Green supramolecular solvent for the liquid phase microextraction of beta-blockers from biological samples: a cationic surfactant-monoterpene system.

Herein, a novel supramolecular solvent based cationic surfactant and monoterpene is developed as a green alterative for the microextraction of beta-blockers (propranolol, carvedilol) from human urine and serum. In an aqueous medium, the cationic surfactant (amylamine) produced an isotropic solution as a result of amphiphilic supramolecular self-assembly. Coacervation facilitated phase separation, while the monoterpenoid alcohol (terpineol) functioned as the coacervation agent, triggering the spontaneous in situ formation of nanosized supramolecular solvent droplets. The determination of the drugs was carried out using a HPLC-fluorescence detector (FLD). Various supramolecular solvents (SUPRAs) were examined composed of cationic surfactants and natural-occurring terpenoid analogs. A proposed mechanism of the extraction of the analytes and the formation of SUPRAs is provided. mechanism was attributed to the formation of mixed aggregates capable of effectively capturing the target analytes. For microextraction optimization, the volumes of amylamine and terpineol, sample pH and sample volume were investigated. Under optimized conditions, extraction recoveries higher than 80% for both drugs were obtained while the analytical method exhibited excellent predictive performance, with coefficients of determination exceeding 0.9909. Method validation demonstrated satisfactory precision (coefficient of variation, CV <13.7%) and accuracy, with relative recoveries ranging from 87.8% to 116.1% (for urine) and 83.4% to 114.7% (for serum). The limit of detection was estimated at 0.1 and 0.2 ng/mL for propranolol and carvedilol, respectively. The method greenness was evaluation using the MA-multicolor tool providing a reasonable balance between environmental sustainability, analytical performance, operational practicality, and safety. Finally, the method was successfully applied to the analysis of authentic human urine and serum samples, validating its effectiveness for real-world biological monitoring.