Development of coatings for automated 96-blade solid phase microextraction-liquid chromatography–tandem mass spectrometry system, capable of extracting a wide polarity range of analytes from biological fluids

This work presents the development and evaluation of biocompatible polyacrylonitrile–polystyrene–divinylbenzene (PAN–PS–DVB) and polyacrylonitrile–phenylboronic acid (PAN–PBA) coatings for automated 96-blades (thin-film) solid phase microextraction (SPME) system, using high performance liquid chromatography (HPLC) coupled with tandem mass spectrometry (MS/MS). The SPME condition was optimized for 60 min equilibrium extraction and 40 min desorption for PAN–PS–DVB, and 120 min equilibrium extraction and 60 min desorption for PAN–PBA for parallel sample preparation of up to 96 samples. The thin film geometry of the SPME blades provided good extraction efficiency due to the larger surface area of the coating, and simultaneous sample preparation provided fast and accurate analysis. The PAN–PS–DVB and PAN–PBA 96-blade SPME coatings were evaluated for extraction of analytes in a wide range of polarity (log P = 2.8 to −3.7), and they demonstrated efficient extraction recovery (3.5–98.9% for PAN–PS–DVB and 4.0–74.1% for PAN–PBA) for both polar and non-polar groups of compounds. Reusability, reproducibility, and reliability of the system were evaluated. The results demonstrated that both coatings presented chemical and mechanical stability and long-lasting extraction efficiency for more than 100 usages in phosphate-buffered saline (PBS) and human plasma.

► Developments and evaluation of two new stationary phases for 96-blade SPME system.
► Coatings were capable of extracting compounds with wide a range of polarity.
► The coatings demonstrated biocompatibility, reusability, and reproducibility for analysis of biological samples.