Determination of the Physical Properties of Room Temperature Ionic Liquids Using a Love Wave Device

In this work, we have shown that a 100 MHz Love wave device can be used to determine whether room temperature ionic liquids (RTILs) are Newtonian fluids and have developed a technique that allows the determination of the density-viscosity product, rho eta of a Newtonian RTIL. In addition, a test for a Newtonian response was established by relating the phase change to insertion loss change. Five concentrations of a water-miscible RTIL and seven pure RTILs were measured. The changes in phase and insertion loss were found to vary linearly with the square root of the density-viscosity product for values up to (rho eta)(1/2) similar to 10 kg m(-2) s(-1/2). The square root of the density-viscosity product was deduced from the changes in either phase or insertion loss using glycerol as a calibration liquid. In both cases, the deduced values of rho eta agree well with those measured using viscosity and density meters. Miniaturization of the device, beyond that achievable with the lower-frequency quartz crystal microbalance approach, to measure smaller volumes is possible. The ability to fabricate Love wave and other surface acoustic wave sensors using planar metallization technologies gives potential for future integration into lab-on-a-chip analytical systems for characterizing ionic liquids.

Development of liposome gel based formulations for intravaginal delivery of the recombinant HIV-1 envelope protein CN54gp140

Mucosally-administered vaccine strategies are widely investigated as a promising means of preventing HIV infection. This study describes the development of liposomal gel formulations, and novel lyophilised variants, comprising HIV-1 envelope glycoprotein, CN54gp140, encapsulated within neutral, positively charged or negatively charged liposomes. The CN54gp140 liposomes were evaluated for mean vesicle diameter, polydispersity, morphology, zeta potential and antigen encapsulation efficiency before being incorporated into hydroxyethyl cellulose (HEC) aqueous gel and subsequently lyophilised to produce a rod-shaped solid dosage form for practical vaginal application. The lyophilised liposome-HEC rods were evaluated for moisture content and redispersibility in simulated vaginal fluid. Since these rods are designed to revert to gel form following intravaginal application, mucoadhesive, mechanical (compressibility and hardness) and rheological properties of the reformed gels were evaluated. The liposomes exhibited good encapsulation efficiency and the gels demonstrated suitable mucoadhesive strength. The freeze-dried liposome-HEC formulations represent a novel formulation strategy that could offer potential as stable and practical dosage form.

Modified Silicone Elastomer Vaginal Gels for Sustained Release of Antiretroviral HIV Microbicides

We previously reported nonaqueous silicone elastomer gels (SEGs) for sustained vaginal administration of the CCR5-targeted entry inhibitor maraviroc (MVC). Here, we describe chemically modified SEGs (h-SEGs) in which the hydrophobic cyclomethicone component was partially replaced with relatively hydrophilic silanol-terminated polydimethylsiloxanes (st-PDMS). MVC and emtricitabine (a nucleoside reverse transcriptase inhibitor), both currently under evaluation as topical microbicides to counter sexual transmission of human immunodeficiency virus type 1 (HIV-1), were used as model antiretroviral (ARV) drugs. Gel viscosity and in vitro ARV release were significantly influenced by st-PDMS molecular weight and concentration in the h-SEGs. Unexpectedly, gels prepared with lower molecular weight grades of st-PDMS showed higher viscosities. h-SEGs provided enhanced release over 24 h compared with aqueous hydroxyethylcellulose (HEC) gels, did not modify the pH of simulated vaginal fluid (SVF), and were shown to less cytotoxic than standard HEC vaginal gel. ARV solubility increased as st-PDMS molecular weight decreased (i.e., as percentage hydroxyl content increased), helping to explain the in vitro release trends. Dye ingression and SVF dilution studies confirmed the increased hydrophilicity of the h-SEGs. h-SEGs have potential for use in vaginal drug delivery, particularly for ARV-based HIV-1 microbicides.

