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Purpose This paper aims to study the mass loss of three-dimensional (3D) printed materials at high temperatures. A preconcentration and analysis technique, static headspace gas chromatography-mass spectrometry (SHS-GC-MS), is demonstrated for the analysis of volatile compounds liberated from fused deposition modeling (FDM) and stereolithography (SLA) 3D printed models under elevated temperatures. Design/methodology/approach A total of seven commercial 3D printing materials were tested using the SHS-GC-MS approach. The printed model mass and mass loss were examined as a function of FDM printing parameters including printcore temperature, model size and printing speed, and the use of SLA postprocessing procedures. A high temperature resin was used to demonstrate that thermal degradation products can be identified when the model is incubated under high temperatures. Findings At higher printing temperatures and larger model sizes, the initial printed model mass increased and showed more significant mass loss after thermal incubation for FDM models. For models produced by SLA, the implementation of a postprocessing procedure reduced the mass loss at elevated temperatures. All FDM models showed severe structural deformation when exposed to high temperatures, while SLA models remained structurally intact. Mass spectra and chromatographic retention times acquired from the high temperature resin facilitated identification of eight compounds (monomers, crosslinkers and several photoinitiators) liberated from the resin. Originality/value The study exploits the high sensitivity of SHS-GC-MS to identify thermal degradation products emitted from 3D printed models under elevated temperatures. The results will aid in choosing appropriate filament/resin materials and printing mechanisms for applications that require elevated temperatures.

Alkylimidazolium chloride ionic liquids (ILs) have many uses in a variety of separation systems, including micro-confined separation systems. To understand the separation mechanism in these systems, the diffusion properties of analytes in ILs under relevant operating conditions, including micro-confinement dimension and temperature, should be known. For example, separation efficiencies for various IL-based microextraction techniques are dependent on the sample volume and temperature. Temperature-dependent (20-100 °C) fluorescence recovery after photobleaching (FRAP) was utilized to determine the diffusion properties of a zwitterionic, hydrophilic dye, ATTO 647, in alkylimidazolium chloride ILs in micro-confined geometries. These micro-confined geometries were generated by sandwiching the IL between glass substrates that were separated by ∼1 to 100 μm. From the measured temperature-dependent FRAP data, we note alkyl chain length-, thickness-, and temperature-dependent diffusion coefficients, with values ranging from 0.021 to 46 μm

A Field Full of Opportunities: Transforming the Future of Separation Science August 1, 2022 Jared L. Anderson LCGC North America, August 2022, Volume 40, Issue 8 Pages: 354–356 For four decades, LCGC has served to keep the field connected with new innovations and exciting product lines while concurrently educating new generations of scientists entering the field. Celebration of the 40th anniversary of LCGC allows us to reflect on future opportunities within the field of separation science. Innovations in separation science continue to be driven by important breakthroughs in speed, selectivity, and resolution. Meanwhile, the field of separation science is being advanced by tremendous discoveries in the fields of mass spectrometry (MS) and sample preparation. A recent consensus study report by the National Academies of Sciences offered recommendations to improve the field of separations. Collaborative opportunities with scientists in other fields, such as material science, spectroscopy, and chemical engineering, will serve to address important challenges and advance discoveries in three-dimensional (3D) printing, stationary phase development, and sustainable separation platforms. The recruitment of young, talented entrepreneurs within academia and industry is needed to tackle many of the challenges that exist today and that will emerge tomorrow.

