can be used to filter statistically less-well-supported genetic data to select more likely candidates. We suggest consensus approaches fail because they penalize novel predictions made from independent underlying databases. To realize their full potential further work needs to be done on prioritization and annotation of genes.

Hydrogen bonded block copolymer systems : from microphase separation in solid state to self-assembly in aqueous solutions

Block copolymer systems with hydrogen bonding interactions have received relatively little attention. Recently, we have investigated the self-assembly and phase separation in such block copolymer systems with an attempt to elucidate the role of hydrogen bonding interactions both theoretically and experimentally [1-4]. In A-b-B/C diblock copolymer/homopolymer systems, the phase behavior was theoretically analyzed according to the random phase approximation and correlated with hydrogen bonding interactions in terms of the difference in inter-association constants (K). To examine how the hydrogen bonding determines the self-assembly and morphological transitions in these systems, we have introduced the K values as a new variable into the phase diagram which we established for the first time (Fig. 1). Multiple vesicular morphologies were formed in aqueous solution of A-b-B/A-b-C diblock copolymer complexes of PS-b-PAA and PS-b-PEO. Interconnected compound vesicles (ICCVs) were observed for the first time as a new morphology (Fig. 2), along with other aggregated nanostructures including vesicles, multilamellar vesicles, thick-walled vesicles and irregular aggregates. Complexation of two amphiphilic diblock copolymers provides a viable approach to vesicles in aqueous media.