Engineering tunable rigid slits and supramolecular soft pockets on silica surfaces for multi-mode chromatographic recognition.

Authors

Yujie Zhang, Mingliang Zhang, Haifeng Han, Shouyong Zhou, Tianpei Cai

Published in

Analytica chimica acta. Volume 1424. Pages 346270. Nov 22, 2026. Epub Sep 14, 2026.

Abstract

Developing advanced chromatographic interfaces capable of discriminatively recognizing rigid structural isomers and highly polar environmental toxins remains a profound challenge. Herein, we report a systematic "structure-dictates-assembly" paradigm to engineer multi-mode polycyclic aromatic stationary phases with precisely controlled surface micro-topographies. Employing a dihydrazide-anchored thiol-ene click strategy on silica micro-particles, three distinct supramolecular architectures were fabricated: a highly aligned 2-phenanthrenyl phase (2-PNTHZD), a tilted angular 9-phenanthrenyl phase (9-PNTHZD), and a flat-oriented 9-anthracenyl phase (9-ANTHZD). Thermodynamic profiles and solvent-modulated responsive behaviors were comprehensively elucidated using diverse stereochemical and electronic probe matrices. The results reveal three divergent molecular recognition mechanisms. The 2-PNTHZD phase constructs high-density, liquid-crystal-like vertical rigid slits, achieving ultimate length-to-width ratio screening that perfectly segregates challenging tetracene and picene isomers. Conversely, the 9-PNTHZD creates a spatially tilted angular pocket for bent isomers, which remarkably transitions into a highly flexible supramolecular "soft pocket" via active acetonitrile intercalation. This solvent-driven induced-fit mechanism provides a distinct departure from classical reversed-phase thermodynamics, unlocking the baseline resolution of heavily twisted polybrominated biphenyl (PBB) congeners. Furthermore, free from lateral steric hindrance, the wide-open 9-ANTHZD functions as an exceptional π-electron donor surface, leveraging its high HOMO energy to conquer electron-deficient perfluorocarbons and deliver peak-capacity breakthroughs for EPA 529 nitro-explosives. Collectively, this work introduces a highly tunable, multi-mode surface platform, providing a fundamentally predictable toolkit for complex environmental and structural isomer analysis.

PMID:
42887947
Bibliographic data and abstract were imported from PubMed on 17 Oct 2026.

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