Enhanced magnetic ionic liquid-based dispersive liquid-liquid microextraction of triazines and sulfonamides through a one-pot, pH-modulated approach.

In this study, an enhanced variant of magnetic ionic liquid (MIL)-based dispersive liquid-liquid microextraction is put forward. The procedure combines a water insoluble solid support and the [P66614+][Dy(III)(hfacac)4-] MIL, in a one-pot, pH-modulated procedure for microextraction of triazines (TZs) and sulfonamides (SAs). The solid supporting material was mixed with the MIL to overcome difficulties concerning the weighing of MIL and to control the uniform dispersion of the MIL, rendering the whole extraction procedure more reproducible. The pH-modulation during extraction step makes possible the one-pot extraction of SAs and TZs, from a single sample, in 15 min. Overall, the new analytical method developed enjoys the benefits of sensitivity (limits of quantification: 0.034-0.091 µg L-1) and precision (relative standard deviation: 5.2-8.1%), while good recoveries (i.e., 89-101%) were achieved from lake water and effluent from a municipal wastewater treatment plant. Owing to all of the above, the new procedure can be used to determine the concentrations of SAs and TZs at levels below the maximum residue limits.

Rapid analysis of ultraviolet filters using dispersive liquid-liquid microextraction coupled to headspace gas chromatography and mass spectrometry.

An ionic-liquid-based in situ dispersive liquid-liquid microextraction method coupled to headspace gas chromatography and mass spectrometry was developed for the rapid analysis of ultraviolet filters. The chemical structures of five ionic liquids were specifically designed to incorporate various functional groups for the favorable extraction of the target analytes. Extraction parameters including ionic liquid mass, molar ratio of ionic liquid to metathesis reagent, vortex time, ionic strength, pH, and total sample volume were studied and optimized. The effect of the headspace temperature and volume during the headspace sampling step was also evaluated to increase the sensitivity of the method. The optimized procedure is fast as it only required ∼7-10 min per extraction and allowed for multiple extractions to be performed simultaneously. In addition, the method exhibited high precision, good linearity, and low limits of detection for six ultraviolet filters in aqueous samples. The developed method was applied to both pool and lake water samples attaining acceptable relative recovery values.

Introducing a new and rapid microextraction approach based on magnetic ionic liquids: Stir bar dispersive liquid microextraction.

With the aim of contributing to the development and improvement of microextraction techniques, a novel approach combining the principles and advantages of stir bar sorptive extraction (SBSE) and dispersive liquid-liquid microextraction (DLLME) is presented. This new approach, termed stir bar dispersive liquid microextraction (SBDLME), involves the addition of a magnetic ionic liquid (MIL) and a neodymium-core magnetic stir bar into the sample allowing the MIL coat the stir bar due to physical forces (i.e., magnetism). As long as the stirring rate is maintained at low speed, the MIL resists rotational (centrifugal) forces and remains on the stir bar surface in a manner closely resembling SBSE. By increasing the stirring rate, the rotational forces surpass the magnetic field and the MIL disperses into the sample solution in a similar manner to DLLME. After extraction, the stirring is stopped and the MIL returns to the stir bar without the requirement of an additional external magnetic field. The MIL-coated stir bar containing the preconcentrated analytes is thermally desorbed directly into a gas chromatographic system coupled to a mass spectrometric detector (TD-GC-MS). This novel approach opens new insights into the microextraction field, by using the benefits provided by SBSE and DLLME simultaneously, such as automated thermal desorption and high surface contact area, respectively, but most importantly, it enables the use of tailor-made solvents (i.e., MILs). To prove its utility, SBDLME has been used in the extraction of lipophilic organic UV filters from environmental water samples as model analytical application with excellent analytical features in terms of linearity, enrichment factors (67-791), limits of detection (low ng L-1), intra- and inter-day repeatability (RSD<15%) and relative recoveries (87-113%, 91-117% and 89-115% for river, sea and swimming pool water samples, respectively).

Rapid preconcentration of viable bacteria using magnetic ionic liquids for PCR amplification and culture-based diagnostics.