3-Methylpiperidinium ionic liquids

A wide range of room temperature ionic liquids based on the 3-methylpiperdinium cation core were produced from 3-methylpiperidine, which is a derivative of DYTEK® A amine. First, reaction with 1-bromoalkanes or 1-bromoalkoxyalkanes generated the corresponding tertiary amines (Rmβpip, R = alkyl or alkoxyalkyl); further quaternisation reactions with the appropriate methylating agents yielded the quaternary [Rmmβpip]X salts (X(-) = I(-), [CF3CO2](-) or [OTf](-); Tf = -SO2CF3), and [Rmmβpip][NTf2] were prepared by anion metathesis from the corresponding iodides. All [NTf2](-) salts are liquids at room temperature. [Rmmβpip]X (X(-) = I(-), [CF3CO2](-) or [OTf](-)) are low-melting solids when R = alkyl, but room temperature liquids upon introduction of ether functionalities on R. Neither of the 3-methylpiperdinium ionic liquids showed any signs of crystallisation, even well below 0 °C. Some related non-C-substituted piperidinium and pyrrolidinium analogues were prepared and studied for comparison. Crystal structures of 1-hexyl-1,3-dimethylpiperidinium tetraphenylborate, 1-butyl-3-methylpiperidinium bromide, 1-(2-methoxyethyl)-1-methylpiperidinium chloride and 1-(2-methoxyethyl)-1-methylpyrrolidinium bromide are reported. Extensive structural and physical data are collected and compared to literature data, with special emphasis on the systematic study of the cation ring size and/or asymmetry effects on density, viscosity and ionic conductivity, allowing general trends to be outlined. Cyclic voltammetry shows that 3-methylpiperidinium ionic liquids, similarly to azepanium, piperidinium or pyrrolidinium counterparts, are extremely electrochemically stable; the portfolio of useful alternatives for safe and high-performing electrolytes is thus greatly extended.

Which biomarkers are predictive specifically for cardiovascular or for non-cardiovascular mortality in men? Evidence from the Caerphilly Prospective Study (CaPS)

OBJECTIVE: To examine a panel of 28 biomarkers for prediction of cardiovascular disease (CVD) and non-CVD mortality in a population-based cohort of men.

METHODS: Starting in 1979, middle-aged men in Caerphilly underwent detailed medical examination. Subsequently 2171 men were re-examined during 1989-1993, and fasting blood samples obtained from 1911 men (88%). Fibrinogen, viscosity and white cell count (WCC), routine biochemistry tests and lipids were analysed using fresh samples. Stored aliquots were later analysed for novel biomarkers. Statistical analysis of CVD and non-CVD mortality follow-up used competing risk Cox regression models with biomarkers in thirds tested at the 1% significance level after covariate adjustment.

RESULTS: During an average of 15.4years follow-up, troponin (subhazard ratio per third 1.71, 95% CI 1.46-1.99) and B-natriuretic peptide (BNP) (subhazard ratio per third 1.54, 95% CI 1.34-1.78) showed strong trends with CVD death but not with non-CVD death. WCC and fibrinogen showed similar weaker findings. Plasma viscosity, growth differentiation factor 15 (GDF-15) and interleukin-6 (IL-6) were associated positively with both CVD death and non-CVD death while total cholesterol was associated positively with CVD death but negatively with non-CVD death. C-reactive protein (C-RP), alkaline phosphatase, gamma-glutamyltransferase (GGT), retinol binding protein 4 (RBP-4) and vitamin B6 were significantly associated only with non-CVD death, the last two negatively. Troponin, BNP and IL-6 showed evidence of diminishing associations with CVD mortality through follow-up.

CONCLUSION: Biomarkers for cardiac necrosis were strong, specific predictors of CVD mortality while many inflammatory markers were equally predictive of non-CVD mortality.

Laboratory measurements of resistivity in warm dense plasmas relevant to the microphysics of brown dwarfs

Since the observation of the first brown dwarf in 1995, numerous studies have led to a better understanding of the structures of these objects. Here we present a method for studying material resistivity in warm dense plasmas in the laboratory, which we relate to the microphysics of brown dwarfs through viscosity and electron collisions. Here we use X-ray polarimetry to determine the resistivity of a sulphur-doped plastic target heated to Brown Dwarf conditions by an ultra-intense laser. The resistivity is determined by matching the plasma physics model to the atomic physics calculations of the measured large, positive, polarization. The inferred resistivity is larger than predicted using standard resistivity models, suggesting that these commonly used models will not adequately describe the resistivity of warm dense plasma related to the viscosity of brown dwarfs.