Nucleic acids are ubiquitous in biological samples and can be sensitively detected using nucleic acid amplification assays. To achieve highly accurate and reliable results, nucleic acid isolation and purification is often required and can limit the accessibility of these assays. Encapsulation of these workflows onto a single device may be achieved through fabrication methodologies featuring commercial three-dimensional (3D) printers. This study aims to characterize fused deposition modeling (FDM) filaments based on their compatibility with nucleic acid storage using quantitative polymerase chain reaction (qPCR). To study the adsorption of nucleic acids, storage vessels were fabricated using six common thermoplastics including: polylactic acid (PLA), nylon, acrylonitrile butadiene styrene (ABS), co-polyester (CPE), polycarbonate (PC), and polypropylene (PP). DNA adsorption of a short 98 base pair and a longer 830 base pair fragment to the walls of the vessel was shown to vary significantly among the polymer materials as well as the color varieties of the same polymer. PLA storage vessels were found to adsorb the least amount of the 98 base pair DNA after 12 hours of storage in 2.5 M NaCl TE buffer whereas the ABS and PC vessels adsorbed up to 97.2 ± 0.2% and 97.5 ± 0.2%. DNA adsorption could be reduced by decreasing the layer height of the 3D printed object, thereby increasing the functionality of the ABS storage vessel. Nylon was found to desorb qPCR inhibiting components into the stored solution which led to erroneous DNA quantification data from qPCR analysis.

Dielectrophoretic capture of circulating melanoma cell (CMC) and white blood cells (WBCs) is quantified as a function of electric field frequency, and the optimized conditions are utilized to isolate CMCs from patient-derived blood samples.

Silver(I) ions undergo selective olefin complexation and have been utilized in various olefin/paraffin separation techniques such as argentation chromatography and facilitated transport membranes. Ionic liquids (ILs) are solvents known for their low vapor pressure, high thermal stability, low melting points, and ability to promote a favorable solvation environment for silver(I) ion-olefin interactions. To develop highly selective separation systems, a fundamental understanding of analyte partitioning to the stationary phase and the thermodynamic driving forces behind solvation is required. In this study, a chromatographic model treating silver(I) ions as a pseudophase is constructed and employed for the first time to investigate the olefin separation mechanism in silver(I) salt/IL mixtures. Stationary phases containing varying amounts of noncoordinated silver(I) salt ([Ag+][NTf2-]) dissolved in the 1-decyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([C10MIM+][NTf2-]) IL are utilized to determine the partition coefficients of various analytes including alkanes, alkenes, alkynes, aromatics, aldehyde, esters, and ketones. As ligand coordination to silver(I) ions is known to lower its olefin complexation capability, this study also examines two different types of coordinated silver(I) ion pseudophases, namely, monocoordinated silver(I) salt ([Ag+(1-decyl-2-methylimidazole, DMIM)][NTf2-]) and dicoordinated silver(I) salt ([Ag+(1-methylimidazole, MIM)(DMIM)][NTf2-]). The extent of olefin partitioning to the coordinated silver(I) ion pseudophases over the carrier gas and IL decreased by up to two orders of magnitude. Values for enthalpy, entropy, and free energy of solvation were determined for the three silver(I) ion-containing systems. Olefin retention was observed to be enthalpically dominated, while ligand coordination to the silver(I) ion pseudophase resulted in variations for both enthalpic and entropic contributions to the free energy of solvation. The developed model can be used to study chemical changes that occur in silver(I) ions over time as well as identify optimal silver(I) salt/IL mixtures that yield high olefin selectivity.

In this work, hydrophobic magnetic deep eutectic solvents (HMDESs) were used in the development of a simple and rapid dispersive liquid-liquid microextraction (DLLME) approach coupled to high performance liquid chromatography with UV detection (HPLC-UV) for the determination of ten organic contaminants including five polycyclic aromatic hydrocarbons, four UV filters, and a pesticide from water at trace levels. The HMDESs were prepared by mixing a hydrogen bond acceptor, metal halide salt, and hydrogen bond donor in suitable molar ratios. Two HMDESs, 2 tetraoctylammonium bromide ([N

Sequence-specific DNA extractions have the potential to improve the detection of low-abundance mutations from complex matrices, making them ideal for circulating tumor DNA analysis during the early stages of cancer. Ion-tagged oligonucleotides (ITOs) are oligonucleotides modified with an allylimidazolium salt via thiolene click chemistry. The allylimidazolium-based tag allows the ITO-DNA duplex to be selectively captured by a hydrophobic magnetic ionic liquid (MIL). In this study, the selectivity of the ITO-MIL method was examined by extracting low abundance of the BRAF V600E mutation—a common single-nucleotide polymorphism associated with several different cancers—from diluted human plasma, artificial urine, and diluted artificial sputum. Quantitative polymerase chain reaction (qPCR) was not able to distinguish a 9% BRAF V600E standard (50 fg·μL−1 BRAF V600E, 500 fg·μL−1 wild-type BRAF) from the 100% wild-type BRAF (50 fg·μL−1) standard. However, introducing the ITO-MIL extraction prior to qPCR allowed for samples consisting of 0.1% BRAF V600E (50 fg·μL−1 V600E BRAF, 50,000 fg·μL−1 wild-type BRAF) to be distinguished from the 100% wild-type BRAF standard.

