Shape-Selective Separation of Model Analytes in Normal-Phase Liquid Chromatography: A Combined Simulation-Experimental Study

Durdyyev R, Supper M, Domagala JC, Hantal G, Kaspereit M, Smith AS (2025)

Publication Type: Journal article

Publication year: 2025

Journal

Analytical Chemistry American Chemical Society

DOI: 10.1021/acs.analchem.5c01710

Abstract

In this study, we demonstrate that liquid chromatographic separation can be effectively achieved based on shape differences, even for analytes of very similar chemical characters. Using a combined experimental-theoretical approach, we investigated the retention behavior of spherical buckminsterfullerene C60 and disk-shaped coronene at a hydroxylated silica stationary phase, with a mobile phase composed of toluene and n-hexane at varying compositions. High-performance liquid chromatography (HPLC) measurements revealed that increasing the n-hexane content enhances the separability of the two analytes, primarily due to coronene’s stronger retention. Molecular simulations, coupled with a two-state model, attributed this effect to the structured layering of toluene at the stationary phase, which differentially influences analyte-wall interactions. Our analysis of Henry coefficients further identified the second solvent layer as the primary region governing adsorption, providing a thermodynamically consistent description of the separation process. These findings highlight the role of shape anisotropy in chromatographic retention and suggest new avenues for designing shape-selective separation strategies for molecules and nanoparticles in liquid chromatography.

Authors with CRIS profile

Rustam Durdyyev Physics Underlying Life Science (PULS) Jan-Christoph Domagala Lehrstuhl für Thermische Verfahrenstechnik (TVT) György Hantal Physics Underlying Life Science (PULS) Malte Kaspereit Professur für Thermische Verfahrenstechnik Ana-Suncana Smith Physics Underlying Life Science (PULS)

Involved external institutions

University of Tokyo JP Japan (JP)

How to cite

APA:

Durdyyev, R., Supper, M., Domagala, J.-C., Hantal, G., Kaspereit, M., & Smith, A.-S. (2025). Shape-Selective Separation of Model Analytes in Normal-Phase Liquid Chromatography: A Combined Simulation-Experimental Study. Analytical Chemistry. https://doi.org/10.1021/acs.analchem.5c01710

MLA:

Durdyyev, Rustam, et al. "Shape-Selective Separation of Model Analytes in Normal-Phase Liquid Chromatography: A Combined Simulation-Experimental Study." Analytical Chemistry (2025).

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