Preparation and Chiral Recognition Ability of Crystalline Cellulose Phenylcarbamate

Yu-Tong Zhang; Xiao Dai; En-Ting Deng; Li-Li Zhang; Ting Zheng; Jun Shen

doi:10.1007/s10118-026-3745-z

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Preparation and Chiral Recognition Ability of Crystalline Cellulose Phenylcarbamate

RESEARCH ARTICLE | Updated：2026-07-25

- Preparation and Chiral Recognition Ability of Crystalline Cellulose Phenylcarbamate
- Preparation and Chiral Recognition Ability of Crystalline Cellulose Phenylcarbamate
- Chinese Journal of Polymer Science 2026年44卷页码：1-8
- Affiliations：
  
  a.Research Institute of Urbanization and Urban Safety, School of Future Cities, University of Science and Technology Beijing, Beijing 100083, China
  b.College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, China
  c.Yangtze River Delta Carbon Fiber & Composite Innovation Center, Changzhou 213126, China
- Author bio：
  
  shenjun@ustb.edu.cn
- Funds：
  
  This work was financially supported by the National Key Research and Development Program of China (No. 2023YFB3711600), the Project of the Natural Science Foundation of Heilongjiang Province (No. LH 2023E063), and Fundamental Research Funds for Central Universities (No. 3072024XX1003).;The authors declare no interest conflict.The related data of this study is data that should not be shared, and can be obtained from the author for reasonable reasons. The author’s contact information: shenjun@ustb.edu.cn.
- DOI：10.1007/s10118-026-3745-z
  中图分类号：
- 收稿：2026-04-21，
  
  录用：2026-05-12，
  
  网络首发：2026-07-24，
  
  纸质出版：2026-06
- Accepted：
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Zhang, Y. T.; Dai, X.; Deng, E. T.; Zhang, L. L.; Zheng, T.; Shen, J. Preparation and chiral recognition ability of crystalline cellulose phenylcarbamate. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3745-z

Yu-Tong Zhang, Xiao Dai, En-Ting Deng, et al. Preparation and Chiral Recognition Ability of Crystalline Cellulose Phenylcarbamate[J/OL]. Chinese Journal of Polymer Science, 2026, 441-8.
Zhang, Y. T.; Dai, X.; Deng, E. T.; Zhang, L. L.; Zheng, T.; Shen, J. Preparation and chiral recognition ability of crystalline cellulose phenylcarbamate. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3745-z DOI：

Yu-Tong Zhang, Xiao Dai, En-Ting Deng, et al. Preparation and Chiral Recognition Ability of Crystalline Cellulose Phenylcarbamate[J/OL]. Chinese Journal of Polymer Science, 2026, 441-8. DOI： 10.1007/s10118-026-3745-z.

摘要

Abstract

As one of the most popular polysaccharide derivatives with high chiral recognition ability

cellulose tris(3

5-dimethylphenylcarbamate) (CDMPC) has been successfully applied in the enantioseparation of a wide range of racemates for various purposes. However

the derivative is usually synthesized with an amorphous structure

and its effect on enantioseparation ability remains obscure. To obtain a better understanding of the correlation between its structure and enantioseparation abil

ity

in this study

CDMPC derivatives with crystalline and amorphous structures were prepared through carbamoylation followed by anti-solvent precipitation. Their chiral recognition abilities were evaluated using high-performance liquid chromatography (HPLC) with chiral stationary phases (CSPs). Interestingly

the ordered arrangement of the helical polymer chains of CDMPC was effectively induced by the aromatic solvent after derivatization

forming a crystalline derivative (

CDMPC

) with a uniform and compact worm-like morphology

whereas the amorphous derivative (

CDMPC

) was obtained by regular treatment with a polar alcoholic solvent. The

CDMPC

–based CSP exhibited higher chiral recognition abilities with much shorter retention times for most racemates in this study

compared to the

CDMPC

–based CSP. In particular

flavanone (

Rac

)

an important chiral drug with anti-inflammatory

anti-tumor

and cardiovascular protective activities

was even better resolved with higher enantioselectivity on crystalline

CDMPC

than on Chiralcel OD

a commercialized chiral column based on CDMPC. This indicates that the crystalline ordered arrangement played a critical role in the chiral recognition ability of the cellulose derivative.

关键词

Keywords

references

[Subramanian, G., in Chiral separation techniques: A practical approach, Wiley, Weinheim, 2008 , p. 618

[Carreira, E.M.; Yamamoto, H., in Separations and Analysis, Comprehensive Chirality, Vol. 8, Elsevier, Amsterdam 2012 , p. 54.

