Fluorous Affinity-Driven Retention of Fluorinated Analytes on a High-Density Fluorinated Silica Gel Stationary Phase
Xin Geng1, Yoshiyuki Watabe1,2, Tetsuya Tanigawa1
1Division of Applied Life Sciences, Graduate School of Life and Environmental Sciences, Kyoto Prefectural University, 1-5 Shimogamo Hangi-cho, Sakyo-ku, Kyoto606-8522, Japan.
Abstract:
A high-density fluoroalkyl-modified silica gel stationary phase (C10-FSG) was prepared and evaluated as an HPLC stationary phase for fluorinated analytes. Material characterization confirmed the successful formation of a highly fluorinated surface. Compared with nonfluorinated alkyl-bonded silica (C10-SG) and single-modified C10-FSG, the double-modified C10-FSG showed a clearer fluorination-dependent trend for fluorinated aromatic compounds, indicating selectivity distinct from that of a conventional hydrocarbon-bonded phase. Under pure organic mobile-phase conditions, perfluorinated esters were retained much more strongly than their nonfluorinated analogues, showing that strong fluorous affinity can be expressed on the C10-FSG phase even in the absence of water. The retention of PFAS-related carboxylic acids was strongly influenced by the mobile-phase environment. Under strongly acidic, water-rich conditions, medium- and long-chain PFAS acids showed strong retention, while even highly polar short-chain PFAS acids were retained on C10-FSG. Compared with single-modified C10-FSG and a commercial fluorinated stationary phase, double-modified C10-FSG showed stronger retention toward short-chain PFAS acids under the tested conditions. Overall, retention on C10-FSG was governed not only by conventional hydrophobicity, but also by analyte fluorination, solvation, and mobile-phase conditions, providing insight into the chromatographic behavior of PFAS-related analytes on a highly fluorinated stationary phase.
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