Kevin J. Fraser

Phosphonium-Based Ionic Liquids: An Overview

Phosphonium cation-based ionic liquids (ILs) are a readily available family of ILs that in some applications offer superior properties as compared to nitrogen cation-based ILs. Applications recently investigated include their use as extraction solvents, chemical synthesis solvents, electrolytes in batteries and super-capacitors, and in corrosion protection. At the same time the range of cation–anion combinations available commercially has also been increasing in recent years. Here, we provide an overview of the properties of these interesting materials and the applications in which they are appearing.

Thermal degradation of cyano containing ionic liquids

The long term thermal stability of ionic liquids containing dicyanamide or tricyanomethide anions is significantly lower than might be expected from temperature ramped TGA studies, and these anions, combined with N-based cations, yield polymeric products during thermal decomposition. Operational upper temperature limits for extended heating have been determined from isothermal decomposition measurements and extraction of t0.99 values, and a simple relationship between onset of decomposition (determined by non-zero 1st derivative) and T0.01/10 (the temperature at which 1% decomposition occurs in 10 h) is derived.

Organic electrochemical transistor incorporating an ionogel as a solid state electrolyte for lactate sensing

Room temperature Ionic liquids (RTILs) have evolved as a new type of solvent for biocatalysis, mainly due to their unique and tunable physical properties.[1] In addition, within the family of organic semiconductor-based sensors, organic electrochemical transistors (OECTs) have attracted particular interest.[2] Here, we present a simple and robust biosensor, based on a OECT, capable of measuring lactic acid using a gel-like polymeric materials that endow RTIL (ionogel)[3] as solid-state electrolyte both to immobilise the enzyme and to serve as a supporting electrolyte.[4] This represents the first step towards the achievement of a fast, flexible, miniaturised and cheap way of measuring lactate concentration in sweat.

Conducting Polymer Composite Materials for Hydrogen Generation

A novel conducting polymer/non-conducting polymer composite (PEDOT/PEG), produced by vapor phase polymerization of PEDOT in the presence of PEG, shows stable electrocatalytic reduction of protons to hydrogen with conversion currents and over-potential comparable to platinum. The swelling of the composite by PEG and especially its ability to coordinate protons seems to be essential for the catalytic activity of the composite.

Biocompatible Ionic Liquids: A New Approach for Stabilizing Proteins in Liquid Formulation

Ionic liquids (ILs) have shown excellent promise as both solutes and solvents for stabilizing proteins at room temperature. Because many modern drugs are protein-based, these stabilizing characteristics have great potential to provide advances in the field of liquid formulation of therapeutic proteins. However, before these developments can be translated into clinical solutions it is essential to establish data related to the biocompatibility of these ILs. The current work investigates the cytotoxicity of several ILs that were rationally synthesized from natural biomolecules and compounds that have already been approved as excipients for drug formulations. The effect of choline dihydrogen phosphate (choline dhp), choline saccharinate, and 1-butyl 3-methyl imidazolium lactate (bmim lactate) on the metabolic activity of a mouse macrophage cell line (J774) was assessed using the reduction in resazurin as an indicator of activity and, by extension, viability. Two formulations of lysozyme (10 mg/ml and 100 mg/ml) in 80 wt % choline dhp (aq) were prepared and the proteins were evaluated for structural stability immediately following formulation and again at 1 month. Equivalent formulations in 0.1 M Na acetate aqueous buffer were evaluated as controls. A differential scanning microcalorimeter (DSC) was used to evaluate the structural stability on the basis of the unfolding temperature and the enthalpy of unfolding, and a micrococcus lysodiekticus activity test was used to evaluate functional activity. All compounds were found to be relatively benign, with toxicity increasing in the order choline dhp<choline saccharinate<bmim lactate. At 1 month lysozyme that had been stored in choline dhp had a higher activity and folded fraction than lysozyme that had been stored in aqueous buffer. These results suggest that biocompatibility and protein stabilization characteristics can be rationally designed into ionic liquids.

Liquids intermediate between “molecular” and “ionic” liquids: Liquid Ion Pairs?

Ionic liquids comprised of tetradecyltrihexyl- and tetrabutyl-phosphonium cations paired with chloride or sulfonyl amide anions exhibit properties that reflect strong ion association, including comparatively low viscosity as well as a degree of volatility, and hence exemplify an interesting intermediate state between true ionic and true molecular liquids.

