Self-assembly of core–shell structured multiwalled nanotubes@covalent organic frameworks composite for solid-phase extraction of four phytohormones from fruit juices

Covalent organic frameworks (COFs) have attracted considerable attention in sample pretreatment because of their unique characteristics. However, the submicron or micron size of COFs has restricted their wider applications in solid-phase extraction (SPE). Herein, multiwalled nanotubes (MWNTs) were used as substrate materials to synthesize core-shell structured MWNTs@COFs composites (MWNTs@SNW-1) using a simple self-assembly method. The as-prepared MWNTs@SNW-1 composite exhibited a high BET surface area, good thermal stability, and good adsorption capacity. The MWNTs@SNW-1 composite was used as an adsorbent in cartridge-based SPE to extract four phytohormones before determining their levels by high-performance liquid chromatography. The experimental parameters affecting extraction efficiency, including the amount of adsorbents, solution pH, ionic strength, eluent type, and eluent volume, were investigated. The developed method showed a wide linear range (0.37-100 ng mL-1), low detection limits (0.11-0.32 ng mL-1), low limits of quantification (0.37-1.07 ng mL-1), high enrichment factors (45.9-49.3), and good reproducibility (<4.8%) for phytohormones. The developed analytical method was used to analyze trace phytohormones in fruit juices with good recoveries, highlighting the potential of the MWNTs@SNW-1 composite as an adsorbent in sample preparation.