Loop-mediated isothermal amplification (LAMP) holds great potential for point-of-care (POC) diagnostics due to its speed and sensitivity. However, differentiation between spurious amplification and amplification of the target sequence is a challenge. Herein, we develop the use of molecular beacon (MB) probes for the sequence-specific detection of LAMP on commercially available lateral flow immunoassay (LFIA) strips. The detection of three unique DNA sequences, including ORF1a from SARS-CoV-2, is demonstrated. In addition, the method is capable of detecting clinically relevant single-nucleotide polymorphisms (BRAF V600E). For all sequences tested, the LFIA method offers similar sensitivity to fluorescence detection using a qPCR instrument. We also demonstrate the coupling of the method with solid-phase microextraction to enable isolation and detection of the target sequences from human plasma, pond water, and artificial saliva. Lastly, a 3D printed device is designed and implemented to prevent contamination caused by opening the reaction containers after LAMP.

Current research efforts at neurological diseases have focused on identifying novel biomarkers to aid in diagnosis, to provide accurate prognostic information, and to monitor disease progression. This study presents the direct coupling of fiber-in-tube solid-phase microextraction to tandem mass spectrometry as a reliable method to determine amyloid beta peptides (Aβ38, Aβ40, and Aβ42) as biomarkers for Alzheimer's disease in cerebrospinal fluid (CSF) samples. To obtain the biocompatible fiber-in-tube SPME capillary, a PEEK tube segment was longitudinally packed with fine fibers [nitinol wires coated with a zwitterionic polymeric ionic liquid], to act as selective extraction medium. The fiber-in-tube SPME-MS/MS method integrated analyte extraction/enrichment and sample cleanup (exclusion of interferents) into one step. The method provided lower limits of quantification (LLOQ: 0.2 ng mL

Deep eutectic solvents (DESs) constitute a rapidly emerging class of sustainable liquids that have been widely studied and employed in chemical separations, catalysis, and electrochemistry. The unique physicochemical and solvation properties of DESs can be highly tailored by choosing the appropriate hydrogen bond acceptor (HBA) and hydrogen bond donor (HBD). Understanding the role of the HBA and HBD on the multiple solvation interactions in DESs is important to enable their judicious selection for particular applications. This work constitutes the first study to exploit chromatography to measure solute–solvent interactions of DESs using a wide array of known probe molecules. The constituent components of 20 DESs, formed by ammonium and phosphonium-based salts and carboxylic acids, are systematically modulated to delineate the contribution of the HBA and HBD toward individual solvation properties. Solute–solvent interactions measured in this study are used to interpret and explain the performance of DESs in desulfurization of fuels and extraction of natural products. The results from this study can be used to predict and understand the performance of DESs in various chemical processes where solvation interactions heavily influence outcomes.

This study reveals the unique role on Janus particles of the solid-solid interface at the boundary in determining particle interactions and assembly. In an aqueous ionic liquid (IL) solution, Janus spheres adopt intriguing orientations with their boundaries pinned on the glass substrate. It was further discovered that the orientation was affected by the particle amphiphilicity as well as the chemical structure and concentration of the IL. Further characterization suggests that the adsorption on the hydrophilic side is due to both an electrostatic interaction and hydrogen bonding, while adsorption on the hydrophobic side is due to hydrophobic attraction. Through the concerted interplay of all these interactions, the amphiphilic boundary may attract an excessive amount of IL cations, which guide the unique orientations of the Janus spheres. The results highlight the importance of the Janus boundary that has not been recognized previously. Adsorption at the solid-solid interfaces may inspire new applications in areas such as separation and catalysis.

