Small angle neutron scattering from 1-alkyl-3-methylimidazolium hexafluorophosphate ionic liquids ([C(n)mim][PF6], n=4, 6, and 8)

The presence of local anisotropy in the bulk, isotropic, and ionic liquid phases-leading to local mesoscopic inhomogeneity-with nanoscale segregation and expanding nonpolar domains on increasing the length of the cation alkyl-substituents has been proposed on the basis of molecular dynamics (MD) simulations. However, there has been little conclusive experimental evidence for the existence of intermediate mesoscopic structure between the first/second shell correlations shown by neutron scattering on short chain length based materials and the mesophase structure of the long chain length ionic liquid crystals. Herein, small angle neutron scattering measurements have been performed on selectively H/D-isotopically substituted 1-alkyl-3-methylimidazolium hexafluorophosphate ionic liquids with butyl, hexyl, and octyl substituents. The data show the unambiguous existence of a diffraction peak in the low-Q region for all three liquids which moves to longer distances (lower Q), sharpens, and increases in intensity with increasing length of the alkyl substituent. It is notable, however, that this peak occurs at lower values of Q (longer length scale) than predicted in any of the previously published MD simulations of ionic liquids, and that the magnitude of the scattering from this peak is comparable with that from the remainder of the amorphous ionic liquid. This strongly suggests that the peak arises from the second coordination shells of the ions along the vector of alkyl-chain substituents as a consequence of increasing the anisotropy of the cation, and that there is little or no long-range correlated nanostructure in these ionic liquids.

Three-dimensional pattern formation, multiple homogeneous soft modes, and nonlinear dielectric electroconvection

Patterns forming spontaneously in extended, three-dimensional, dissipative systems are likely to excite several homogeneous soft modes (approximate to hydrodynamic modes) of the underlying physical system, much more than quasi-one- (1D) and two-dimensional (2D) patterns are. The reason is the lack of damping boundaries. This paper compares two analytic techniques to derive the pattern dynamics from hydrodynamics, which are usually equivalent but lead to different results when applied to multiple homogeneous soft modes. Dielectric electroconvection in nematic liquid crystals is introduced as a model for 3D pattern formation. The 3D pattern dynamics including soft modes are derived. For slabs of large but finite thickness the description is reduced further to a 2D one. It is argued that the range of validity of 2D descriptions is limited to a very small region above threshold. The transition from 2D to 3D pattern dynamics is discussed. Experimentally testable predictions for the stable range of ideal patterns and the electric Nusselt numbers are made. For most results analytic approximations in terms of material parameters are given. [S1063-651X(00)09512-X].

Robust Room Temperature Hysteresis in an FeIII Spin Crossover Metallomesogen

The high temperature magnetic and structural properties of an amphiphilic iron(III) spin crossover complex are reported. Thermal cycling reveals a scan rate-dependent 20 K thermal hysteresis in the mT vs. T data close to room temperature. A fast scan rate is essential for the hysteresis but it is robust and reproducible after multiple thermal cycles. Differential scanning calorimetry and cross polarized microscopy are used to show that the magnetic switching aligns with a material state change from solid to ordered liquid phase on warming.

ThermoSpots to detect hypothermia in children with severe acute malnutrition

INTRODUCTION: Hypothermia is a risk factor for increased mortality in children with severe acute malnutrition (SAM). Yet frequent temperature measurement remains unfeasible in under-resourced units in developing countries. ThermoSpot is a continuous temperature monitoring sticker designed originally for neonates. When applied to skin, its liquid crystals are designed to turn black with hypothermia and remain green with normothermia.

AIMS: To (i) estimate the diagnostic accuracy of ThermoSpots for detecting WHO-defined hypothermia (core temperature <35.5°C or peripheral temperature <35.0°C) in children with SAM and (ii) determine their acceptability amongst mothers.

METHODS: Children with SAM in a malnutrition unit in Malawi were enrolled during March-July 2010. The sensitivity and specificity of ThermoSpots were calculated by comparing the device colour against 'gold standard' rectal temperatures taken on admission and follow up peripheral temperatures taken until discharge. Guardians completed a questionnaire to assess acceptability.

RESULTS: Hypothermia was uncommon amongst the 162 children enrolled. ThermoSpot successfully detected the one rectal temperature and two peripheral temperatures recorded that met the WHO definition of hypothermia. Overall, 3/846 (0.35%) temperature measurements were in the WHO-defined hypothermia range. Interpreting the brown transition colour (between black and green) as hypothermia improved sensitivities. For milder hypothermia definitions, sensitivities declined (<35.4°C, 50.0%; <35.9°C, 39.2%). Specificity was consistently above 94%. From questionnaires, 40/43 (93%) mothers reported they were 90-100% happy with the device overall. Free-text answers revealed themes of "Skin Rashes", "User-satisfaction" and "Empowerment".

