Honglian Yu

Extraction of DNA by magnetic ionic liquids: tunable solvents for rapid and selective DNA analysis.

DNA extraction represents a significant bottleneck in nucleic acid analysis. In this study, hydrophobic magnetic ionic liquids (MILs) were synthesized and employed as solvents for the rapid and efficient extraction of DNA from aqueous solution. The DNA-enriched microdroplets were manipulated by application of a magnetic field. The three MILs examined in this study exhibited unique DNA extraction capabilities when applied toward a variety of DNA samples and matrices. High extraction efficiencies were obtained for smaller single-stranded and double-stranded DNA using the benzyltrioctylammonium bromotrichloroferrate(III) ([(C8)3BnN(+)][FeCl3Br(-)]) MIL, while the dicationic 1,12-di(3-hexadecylbenzimidazolium)dodecane bis[(trifluoromethyl)sulfonyl]imide bromotrichloroferrate(III) ([(C16BnIM)2C12(2+)][NTf2(-), FeCl3Br(-)]) MIL produced higher extraction efficiencies for larger DNA molecules. The MIL-based method was also employed for the extraction of DNA from a complex matrix containing albumin, revealing a competitive extraction behavior for the trihexyl(tetradecyl)phosphonium tetrachloroferrate(III) ([P6,6,6,14(+)][FeCl4(-)]) MIL in contrast to the [(C8)3BnN(+)][FeCl3Br(-)] MIL, which resulted in significantly less coextraction of albumin. The MIL-DNA method was employed for the extraction of plasmid DNA from bacterial cell lysate. DNA of sufficient quality and quantity for polymerase chain reaction (PCR) amplification was recovered from the MIL extraction phase, demonstrating the feasibility of MIL-based DNA sample preparation prior to downstream analysis.

Polymeric ionic liquid coatings versus commercial solid-phase microextraction coatings for the determination of volatile compounds in cheeses.

The extraction performance of four polymeric ionic liquid (PIL)-based solid-phase microextraction (SPME) coatings has been studied and compared to that of commercial SPME coatings for the extraction of 16 volatile compounds in cheeses. The analytes include 2 free fatty acids, 2 aldehydes, 2 ketones and 10 phenols and were determined by headspace (HS)-SPME coupled to gas chromatography (GC) with flame-ionization detection (FID). The PIL-based coatings produced by UV co-polymerization were more efficient than PIL-based coatings produced by thermal AIBN polymerization. Partition coefficients of analytes between the sample and the coating (Kfs) were estimated for all PIL-based coatings and the commercial SPME fiber showing the best performance among the commercial fibers tested: carboxen-polydimethylsyloxane (CAR-PDMS). For the PIL-based fibers, the highest K(fs) value (1.96 ± 0.03) was obtained for eugenol. The normalized calibration slope, which takes into account the SPME coating thickness, was also used as a simpler approximate tool to compare the nature of the coating within the determinations, with results entirely comparable to those obtained with estimated K(fs) values. The PIL-based materials obtained by UV co-polymerization containing the 1-vinyl-3-hexylimidazolium chloride IL monomer and 1,12-di(3-vinylimiazolium)dodecane dibromide IL crosslinker exhibited the best performance in the extraction of the select analytes from cheeses. Despite a coating thickness of only 7 µm, this copolymeric sorbent coating was capable of quantitating analytes in HS-SPME in a 30 to 2000 µg L(-1) concentration range, with correlation coefficient (R) values higher than 0.9938, inter-day precision values (as relative standard deviation in %) varying from 6.1 to 20%, and detection limits down to 1.6 µg L(-1).

Crosslinked polymeric ionic liquids as solid-phase microextraction sorbent coatings for high performance liquid chromatography

Neat crosslinked polymeric ionic liquid (PIL) sorbent coatings for solid-phase microextraction (SPME) compatible with high-performance liquid chromatography (HPLC) are reported for the first time. Six structurally different PILs were crosslinked to nitinol supports and applied for the determination of select pharmaceutical drugs, phenolics, and insecticides. Sampling conditions including sample solution pH, extraction time, desorption solvent, desorption time, and desorption solvent volume were optimized using design of experiment (DOE). The developed PIL sorbent coatings were stable when performing extractions under acidic pH and remained intact in various organic desorption solvents (i.e., methanol, acetonitrile, acetone). The PIL-based sorbent coating polymerized from the IL monomer 1-vinyl-3-(10-hydroxydecyl) imidazolium chloride [VC10OHIM][Cl] and IL crosslinker 1,12-di(3-vinylbenzylimidazolium) dodecane dichloride [(VBIM)2C12] 2[Cl] exhibited superior extraction performance compared to the other studied PILs. The extraction efficiency of pharmaceutical drugs and phenolics increased when the film thickness of the PIL-based sorbent coating was increased while many insecticides were largely unaffected. Satisfactory analytical performance was obtained with limits of detection (LODs) ranging from 0.2 to 2 μg L(-1) for the target analytes. The accuracy of the analytical method was examined by studying the relative recovery of analytes in real water samples, including tap water and lake water, with recoveries varying from 50.2% to 115.9% and from 48.8% to 116.6%, respectively.

