The effect of water content on room-temperature ionic liquids (RTILs) was studied by Karl Fischer titration and cyclic voltammetry in the following ionic liquids: tris(P-hexyl)tetradecylphosphonium trifluorotris(pentafluoroethyl)phosphate [P14,6,6,6][NTf2], N-butyl-N-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide [C4mpyrr][NTf2], 1-hexyl-3-methylimidazolium tris(perfluoroethyl)trifluorophosphate [C6mim][FAP], 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [C4mim][NTf2], 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [C4dmim][NTf2], N-hexyltriethylammonium bis(trifluoromethylsolfonyl)imide [N6,2,2,2][NTf2], 1-butyl-3-methylimidazolium hexafluorophosphate [C4mim][PF6], 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [C2mim][NTf2], 1-butyl-3-methylimidazolium tetrafluoroborate [C4mim][BF4], 1-hexyl-3-methylimidazolium iodide [C4mim][I], 1-butyl-3-methylimidazolium trifluoromethylsulfonate [C4mim][OTf], and 1-hexyl-3-methylimidazolium chloride [C6mim][Cl]. In addition, electrochemically relevant properties such as viscosity, conductivity, density, and melting point of RTILs are summarized from previous literature and are discussed. Karl Fisher titrations were carried out to determine the water content of RTILs for vacuum-dried, atmospheric, and wet samples. The anion in particular was found to affect the level of water uptake. The hydrophobicity of the anions adhered to the following trend: [FAP]− > [NTf2]− > [PF6]− > [BF4]− > halides. Cyclic voltammetry shows that an increase in water content significantly narrows the electrochemical window of each ionic liquid. The electrochemical window decreases in the following order: vacuum-dried > atmospheric > wet at 298 K > 318 K > 338 K. The anodic and cathodic potentials vs ferrocene internal reference are also listed under vacuum-dried and atmospheric conditions. The data obtained may aid the selection of a RTIL for use as a solvent in electrochemical applications.

The recent literature is surveyed to explore the nature of voltammetry in room temperature ionic liquids. The extent of similarities with conventional electrochemical solvents is reported and some surprising differences are noted.

Microelectrode arrays have unique electrochemical properties such as small capacitive-charging currents, reduced iR drop, and steady-state diffusion currents. These properties enable the use of microelectrode arrays and have captured much interest in the field of electrochemistry. Techniques for the fabrication of such arrays are reviewed. The relative features and merits of different techniques are also discussed.

Room temperature ionic liquids (RTILs) have been applied to a microelectrode array and been demonstrated to form effective, membrane-free amperometric gas sensors. Determining the RTIL [P(6,6,6,14)][FAP] as the most appropriate choice for extended use, the amperometric quantification of oxygen has been demonstrated. The response of the sensor was quantified by both cyclic voltammetry and chronoamperometry. A range of O(2) contents (2-13% v/v) and RTIL layer thicknesses (from ca. 6 to 125 mum) have been investigated. The combination of microelectrode array and RTIL, as well as the absence of membrane and volatile solvent, results in an elegant, easy to calibrate gas sensor with potential utility in standard and nonstandard conditions.

A new approach to the synthesis of amphiphilic β-cyclodextrins has used 'click' chemistry to selectively modify the secondary 2-hydroxyl group. The resulting extended polar groups can be either polycationic or neutral PEGylated groups and these two amphiphile classes are compatible in dual cyclodextrin formulations for delivery of siRNA. When used alone with an siRNA, a cationic cyclodextrin was shown to have good transfection properties in cell culture. Co-formulation with a PEGylated cyclodextrin altered the physicochemical properties of nanoparticles formed with siRNA. Improved particle properties included lower surface charges and reduced tendency to aggregate. However, as expected, the transfection efficiency of the cationic vector was lowered by co-formulation with the PEGylated cyclodextrin, requiring future surface modification of particles with targeting ligands for effective siRNA delivery.

The blood-brain barrier is a unique cell-based restrictive barrier that prevents the entry of many substances, including most therapeutics, into the central nervous system. A wide range of nanoparticulate delivery systems have been investigated with the aim of targeting therapeutics (drugs, nucleic acids, proteins) to the brain following administration by various routes. This review provides a comprehensive description of the design and formulation of these nanoparticles including the rationale behind individual approaches. In addition, the ability of currently available in-vitro BBB models to accurately predict the in-vivo performance of targeted nanoparticles is critically assessed.

While cathodic voltammetric measurements based on the reduction of nitro-containing explosive compounds have been well documented, little attention has been given for exploiting their anodic response, associated with the oxidation of their reaction products, for qualitative and quantitative security and forensic information. We demonstrate here that cyclic square-wave volammetry, combining the cathodic and anodic signals, offers distinct electrochemical profiles for trace nitroaromatic, nitramine and nitrate ester explosives compared to analogous cyclic-voltammetric and cathodic square-wave-voltammetric measurements. Unique electrochemical signatures are also obtained for commonly used explosive mixtures. Such distinct explosive signatures at disposable strip electrodes should facilitate rapid decentralized security screening applications.

Physicochemical changes and substantially modified electrochemical behavior have been reported when ionic liquids are degassed with nitrogen. In conventional experiments in aqueous and organic media, degassing with N(2) is commonly used to remove the electroactive dissolved oxygen. However, in hydrophilic ionic liquid media, degassing with N(2) removes not only the dissolved oxygen but also a significant amount of the adventitious water present. Given the low viscosity of water, this in turn leads to a dramatic change of the viscosity of the degassed ionic liquid and hence mass transport properties that influence voltammetric responses. In the widely used and relatively viscous room temperature ionic liquid, 1-n-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF(4)) containing the redox probe tetracyanoquinodimethane (TCNQ) and 9% (v/v) deliberately added water, 1 h degassing with very dry N(2) under benchtop conditions results in a dramatic decrease of the TCNQ reduction current obtained under steady-state conditions at a 1 mum diameter microdisc electrode. This is reflected by a change of diffusion coefficient of TCNQ (D(TCNQ)) from 2.6 x 10(-7) to 4.6 x 10(-8) cm(2) s(-1). Karl Fischer titration measurements show that almost complete removal of the deliberately added 9% water is achieved by degassing under benchtop conditions. However, displacement of oxygen by nitrogen in the ionic liquid solution results in the decrease of electrochemical reduction current by 6%, implying that dissolved gases need not be inert with respect to solvent properties. Oxygen removal by placing the BMIMBF(4) ionic liquid in a nitrogen-filled glovebox or in a vacuum cell also simultaneously leads to removal of water and alteration of voltammetric data. This study highlights that (i) important physicochemical differences may arise upon addition or removal of a solute from viscous ionic liquids; (ii) degassing with dry nitrogen removes water as well as oxygen from ionic liquids, which may have implications on the viscosity and structure of the medium; (iii) particular caution must be exercised when deoxygenation is applied in ionic liquid media as part of the protocol used in electrochemical experiments to remove oxygen; (iv) gases such as oxygen, argon, and nitrogen dissolved in ionic liquids need not be innocent with respect to the properties of an ionic liquid. The use of vacuum based techniques to eliminate all volatile solutes, including water and oxygen, is advocated.