Effect of Water on the Electrochemical Window and Potential Limits of Room-Temperature Ionic Liquids

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 [P-14,P-6,P-6,P-6][NTf2], N-butyl-N-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide [C(4)mpyrr][NTf2], 1-hexyl-3-methylimidazolium tris(perfluoroethyl)trifluorophosphate [C(6)mim][FAP], 1-butyl3-methylimidazolium bis(trifluoromethylsulfonyl)imide [C(4)mim][NTf2], 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [C(4)dmim][NTf2], N-hexyltriethylammonium bis(trifluoromethylsolfonyl)imide [N-6,N-2,N-2,N-2][NTf2], 1-butyl-3-methylirnidazolium hexafluorophosphate [C(4)mim][PF6], F6], 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [C(2)mim][NTf2], 1-butyl-3-methylimidazolium tetrafluoroborate [C(4)mim][BF4], 1-hexyl-3-methylimidazolium iodide [C(4)mim][I], 1-butyl-3-methylimidazolium trifluoromethylsulfonate [C(4)mim][OTf], and 1-hexyl-3-methylimidazolium chloride [C(6)mim][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.

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.

Phase transition and decomposition temperatures, heat capacities and viscosities of pyridinium ionic liquids

Ionic liquids are organic salts with low melting points. Many of these compounds are liquid at room temperature in their pure state. Since they have negligible vapor pressure and would not contribute to air pollution, they are being intensively investigated for a variety of applications, including as solvents for reactions and separations, as non-volatile electrolytes, and as heat transfer fluids. We present melting temperatures, glass transition temperatures, decomposition temperatures, heat capacities, and viscosities for a large series of pyridinium-based ionic liquids. For comparison, we include data for several imidazolium and quaternary ammonium salts. Many of the compounds do not crystallize, but form glasses at temperatures between 188 K and 223 K. The thermal stability is largely determined by the coordinating ability of the anion, with ionic liquids made with the least coordinating anions, like bis(trifluoromethylsulfonyl)imide, having the best thermal stability. In particular, dimethylaminopyridinium bis(trifluoromethylsulfonyl)imide salts have some of the best thermal stabilities of any ionic liquid compounds investigated to date. Heat capacities increase approximately linearly with increasing molar mass, which corresponds with increasing numbers of translational, vibrational, and rotational modes. Viscosities generally increase with increasing number and length of alkyl substituents on the cation, with the pyridinium salts typically being slightly more viscous than the equivalent imidazolium compounds. (c) 2005 Elsevier Ltd. All rights reserved.

Designing ionic liquids with boron cluster anions: alkylpyridinium and imidazolium [nido-C(2)B(9)H(11)] and [closo-CB(11)H(12)] carborane salts

A range of new alkylpyridinium and imidazolium carborane salts with [nido-C2B9H12](-), [closo-CB11H12](-), and [RC2B11H11](-) (R = methyl or butyl) anions have been prepared and characterized by physical and thermal methods, including the solid state structures of five of the salts determined by single crystal X-ray diffraction. The tendency of the salts to form low-melting ionic liquids has been assessed; all the salts studied with [nido-C2B9H12](-) anions melted below 100 degrees C and, significantly, have melting points that are 25-85 degrees C lower than those of the corresponding [closo-CB11H12](-) analogs, demonstrating that a wider range of boron-rich ionic liquid materials can be readily accessed.

Desulfurisation of oils using ionic liquids: selection of cationic and anionic components to enhance extraction efficiency

Extraction of dibenzothiophene from dodecane using ionic liquids as the extracting phase has been investigated for a range of ionic liquids with varying cation classes (imidazolium, pyridinium, and pyrrolidinium) and a range of anion types using liquid-liquid partition studies and QSPR (quantitative structure-activity relationship) analysis. The partition ratio of dibenzothiophene to the ionic liquids showed a clear variation with cation class (dimethylpyridinium > methylpyridinium > pyridinium approximate to imidazolium approximate to pyrrolidinium), with much less significant variation with anion type. Polyaromatic quinolinium-based ionic liquids showed even greater extraction potential, but were compromised by higher melting points. For example, 1-butyl-6-methylquinolinium bis{(trifluoromethyl)sulfonyl} amide (mp 47 degrees C) extracted 90% of the available dibenzothiophene from dodecane at 60 degrees C.

Approaches to crystallization from ionic liquids: complex solvents-complex results, or, a strategy for controlled formation of new supramolecular architectures?

There are now more than 1200 papers a year describing research results using the 'neoteric' solvents, known as ionic liquids (ILs). If ILs are such highly studied solvents, why has there been so comparatively little research in their use in crystallization? Here we explore this question and discuss possible strategies for utilization of the mundane and the unique aspects of ILs for novel crystallization strategies including crystallization of high and low melting solids using thermal shifts; ''solvothermal'' techniques; slow diffusion; electrocrystallization; and use of a co-solvent. The results presented here and those appearing in the literature indicate both the complex nature of these solvents and their promise in delivering unique solvation, metal ion coordination numbers, coordination polymer motifs, and metal-anion interactions, to name but a few. These complex, but fascinating, results and the promise of much more intimate control over crystallization processes will drive a growing interest in using ILs as crystallization solvents.

Strategies toward the design of energetic ionic liquids: nitro- and nitrile-substituted N,N '-dialkylimidazolium salts

Twelve novel 1,3-dialkylimidazolium salts containing strongly electron-withdrawing nitro-and cyano-functionalities directly appended to the cationic heterocyclic rings have been synthesized; the influences of the substituents on both formation and thermal properties of the resultant ionic liquids have been determined by DSC, TGA, and single crystal X-ray diffraction, showing that an electron-withdrawing nitro-substituent can be successfully appended and has a similar influence on the melting behaviour as that of corresponding methyl group substitution. Synthesis of di-, or trinitro-substituted 1,3-dialkylimidazolium cations was unsuccessful due to the resistance of dinitro-substituted imidazoles to undergo either N-alkylation or protonation, while 1-alkyl- 4,5-dicyanoimidazoles were successfully alkylated to obtain 1,3-dialkyl-4,5-dicyanoimidazolium salts. Five crystal structures ( one of each cation type) show that, in the solid state, the NO2-group has little significant effect, beyond the steric contribution, on the crystal packing.

1-butyl-3-methylimidazolium 3,5-dinitro-1,2,4-triazolate: a novel ionic liquid containing a rigid, planar energetic anion

The novel ionic liquid, 1-butyl-3-methylimidazolium 3,5-dinitro-1,2,4-triazolate has been synthesized and exhibits an unexpectedly low melting point (35 degreesC) considering the size and shape of the rigid, planar anion; analogous tetraalkylammonium salts (methyl, ethyl and n-butyl) have also been prepared and the tetraethylammonium example was characterized by single crystal X-ray diffraction.

Designing ionic liquids: Imidazolium melts with inert carborane anions

A new class of low-melting N,N'-dialkylimidazolium salts has been prepared with carborane counterions, some of the most inert and least nucleophilic anions presently known. The cations and anions have been systematically varied with combinations of 1-ethyl-3-methyl-(EMIM+), 1-octyl-3-methyl-(OMIM+), 1-ethyl-2,3-dimethyl- (EDMIM+), and 1-butyl-2,3-dimethyl- (BDMIM+) imidazolium cations and CB11H12-CB11H6Cl6-, and CB11H6Br6- carborane anions to elucidate the factors which affect their melting points. From trends in melting points, which range from 156 degrees C down to 45 degrees C, it is clear that the alkylation pattern on the imidazolium cation is the main determinant of melting point and that packing inefficiency of the cation is the intrinsic cause of low melting points. C-Alkylation of the anion can also contribute to low melting points by the introduction of a further packing inefficiency. Nine of the thirteen salts have been the subject of X-ray crystal structural determination. Notably, crystallographic disorder of the cation is observed in all but one of these salts. It is the most direct evidence to date that packing inefficiency is the major reason unsymmetrical N,N'-dialkylimidazolium salts can be liquids at room temperature.

Hydrophobic ionic liquids incorporating N-alkylisoquinolinium cations and their utilization in liquid-liquid separations

The first examples of Room Temperature Ionic Liquids (RTIL) containing fused polycyclic N-alkylisoquinolinium cations ([C(n)isoq](+)) in combination with the bis(perfluoroethylsulfonyl) imide anion ([BETI](-)) have been synthesized, characterized, and utilized in liquid-liquid partitioning from water; these salts have unexpectedly low melting points and give high distribution ratios for aromatic solutes, especially chlorobenzenes, between the RTIL and water.

Aminolevulinic acid-loaded Witepsol microparticles manufactured using a spray congealing procedure: implications for topical photodynamic therapy

Objectives The aim was to enhance aminolevulinic acid (ALA) stability by incorporation into low-melting microparticles prepared using a spray congealing procedure and to evaluate temperature-triggered release, allowing topical bioavailability following melting at skin temperature.

Structure-Property Relationships in Biaxially Deformed Polypropylene Nanocomposites

Semi-solid forming processes such as thermoforming and injection blow moulding are used to make much of today’s packaging. As for most packaging there is a drive to reduce product weight and improve properties such as barrier performance. Polymer nanocomposites offer the possibility of increased modulus
(and hence potential product light weighting) as well as improved barrier properties and are the subject of much research attention. In this particular study, polypropylene–clay nanocomposite sheets produced via biaxial deformation are investigated and the structure of the nanocomposites is quantitatively determined in order to gain a better understanding of the influence of the composite structure on mechanical properties. Compression moulded sheets of polypropylene and polypropylene/Cloisite 15A nanocomposite (5 wt.%) were biaxially stretched to different stretching ratios, and then the structure of
the nanocomposite was examined using XRD and TEM techniques. Different stretching ratios produced different degrees of exfoliation and orientation of the clay tactoids. The sheet properties were then investigated using DSC, DMTA, and tensile tests .It was found that regardless of the degree of exfoliation or
orientation, the addition of clay has no effect on percentage crystallinity or melting temperature, but it has an effect on the crystallization temperature and on the crystal size distribution. DMTA and tensile tests show that both the degree of exfoliation and the degree of orientation positively correlate with the dynamic mechanical properties and the tensile properties of the sheet.

Microneedle-based drug delivery systems: Microfabrication, drug delivery, and safety

Many promising therapeutic agents are limited by their inability to reach the systemic circulation, due to the excellent barrier properties of biological membranes, such as the stratum corneum (SC) of the skin or the sclera/cornea of the eye and others. The outermost layer of the skin, the SC, is the principal barrier to topically-applied medications. The intact SC thus provides the main barrier to exogenous substances, including drugs. Only drugs with very specific physicochemical properties (molecular weight <500 Da, adequate lipophilicity, and low melting point) can be successfully administered transdermally. Transdermal delivery of hydrophilic drugs and macromolecular agents of interest, including peptides, DNA, and small interfering RNA is problematic. Therefore, facilitation of drug penetration through the SC may involve by-pass or reversible disruption of SC molecular architecture. Microneedles (MNs), when used to puncture skin, will by-pass the SC and create transient aqueous transport pathways of micron dimensions and enhance the transdermal permeability. These micropores are orders of magnitude larger than molecular dimensions, and, therefore, should readily permit the transport of hydrophilic macromolecules. Various strategies have been employed by many research groups and pharmaceutical companies worldwide, for the fabrication of MNs. This review details various types of MNs, fabrication methods and, importantly, investigations of clinical safety of MN.

Solid and liquid charge-transfer complex formation between 1-methylnaphthalene and 1-alkyl-cyanopyridinium bis{(trifluoromethyl)sulfonyl}imide ionic liquids

Liquid charge-transfer (CT) complexes were observed to form on contacting electron-rich aromatics with electron withdrawing group appended 1-alkyl-4-cyanopyridinium ionic liquids (ILs). Cooling below the melting point of the ionic liquid resulted in crystallisation of ionic liquid from the complex for 2-cyano and 3-cyano pyridinium isomers and in the formation of a 1 : 1 IL : aromatic crystalline CT-complex with the 4-cyanopyridinium isomer. The liquid structure of a 1 : 1 mixture of 1-methyl-4-cyanopyridinium bis{(trifluoromethyl)sulfonyl} imide with 1-methylnaphthalene has been probed by neutron diffraction experiments and molecular dynamics simulations. A high degree of correlation between the experimental data and the simulations was found with a significant displacement of the anions from around the cation by the aromatic species and the resulting structure having pi-pi stacks between the cations and the aromatic.

Viscoelastic Material Models of Polypropylene for Thermoforming Applications

Polypropylene (PP), a semi-crystalline material, is typically solid phase thermoformed at temperatures associated with crystalline melting, generally in the 150° to 160°Celsius range. In this very narrow thermoforming window the mechanical properties of the material rapidly decline with increasing temperature and these large changes in properties make Polypropylene one of the more difficult materials to process by thermoforming. Measurement of the deformation behaviour of a material under processing conditions is particularly important for accurate numerical modelling of thermoforming processes. This paper presents the findings of a study into the physical behaviour of industrial thermoforming grades of Polypropylene. Practical tests were performed using custom built materials testing machines and thermoforming equipment at Queen′s University Belfast. Numerical simulations of these processes were constructed to replicate thermoforming conditions using industry standard Finite Element Analysis software, namely ABAQUS and custom built user material model subroutines. Several variant constitutive models were used to represent the behaviour of the Polypropylene materials during processing. This included a range of phenomenological, rheological and blended constitutive models. The paper discusses approaches to modelling industrial plug-assisted thermoforming operations using Finite Element Analysis techniques and the range of material models constructed and investigated. It directly compares practical results to numerical predictions. The paper culminates discussing the learning points from using Finite Element Methods to simulate the plug-assisted thermoforming of Polypropylene, which presents complex contact, thermal, friction and material modelling challenges. The paper makes recommendations as to the relative importance of these inputs in general terms with regard to correlating to experimentally gathered data. The paper also presents recommendations as to the approaches to be taken to secure simulation predictions of improved accuracy.