Incorporating chiral molecules in the covalent organic frameworks (COFs) with uniformly ordered pores results in chiral COFs, which have been highly promising candidates for enantioseparation. Herein, a homochiral COF nanochannel membrane is reported by introducing chiral centers (L-phenylalanine methyl ester) into one of the organic ligands for the enantioseparation of chiral amino acids. The separation results show that the D-isomer is preferentially transported through the porous membrane channel. This composite membrane exhibits excellent selectivity for racemic phenylalanine with the highest enantiomeric excess value of up to 99.4 %. The adsorption and molecular modeling studies substantiate the experiment results by showing higher bonding affinity towards D-isomer over L-isomer. The excellent enantioselective gating performance unveils the porous COF skeleton with chiral selectors and the size-matching synergy for stereoselective interactions with chiral isomers.
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http://dx.doi.org/10.1002/anie.202417088 | DOI Listing |
Adv Mater
December 2024
School of Chemistry and Chemical Engineering and State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai, 200240, China.
Asymmetric catalysis is essential for addressing the increasing demand for enantiopure compounds. Recent advances in reticular chemistry have demonstrated that metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) possess highly regular porous architectures, exceptional tunability, and the ability to incorporate chiral functionalities through their open channels or cavities. These characteristics make them highly effective and enantioselective catalysts for a wide range of asymmetric transformations.
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
College of Chemistry and Molecular Engineering, Beijing National Laboratory for Molecular Sciences, Peking University, Beijing 100871, China.
The crystallization of organic polymers is often hindered by chiral units, hence resulting in chiral organic polymers typically existing as amorphous or partially crystalline phases such as natural rubber and cellulose. Similarly, as an emerging crystalline chiral polymer, chiral covalent organic frameworks (COFs) also inevitably face a delicate balance between chiral units and crystallization, limiting their production and applications in separation, catalysis, and optics. Here, we present a general strategy for producing a series of conformational chiral COFs with high crystallinity through breaking the meso conformation of achiral COFs.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2024
Key Laboratory of Biopharmaceutical Preparation and Delivery, State Key Laboratory of Biochemical Engineering, Chinese Academy of Sciences, Beijing, 100190, China.
Chiral separation plays a pivotal role in both practical applications and industrial productions. However, traditional chiral stationary phases (CSPs) exhibit inherent instability in alkaline environments, presenting a significant challenge despite their importance. Herein, basophilic alcalase is creatively developed to fabricate ultrastable protein-based CSPs that can efficiently work under alkaline conditions.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2024
College of Chemistry, Chemical Engineering and Materials Science, Jiangsu Key Laboratory of Advanced Functional Polymer Materials, & Suzhou key Laboratory of Macromolecular Design and Precision Synthesis, Soochow University, Suzhou, 215123, P.R. China.
Incorporating chiral molecules in the covalent organic frameworks (COFs) with uniformly ordered pores results in chiral COFs, which have been highly promising candidates for enantioseparation. Herein, a homochiral COF nanochannel membrane is reported by introducing chiral centers (L-phenylalanine methyl ester) into one of the organic ligands for the enantioseparation of chiral amino acids. The separation results show that the D-isomer is preferentially transported through the porous membrane channel.
View Article and Find Full Text PDFMolecules
October 2024
College of Chemistry and Environmental Science, Qujing Normal University, Qujing 655011, China.
The use of light energy to drive asymmetric organic transformations to produce high-value-added organic compounds is attracting increasing interest as a sustainable strategy for solving environmental problems and addressing the energy crisis. Chiral covalent organic frameworks (COFs), as porous crystalline chiral materials, have become an important platform on which to explore new chiral photocatalytic materials due to their precise tunability, chiral structure, and function. This review highlights recent research progress on chiral COFs and their crystalline composites, evaluating their application as catalysts in asymmetric photocatalytic organic transformations in terms of their structure.
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