Organic–inorganic hybrid fluorous monolithic capillary column for selective solid‐phase microextraction of perfluorinated persistent organic pollutants

Abstract

A novel construction strategy of monolithic capillary column for selectively enriching perfluorinated persistent organic pollutants was proposed. The organic-inorganic hybrid fluorous monolithic capillary column was synthesized by a "one-pot" approach via the polycondensation of γ-methacryloxypropyltrimethoxy-silane, then in situ copolymerization of 1H,1H,7H-dodecafluoroheptyl methacrylate and vinyl group on the precondensed siloxanes. The obtained monolithic columns were systematically characterized. The results demonstrated that the optimal column possessed good mechanical stability and high permeability. The adsorption capacities of the optimized monolithic column for perfluorooctanoic acid and perfluorooctane sulfonate were 0.257 and 0.513 μg/mg, respectively. Adsorption capacities of the monoliths were proved to increasing with increasing the amounts of fluorinated monomers in the fluorous monoliths. Sodium 1-octanesulfonate, as a comparison compound, was hardly adsorbed on the fluorous monolith. In addition, the trace amounts of perfluorooctanoic acid and perfluorooctane sulfonate in water samples can be successfully concentrated about 160 times to their original concentrations by this monolithic column. These results demonstrated that the capacity and selectivity of the affinity fluorous column is high and can be applied to the selective enrichment for the perfluorinated persistent organic pollutants from environmental samples.

Ampholine-functionalized hybrid organic–inorganic silica material as sorbent for solid-phase extraction of acidic and basic compounds

“…The adsorption amounts of PHB and BHB were achieved maximum at 1.43 g mg −1 . Of note, the adsorption capacities are higher than those reported in previous work [28].…”

“…In addition, organic-inorganic hybrid fluorous monolithic capillary columns were prepared for selective solid-phase microextraction of perfluorinated persistent organic pollutants [28]. Although different functional groups of modifiers are supposed to provide interactions with different analytes, almost all monolithic sorbents are limited mainly to have one functional group, such as octyl [24], sulfonic acid group [25], amino group [27], or fluorous group [28], with only a few publications reporting the coimmobilization of two functional groups (i.e., octyl and sulfonic acid group) [26].…”

Selective and sensitive liquid chromatographic determination method of 5-hydroxyindoles with fluorous and fluorogenic derivatization

“…Therefore, this method could selectively and sensitively analyze 5-HIs with simple pretreatment and derivatization, and detect the requisite analytes without interference from contaminants in the human plasma samples. It is expected that this method could be applied as a more sensitive analytical technique for very diluted and small samples such as microdialysates by using a fluorous column-switching LC system [39] and/or fluorous solid-phase microextraction technique [40].…”

Advances in the development and applications of organic–silica hybrid monoliths

“…A one‐pot methodology with organic monomers and MPTMS as the only source of alkoxysilane can also be utilized toward preparation of monomers with varying surface functionalities. For example fluorous SPE cartridges were prepared by thermal polymerization of MPTMS and 1 H ,1 H ,7 H ‐dodecafluoroheptyl methacrylate monomer, ethylene dimethacrylate (EDMA) cross‐linker, AIBN initiator and an aqueous acid catalyst . A mixture of three porogens, 1‐propanol, 1‐octanol and 1‐dodecanol, was needed for the formation of through‐pores and to achieve enhanced surface area.…”