Facile Synthesis of Mixed-Mode Weak Anion-Exchange Microspheres via One-Step Pickering Emulsion Polymerization for Efficient Simultaneous Extraction of Strongly and Weakly Acidic Drugs from Reservoir Water.

Poly(2-(diethylamino)ethyl methacrylate-co-divinylbenzene) (poly(DEAEMA-co-DVB)) microspheres with mixed-mode weak anion-exchange (WAX) character were successfully fabricated for the first time via facile one-step Pickering emulsion polymerization. The obtained poly(DEAEMA-co-DVB) particles had good spherical geometry, uniform particle size in the range of 30-40 µm, a large specific surface area of 575 m/g, and a pore size range of 5-30 nm, according to the SEM and nitrogen adsorption-desorption results. Using these mixed-mode WAX microspheres as packing material, a reliable and robust analytical method based on solid phase extraction and high performance liquid chromatography with ultraviolet detection (SPE-HPLC-UV) was developed for simultaneous determination of six strongly and weakly acidic nonsteroidal anti-inflammatory drugs (NSAIDs, niflumic acid, diflunisal, naproxen, ketoprofen, mefenamic acid, and diclofenac) in reservoir water. Under optimized conditions, it was applicable to preconcentrate up to 500 mL of reservoir water samples on the WAX cartridges with satisfying recoveries (88-96%) for all the NSAIDs tested. The limits of detection were in the range of 0.002-0.025 μg L, respectively. Our results showed that the developed mixed-mode WAX poly(DEAEMA-co-DVB) phase containing a tertiary amine with a pKa value of approximately 10.7 could be used for simultaneous clean-up and preconcentration of strongly and weakly acidic organic pollutants in real environmental water, which could not be achieved by single use of quaternary ammonium strong anion-exchange phase or weaker primary and secondary amine anion-exchange.