Okamoto, Y. Chiral polymers for the resolution of enantiomers. J. Polym. Sci. Part A: Polym. Chem. 2009 , 47 , 1731−1739..

Gao, R. T.; Li, S. Y.; Liu, N.; Liu, B. H.; Wu, Z. Q. Helical polymer: From precise synthesis to structures and functions. Chem. Rev. 2026 , 126 , 297−403..

Gao, R. T.; Duan, B. H.; Zong, Y.; Liu, N.; Wu, Z. Q. Controlled isocyanide pol ymerization:towards helical polymers with chiral functions. Prog. Polym. Sci. 2026 , 172 , 102056..

Chankvetadze, B. Recent trends in preparation, investigation, and application of polysaccharide-based chiral stationary phases for separation of enantiomers in high-performance liquid chromatography. Trends Anal. Chem. 2020 , 122 , 115709..

Yashima, E.; Okamoto, Y. Chiral discrimination of polysaccharide derivatives. Bull. Chem. Soc. Jpn. 1995 , 68 , 3289−3307..

Okamoto, Y.; Kawashima, M.; Yamamoto, K.; Hatada, K. Useful chiral packing materials for high-performance liquid chromatographic resolution. Cellulose triacetate and tribenzoate were coated onto a macroporous silica gel. Chem. Lett. 2006 , 13 , 739−742..

Okamoto Y.; Kaida Y. Resolution by high-performance liquid chromatography using polysaccharide carbamates and benzoates as chiral stationary phases. J. Chromatogr. A 1994 , 666 , 403−419..

Shen, J.; Okamoto, Y. Efficient separation of enantiomers using stereoregular chiral polymer s. Chem. Rev. 2016 , 116 , 1094−1138..

Ikai, T.; Okamoto, Y. Structural control of polysaccharide derivatives for efficient separation of enantiomers by chromatography. Chem. Rev. 2009 , 109 , 6077−6101..

Chankvetadze, B. Recent developments in polysaccharide-based chiral stationary phases for liquid-phase separation of enantiomers. J. Chromatogr. A 2012 , 1269 , 26−51..

Shen, J.; Ikai, T.; Okamoto, Y. Synthesis and application of immobilized polysaccharide-based chiral stationary phases for enantioseparation by high-performance liquid chromatography. J. Chromatogr. A 2014 , 1363 , 51−61..

Shen, J.; Wang, F.; Bi, W. Y.; Liu, B.; Liu, S. Y.; Okamoto, Y. Synthesis of cellulose carbamates bearing regioselective substituents at the 2,3-and 6-positions for efficient chromatographic enantioseparation. J. Chromatogr. A 2018 , 1572 , 54−61..

Wang, F.; Wang, Y. Q.; Min, Y. X.; Li, J. Q.; Zhang, L. L.; Zheng, T.; Shen, J.; Okamoto, Y. Preparation of cellulose derivative bearing bulky 4-(2 -benzothienyl)phenylcarbamate substituents as chiral stationary phase for enantioseparation. Chirality 2022 , 34 , 701−710..

Okamoto, Y.; Yashima, E. Polysaccharide derivatives for chromatographic separation of enantiomers. Angew. Chem. Int. Ed. 1998 , 37 , 1020−1043..

Peluso, P.; Chankvetadze, B. Recognition in the domain of molecular chirality: from noncovalent interactions to separation of enantiomers. Chem. Rev. 2022 , 122 , 13235−13400..

Ichida, A.; Shibata, T.; Okamoto, I.; Yuki, Y.; Namikoshi, H.; Toga, Y. Resolution of enantiomers by high-performance liquid chromatography (HPLC) on cellulose derivatives. Chromatographia 1984 , 19 , 280−284..

[Li, G., Dai X., Min Y. X., Yu C., Ikai T., Zhang L. L., Shen J., Okamoto Y, Cellulose phenylcarbamate-derived hybrid bead-type chiral packing materials for efficient chiral recognition. Cellulose 2021 , 28 , 347−358..

[Yashima, E.; Iida, H.; Okamoto, Y. Enantiomeric differentiation using synthetic helical polymers. Topics Curr. Chem. Schurig . 2013 , 340 , 41−72..

Ikai, T.; Yamamoto, C.; Kamigaito, M.; Okamoto, Y. Organic-inorganic hybrid materials for efficient enantioseparation using cellulose 3,5-dimethylphenylcarbamate and tetraethyl orthosilicate. Chem. Asian. J. 2008 , 3 , 1494−1499..

