Exploring a new generation of bimetallic magnetic ionic liquids with ultra-low viscosity in microextraction that enable direct coupling with high-performance liquid-chromatography.

BACKGROUND: The incorporation of bimetallic magnetic ionic liquids (MILs) in microextraction methods is an emerging trend due to the improved magnetic susceptibility offered by these solvents, which relies on the presence of metallic components in both the cation and the anion. This feature favors easy magnetic separation of these solvents in analytical sample preparation strategies. However, reported liquid-phase microextraction methods based on bimetallic MILs still present an important drawback in that the MILs are highly viscous, making a dispersive solvent during the microextraction procedure necessary, while also requiring a tedious back-extraction step prior to the chromatographic analysis. RESULTS: We propose for the first time a new generation of ultra-low viscosity bimetallic MILs composed of two paramagnetic Mn(II) complexes characterized by their easy usage in dispersive liquid-liquid microextraction (DLLME). The approach does not require dispersive solvent and the MIL-DLLME setup was directly combined with high-performance liquid chromatography (HPLC) and fluorescence detection (FD), without any back-extraction step. The approach was evaluated for the determination of five monohydroxylated polycyclic aromatic hydrocarbons, as carcinogenic biomarkers, in human urine. Optimum conditions of the MIL-DLLME method included the use of a low MIL volume (75 µL), a short extraction time (5 min), and no need of any dispersive solvent neither NaCl. The method presented limits of detection down to 7.50 ng L-1, enrichment factors higher than 17, and provided inter-day relative standard deviation lower than 11%. Analysis of urine samples was successfully performed, with biomarker content found at levels between 0.24 and 7.8 ng mL-1. SIGNIFICANCE: This study represents the first liquid-phase microextraction method using the new generation of low-viscous bimetallic MILs. The proposed MIL-DLLME approach represents 2 important advances with respect to previous methods employing bimetallic MILs: 1) no dispersive solvent is required, and 2) direct injection of the MIL in the HPLC is possible after minor dilution (no back extraction steps are required). Therefore, the microextraction strategy is simple, rapid, and consumes very small amounts of energy.

A magnetic stir bar sorbent of metal organic frameworks, carbon foam decorated zinc oxide and cryogel to enrich and extract parabens and bisphenols from food samples.

A porous composite magnetic stir bar adsorbent was fabricated for the extraction and enrichment of parabens and bisphenols from selected beverage samples. The adsorbent comprised a metal organic framework, carbon foam decorated zinc oxide and magnetic nanoparticles embedded in polyvinyl alcohol cryogel. The porous composite stir bar adsorbent could adsorb parabens and bisphenols via hydrogen bonding, π-π and hydrophobic interactions. In the best conditions, linearity was good from 5.0 to 200.0 µg/L for methyl paraben, ethyl paraben and bisphenol A and from 10.0 to 200.0 µg/L for bisphenol B and butyl paraben. Limits of detection ranged from 1.5 to 3.0 µg/L. The developed composite stir bar was successfully applied to extract and determine parabens and bisphenols in fruit juice, beer and milk. Recoveries ranged from 89.5 to 99.5 % with RSDs lower than 6 %. The developed sorbent and new methodology were evaluated in terms of its green character with satisfactory results.

A hierarchical porous composite magnetic sorbent of reduced graphene oxide embedded in polyvinyl alcohol cryogel for solvent-assisted-solid phase extraction of polycyclic aromatic hydrocarbons.

A hierarchical porouscomposite magnetic sorbent was fabricated and applied to the dispersive solvent-assisted solid-phase extraction of five polycyclic aromatic hydrocarbons. A sorbent was first prepared by incorporating graphene oxide, calcium carbonate, and magnetite nanoparticles into a polyvinyl alcohol cryogel. The graphene oxide was converted to reduced graphene oxide using ascorbic acid and a hierarchical porous structure was produced by reacting hydrochloric acid with incorporated calcium carbonate to generate carbon dioxide bubbles which created a second network. Before extracting the target analytes, the extraction solvent was introduced into the hierarchical pore network of the sorbent. The extraction was based on the partition between the analytes and introduced extraction solvent and the adsorption of analytes on reduced graphene oxide.The extraction efficiency was enhanced through π-π and hydrophobic interactions between polycyclic aromatic hydrocarbons and reduced graphene oxide and extraction solvent. The extracted polycyclic aromatic hydrocarbons were determined by using high-performance liquid chromatography coupled with a fluorescence detector. The developed method was applied to extract polycyclic aromatic hydrocarbons in disposable diaper, coffee, and tea samples and recoveries from 84.5 to 99.4% were achieved with relative standard deviations below 7%. The developed sorbent exhibited good reproducibility and could be reused for 10 cycles.The developed sorbent exhibited good reproducibility and could be reused for 10 cycles.The developed sorbent exhibited good reproducibility and could be reused for 10 cycles.