An Ultrasonic Relaxation Study of 1-Alkyl-3-Methylmidazolium-Based Room Temperature Ionic Liquids: Probing the Role of Alkyl Chain Length in the Cation

Ultrasound absorption spectra of four 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide were determined as a function of the alkyl chain length on the cation from 1-propyl- to 1-hexyl- from 293.15 to 323.15 K at ambient pressure. Herein, the ultrasound absorption measurements were carried out using a standard pulse technique within a frequency range from 10 to 300 MHz. Additionally the speed of sound, density and viscosity have been measured. The presence of strong dissipative processes during the ultrasound wave propagation was found experimentally, i.e. relaxation processes in the megahertz range were observed for all compounds over the whole temperature range. The relaxation spectra (both relaxation amplitude and relaxation frequency) were shown to be dependent on the alkyl side chain length of the 1-alkyl-3-methylimidazolium ring. In most cases, a single Debye model described the absorption spectra very well. However, a comparison of the determined spectra with the spectra of a few other imidazolium-based ionic liquids reported in the literature (in part recalculated in this work) shows that the complexity of the spectra increases rapidly with the elongation of the alkyl chain length on the cation. This complexity indicates that both the volume viscosity and the shear viscosity are involved in relaxation processes even in relatively low frequency ranges. As a consequence, the sound velocity dispersion is present at relatively low megahertz frequencies.

An ether-functionalised cyclic sulfonium based ionic liquid as an electrolyte for electrochemical double layer capacitors

A novel cyclic sulfonium cation-based ionic liquid (IL) with an ether-group appendage and the bis{(trifluoromethyl)sulfonyl}imide anion was synthesised and developed for electrochemical double layer capacitor (EDLC) testing. The synthesis and chemical-physical characterisation of the ether-group containing IL is reported in parallel with a similarly sized alkyl-functionalised sulfonium IL. Results of the chemical-physical measurements demonstrate how important transport properties, i.e. viscosity and conductivity, can be promoted through the introduction of the ether-functionality without impeding thermal, chemical or electrochemical stability of the IL. Although the apparent transport properties are improved relative to the alkyl-functionalised analogue, the ether-functionalised sulfonium cation-based IL exhibits moderately high viscosity, and poorer conductivity, when compared to traditional EDLC electrolytes based on organic solvents (propylene carbonate and acetonitrile). Electrochemical testing of the ether-functionalised sulfonium IL was conducted using activated carbon composite electrodes to inspect the performance of the IL as a solvent-free electrolyte for EDLC application. Good cycling stability was achieved over the studied range and the performance was comparable to other solvent free,
IL-based EDLC systems. Nevertheless, limitations of the attainable performance are primarily the result of sluggish transport properties and a restricted operative voltage of the IL, thus highlighting key aspects of this field which require further attention.

Optimisation of rheological parameters and mechanical properties of superplasticised cement grouts containing metakaolin and viscosity modifying admixture

The objective of this research was to optimise the rheological parameters, hardened properties, and setting times of cement grouts containing metakaolin (MTK), viscosity-modifying agent (VMA) and superplasticiser (SP). All mixes were made with water-to-binder ratio (W/B) of 0.40. The replacement of cement by MTK was varied from 6% to 20% (by mass), and dosages of SP and VMA were varied from 0.3% to 1.4%, and 0.01% and 0.06% (by mass of binder), respectively. Increased SP led to an increase in fluidity, reduction in flow time, plate cohesion, rheological parameters, and an increase in the setting times. Increased VMA demonstrated a reduction in fluidity, an increase in Marsh cone time, plate cohesion, yield stress, and plastic viscosity. Results indicate that the use of MTK increased yield stress, plastic viscosity, cohesion plate, and flow time due to the higher surface area associated with an increase in the water demand. MTK reduced mini-slump and setting times, and improved compressive strength.