A portable centrifugal analyser for liver function screening

Mortality rates of up to 50% have been reported after liver failure due to drug-induced hepatotoxicity and certain viral infections (Gao et al., 2008). These adverse conditions frequently affect HIV and tuberculosis patients on regular medication in resource-poor settings. Here, we report full integration of sample preparation with the read-out of a 5-parameter liver assay panel (LAP) on a portable, easy-to-use, fast and cost-efficient centrifugal microfluidic analysis system (CMAS). Our unique, dissolvable-film based centrifugo-pneumatic valving was employed to provide sample-to-answer fashion automation for plasma extraction (from finger-prick of blood), metering and aliquoting into separate reaction chambers for parallelized colorimetric quantification during rotation. The entire LAP completes in less than 20 min while using only a tenth the reagent volumes when compared with standard hospital laboratory tests. Accuracy of in-situ liver function screening was validated by 96 separate tests with an average coefficient of variance (CV) of 7.9% compared to benchtop and hospital lab tests. Unpaired two sample statistical t-tests were used to compare the means of CMAS and benchtop reader, on one hand; and CMAS and hospital tests on the other. The results demonstrate no statistical difference between the respective means with 94% and 92% certainty of equivalence, respectively. The portable platform thus saves significant time, labour and costs compared to established technologies, and therefore complies with typical restrictions on lab infrastructure, maintenance, operator skill and costs prevalent in many field clinics of the developing world. It has been successfully deployed to a centralised lab in Nigeria.

An Electrochromic Ionic Liquid: Design, Characterization, and Performance in a Solid-State Platform

This work describes the synthesis and characteristics of a novel electrochromic ionic liquid (IL) based on a phosphonium core tethered to a viologen moiety. When integrated into a solid-state electrochromic platform, the viologen modified IL behaved as both the electrolyte and the electrochromic material. Platform fabrication was achieved through in situ photo-polymerization and encapsulation of this novel IL within a hybrid sol–gel. Important parameters of the platform performance, including its coloration efficiency, switching kinetics, and optical properties were characterised using UV–vis spectroscopy and cyclic voltammetry in tandem. The electrochromic platform exhibits a coloration efficiency of 10.72 cm2 C–1 and a varied optical output as a function of the incident current. Despite the rather viscous nature of the material, the platform exhibited approximately 2 orders of magnitude faster switching kinetics (221 s to reach 95 % absorbance) when compared to previously reported electrochromic ILs (18 000 s).

N-methyl-N-alkylpyrrolidinium nonafluoro-1-butanesulfonate salts: Ionic liquid properties and plastic crystal behaviour

A series of N-methyl-N-alkylpyrrolidinium nonafluoro-1-butanesulfonate salts were synthesised and characterised. The thermophysical characteristics of this family of salts have been investigated with respect to potential use as ionic liquids and solid electrolytes. N-Methyl-N-butylpyrrolidinium nonafluoro-1-butanesulfonate (p1,4NfO) has the lowest melting point of the family, at 94 °C. Electrochemical analysis of p1,4 NfO in the liquid state shows an electrochemical window of ∼6 V. All compounds exhibit one or more solid–solid transitions at sub-ambient temperatures, indicating the existence of plastic crystal phases.

CMAS: fully integrated portable centrifugal microfluidic analysis system for on-site colorimetric analysis

A portable, wireless system capable of in situ reagent-based colorimetric analysis is demonstrated. The system is based on a reconfigurable low cost optical detection method employing a paired emitter detector diode device, which allows a wide range of centrifugal microfluidic layouts to be implemented. Due to the wireless communication, acquisition parameters can be controlled remotely and results can be downloaded in distant locations and displayed in real time. The stand-alone capabilities of the system, combined with the portability and wireless communication, provide the flexibility crucial for on-site water monitoring. The centrifugal microfluidic disc presented here is designed for nitrite detection in water samples, as a proof of principle. A limit of detection of 9.31 ppb, along with similar coefficients of correlation and precision, were obtained from the Centrifugal Microfluidic Analysis System compared with the same parameters measured using a UV-Vis spectrophotometer.