Okamoto, Y.; Kawashima, M.; Hatada, K. Chromatographic Resolution. XI. Controlled chiral recognition of cellulose triphenylcarbamate derivatives supported on silica gel. J. Chromatogr. A. 1986 , 363 , 173−186..

Okamoto, Y.; Aburatani, R.; Hatada, K. Chromatographic optical resolution on 3,5-disubstituted phenylcarbamates of cellulose and amylose. Bull. Chem. Soc. Jpn. 2006 , 63 , 955−957..

Chankvetadze, B.; Yashima, E.; Okamoto, Y. Chloromethylphenylcarbamate derivatives of cellulose as chiral stationary phases for high-performance liquid chromatography. Chem. J. Chromatogr. A 1994 , 690 , 39−49..

Kubota, T.; Yamamoto, C.; Okamoto , Y. Tris(cyclohexylcarbamate) of cellulose and amylose as potential chiral stationary phases for high-performance liquid chromatography and thin-layer chromatography. J. Am. Chem. Soc. 2000 , 122 , 4056−4059..

Wang, F.; Wang, W. Q.; Wang, Y. Q.; Zheng, W.; Zheng, T.; Zhang, L. L.; Okamoto, Y.; Shen, J. Synthesis of amylose and cellulose derivatives bearing bulky pendants for highly efficient chiral fluorescent sensing. Carbohydr. Polym. 2023 , 311 , 120769..

Gong, W.; Chen, Z. J.; Dong, J. Q.; Liu, Y.; Cui, Y. Chiral metal-organic framework. Chem. Rev. 2022 , 122 , 9078−9144..

Lohse, M. S.; Bein, T. Covalent organic framework: structures, synthesis, and applications. Adv. Funct. Mater. 2018 , 28 , 1705553..

Chen, L.; Reiss, P. S.; Chong, S. Y.; Holden, D.; Jelfs, K. E.; Hasell, T.; Little, M.A.; Kewley, A.; Briggs, M. E.; Stephenson, A.; Thomas, K. M.; Armstrong, J. A.; Bell, J.; Busto, J.; Noel, R.; Liu, J.; Strachan, D. M.; Thallapally, P. K.; Cooper, A. I. Separation of rare gases and chiral molecules by selective binding in porous organic cages. Nat. Mater. 2014 , 13 , 954−960..

Zhang, J. H.; Xie, S. M.; Wang, B. J.; He, P. G.; Yuan, L. M. Highly selective separation of enantiomers using a chiral porous organic cage. J. Chromatogr. A 2015 , 1426 , 174−182..

Wang, F. M. J.; He, K. Q.; Wang, R. X.; Ma, H. Y.; Marriott, P. J.; Hill, M. R.; Simon, G. P.; Holl, M. M. B.; Wang, H. T. Homochiral porous organic cage-polymer membranes for enantioselective resolution. Adv. Mater. 2024 , 36 , 2400709..

Wang, F. M. J.; Lu, Y. Z. H.; He, K. Q.; Marriott, P. J.; Hill, M. R.; Wang, H. T. Preparation of COF-based membranes via chiral induction for efficient enantioselective resolution. Adv. Membr. 2025 , 5 , 100113..

Yuan, C.; Fu, S. G.; Yang, K. W.; Hou, B.; Liu, Y.; Jiang, J. W.; Cui,Y. Crystalline C-C and C=C bond-linked chiral covalent organic frameworks. J. Am. Chem. Soc. 2021 , 143 , 369−381..

Ma, H. C.; Jiang, H. P.; Yao, Z. H.; Tan, J. F.; Xing, Y. Y.; Chen, G. J.; Dong, Y. B. Binaphthyl-based chiral covalent organic frameworks for chiral drug separation. Chem. Commun. 2024 , 60 , 10580−10583..

Wu, J. Q.; Li, L. Y.; Cao, L. Q.; Liu, X.; Li, R. J.; Ji, Y. B. Chirality-controlled mercapto-β-cyclodextrin covalent organic frameworks for selective adsorption and chromatographic enantioseparation. Acs. Appl. Mater. Inter. 2023 , 15 , 27214−27222..

Ma, J. Q.; Huang, W. Y.; Huang, X. Y.; Yang, N.; Gong, J.; Xie, Z. Y.; Li, G. K.; Liao, Q. F.; Chen, Y. L. Construction of dual-chiral covalent organic frameworks for enantioselective separation. J. Chromatogr. A. 2024 , 1728 , 465014..

