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Cross-linked γ-cyclodextrin metal-organic framework—a new stationary phase for the separations of benzene series and polycyclic aromatic hydrocarbons

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Abstract

The cross-linked γ-cyclodextrin metal-organic framework (CL-CD-MOF) was synthesized by crosslinking γ-cyclodextrin metal-organic framework (γ-CD-MOF) with diphenyl carbonate to separate benzene series and polycyclic aromatic hydrocarbons (PAHs). The separation ability of the CL-CD-MOF packed column was assessed in both reverse-phase (RP-) and normal-phase (NP-) modes. The retention mechanisms of these compounds were discussed and confirmed by combining molecular simulations in detail. It was found that baseline separation could be obtained in RP-HPLC mode and it was superior to commercial C18 column in separating xylene isomers. The interaction between CL-CD-MOF and analytes, such as dipole-dipole interaction, π-electron transfer interaction, hydrophobic interaction, and van der Waals force, may dominate the chromatographic separation, and CL-CD-MOF column had a certain shape recognition ability. In addition, the composition of the mobile phase also had a crucial effect. Moreover, the column demonstrated satisfactory stability and repeatability (the relative standard deviations of retention time, peak height, peak area, and half peak width for six replicate separations of the tested analytes were within the ranges 0.17–1.1%, 0.96–1.9%, 0.23–1.7%, and 0.32–1.9%, respectively) and there was no significant change in the separation efficiency for at least 3 years of use. Thermodynamic characteristics indicated that the process of separations on the CL-CD-MOF column was both negative enthalpy change (ΔH) and entropy change (ΔS) controlled. The excellent performance made CL-CD-MOF a promising HPLC stationary phase material for separation and determination of benzene series and PAHs.

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Abbreviations

γ-CD:

γ-Cyclodextrin

MOF:

Metal-organic framework

γ-CD-MOF:

γ-Cyclodextrin metal-organic framework

CL-CD-MOF:

Cross-linked γ-cyclodextrin metal-organic framework

PAHs:

Polycyclic aromatic hydrocarbons

ΔH:

Enthalpy change

ΔS:

Entropy change

ΔG:

Gibbs free energy

EB:

Ethylbenzene

H2O:

Water

MeOH:

Methanol

Hex:

n-Hexane

DCM:

Dichloromethane

TGA:

Thermogravimetric analysis

FT-IR:

Fourier transform infrared

SEM:

Scanning electron microscope

PXRD:

Powder X-ray diffraction

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Funding

This work was supported by the National Natural Science Foundation of China (No. 81573392).

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Authors and Affiliations

  1. School of Pharmacy, Shenyang Pharmaceutical University, Wenhua Road 103, Shenyang, Liaoning Province, People’s Republic of China

    Hanyue Li, Chengcheng Li, Caifen Wang, Jiwen Zhang & Lixin Sun

  2. Key Laboratory of Structure-Based Drug Design & Discovery, Ministry of Education, Shenyang Pharmaceutical University, Wenhua Road 103, Shenyang, Liaoning Province, People’s Republic of China

    Yiheng Wu

  3. Center for Drug Delivery Systems, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, Haike Road 501, Pudong, Shanghai, People’s Republic of China

    Caifen Wang, Tao Guo & Jiwen Zhang

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  1. Hanyue Li
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  2. Chengcheng Li
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  5. Tao Guo
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Correspondence to Lixin Sun.

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Li, H., Li, C., Wu, Y. et al. Cross-linked γ-cyclodextrin metal-organic framework—a new stationary phase for the separations of benzene series and polycyclic aromatic hydrocarbons. Microchim Acta 188, 245 (2021). https://doi.org/10.1007/s00604-021-04899-7

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  • DOI: https://doi.org/10.1007/s00604-021-04899-7

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