Effect of Mix Proportions on Rheological and Hardened Properties of Composite Cement Pastes

There is an increasing need to identify the effect of mix composition on the rheological properties of composite cement pastes using simple tests to determine the fluidity, the cohesion and other mechanical properties of grouting applications such as compressive strength. This paper reviews statistical models developed using a fractional factorial design which was carried out to model the influence of key parameters on properties affecting the performance of composite cement paste. Such responses of fluidity included mini-slump, flow time using Marsh cone and cohesion measured by Lombardi plate meter and unit weight, and compressive strength at 3 d, 7 d and 28 d. The models are valid for mixes with 0.35 to 0.42 water-to-binder ratio (W/B), 10% to 40% of pulverised fuel ash (PFA) as replacement of cement by mass, 0.02 to 0.06% of viscosity enhancer admixture (VEA), by mass of binder, and 0.3 to 1.2% of superplasticizer (SP), by mass of binder. The derived models that enable the identification of underlying primary factors and their interactions that influence the modelled responses of composite cement paste are presented. Such parameters can be useful to reduce the test protocol needed for proportioning of composite cement paste. This paper attempts also to demonstrate the usefulness of the models to better understand trade-offs between parameters and compare the responses obtained from the various test methods which are highlighted. The multi parametric optimization is used in order to establish isoresponses for a desirability function of cement composite paste. Results indicate that the replacement of cement by PFA is compromising the early compressive strength and up 26%, the desirability function decreased.

Optimization of Cement Grouts Containing Silica Fume and Viscosity Modifying Admixture

There is an increasing need to identify the effect of mix composition on the rheological properties of cementitious grouts using minislump, Marsh cone, cohesion plate, washout test, and cubes to determine the fluidity, the cohesion, and other mechanical properties of grouting applications. Mixture proportioning involves the tailoring of several parameters to achieve adequate fluidity, cohesion, washout resistance and compressive strength. This paper proposes a statistical design approach using a composite fractional factorial design which was carried out to model the influence of key parameters on the performance of cement grouts. The responses relate to performance included minislump, flow time using Marsh cone, cohesion measured by Lombardi plate meter, washout mass loss and compressive strength at 3, 7, and 28 days. The statistical models are valid for mixtures with water-to-binder ratio of 0.37–0.53, 0.4–1.8% addition of high-range water reducer (HRWR) by mass of binder, 4–12% additive of silica fume as replacement of cement by mass, and 0.02–0.8% addition of viscosity modifying admixture (VMA) by mass of binder. The models enable the identification of underlying factors and interactions that influence the modeled responses of cement grout. The comparison between the predicted and measured responses indicated good accuracy of the established models to describe the effect of the independent variables on the fluidity, cohesion, washout resistance and the compressive strength. This paper demonstrates the usefulness of the models to better understand trade-offs between parameters. The multiparametric optimization is used to establish isoresponses for a desirability function for cement grout. An increase of HRWR led to an increase of fluidity and washout, a reduction in plate cohesion value, and a reduction in the Marsh cone time. An increase of VMA demonstrated a reduction of fluidity and the washout mass loss, and an increase of Marsh cone time and plate cohesion. Results indicate that the use of silica fume increased the cohesion plate and Marsh cone, and reduced the minislump. Additionally, the silica fume improved the compressive strength and the washout resistance.

Neural Network Modeling of Rheological Parameters of Grouts Containing Viscosity-Modifying Agent

The development of artificial neural network (ANN) models to predict the rheological behavior of grouts is described is this paper and the sensitivity of such parameters to the variation in mixture ingredients is also evaluated. The input parameters of the neural network were the mixture ingredients influencing the rheological behavior of grouts, namely the cement content, fly ash, ground-granulated blast-furnace slag, limestone powder, silica fume, water-binder ratio (w/b), high-range water-reducing admixture, and viscosity-modifying agent (welan gum). The six outputs of the ANN models were the mini-slump, the apparent viscosity at low shear, and the yield stress and plastic viscosity values of the Bingham and modified Bingham models, respectively. The model is based on a multi-layer feed-forward neural network. The details of the proposed ANN with its architecture, training, and validation are presented in this paper. A database of 186 mixtures from eight different studies was developed to train and test the ANN model. The effectiveness of the trained ANN model is evaluated by comparing its responses with the experimental data that were used in the training process. The results show that the ANN model can accurately predict the mini-slump, the apparent viscosity at low shear, the yield stress, and the plastic viscosity values of the Bingham and modified Bingham models of the pseudo-plastic grouts used in the training process. The results can also predict these properties of new mixtures within the practical range of the input variables used in the training with an absolute error of 2%, 0.5%, 8%, 4%, 2%, and 1.6%, respectively. The sensitivity of the ANN model showed that the trend data obtained by the models were in good agreement with the actual experimental results, demonstrating the effect of mixture ingredients on fluidity and the rheological parameters with both the Bingham and modified Bingham models.