Fabrication and evaluation of tetraazahexaphenylmacrocycle-bonded stationary phase with multiple retention mechanisms

Junnan Li; Yaming Sun; Longhui Liu; Hailiang Zhao; Wenjie Zhao; Lijun He; Shusheng Zhang

doi:10.1016/j.chroma.2021.462296

Fabrication and evaluation of tetraazahexaphenylmacrocycle-bonded stationary phase with multiple retention mechanisms

J Chromatogr A. 2021 Aug 16:1651:462296. doi: 10.1016/j.chroma.2021.462296. Epub 2021 May 28.

Authors

Junnan Li¹, Yaming Sun², Longhui Liu¹, Hailiang Zhao³, Wenjie Zhao⁴, Lijun He⁵, Shusheng Zhang⁶

Affiliations

¹ School of Chemistry and Chemical Engineering, Henan University of Technology, Zhengzhou 450001, China.
² School of Chemistry and Chemical Engineering, Henan University of Technology, Zhengzhou 450001, China; Key Laboratory of Accurate Separation and Analysis for Complex Matrix of Zhengzhou City, Zhengzhou 450001, China. Electronic address: sunyami@haut.edu.cn.
³ School of Environmental Engineering, Henan University of Technology, Zhengzhou, 450001, China.
⁴ School of Chemistry and Chemical Engineering, Henan University of Technology, Zhengzhou 450001, China; Key Laboratory of Accurate Separation and Analysis for Complex Matrix of Zhengzhou City, Zhengzhou 450001, China.
⁵ School of Chemistry and Chemical Engineering, Henan University of Technology, Zhengzhou 450001, China; Key Laboratory of Accurate Separation and Analysis for Complex Matrix of Zhengzhou City, Zhengzhou 450001, China. Electronic address: lijunhe@haut.edu.cn.
⁶ Center for Modern Analysis and Gene Sequencing, Zhengzhou University, Zhengzhou 450001, China.

PMID: 34144400
DOI: 10.1016/j.chroma.2021.462296

Abstract

A 34-membered tetraazahexaphenylmacrocycle (N₄Ph₆) with a rigid π-conjugated moiety was chemically bonded to silica gel with 3-chloropropyltrimethoxysilane as the coupling agent to prepare a novel SiO₂@N₄Ph₆ stationary phase. Several common organic analytes, including alkylbenzenes, polycyclic aromatic hydrocarbons, anilines, phenols, phthalates, and folic acid, were selected as probes to investigate its chromatographic performance. The as-developed SiO₂@N₄Ph₆ stationary phase showed superiority retention and high selectivity for probe molecules through multiple interactions, including hydrophobic, π-π, hydrogen-bonding, and steric interactions. Density functional theory calculation results using folic acid as model solute provided an intuitive and a quantitative description of the multiple retention mechanisms.

Keywords: Density functional theory calculations; Multiple retention mechanisms; Stationary phase; Tetraazahexaphenylmacrocycle.

MeSH terms

Aza Compounds / chemistry*
Density Functional Theory
Hydrophobic and Hydrophilic Interactions
Macrocyclic Compounds / chemistry*
Phenols / analysis
Polycyclic Aromatic Hydrocarbons / analysis
Reference Standards
Reproducibility of Results
Silicon Dioxide / chemistry
Spectroscopy, Fourier Transform Infrared
Static Electricity
Thermodynamics

Substances

Aza Compounds
Macrocyclic Compounds
Phenols
Polycyclic Aromatic Hydrocarbons
Silicon Dioxide