Trace enrichment of phenylcarboxylic acids from a model biological fluid and serum of human blood.

The study was focused on the development of a solid-phase extraction protocol for seven phenylcarboxylic acids from albumin solutions by using unmodified hyper-cross-linked polystyrene restricted access materials with crosslinking degrees varying from 100 to 400% (four of the acids are known to be markers of sepsis). The breakthrough volume of the most hydrophilic 3,4-dihydroxybenzoic acid rises as the sorbent bridging extent grows. Inversely, the breakthrough volume of the most hydrophobic 3-phenylpropionic acid was found to decrease considerably when the degree of crosslinking exceeds 200%. This unusual pattern is because of the superposition of two opposite tendencies. Increasing substitution extent of phenyls facilitates their π-π-interactions with polar compounds whereas rising density of the network reduces the accessibility of sorption sites to all solutes. Mini-cartridges containing 30 mg of an optimal sorbent take up the acids completely and reversibly, the recoveries being close to 100% even in the presence of high concentrations of albumin. By coupling the developed solid-phase extraction with high-performance liquid chromatography and diode array detection technique, we managed to determine quantitatively phenylcarboxylic acids in the serum of a healthy patient blood, and the recoveries varied from 93 to 100% while the limit of quantification was (4-9) × 10  M.