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.
The properties of low viscosity, hydrophobic magnetic ionic liquids featuring transition and rare earth metal hexafluoroacetylacetonate chelated anions paired with the trihexyl(tetradecyl)phosphonium cation are studied.
Magnetic ionic liquids (MILs) are
a subclass of ionic liquids (ILs)
containing paramagnetic components and are readily manipulated by
an external magnetic field. Due to their hydrophilic nature, very
few applications of MILs in aqueous systems have been reported. In
this study, three general classes of hydrophobic MILs including monocationic,
symmetrical/unsymmetrical dicationic, and symmetrical/unsymmetrical
tricationic MILs were synthesized and characterized. By tuning the
structure of the MIL, various physicochemical properties including
water solubility, magnetic susceptibility, and melting point were
regulated. MILs synthesized with the benzimidazolium cation were shown
to exhibit lower water solubility (0.1% (w/v)) when compared to those
containing imidazolium cations (0.25% (w/v)). By incorporating asymmetry
into the cationic component of the MIL, the melting point of dicationic
MILs was lowered while the effective magnetic moment (μeff) and hydrophobicity remained unchanged. Tricationic MILs
paired with three [FeCl3Br–] anions exhibited
an μeff as high as 11.76 Bohr magnetons (μB), the highest ever reported for MILs. The synthetic strategies
employed in this study facilitate the generation of hydrophobic MILs
that show great promise for liquid–liquid extraction and catalytic
studies where the MIL can be easily removed or in microfluidic applications
where the MIL microdroplet can be manipulated by an external field.
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