Nucleic acid analysis has been at the forefront of the COVID-19 global health crisis where millions of diagnostic tests have been used to determine disease status as well as sequencing techniques that monitor the evolving genome of SARS-CoV-2. In this study, we report the development of a sample preparation method that decreases the time required for DNA isolation while significantly increasing the sensitivity of downstream analysis. Functionalized planar supports are modified with a polymeric ionic liquid sorbent coating to form thin film microextraction (TFME) devices. The extraction devices are shown to have a high affinity for DNA while also exhibiting high reproducibility and reusability. Using quantitative polymerase chain reaction (qPCR) analysis, the TFME devices are shown to require low equilibration times while achieving higher preconcentration factors than solid-phase microextraction (SPME) by extracting larger masses of DNA. Rapid desorption kinetics enable higher DNA recoveries using desorption solutions that are less inhibitory to qPCR and loop-mediated isothermal amplification (LAMP). To demonstrate the advantageous features of the TFME platform, a customized leuco crystal violet LAMP assay is used for visual detection of the ORF1ab DNA sequence from SARS-CoV-2 spiked into artificial oral fluid samples. When coupled to the TFME platform, 100% of LAMP reactions were positive for SARS-CoV-2 compared to 66.7% obtained by SPME for a clinically relevant concentration of 4.80 × 10

Ribonucleic acid (RNA) is particularly sensitive to enzymatic degradation by endonucleases prior to sample analysis. In-field preservation has been a challenge for RNA sample preparation. Very recently, hydrophobic magnetic ionic liquids (MIL) have shown significant promise in the area of RNA extraction. In this study, MILs were synthesized and employed as solvents for the extraction and preservation of RNA in aqueous solution. RNA samples obtained from yeast cells were extracted and preserved by the trihexyl(tetradecyl) phosphonium tris(hexafluoroacetylaceto)cobaltate(II) ([P66614+][Co(hfacac)3–]) and trihexyl(tetradecyl) phosphonium tris(phenyltrifluoroacetylaceto)cobaltate(II) ([P66614+][Co(Phtfacac)3–]) MIL with a dispersion of the supporting media, polypropylene glycol, at room temperature for up to a 7 and 15 day period, respectively. High-quality RNA treated with ribonuclease A (RNase A) was recovered from the tetra(1-octylimidazole)cobaltate(II) di(l-glutamate) ([Co(OIM)42+][Glu–]2) and tetra(1-octylimidazole)cobaltate(II) di(l-aspartate) ([Co(OIM)42+][Asp–]2) MILs after a 24 h period at room temperature. Quantitative reverse transcription polymerase chain reaction (qRT-PCR) and agarose gel electrophoresis were used to determine the effect of RNA preservation. Furthermore, the preservation mechanism was investigated by exploring the partitioning of RNase A into the MIL using high-performance liquid chromatography.

Magnetic ionic liquids (MILs) with metal-containing cations are promising extraction solvents that provide fast and high efficiency extraction of DNA. Hydrophobic MILs can be generated in situ in a methodology called in situ dispersive liquid-liquid microextraction. To consolidate the sample preparation workflow, it is desirable to directly use the DNA-enriched MIL microdroplet in the subsequent analytical detection technique. Fluorescence-based techniques employed for DNA detection often utilize SYBR Green I, a DNA binding dye that exhibits optimal fluorescence when bound to double-stranded DNA. However, the MIL may hinder the fluorescence signal of the SYBR Green I-dsDNA complex due to quenching. In this study, MILs with metal-containing cations were selected and their fluorescence quenching effects evaluated using Fӧrster Resonance Energy Transfer and quantified using Stern-Volmer models. The MILs were based on N-substituted imidazole ligands (with butyl- and benzyl- groups as substituents) coordinated to Ni2+ or Co2+ metal centers as cations, and paired with chloride anions. The effects of NiCl2 and CoCl2 salts and of the 1-butyl-3-methylimidazolium chloride ionic liquid on the fluorophore complex were also studied to understand the components of the MIL structure that are responsible for quenching. The metal within the MIL chemical structure was found to be the main component contributing to fluorescence quenching. Fӧrster critical distances between 11.9 and 18.8 A were obtained for the MILs, indicating that quenching is likely not due to non-radiative energy transfer but rather to spin-orbit coupling or excited-state electron transfer. The MILs were able to be directly used in qPCR and fluorescence emission measurements using a microplate reader for detection, demonstrating their applicability in fluorescence-based detection methods.