CONCLUSION: Although hypothermia was uncommon in this study, ThermoSpots successfully detected these episodes in malnourished children and were acceptable to mothers. Research in settings where hypothermia is common is needed to determine performance with certainty. Instructing users to act when the device's transition colour appears could improve accuracy. If reliable, ThermoSpots may offer simple, acceptable and continuous temperature measurement for high-burden areas and reduce the workload of over-stretched staff.

An efficient recyclable peroxometalate-based polymer-immobilised ionic liquid phase (PIILP) catalyst for hydrogen peroxide-mediated oxidation

A linear cation-decorated polymeric support with tuneable surface properties and microstructure has been prepared by ring-opening metathesis polymerisation (ROMP) of a pyrrolidinium-functionalised norbornene-based monomer with cyclooctene. The derived peroxophosphotungstate-based polymer-immobilised ionic liquid phase (PIILP) catalyst is an efficient and recyclable system for the epoxidation of allylic alcohols and alkenes, with only a minor reduction in performance on successive cycles.

An efficient Cu(II)-bis(oxazoline)-based polymer immobilised ionic liquid phase catalyst for asymmetric carbon–carbon bond formation

The asymmetric Diels-Alder reaction between N-acryloyloxazolidinone and cyclopentadiene and the Mukaiyama-aldol reaction between methylpyruvate and 1-phenyl-1-trimethylsilyloxyethene have been catalysed by heterogeneous copper(II)-bis(oxazoline)-based polymer immobilised ionic liquid phase (PIILP) systems generated from a range of linear and cross linked ionic polymers. In both reactions selectivity and ee were strongly influenced by the choice of polymer. A comparison of the performance of a range of Cu(II)-bis(oxazoline)-PIILP catalyst systems against analogous supported ionic liquid phase (SILP) heterogeneous catalysts as well as their homogeneous counterparts has been undertaken and their relative merits evaluated.

Efficient and selective hydrogen peroxide-mediated oxidation of sulfides in batch and segmented and continuous flow using a peroxometalate-based polymer immobilised ionic liquid phase catalyst

The peroxometalate-based polymer immobilized ionic liquid phase catalyst [PO4{WO(O-2)(2)}(4)]@PIILP has been prepared by anion exchange of ring opening metathesis-derived pyrrolidinium-decorated norbornene/ cyclooctene copolymer and shown to be a remarkably efficient system for the selective oxidation of sulfides under mild conditions. A cartridge packed with a mixture of [PO4{WO(O-2)(2)}(4)]@PIILP and silica operated as a segmented or continuous flow process and gave good conversions and high selectivity for either sulfoxide (92% in methanol at 96% conversion for a residence time of 4 min) or sulfone (96% in acetonitrile at 96% conversion for a residence time of 15 min). The immobilized catalyst remained active for 8 h under continuous flow operation with a stable activity/selectivity profile that allowed 6.5 g of reactant to be processed (TON = 46 428) while a single catalyst cartridge could be used for the consecutive oxidation of multiple substrates giving activity-selectivity profiles that matched those obtained with fresh catalyst.

Polymer conditioning of alum sludge and discrepancies between estimates of the optimum dosage

The paper outlines the effects of polymer conditioning on alum sludge properties, such as floc size, density, fractal dimension (DF) and rheological properties. Experimental results demonstrate that polymer conditioning of alum sludge leads to: larger floc size with a plateau reached in higher doses; higher densities associated with higher doses; increased degree of compactness; and an initial decrease followed by an increase of supernatant viscosity with continued increase in polymer dose. The secondary focus of this paper dwells on a comparison of the estimates of optimum dose using different criteria that emanate from established dewatering tests such as CST, SRF, liquid phase viscosity and modified SRF as well as a simple settlement test in terms of CML30. Alum sludge was derived from a water works treating coloured, low-turbidity raw waters.