In this study, a series of magnetic ionic liquids (MILs) were investigated for the extraction and preconcentration of bacteria from aqueous samples. By dispersing small volumes (e.g., 15 µL) of MIL within an aqueous cell suspension, bacteria were rapidly extracted and isolated using a magnetic field. Of the seven hydrophobic MILs examined, the trihexyl(tetradecyl)phosphonium Ni(II) hexafluoroacetylacetonate ([P66614+][Ni(hfacac)3-]) MIL exhibited the greatest enrichment of viable Escherichia coli K12 when coupled with microbiological culture as the detection method. The MIL-based strategy was applied for the preconcentration of E. coli from aqueous samples to obtain enrichment factors (E F) as high as 44.6 in less than 10 min. The MIL extraction approach was also interfaced with polymerase chain reaction (PCR) amplification where the positive detection of E. coli was achieved with the [P66614+][Co(hfacac)3-], [P66614+][Ni(hfacac)3-], [P66614+][Dy(hfacac)4-], and [P66614+][Nd(hfacac)4-] MILs. While direct sampling of an aqueous cell suspension at a concentration of 1.68 × 104 colony-forming units (CFUs) mL-1 yielded no amplicon when subjected to PCR, extraction of the sample with the [P66614+][Ni(hfacac)3-] MIL under optimized conditions provided sufficient enrichment of E. coli for amplicon detection. Importantly, the enrichment of bacteria using the Ni(II)-, Co(II)-, and Dy(III)-based MILs was compatible with real-time quantitative PCR amplification to dramatically improve sample throughput and lower detection limits to 1.0 × 102 CFUs mL-1. The MIL-based method is much faster than existing enrichment approaches that typically require 24-h cultivation times prior to detection and could potentially be applied for the preconcentration of a variety of Gram-negative bacteria from aqueous samples. Graphical abstract Magnetic ionic liquid solvents rapidly preconcentrate viable E. coli cells for unambiguous pathogen detection using microbiological culture and qPCR.

Rapid and sensitive analysis of polychlorinated biphenyls and acrylamide in food samples using ionic liquid-based in situ dispersive liquid-liquid microextraction coupled to headspace gas chromatography.

A simple and rapid ionic liquid (IL)-based in situ dispersive liquid-liquid microextraction (DLLME) method was developed and coupled to headspace gas chromatography (HS-GC) employing electron capture (ECD) and mass spectrometry (MS) detection for the analysis of polychlorinated biphenyls (PCBs) and acrylamide at trace levels from milk and coffee samples. The chemical structures of the halide-based ILs were tailored by introducing various functional groups to the cations to evaluate the effect of different structural features on the extraction efficiency of the target analytes. Extraction parameters including the molar ratio of IL to metathesis reagent and IL mass were optimized. The effects of HS oven temperature and the HS sample vial volume on the analyte response were also evaluated. The optimized in situ DLLME method exhibited good analytical precision, good linearity, and provided detection limits down to the low ppt level for PCBs and the low ppb level for acrylamide in aqueous samples. The matrix-compatibility of the developed method was also established by quantifying acrylamide in brewed coffee samples. This method is much simpler and faster compared to previously reported GC-MS methods using solid-phase microextraction (SPME) for the extraction/preconcentration of PCBs and acrylamide from complex food samples.

Magnetic ionic liquids in analytical chemistry: A review.

Magnetic ionic liquids (MILs) have recently generated a cascade of innovative applications in numerous areas of analytical chemistry. By incorporating a paramagnetic component within the cation or anion, MILs exhibit a strong response toward external magnetic fields. Careful design of the MIL structure has yielded magnetoactive compounds with unique physicochemical properties including high magnetic moments, enhanced hydrophobicity, and the ability to solvate a broad range of molecules. The structural tunability and paramagnetic properties of MILs have enabled magnet-based technologies that can easily be added to the analytical method workflow, complement needed extraction requirements, or target specific analytes. This review highlights the application of MILs in analytical chemistry and examines the important structural features of MILs that largely influence their physicochemical and magnetic properties.