Previously, we demonstrated capture and concentration of Salmonella enterica subspecies enterica ser. Typhimurium using magnetic ionic liquids (MILs), followed by rapid isothermal detection of captured cells via recombinase polymerase amplification (RPA). Here, we report work intended to explore the broader potential of MILs as novel pre-analytical capture reagents in food safety and related applications. Specifically, we evaluated the capacity of the ([P66614+][Ni(hfacac)3−]) (“Ni(II)”) MIL to bind a wider range of human pathogens using a panel of Salmonella and Escherichia coli O157:H7 isolates, including a “deep rough” strain of S. Minnesota. We extended this exploration further to include other members of the family Enterobacteriaceae of food safety and clinical or agricultural significance. Both the Ni(II) MIL and the ([P66614+][Dy(hfacac)4−]) (“Dy(III)”) MIL were evaluated for their effects on cell viability and structure-function relationships behind observed antimicrobial activities of the Dy(III) MIL were determined. Next, we used flow imaging microscopy (FIM) of Ni(II) MIL dispersions made in model liquid media to examine the impact of increasing ionic complexity on MIL droplet properties as a first step towards understanding the impact of suspension medium properties on MIL dispersion behavior. Finally, we used FIM to examine interactions between the Ni(II) MIL and Serratia marcescens, providing insights into how the MIL may act to capture and concentrate Gram-negative bacteria in aqueous samples, including food suspensions. Together, our results provide further characterization of bacteria-MIL interactions and support the broader utility of the Ni(II) MIL as a cell-friendly capture reagent for sample preparation prior to cultural or molecular analyses.

Detection of circulating tumor DNA (ctDNA) presents several challenges due to single-nucleotide polymorphisms and large amounts of background DNA. Previously, we reported a sequence-specific DNA extraction procedure utilizing functionalized oligonucleotides called ion-tagged oligonucleotides (ITOs) and disubstituted ion-tagged oligonucleotides (DTOs). ITOs and DTOs are capable of hybridizing to complementary DNA for subsequent capture by a magnetic ionic liquid (MIL) through hydrophobic interactions, π-π stacking, and fluorophilic interactions. However, the performance of the ITOs and DTOs in complex sample matrices has not yet been evaluated. In this study, we compare the amount of KRAS DNA extracted using ITO and DTOs from saline, 2-fold diluted plasma, 10-fold diluted plasma, and 10-fold diluted blood. We demonstrate that ITO/DTO-MIL extraction is capable of selectively preconcentrating DNA from diluted plasma and blood without additional sample preparation steps. In comparison, streptavidin-coated magnetic beads were unable to selectively extract DNA from 10-fold diluted plasma and 10-fold diluted blood without additional sample clean-up steps. Significantly more DNA could be extracted from 2-fold diluted plasma and 10-fold diluted blood matrices using the DTO probes compared to the ITO probes, likely due to stronger interactions between the probe and MIL. The ability of the DTO-MIL method to selectively preconcentrate small concentrations of DNA from complex biological matrices suggests that this method could be beneficial for ctDNA analysis.

Selective DNA extraction is immensely useful for the isolation and detection of low-abundance sequences. Oligonucleotide-modified substrates are often used to capture sequences of interest for downstream analysis. In this study, we explore the chemical modification of commercial-available polyacrylate solid-phase microextraction fibers for selective DNA analysis using carbodiimide crosslinker chemistry. Reproducible modification conditions are found and the fibers were subsequently applied for selective DNA analysis. Several experimental parameters such as stir-rate, desorption time, and buffer-type are optimized. The developed method was able to selectively extract the target DNA sequence (260 bp) in the presence of 100-fold excess interfering salmon testes DNA.