A dumbbell-shaped stir bar made from poly(3,4-ethylenedioxythiophene)-coated porous cryogel incorporating metal organic frameworks for the extraction of synthetic phenolic antioxidants in foodstuffs.

A dumbbell-shaped stir bar adsorbent of MIL-101 entrapped in PVA cryogel coated with poly(3,4-ethylenedioxythiophene) was fabricated to extract synthetic phenolic antioxidants in foodstuffs. The interconnected porous of cryogel allowed the entrapment of MIL-101 and enhanced the surface areas of poly(3,4-ethylenedioxythiophene) coating which facilitated multiple adsorptions. The fabricated adsorbent was characterized and measured the adsorption capacities for synthetic phenolic antioxidants. Extraction efficiency was optimized by evaluating the effect of adsorbent compositions, extraction time, stirring speed, sample pH, desorption conditions, sample volume and ionic strength. The analysis of extracted synthetic phenolic antioxidants was carried out using high performance liquid chromatography. The developed analysis method provided a wide linear range of 0.20 - 200 µg kg-1 for butylated hydroxyanisole and 0.50 - 200 µg kg-1 for tert­butylhydroquinone and butylated hydroxytoluene. The limits of detection were between 0.05 and 0.15 µg kg-1. The developed stir bar adsorbent was utilized to extract these three synthetic phenolic antioxidants from juice, milk, infant formula and coffee creamer. Recoveries ranged from 87 to 101% with RSDs below 7%. The developed composite stir bar adsorbent was convenient to use, and good physical and chemical stability allowed efficient extraction for 12 extraction cycles.

A nanocomposite adsorbent of metallic copper, polypyrrole, halloysite nanotubes and magnetite nanoparticles for the extraction and enrichment of sulfonamides in milk.

A composite adsorbent composed of metallic copper (Cu), polypyrrole (PPy), halloysite nanotubes (HNTs) and magnetite nanoparticles (Fe3O4) was developed to extract and enrich sulfonamides by dispersive magnetic solid phase extraction. The composite could adsorb sulfonamides via hydrogen bonding and hydrophobic, π-π and π-electron-metal interactions. The extraction conditions were optimized and the developed composite adsorbent was characterized and provided a large surface area that enhanced extraction efficiency for sulfonamides. Coupled with high performance liquid chromatography, the adsorbent was used to quantitatively determine sulfonamides found in milk samples. The response of the developed method exhibited linearity from 5.0 to 150.0 µg kg-1 for sulfathiazole, and from 2.5 to 100.0 µg kg-1 for sulfamerazine, sulfamonomethoxine and sulfadimethoxine. Limits of detection were between 2.5 and 5.0 µg kg-1. Recoveries of sulfonamides in milk samples ranged from 83.0 to 99.2% with RSDs lower than 6%. The developed composite adsorbent showed good reproducibility and reusability.

Solvent-assisted dispersive liquid-solid phase extraction of organophosphorus pesticides using a polypyrrole thin film-coated porous composite magnetic sorbent prior to their determination with GC-MS/MS.

A porous composite magnetic sorbent was developed and used as a solid phase for the solvent-assisted preconcentration of organophosphorus pesticides. The hierarchical porous composite sorbent was composed of polypyrrole thin film coated on the surface of porous alginate beads with embedded magnetite nanoparticles. The pores in the alginate hydrogel beads were produced by carbon dioxide bubbles from the reaction of incorporated calcium carbonate with hydrochloric acid. The porous network was filled with dichloromethane to assist extraction. The fabricated porous composite sorbent was characterized and sorbent fabrication and extraction conditions were optimized to obtain the best extraction performance. The developed sorbent was coupled with GC-MS/MS to determine organophosphorus pesticides in fruit juices and vegetable. Under optimized condition, the developed method provided good linear range of 0.03-200 µg L-1 for dichlorvos, malathion, and fenthion, and 0.075-200 µg L-1 for mevinphos, dimethoate, and parathion methyl, respectively. Limits of detection were in the range 0.010 to 0.025 µg L-1. This method exhibited good relative recoveries in the range 84 to 99% and RSDs lower than 8%. The good stability of the sorbent enabled up to eight cycles of reuse.Graphical abstract.