A carboxyl-functionalized covalent organic polymer for the efficient adsorption of saxitoxin

Saxitoxin (STX), the most widely distributed neurotoxin in marine waters and emerging cyanotoxin of concern in freshwaters, causes paralytic shellfish poisoning in humans upon consumption of contaminated shellfish. To allow for the efficient monitoring of this biotoxin, it is of high importance to find high-affinity materials for its adsorption. Herein, we report the design and synthesis of a covalent organic polymer for the efficient adsorption of STX. Two β-keto-enamine-based materials were prepared by self-assembly of 2,4,6-triformylphloroglucinol (Tp) with 2,5-diaminobenzoic acid (Pa-COOH) to give TpPa-COOH and with 2,5-diaminotoluene (Pa-CH₃) to give TpPa-CH₃. The carboxylic acid functionalized TpPa-COOH outperformed the methyl-bearing counterpart TpPa-CH₃ by an order of magnitude despite the higher long-range order and surface area of the latter. The adsorption of STX by TpPa-COOH was fast with equilibrium reached within 1 h, and the Langmuir adsorption model gave a calculated maximum adsorption capacity, Q_m, of 5.69 mg g^-1, making this material the best reported adsorbent for this toxin. More importantly, the prepared TpPa-COOH also showed good reusability and high recovery rates for STX in natural freshwater, thereby highlighting the material as a good candidate for the extraction and pre-concentration of STX from aquatic environments.