The high abundance of cannabinoids within cannabis samples presents an issue for pesticide testing as cannabinoids are often co-extracted with pesticides using various sample preparation techniques. Cannabinoids may also chromatographically co-elute with moderate polarity pesticides and inhibit the ionization of pesticides when using mass spectrometry. To circumvent these issues, we have developed a new approach to isolate commonly regulated pesticides and cannabinoids from aqueous samples using tunable, crosslinked imidazolium polymeric ionic liquid (PIL)-based sorbent coatings for direct immersion solid-phase microextraction (DI-SPME). The selectivity of four PIL sorbent coatings towards 20 pesticides and six cannabinoids, including cannabidiol and Δ

A new class of magnetic ionic liquids (MILs) with metal-containing cations was applied in in situ dispersive liquid–liquid microextraction (DLLME) for the extraction of long and short double-stranded DNA. For developing the method, MILs comprised of N-substituted imidazole ligands (with butyl-, benzyl-, or octyl-groups as substituents) coordinated to different metal centers (Ni2+, Mn2+, or Co2+) as cations, and chloride anions were investigated. These water-soluble MILs were reacted with the bis[(trifluoromethyl)sulfonyl]imide anion during the extraction to generate a water-immiscible MIL capable of preconcentrating DNA. The feasibility of combining the extraction methodology with anion-exchange high-performance liquid chromatography with diode array detection (HPLC-DAD) or fluorescence spectroscopy was studied. The method with the Ni2+- and Co2+-based MILs was easily combined with fluorescence spectroscopy and provided a faster and more sensitive method than HPLC-DAD for the determination of DNA. In addition, the method was compared to conventional DLLME using analogous water-immiscible MILs. The developed in situ MIL-DLLME method required only 3 min for DNA extraction and yielded 1.1–1.5 times higher extraction efficiency (EFs) than the conventional MIL-DLLME method. The in situ MIL-DLLME method was also compared to the trihexyl(tetradecyl)phosphonium tris(hexafluorocetylaceto)nickelate(II) MIL, which has been used in previous DNA extraction studies. EFs of 42–99% were obtained using the new generation of MILs, whereas EFs of only 20–38% were achieved with the phosphonium MIL. This new class of MILs is simple and inexpensive to prepare. In addition, the MILs present operational advantages such as easier manipulation in comparison to hydrophobic MILs, which can have high viscosities. These MILs are a promising new class of DNA extraction solvents that can be manipulated using an external magnetic field.

Circulating tumor DNA (ctDNA) is a source of mutant DNA found in plasma and holds great promise in guiding cancer diagnostics, prognostics, and treatment. However, ctDNA fragments are challenging to detect in plasma due to their low abundance compared to wild-type DNA. In this study, a series of ion-tagged oligonucleotides (ITO) were synthesized using thiol-ene click chemistry and designed to selectively anneal target DNA. The ITO-DNA duplex was subsequently captured using a hydrophobic magnetic ionic liquid (MIL) as a liquid support. Extracted target DNA was quantified by adding the DNA-enriched MIL to the quantitative polymerase chain reaction (qPCR) buffer to streamline the extraction procedure. Clinically relevant concentrations of the mutation prone KRAS fragment, which has been linked to colorectal, lung, and bladder cancer, were preconcentrated using the ITO-MIL strategy allowing for enrichment factors as high as 19.49 ± 1.44 from pure water and 4.02 ± 0.50 from 10-fold diluted plasma after a 1 min extraction. Preconcentration could only be achieved when adding the ITO probe to the sample validating the selectivity of the ITO in the capture process. In addition, the amplification efficiency of qPCR was not affected when performing extractions from a diluted-plasma matrix demonstrating that the ITO-MIL approach coupled to direct-qPCR can be used to quantitate DNA from complex matrices. In comparison, commercially available steptavidin-coated magnetic beads were observed to lose selectivity when performing extractions from a 10-fold diluted plasma matrix. The selectivity of the ITO-MIL method, coupled with the ability to rapidly preconcentrate clinically relevant concentrations of target DNA from 10-fold diluted plasma, suggests that this method has the potential to be applied towards the extraction of ctDNA fragments from clinical samples.

Loop-mediated isothermal amplification (LAMP) is a powerful nucleic acid amplification technique due to its rapid and sensitive nature. These characteristics, in addition to low-cost and robustness, make LAMP an attractive alternative to polymerase chain reaction for point-of-care applications. However, sequence-specific detection remains a formidable challenge, particularly when single-nucleotide resolution is required. In this study, a LAMP method is developed for facile visual detection of single-nucleotide polymorphisms (SNPs) using molecular beacons (MBs) by exploiting the dual-fluorescence of fluorescein (6-FAM) and hydoxynaphthol blue (HNB). The method is coupled with solid-phase microextraction (SPME) to facilitate rapid extraction and detection of the target sequence. This work expands the use of MBs in LAMP for the visual detection of SNPs and facilitates the development of future LAMP assays for a wide-range of targets.

Fluorescence correlation spectroscopy (FCS) is applied to investigate the diffusional dynamics of hydrophilic (Atto 590) and amphiphilic (DiD) fluorophores in a series of alkylphosphonium ionic liquid (IL) films ([P

For the first time, an in situ stir bar dispersive liquid-liquid microextraction approach has been developed and coupled with headspace gas chromatography-mass spectrometry for the determination of a group of organic pollutants. The method exploits a new generation of magnetic ionic liquids (MILs) that contain paramagnetic cations based on Ni2+ or Co2+ metal centers coordinated with either N-butylimidazole or N-octylimidazole ligands and chloride anions. The reactants are added to an aqueous solution containing a high field neodymium rod magnet, followed by the addition of the bis[(trifluoromethyl)sulfonyl]imide anion that promotes a metathesis reaction for the in situ generation of a hydrophobic MIL. Concurrently, a high stirring rate is maintained to exceed the magnetic field of the rod magnet and disperse the generated MIL in the sample solution. When stirring is stopped, the MIL coats the rod magnet due to its paramagnetic nature, facilitating the MIL transfer and subsequent desorption and analysis. Under optimum conditions, the method required a 2.5–18% (w/v) aqueous solution of sodium chloride, 10 mL of sample, 20 or 30 mg of MIL, the addition of a small volume of dispersive solvent, and stirring for 5–7.5 min, depending on the MIL. The method provided limits of detection (LODs) down to 10 μg L−1, adequate reproducibility (with relative standard deviation values lower than 10% for a spiked level of 80 μg L−1), and relative recoveries between 72.5% and 102%. Furthermore, the method was successfully applied in the analysis of tap and mineral water.

A new class of magnetic ionic liquid (MIL) containing paramagnetic cations has been applied for in situ dispersive liquid-liquid microextraction in the determination of both polar and non-polar pollutants, including ultraviolet filters, polycyclic aromatic hydrocarbons, alkylphenols, a plasticizer and a preservative in aqueous samples. The MILs were based on cations containing Ni(II) metal centers coordinated with four N-alkylimidazole ligands and chloride anions. The MILs were capable of undergoing in situ metathesis reaction with the bis[(trifluoromethyl)sulfonyl]imide ([NTf2−]) anion during the microextraction procedure, generating a water-immiscible extraction solvent containing the preconcentrated analytes. The MIL was then isolated by magnetic separation, followed by direct analysis using reversed-phase high performance liquid chromatography with diode array detection. Among all of the studied MILs, those containing the N-butylimidazole and N-benzylimidazole ligands ([Ni(C4IM)42+]2[Cl-] and [Ni(BeIM)42+]2[Cl-], respectively) exhibited the best extraction performance. The method under optimum conditions required 5 mL of sample at pH 3, 20 mg of [Ni(C4IM)42+]2[Cl-] or 30 mg of [Ni(BeIM)42+]2[Cl-], 300 μL of acetone or acetonitrile as dispersive solvent (depending on the MIL), a 1:2 M ratio of MIL to [NTf2−], and 3 min of vortex. The developed method achieved higher extraction efficiency compared to the conventional MIL-dispersive liquid-liquid microextraction mode, with extraction efficiencies of 46.8–88.6% and 65.4–97.0% for the [Ni(C4IM)42+]2[Cl-] and the [Ni(BeIM)42+]2[Cl-] MILs (at a spiked level of 81 μg L-1), respectively, limits of detection down to 5.2 μg L-1, and inter-day relative standard deviation lower than 16%.

In this study, magnetic ionic liquids (MILs) consisting of Ni(II), Co(II), and Mn(II) and paired with the bis[(trifluoromethyl)sulfonyl]imide [NTf2−] anion were synthesized from their water soluble chloride intermediates. The MILs feature low viscosity, high hydrophobicity, and hydrolytic stability making them attractive candidates for a number of highly interdisciplinary applications.

Magnetic ionic liquids (MILs) are a subclass of ionic liquids that possess a paramagnetic metal within their chemical structure, making them susceptible to external magnetic fields. A total of twenty-four (24) MILs were prepared and characterized to investigate the effect of the ligand, cation and anion on the physiochemical properties of acetylacetonate-based MILs. It was found that thermal stabilities as high as 260 °C could be achieved by incorporating aromatic moieties in the anion structure. Additionally, the magnetic moment could be modulated by simply changing the transition metal in the anion. Magnetic moment values of 2.8 μB, 4.5 μB and 5.6 μB were obtained by using Ni(II), Co(II), and Mn(II) as the metal centers, respectively. Furthermore, the viscosity of the MILs could be tailored from a few hundred centipoise to several thousand centipoise, increasing their potential applications in numerous interdisciplinary fields. Moreover, the MILs synthesized in this study were found to be insoluble in water at a MIL-to-solvent ratio of 0.01% (w/v), making them potentially useful in targeted separations, where very hydrophobic solvents are highly desired.

This study describes the design, synthesis, and application of polymeric ionic liquid sorbent coatings featuring nickel metal centers for the determination of volatile and semivolatile amines from water samples using headspace solid-phase microextraction. The examined polymeric ionic liquid (PIL) sorbent coatings were composed of two ionic liquid monomers (tetra(3-vinylimidazolium)nickel bis[(trifluoromethyl)sulfonyl]imide [Ni2+ (VIM)4 ] 2[NTf2- ] and 1-vinyl-3-hexylimidazolium [HVIM+ ][NTf2- ]), and an ionic liquid cross-linker (1,12-di(3-vinylimidazolium)dodecane [(VIM)2 C122+ ] 2[NTf2- ]). With these ionic liquid monomers and cross-linkers, three different types of coatings were prepared: PIL 1 based on the neat [Ni2+ (VIM)4 ] 2[NTf2- ] monomer, PIL 2 consisting of the [Ni2+ (VIM)4 ] 2[NTf2- ] monomer with addition of cross-linker, and PIL 3 composed of the [HVIM+ ][NTf2- ] monomer and cross-linker. Analytical performance of the prepared sorbent coatings using headspace solid-phase microextraction gas chromatography-mass spectrometry was compared with the polydimethylsiloxane and polyacrylate commercial coatings. The PIL 2 sorbent coating yielded the highest enrichment factors ranging from 5500 to over 160 000 for the target analytes. The developed headspace solid-phase microextraction gas chromatography-mass spectrometry method was applied for the analysis of real samples (the concentration of amines was 200 μg/L), producing relative recovery values in the range of 90.9-120.0% (PIL 1) and 83.0-122.7% (PIL 2) from tap water, and 84.8-112.4% (PIL 1) and 79.2-119.3% (PIL 2) from lake water.

Detection of mutations and single-nucleotide polymorphisms is highly important for diagnostic applications. Loop-mediated isothermal amplification (LAMP) is a powerful technique for the rapid and sensitive detection of nucleic acids. However, LAMP traditionally does not possess the ability to resolve single-nucleotide differences within the target sequence. Because of its speed and isothermal nature, LAMP is ideally suited for point-of-care applications in resource-limited settings. Recently, different approaches have been developed and applied to enable single-nucleotide differentiation within target sequences. This Mini-Review highlights advancements in mutation detection using LAMP. Methods involving primer design and modification to enable sequence differentiation are discussed. In addition, the development of probe-based detection methods for mutation detection are also covered.