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Chiral Recognition and Enantioseparation

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Analytical Chemistry".

Deadline for manuscript submissions: closed (30 June 2023) | Viewed by 5004

Special Issue Editor


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Guest Editor
Department of Chemistry, Sant Longowal Institute of Engineering and Technology, Longowal, India
Interests: organic synthesis; green chemistry; food chemistry; catalysis

Special Issue Information

Dear Colleagues,

Chiral recognition has received considerable attention in different aspects of chemistry, life sciences, and separation sciences. In the natural world, most bioactive substances exhibit chirality; thus, chirality influences biological, chemical, and clinical research. Therefore, to explain chiral recognition by a chiral selector (chiral sensor), new effective methods have been explored. In recent years, various media, materials, and enantioselective surfaces have been proposed to obtain chiral sensing with different enantioselectivity degrees as well as transduction modes. The discrimination and detection of chiral molecules have been achieved through different transduction principles such as QCM, electrochemical, and optical measurements.

The healthcare and pharmaceutical industries focus on the pure enantiomer of a compound as a racemic species can possess different pharmacological activities; therefore, enantioseparation is an important task in the food, pharmaceutical, drug discovery, and agricultural industries. In this research area, there are still some challenges to overcome. Enantioseparation occurs only in the chiral environment; thus, a pure and convenient chiral selector is required to show diastereomeric interactions. To obtain high selectivity for one enantiomer, high-specificity chiral selectors have been designed. Commonly, the determination and separation of enantiomers have been achieved through chromatographic methods. However, in chromatographic applications, an inadequate chiral selector may provide uncertainties. To achieve enantioseparations through capillary electrophoresis and chromatography, the formation of the transient diastereomeric complex between enantiomers of an analyte and a chiral selector is the basic requirement. In recent decades, several chiral sensors and techniques have been proposed. In the last 10 years, more than 1000 related articles have been published. In the separation sciences, a variety of chiral selectors based on cyclodextrins, macrocyclic glycopeptides, cyclofructan derivatives, ion exchangers, polysaccharide derivatives, ligand exchangers, polymers, proteins, crown ethers, aptamers, Pirkle-type selectors, ionic liquids, micelle-forming agents, and calixarenes have been explored. Chiral recognition by chiral selectors has been determined through different analytical techniques, such as NMR spectroscopy, vibrational circular dichroism spectroscopy, molecular modeling, and circular dichroism. In addition, the HPLC technique has also been used to study the structure–separation relationship.

In view of the above-discussed importance of this topic, a Special Issue of the journal Molecules is being planned on the topic of Chiral Recognition and Enantioseparation.

Prof. Dr. Harish Kumar Chopra
Guest Editor

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Keywords

  • chiral recognition
  • enantioseparation
  • analytical methods
  • chiral selector
  • chirality
  • enantioselectivity
  • asymmetry
  • separation methods

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Published Papers (2 papers)

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Research

14 pages, 3697 KiB  
Article
Preparation of Chiral Porous Organic Cage Clicked Chiral Stationary Phase for HPLC Enantioseparation
by Ya-Nan Gong, Qi-Yu Ma, Ying Wang, Jun-Hui Zhang, You-Ping Zhang, Rui-Xue Liang, Bang-Jin Wang, Sheng-Ming Xie and Li-Ming Yuan
Molecules 2023, 28(7), 3235; https://doi.org/10.3390/molecules28073235 - 4 Apr 2023
Cited by 5 | Viewed by 2254
Abstract
Porous organic cages (POCs) are a new subclass of porous materials, which are constructed from discrete cage molecules with permanent cavities via weak intermolecular forces. In this study, a novel chiral stationary phase (CSP) has been prepared by chemically binding a [4 + [...] Read more.
Porous organic cages (POCs) are a new subclass of porous materials, which are constructed from discrete cage molecules with permanent cavities via weak intermolecular forces. In this study, a novel chiral stationary phase (CSP) has been prepared by chemically binding a [4 + 6]-type chiral POC (C120H96N12O4) with thiol-functionalized silica gel using a thiol-ene click reaction and applied to HPLC separations. The column packed with this CSP presented good separation capability for chiral compounds and positional isomers. Thirteen racemates have been enantioseparated on this column, including alcohols, diols, ketones, amines, epoxides, and organic acids. Upon comparison with a previously reported chiral POC NC1-R-based column, commercial Chiralpak AD-H, and Chiralcel OD-H columns, this column is complementary to these three columns in terms of its enantiomeric separation; and can also separate some racemic compounds that cannot be separated by the three columns. In addition, eight positional isomers (iodoaniline, bromoaniline, chloroaniline, dibromobenzene, dichlorobenzene, toluidine, nitrobromobenzene, and nitroaniline) have also been separated. The influences of the injection weight and column temperature on separation have been explored. After the column has undergone multiple injections, the relative standard deviations (RSDs) for the retention time and selectivity were below 1.0 and 1.5%, respectively, indicating the good reproducibility and stability of the column for separation. This work demonstrates that POCs are promising materials for HPLC separation. Full article
(This article belongs to the Special Issue Chiral Recognition and Enantioseparation)
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12 pages, 6185 KiB  
Article
Chiral Covalent-Organic Framework MDI-β-CD-Modified COF@SiO2 Core–Shell Composite for HPLC Enantioseparation
by Xiaoyan Ran, Ping Guo, Caifang Liu, Yulan Zhu, Cheng Liu, Bangjin Wang, Junhui Zhang, Shengming Xie and Liming Yuan
Molecules 2023, 28(2), 662; https://doi.org/10.3390/molecules28020662 - 9 Jan 2023
Cited by 10 | Viewed by 2311
Abstract
The chiral covalent-organic framework (CCOF) is a new kind of chiral porous material, which has been broadly applied in many fields owing to its high porosity, regular pores, and structural adjustability. However, conventional CCOF particles have the characteristics of irregular morphology and inhomogeneous [...] Read more.
The chiral covalent-organic framework (CCOF) is a new kind of chiral porous material, which has been broadly applied in many fields owing to its high porosity, regular pores, and structural adjustability. However, conventional CCOF particles have the characteristics of irregular morphology and inhomogeneous particle size distribution, which lead to difficulties in fabricating chromatographic columns and high column backpressure when the pure CCOFs particles are directly used as the HPLC stationary phases. Herein, we used an in situ growth strategy to prepare core–shell composite by immobilizing MDI-β-CD-modified COF on the surface of SiO2-NH2. The synthesized MDI-β-CD-modified COF@SiO2 was utilized as a novel chiral stationary phase (CSP) to explore its enantiomeric-separation performance in HPLC. The separation of racemates and positional isomers on MDI-β-CD-modified COF@SiO2-packed column (column A) utilizing n-hexane/isopropanol as the mobile phase was investigated. The results demonstrated that column A displayed remarkable separation ability for racemic compounds and positional isomers with good reproducibility and stability. By comparing the MDI-β-CD-modified COF@SiO2-packed column (column A) with commercial Chiralpak AD-H column and the previously reported β-CD-COF@SiO2-packed column (column B), the chiral recognition ability of column A can be complementary to that of Chiralpak AD-H column and column B. The relative standard deviations (RSDs) of the retention time and peak area for the separation of 1,2-bis(4-fluorophenyl)-2-hydroxyethanone were 0.28% and 0.79%, respectively. Hence, the synthesis of CCOFs@SiO2 core–shell composites as the CSPs for chromatographic separation has significant research potential and application prospects. Full article
(This article belongs to the Special Issue Chiral Recognition and Enantioseparation)
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