Zhang, S. N.; Zheng, Y. L.; An, H. D.; Aguila, B.; Yang, C. X.; Dong, Y. Y.; Xie, W.; Cheng, P.; Zhang, Z. J.; Chen, Y.; Ma, S. Q. Covalent organic frameworks with chirality enriched by biomolecules for efficient chiral separation. Angew. Chem. Int. Edit. 2018 , 57 , 16754−16759..

[Gao, R. T.; Kang, S. M.; Zong, Y.; Li, T. T.; Liu, N.; Wu, Z. Q. Polymer frameworks with controllable pore size and chirality for enantioseparation of racemates with different sizes and chiralities. CCS Chem . 2026 , DOI: 10.31635/ccschem.026.202506825..

Gao, R. T.; Yu, J. X.; Ti, Q. H.; Mo, M. Y.; Liu, N.; Wu, Z. Q. Precise synthesis of racemate-based one-handed helical polymers as recyclable homogeneous chiral catalysts for multiple asymmetric reactions. J. Am. Chem. Soc. 2025 , 147 , 37521−37533..

Koller, H.; Rimbck, K. H.; Mannschreck, A. High-pressure liquid chromatography on triacetylcellulose. Characterization of sorbent for separation of enantiomers. J. Chromatogr. 1983 , 282 , 89−94..

Kaida, Y.; Okamoto, Y. Optical resolution of regioselectively carbamoylated cellulose and amylose with 3,5-dimethylphenyl and 3,5-dichlorophenyl isocyanates. Chem. Bull. Chem. Soc. Jpn. 2006 , 66 , 2225−2232..

Yamamoto, C.; Yashima, E.; Okamoto, Y. Computational studies on the chiral discrimination mechanism of phenylcarbamate derivatives of cellulose. Bull. Chem. Soc. Jpn. 2004 , 72 , 1815−1825..

[Chankvetadze, B.; Chankvetadze, L.; Sidamonidze, S.; Kasashima, E.; Yashima, E.; Okamoto, Y. 3-Fluoro-, 3-chloro-, and 3-bromo-5-methylphenylcarbamates of cellulose and amylose as chiral stationary phases for high-performance liquid chromatographic enantioseparation. J. Chromatogr. A . 1997 , 787 , 67−77..

Sharma, P. R.; Rajamohanan, P. R.; Varma, A. J. Supramolecular transitions in native cellulose I during progressive oxidation reaction leading to quasi-spherical nanoparticles of 6-carboxycellulose. Carbohydr. Polym. 2014 , 113 , 615−623..

Kasat, R. B.; Wang, N. H. L.; Franses, E. I. Effects of backbone and side chain on the molecular environments of chiral cavities in polysaccharide-based biopolymers. Biomacromolecules 2007 , 8 , 1676−1685..

Chen, X. M.; Yamamoto, C.; Okamoto, Y. Influence of vinyl monomers and temperature on immobilization of cellulose 3,5-dimethylphenylcarbamate onto silica gel as chiral stationary phases for high-performance liquid chromatography. Chem. J. Chromatogr. A. 2006 , 1104 , 62−68..

Yan, Y. L.; Guo, D.; Wu, J. L.; Tang, X. H.; Luo, J. J.; Li, S. Q.; Fan, J.; Zheng, S. R.; Zhang, W. G.; Cai, S. L. Fabrication of cellulose derivative-coated spherical covalent organic frameworks as chiral stationary phases for high-performance liquid chromatographic enantioseparation. J. Chromatogr. A 2022 , 1675 , 463155..

Asztemborska, M.; Zukowski, J. Determination of diastereomerization barrier of some flavanones by high-performance liquid chromatography. J. Chromatogr. A 2006 , 1134 , 95−100..

Gao, R. T.; Zong, Y.; Li, T. T.; Liu, N.; Wu, Z. Q. Three-dimensional supramolecular polymer frameworks with precisely tunable and large apertures for enzyme encapsulation. Chinese Chem. Lett. 2026 , 1 , 361−367..

Liu, B. H.; Zong, Y.; Liu, N.; Wu, Z. Q. Advances in self-assembly-based circularly polarized luminescent materials. Sci. China Chem. 2024 , 67 , 3247−3257..

[Gao, R. T.; Ma, Y. Y.; Xu, Y.; Wang, J.; Liu, N.; Liu, F.; Wu, Z. