Trigonal tricationic ionic liquids (ILs) are a new class of ILs that appear to be unique when used as gas chromatographic stationary phases. They consist of four core structures; (1) A = mesitylene core, (2) B = benzene core, (3) C = triethylamine core, and (4) D = tri(2-hexanamido)ethylamine core; to which three identical imidazolium or phosphonium cationic moieties were attached. These were coated on fused silica capillaries, and their gas chromatographic properties were evaluated. They were characterized using a linear solvation parameter model and a number of test mixtures. On the basis of the literature, it is known that both monocationic and dicationic ILs possess almost identical polarities, solvation characteristics, and chromatographic selectivities. However, some of the trigonal tricationic ILs were quite different. The different solvation parameters and higher apparent polarities appear to generate from the more rigid trigonal geometry of these ILs, as well as their ability to retain the positive charges in relatively close proximity to one another in some cases. Their unique selectivities, retention behaviors, and separation efficiencies were demonstrated using the Grob mixture, a flavor and fragrance test mixture, alcohols/alkanes test, and FAME isomer separations. Two ILs C1 (methylimidazolium substitution) and C4 (2-hydroxyethylimidazolium substitution) had higher apparent polarities than any know IL (mono, di, and tricationic ILs) or commercial stationary phases. The tri(2-hexanamido)ethylamine core IL series proved to be very interesting in that it not only showed the highest separation efficiency for all test mixtures, but it also is the first IL stationary phase (containing NTf(2)(-) anions) that eliminates peak tailing for alcohols and other H-bonding analytes. The thermal stabilities were investigated using three methods: thermogravimetric analysis (TGA) method, temperature programmed gas chromatographic method (TPGC), and isothermal gas chromatographic method. The D core series had a high working temperature range, exceptional selectivities, and higher separation efficiencies than comparable polarity commercial columns. It appears that this specific type of multifunctional ILs may have the most promising future as a new generation of gas chromatographic stationary phases.

This paper presents a study of electrowetting of ionic liquids (ILs) under AC voltages, where nine different ILs (including mono-, di-, and tricationic varieties) with three different AC frequencies (60 Hz, 1 kHz, 10 kHz) were experimentally investigated. The main foci of this study are (i) an investigation of AC frequency dependence on the electrowetting of ILs; (ii) obtaining theoretical relationships between the relevant factors that explain the experimentally achieved frequency dependence; and (iii) a systematic comparison of electrowetting of ILs using AC vs DC voltage fields. The frequency of the AC voltage was found to be directly related to the apparent contact angle change (Deltatheta) of the ILs. This relationship was further analyzed and explained theoretically. The electrowetting properties of ILs under AC voltages were compared to that under DC voltages. All tested ILs showed greater apparent contact angle changes with AC voltage conditions than with DC voltage conditions. The effect of structure and charge density also was examined. Electrowetting reversibility under AC voltage conditions was studied for few ILs. Finally, the physical properties and AC electrowetting properties of ILs were measured and tabulated.

The analysis of anions remains an important task for many areas of science, and new sensitive analytical methods continue to be of great interest. In this study, we present the use of 17 tricationic reagents for use as gas-phase ion pairing agents for divalent anions. When the anion pairs with the tricationic reagent, an overall positive charge is retained and enables detection by ESI-MS in the positive mode. The 17 tricationic reagents were made from 1 of 4 core structures and 7 terminal charged groups. The effect of these structural elements on the detection sensitivity of the complex is examined empirically. A comparison of signal-to-noise ratios achieved in positive and negative modes also is presented.

Recently, we have shown that dilute multivalent cationic reagents can be paired with analyte anions in ESI-MS, thereby allowing them to be detected in the positive mode at very low limits of detection. However, there can be differences in the efficiency of this technique depending on the nature of the cationic pairing agent and the anion being analyzed. In this study, three dicationic ion-pairing agents and four singly charged anionic species were examined in a series of experiments to elucidate the mechanism of action that allows for such sensitive detection and the profound differences in the selectivity of this ion-pairing method. The binding constants for the dication/anion complexes were determined by NMR and ESI-MS. The results indicated that the binding of these species is greatly enhanced as they move from the solution phase to the gas phase. Furthermore, surface tension measurements for the complexes were performed. This test revealed that, as the dication pairs with the anion, it creates a surface-active species within the ESI droplet. This is determined to be one of the major factors that leads to the overall sensitivity enhancement. This has led to a better understanding of how this ion-pairing technique produces unprecedented limits of detection for anions and why there are selectivity differences in pairing agents of different structures.

Anion analysis is of great importance to many scientific areas of interest. Problems with negative mode ESI-MS prevent researchers from achieving sensitive detection for anions. Recently, we have shown that cationic reagents can be paired with anions, such that detection can be done in the positive mode, allowing for low limits of detections for anions using ESI-MS. In this analysis, we present the use of 16 newly synthesized flexible linear tricationic ion-paring reagents for the detection of 11 divalent anions. These reagents greatly differ in structure from previously reported trigonal tricationic ion-pairing agents, such that they are far more flexible. Here we present the structural features of these linear trications that make for good ion-pairing agents as well as show the advantage of using these more flexible ion-pairing reagents. In fact, the limit of detection for sulfate using the best linear trication was found to be 25 times lower than when the best rigid trication was used. Also, MS/MS experiments were performed on the trication-dianion complex to significantly reduce the detection limit for many dianions. Limits of detection in this analysis were as low as 50 fg.

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Four new ionic liquids (IL) were prepared and bonded onto 5-microm silica particles for use as adsorbent in solid-phase microextraction (SPME). Two ILs contained styrene units that allowed for polymerization and higher carbon content of the bonded silica particles. Two polymeric ILs differing by their anion were used to prepare two SPME fibers that were used in both headspace and immersion extractions and compared to commercial fibers. In both sets of experiments, ethyl acetate was used as an internal standard to take into account adsorbent volume differences between the fibers. The polymeric IL fibers are very efficient in headspace SPME for short-chain alcohols. Immersion SPME also can be used with the IL fibers for short-chain alcohols as well as for polar and basic amines that can be extracted at pH 11 without damage to the IL-bonded silica particles. The sensitivities of the two IL fibers differing by the anion were similar. Their efficacy compares favorably to that of commercial fibers for polar analytes. The mechanical strength and durability of the polymeric IL fibers were excellent.

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