Enhanced extraction of negatively charged emerging contaminants by amine-modified amphiphilic materials-based solid phase microextraction fibers

The solid phase microextraction (SPME) technique is an efficient method for emerging contaminants (ECs) detection, however, many commercial fibers are not suitable for extracting negatively charged ECs. Herein, three amine-functionalized amphiphilic materials(MAM) were synthesized via a high-speed shear dispersion emulsification technique. These materials were employed as SPME fiber coatings to enhance the selectivity for negatively charged ECs, attributed to their substantial specific surface area (679-693 m 2 /g), high ion-exchange capacity (1.55-2.57 mmol/g) and good hydrophilicity (contact Angle of 63.8-83.9°). The MAM-PIP coating demonstrates superior selectivity and efficiency for negatively charged compounds across a broad spectrum of polarities compared to Oasis® WAX, commercial C18, and CAR coatings. A novel analytical method employing SPME (piperazine-modified MAM) in conjunction with LC-MS/MS was developed. The enrichment factors for 21 ECs ranged from 408 to 7,129. The method exhibited excellent linearity within the concentration range of 10-5,000 ng/L, with limits of detection (LOD) ranging from 0.03 to 2.59 ng/L and limits of quantitation (LOQ) from 0.1 to 8.62 ng/L. The relative standard deviations were consistently below 15%. Comparative analysis with existing literature indicates that the developed method holds significant potential for commercial application in extracting ECs from environmental water samples.