A reactive force field simulation of liquid-liquid phase transitions in phosphorus

A force field model of phosphorus has been developed based on density functional (DF) computations and experimental results, covering low energy forms of local tetrahedral symmetry and more compact (simple cubic) structures that arise with increasing pressure. Rules tailored to DF data for the addition, deletion, and exchange of covalent bonds allow the system to adapt the bonding configuration to the thermodynamic state. Monte Carlo simulations in the N-P-T ensemble show that the molecular (P-4) liquid phase, stable at low pressure P and relatively low temperature T, transforms to a polymeric (gel) state on increasing either P or T. These phase changes are observed in recent experiments at similar thermodynamic conditions, as shown by the close agreement of computed and measured structure factors in the molecular and polymer phases. The polymeric phase obtained by increasing pressure has a dominant simple cubic character, while the polymer obtained by raising T at moderate pressure is tetrahedral. Comparison with DF results suggests that the latter is a semiconductor, while the cubic form is metallic. The simulations show that the T-induced polymerization is due to the entropy of the configuration of covalent bonds, as in the polymerization transition in sulfur. The transition observed with increasing P is the continuation at high T of the black P to arsenic (A17) structure observed in the solid state, and also corresponds to a semiconductor to metal transition. (C) 2004 American Institute of Physics.

Optical bistability in nonlinear surface-plasmon polaritonic crystals

Nonlinear optical transmission through periodically nanostructured metal films (surface-plasmon polaritonic crystals) has been studied. The surface polaritonic crystals have been coated with a nonlinear polymer. The optical transmission of such nanostructures has been shown to depend on the control-light illumination conditions. The resonant transmission exhibits bistable behavior with the control-light intensity. The bistability is different at different resonant signal wavelengths and for different wavelengths of the control light. The effect is explained by the strong sensitivity of the surface-plasmon mode resonances at the signal wavelength to the surrounding dielectric environment and the electromagnetic field enhancement due to plasmonic excitations at the controlled light wavelengths.

Mono- and dimethyl-1,2,4-triazolate as ligands for the mercuric ion in the cationic three-dimensional coordination polymer of [Hg-2(Mmt)(Dmt)(2)](NO3)(H2O))

Colourless crystals of [Hg-2(Mmt)(Dmt)(2)](NO3)(H2O) were obtained from a reaction of mercuric nitrate with nionomethyl- and dimethyl-1,2.4-triazolate (Mmt(-) and Dmt(-), respectively). In the crystal structure (monoclinic, C2/c (no. 15), a = 2579.4(4) b = 1231.1(2), c = 1634.8(2) pm, beta = 128.32(1)degrees V = 4073.3(11).10(6).pm(3): Z = 8, R-1 [I-0 > 2 sigma(I-0)]: 0.0355), half of the mercuric ions are essentially two-coordinate (Hg-N: 210-215 pm), the other half are tetrahedrally surrounded by N-donor atoms (Hg-N: 221, 225 pm) of the Mmt(-) and Dmt(-) anions. These three-N ligands construct a three-dimensional framework.

Temperature-Driven Mixing-Demixing Behavior of Binary Mixtures of the Ionic Liquid Choline Bis(trifluoromethylsulfonyl)imide and Water

The ionic liquid (2-hydroxyethylammonium)trimethylammonium) bis(trifluoromethylsulfonyl)imide (choline bistriflimide) was obtained as a supercooled liquid at room temperature (melting point = 30 degrees C). Crystals of choline bistriflimide suitable for structure determination were grown from the melt in situ on the X-ray diffractometer. The choline cation adopts a folded conformation, whereas the bistriflimide anion exhibits a transoid conformation. The choline cation and the bistriflimide anion are held together by hydrogen bonds between the hydroxyl proton and a sulfonyl oxygen atom. This hydrogen bonding is of importance for the temperature-dependent solubility proper-ties of the ionic liquid. Choline bistriflimide is not miscible with water at room temperature, but forms one phase with water at temperatures above 72 degrees C (equals upper critical solution temperature). H-1 NMR studies show that the hydrogen bonds between the choline cation and the bistriflimide anion are substantially weakened above this temperature. The thermophysical properties of water-choline bistriflimide binary mixtures were furthermore studied by a photopyroelectric technique and by adiabatic scanning calorimetry (ASC). By photothermal analysis, besides highly accurate values for the thermal conductivity and effusivity of choline bistriflimide at 30 degrees C, the detailed temperature dependence of both the thermal conductivity and effusivity of the upper and lower part of a critical water-choline bistriflimide mixture in the neighborhood of the mixing-demixing phase transition could be determined with high resolution and accuracy. Together with high resolution ASC data for the heat capacity, experimental values were obtained for the critical exponents alpha and beta, and for the critical amplitude ratio G(+)/G(-). These three values were found to be consistent with theoretical expectations for a three dimensional Ising-type of critical behavior of binary liquid mixtures.