Rapid and sensitive analysis of microcystins using ionic liquid-based in situ dispersive liquid–liquid microextraction

Three structurally different ionic liquids (ILs), namely 1-butyl-3-methylimidazolium chloride ([BMIM][Cl]), 1-(6-hydroxyethyl)-3-methylimidazolium chloride ([HeOHMIM][Cl]) and 1-benzyl-3-(2-hydroxyethyl)imidazolium bromide ([BeEOHIM][Br]), were applied as extraction solvents using in situ dispersive liquid-liquid microextraction (in situ DLLME) for the preconcentration of two microcystin variants, microcystin-RR (MC-RR) and microcystin-LR (MC-LR) from aqueous samples. Extraction parameters including sample solution pH, ratio of IL to metathesis reagent, sample volume, IL quantity, and salt concentration were optimized to achieve the best extraction efficiency. The [BeEOHIM][Br] IL, which contains both an aromatic moiety and a hydroxyl group within its chemical structure, exhibited superior extraction efficiency compared to the other two ILs. The analytical performance of the [BeEOHIM][Br] IL as an extraction solvent for in situ DLLME of microcystins was investigated using HPLC-UV and HPLC-MS. The limits of detection (LODs) for MC-RR and MC-LR were 0.7μgL(-1) using UV detection with a linear range from 1 to 50μgL(-1). The separation method was successfully adapted for ESI-MS/SIM detection, wherein the LODs for MC-RR and MC-LR were greatly improved to 0.005 and 0.003μgL(-1), respectively. The accuracy of the method was demonstrated by examining the relative recovery using tap water and river water and produced recoveries ranging from 45.0 to 109.7% and from 46.3 to 103.2%, respectively.

Faster dispersive liquid-liquid microextraction methods using magnetic ionic liquids as solvents

Three hydrophobic magnetic ionic liquids (MILs) containing the tetrachloromanganate(II) (MnCl4(2-)) anion, namely, aliquat tetrachloromanganate(II) ([Aliquat(+)]2[MnCl4(2-)]), methyltrioctylammonium [MnCl4(2-)] ([N1,8,8,8(+)]2[MnCl4(2-)]), and trihexyltetradecylphosphonium [MnCl4(2-)] ([P6,6,6,14(+)]2[MnCl4(2-)]) were employed as extraction solvents in DLLME coupled to high-performance liquid chromatography (HPLC) employing UV detection. The MILs were developed with the features of magnetic susceptibility to permit rapid retrieval of the extraction solvent, hydrophobicity to allow for phase separation from water, and mobile phase compatibility with reversed phase HPLC. Additionally, the MILs were customized to minimize hydrolysis of the anionic component in aqueous media as well as reduce absorbance when subjected to HPLC. The three MILs were applied for the extraction of pharmaceutical drugs, phenolics, insecticides, and polycyclic aromatic hydrocarbons. The disperser solvent type, disperser solvent volume, mass of MIL, extraction time, the pH of the sample solution, and salt concentration were studied in order to achieve optimal extraction efficiency for each MIL. The [P6,6,6,14(+)]2[MnCl4(2-)] MIL exhibited the best extraction efficiencies for most of the target analytes compared to the other MILs. Good linearity was obtained using this MIL with correlation coefficients (R) varying from 0.997 to 0.999. The limits of detection (LODs) of all analytes ranged from 0.25 to 1.00μgL(-1). The relative recovery was studied in lake water and river water. The relative recovery in lake water varied from 53.8% to 114.7% at a spiked concentration of 20μgL(-1) (5μgL(-1) for phenanthrene) and from 52.1% to 106.7% at 150μgL(-1) (37.5μgL(-1) for phenanthrene). In river water, the relative recovery varied from 44.6% to 110.7% at a spiked concentration of 20μgL(-1) (5μgL(-1) for phenanthrene) and 42.9% to 83.6% at 150μgL(-1) (37.5μgL(-1) for phenanthrene).

Determination of compounds with varied volatilities from aqueous samples using a polymeric ionic liquid sorbent coating by direct immersion-headspace solid-phase microextraction

The use of highly robust polymeric ionic liquid (PIL) sorbent coatings combined with direct immersion (DI) and headspace (HS) modes in a single solid-phase microextraction (SPME) procedure coupled to gas chromatography (GC) is reported. Target analytes with a wide range of volatilities including polycyclic aromatic hydrocarbons, organochlorine pesticides, and phthalate esters were studied. Three PIL-based sorbent coatings were evaluated and the highest extraction efficiency for most analytes was obtained using the PIL coating consisting of the 1-vinylbenzyl-3-hexadecylimidazolium bis[(trifluoromethyl)sulfonyl]imide [VBC16IM][NTf2] IL monomer and the [(VBIM)2C12]2[NTf2] IL crosslinker. The combined DI-HS mode allowed for a compromise extraction condition among the different classes of analytes compared to the use of DI and HS modes separately. An extraction temperature of 40 °C and an extraction time of 50 min with 50% of this time in HS mode was optimized by application of a central composite design. Satisfactory analytical performance was achieved with limits of detection varying from 0.003 to 0.15 μg L−1 and calibration curve correlation coefficients ranging from 0.980 to 0.999. Analyte relative recoveries from tap and lake water ranged from 52.3 to 116.8% with relative standard deviations ranging from 0.3 to 19.3%.

Ionic Liquids and Polymeric Ionic Liquids in Analytical Environmental Applications

Ionic liquids (ILs) are a class of organic salts with unique properties and have been shown to be particularly useful for the development and improvement of sample preparation and detection methodologies. ILs and polymeric ionic liquids (PILs) have played an important role in the analysis of environmental samples. These compounds have been widely applied in various microextraction techniques due to their tunable analyte selectivity, low volatility, good thermal stability, as well as variable viscosity and solvent miscibility. The unique properties also make ILs and PILs an emerging class of stationary phases in gas chromatography (GC). IL/PIL-based stationary phases exhibit excellent applicability in multidimensional GC separations. This chapter will highlight the applications of ILs and PILs in a number of microextraction techniques in addition to their utilization in separation science with a particular emphasis on their use in environmental analysis.