Second generation ionic liquid matrices are developed, examined, and tested. They have shown a wide mass detection range (Ͻ1000 Da to Ͼ270,000 Da) for proteins and peptides with greater S/N ratios than solid matrices. These ionic liquid matrices also exhibit the ability to effectively ionize proteins of large mass without disrupting noncovalent interactions between monomers. Both the anionic and cationic moieties have been varied systematically to find an ionic liquid matrix with the best physical properties, analyte signal intensity, and widest mass detection range. It was determined that both the proton affinity and pK a of the cation have a large effect on the ionic liquid matrices' ability to effectively ionize the analyte. The ionic liquid matrices can be used to detect polysaccharides with fewer degradation products than solid matrices. N,N-diisopropylethylammonium ␣-cyano-4-hydroxycinnamate and N-isopropyl-Nmethyl-t-butylammonium ␣-cyano-4-hydroxycinnamate were the best matrices for proteins and peptides, while N,N-diisopropylethylammonium ␣-cyano-4-hydroxycinnamate and N,Ndiisopropylethylammonium ferulate were the best matrices for carbohydrates. (J Am Soc

Water or aqueous electrolytes are the dominant components in electrowetting on dielectric (EWOD)-based microfluidic devices. Low thermal stability, evaporation, and a propensity to facilitate corrosion of the metal parts of integrated circuits or electronics are drawbacks of aqueous solutions. The alternative use of ionic liquids (ILs) as electrowetting agents in EWOD-based applications or devices could overcome these limitations. Efficient EWOD devices could be developed using task-specific ILs. In this regard, a fundamental study on the electrowetting properties of ILs is essential. Therefore electrowetting properties of 19 different ionic liquids, including mono-, di-, and tricationic, plus mono- and dianionic ILs were examined. All tested ILs showed electrowetting of various magnitudes on an amorphous flouropolymer layer. The effects of IL structure, functionality, and charge density on the electrowetting properties were studied. The enhanced stability of ILs in electrowetting on dielectric at higher voltages was studied in comparison with water. Deviations from classical electrowetting theory were confirmed. The physical properties of ILs and their electrowetting properties were tabulated. These data can be used as references to engineer task-specific electrowetting agents (ILs) for future electrowetting-based applications.

Twenty-three different dications were investigated for their effectiveness in pairing with singly charged anions, thereby allowing the electrospray ionization mass spectrometry (ESI-MS) detection of anions as positively charged complexes. Nitrate, iodide, cyanate, monochloroacetate, benzenesulfonate, and perfluoro-octanoate were chosen as representative test anions as they differ in mass, size-to-charge ratio, chaotropic nature, and overall complexity. Detection limits were found using direct injection of the anion into a carrier liquid containing the dication. Detection limits are given for all six anions with each of the 23 dications. Each anion was easily detected at the ppb (g/L) and often the ppt (ng/L) levels using certain dicationic reagents. The ability of dicationic reagents to pair with anions and produce ESI-MS signals varied tremendously. Indeed, only a few dications can be considered broadly useful and able to produce sensitive results. Liquid chromatography (LC)-ESI-MS also was investigated and used to show how varying the dicationic reagent produced significantly different peak intensities. Also, the use of tandem mass spectrometry can lead to even greater sensitivity when using imidazolium based dications. (J

Dynamic solvation of the dye coumarin 153 is studied in a phosphonium ionic liquid: hexadecyltributylphosphonium bromide, [(C4)3C16P+][Br-]. It forms micelles in water, and the bulk also exists as a liquid under our experimental conditions. This system permits a comparison with an imidazolium ionic liquid studied earlier, which also formed micelles in water (J. Phys. Chem. A 2006, 110, 10725−10730). We conclude that our analysis of the comparable situation in a phosphonium liquid is not as definitive as we had proposed earlier, i.e., that the majority of the early-time solvation arises from the organic cation. Part of the difficulty in performing this analysis is most likely due to the amount of water that is associated with the micelle. In the course of this work, we have focused on the calculation of the solvation correlation function, C(t), and investigated how it depends upon the methods with which the "zero-time" spectrum is constructed. Arlington, Box 19065, Arlington, Texas 76019 ReceiVed: NoVember 8, 2007; In Final Form: December 7, 2007 Dynamic solvation of the dye coumarin 153 is studied in a phosphonium ionic liquid: hexadecyltributylphosphonium bromide, [(C 4 ) 3 C 16 P + ][Br -]. It forms micelles in water, and the bulk also exists as a liquid under our experimental conditions. This system permits a comparison with an imidazolium ionic liquid studied earlier, which also formed micelles in water (J. Phys. Chem. A 2006, 110, 10725-10730). We conclude that our analysis of the comparable situation in a phosphonium liquid is not as definitive as we had proposed earlier, i.e., that the majority of the early-time solvation arises from the organic cation. Part of the difficulty in performing this analysis is most likely due to the amount of water that is associated with the micelle. In the course of this work, we have focused on the calculation of the solvation correlation function, C(t), and investigated how it depends upon the methods with which the "zero-time" spectrum is constructed. Keywords

We report a rapid and sensitive stochastic nanopore sensing method for the detection of monovalent cations and liquid explosive components and their sensitizers. The sensing element is a wild-type alpha-hemolysin protein pore with boromycin as a molecular adaptor, while a solution containing an ionic liquid was used as the background electrolyte. The analyte-boromycin complexes showed significantly different signatures. Specifically, their event mean dwell times and amplitudes were sufficiently distinct to permit the convenient differentiation and even simultaneous detection of liquid explosive components in aqueous environments. In addition, the results also demonstrate that the usage of specific ionic liquid salt solutions instead of NaCl or KCl solution as supporting electrolyte provides a useful means to greatly enhance the sensitivity of the nanopore for some analytes in stochastic sensing.

Dynamic solvation of the dye, coumarin 153, is compared in an ionic liquid that forms micelles in water against the bulk solvent. This provides the unprecedented opportunity of investigating the behavior of the ionic liquid in two globally different configurations. It is proposed that the imidazolium moiety is in both cases responsible for the majority of the solvation, which manifests itself in the first 100 ps. Exploiting the use of ionic liquids capable of accommodating specific structures thus provides a deeper insight into how solutes interact with these fascinating and interesting solvents (at least those that are imidazolium based) that are gaining ever increasing interest in the scientific community.

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.

A second generation ionic liquid matrix (ILM), N,N-diisopropylethylammonium alpha-cyano-4-hydroxycinnamate (DEA-CHCA), was developed for the characterization of polar biodegradable polymers. It is compared with five solid matrices typically used for the characterization of these polymers and one other new ILM. It is shown that use of the ILM, DEA-CHCA, allows maximum signal with minimum laser intensity which minimizes polymer degradation. In these conditions, the DEA-CHCA ILM is able to assist in the ionization of analytes in an efficient but soft manner. These qualities produce spectra that allow an accurate and sensitive determination of the number average molecular weights, weight average m.w., and polydispersity index of labile polar polymers. With such polymers, many solid matrices produce spectra showing extensive polymer degradation leading to the underestimation of molecular weights. The distribution of intact analyte peaks obtained with the ILM DEA-CHCA allows for identification of the fine structure of complex copolymers. ILMs were much less susceptible to effects of extraction delay times on molecular weight determination than were solid matrices. The liquid nature of the matrix is an important reason for the outstanding results obtained for labile analyte polymers. No comparable results could be obtained with any known solid matrices or other ILMs. In many cases, the manufacturers' listed molecular weights and polydispersity measurements for biodegradable polymers are determined by size-exclusion chromatography and the data obtained by that method may differ considerably from the high-precision matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) results presented here.