Silica-based ionic liquid coating for 96-blade system for extraction of aminoacids from complex matrixes

Graphical abstract: -- Highlights: •Silica-based 1-vinyl-3-octadecylimidazolium bromide ionic liquid was synthesized and characterized. •The synthesized polymer was immobilized on the stainless steel blade using polyacrylonitrile glue. •SiImC18-PAN 96-blade SPME was applied as an extraction phase for extraction of highly polar compounds in grape matrix. •This system provides high extraction efficiency and reproducibility for up to 50 extractions from tartaric buffer and 20 extractions from grape pulp. -- Abstract: 1-Vinyl-3-octadecylimidazolium bromide ionic liquid [C18VIm]Br was prepared and used for the modification of mercaptopropyl-functionalized silica (Si-MPS) through surface radical chain-transfer addition. The synthesized octadecylimidazolium-modified silica (SiImC18) was characterized by thermogravimetric analysis (TGA), infrared spectroscopy (IR), 13C NMR and 29Si NMR spectroscopy and used as an extraction phase for the automated 96-blade solid phase microextraction (SPME) system with thin-film geometry using polyacrylonitrile (PAN) glue. The new proposed extraction phase was applied for extraction of aminoacids from grape pulp, and LC–MS–MS method was developed for separation of model compounds. Extraction efficiency, reusability, linearity, limit of detection, limit of quantitation and matrix effect were evaluated. The whole process of sample preparation for the proposed method requires 270 min for 96 samples simultaneously (60 min preconditioning, 90 min extraction, 60 min desorption and 60 min for carryover step) using 96-blade SPME system. Inter-blade and intra-blade reproducibility were in the respective ranges of 5–13 and 3–10% relative standard deviation (RSD) for all model compounds. Limits of detection and quantitation of the proposed SPME-LC–MS/MS system for analysis of analytes were found to range from 0.1 to 1.0 and 0.5 to 3.0 μg L−1, respectively. Standard addition calibration was applied for quantitative analysis of aminoacids from grape juice and the results were validated with solvent extraction (SE) technique