A Chiral Porous Organic Polymer COP-1 Used As Stationary Phase for HPLC Enantioseparation Under Normal-phase and Reversed-phase Conditions

Overview

Journal Mikrochim Acta

Specialties Biotechnology
Chemistry

Date 2022 Aug 30

PMID 36042107

Authors

Yu-Ping Yang

Ji-Kai Chen

Ping Guo

Yan-Rui Lu

Cai-Fang Liu

Bang-Jin Wang

Jun-Hui Zhang

Sheng-Ming Xie

Li-Ming Yuan

Affiliations

Soon will be listed here.

Abstract

A spherical chiral porous organic polymer (POPs) COP-1 is synthesized by the Friedel-Crafts alkylation reaction of Boc-3-(4-biphenyl)-L-alanine (BBLA) and 4,4'-bis(chloromethyl)-1,1'-biphenyl (BCMBP), which was used as a novel chiral stationary phase (CSPs) for mixed-mode high-performance liquid chromatography (HPLC) enantioseparation. The racemic compounds were resolved in normal-phase liquid chromatography (NPLC) using n-hexane/isopropanol as mobile phase and reversed-phase liquid chromatography (RPLC) using methanol/water as mobile phase. The COP-1-packed column exhibited excellent separation performance toward various racemic compounds including alcohols, amines, ketones, esters, epoxy compounds, organic acids, and amino acids in NPLC and RPLC modes. The effects of analyte mass and column temperature on the separation efficiency of racemic compounds were investigated. In addition, the chiral resolution ability of the COP-1-packed column not only can be complementary in RPLC/NPLC modes but also exhibit a good chiral recognition complementarity with Chiralpak AD-H column and chiral porous organic cage (POC) NC1-R column. The relative standard deviations (RSD) (n = 5) of the retention time, resolution value, and peak area by repeated separation of 1-(4-chiorophenyl)ethanol are all below 3.0%. The COP-1 column shows high column efficiency (e.g., 17,320 plates m for 1-(4-chlorophenyl)ethanol on COP-1 column in NPLC), high enantioselectivity, and good reproducibility toward various racemates. This work demonstrates that chiral POPs microspheres are promising chiral materials for HPLC enantioseparation.

Citing Articles

Preparation of Chiral Porous Organic Cage Clicked Chiral Stationary Phase for HPLC Enantioseparation.

Gong Y, Ma Q, Wang Y, Zhang J, Zhang Y, Liang R Molecules. 2023; 28(7).

PMID: 37049997 PMC: 10096354. DOI: 10.3390/molecules28073235.

References

Tan L, Tan B . Hypercrosslinked porous polymer materials: design, synthesis, and applications. Chem Soc Rev. 2017; 46(11):3322-3356. DOI: 10.1039/c6cs00851h. View

Qian X, Wang B, Zhu Z, Sun H, Ren F, Mu P . Novel N-rich porous organic polymers with extremely high uptake for capture and reversible storage of volatile iodine. J Hazard Mater. 2017; 338:224-232. DOI: 10.1016/j.jhazmat.2017.05.041. View

Li X, Cui Y, Yang C . Covalent coupling fabrication of microporous organic network bonded capillary columns for gas chromatographic separation. Talanta. 2020; 224:121914. DOI: 10.1016/j.talanta.2020.121914. View

Yamashita H, Mori K, Kuwahara Y, Kamegawa T, Wen M, Verma P . Single-site and nano-confined photocatalysts designed in porous materials for environmental uses and solar fuels. Chem Soc Rev. 2018; 47(22):8072-8096. DOI: 10.1039/c8cs00341f. View

Navarro-Sanchez J, Argente-Garcia A, Moliner-Martinez Y, Roca-Sanjuan D, Antypov D, Campins-Falco P . Peptide Metal-Organic Frameworks for Enantioselective Separation of Chiral Drugs. J Am Chem Soc. 2017; 139(12):4294-4297. DOI: 10.1021/jacs.7b00280. View

Tan H, Chen Q, Chen T, Liu H . Effects of Rigid Conjugated Groups: Toward Improving Enantioseparation Performances of Chiral Porous Organic Polymers. ACS Appl Mater Interfaces. 2019; 11(40):37156-37162. DOI: 10.1021/acsami.9b14144. View

Zhou H, Chen J, Li H, Quan K, Zhang Y, Qiu H . Imidazolium ionic liquid-enhanced poly(quinine)-modified silica as a new multi-mode chromatographic stationary phase for separation of achiral and chiral compounds. Talanta. 2020; 211:120743. DOI: 10.1016/j.talanta.2020.120743. View

Wang Y, Chen J, Xiong L, Wang B, Xie S, Zhang J . Preparation of Novel Chiral Stationary Phases Based on the Chiral Porous Organic Cage by Thiol-ene Click Chemistry for Enantioseparation in HPLC. Anal Chem. 2022; 94(12):4961-4969. DOI: 10.1021/acs.analchem.1c03626. View

Fan C, Chen J, Li H, Quan K, Qiu H . Preparation and evaluation of two silica-based hydrophilic-hydrophobic and acid-base balanced stationary phases via in-situ surface polymerization. J Chromatogr A. 2022; 1667:462912. DOI: 10.1016/j.chroma.2022.462912. View

10.

Zhang K, Cai S, Yan Y, He Z, Lin H, Huang X . Construction of a hydrazone-linked chiral covalent organic framework-silica composite as the stationary phase for high performance liquid chromatography. J Chromatogr A. 2017; 1519:100-109. DOI: 10.1016/j.chroma.2017.09.007. View

11.

Yu Y, Xu N, Zhang J, Wang B, Xie S, Yuan L . Chiral Metal-Organic Framework d-His-ZIF-8@SiO Core-Shell Microspheres Used for HPLC Enantioseparations. ACS Appl Mater Interfaces. 2020; 12(14):16903-16911. DOI: 10.1021/acsami.0c01023. View

12.

Han X, Huang J, Yuan C, Liu Y, Cui Y . Chiral 3D Covalent Organic Frameworks for High Performance Liquid Chromatographic Enantioseparation. J Am Chem Soc. 2018; 140(3):892-895. DOI: 10.1021/jacs.7b12110. View

13.

Chen Y, Lu Z, Li G, Hu Y . β-Cyclodextrin porous polymers with three-dimensional chiral channels for separation of polar racemates. J Chromatogr A. 2020; 1626:461341. DOI: 10.1016/j.chroma.2020.461341. View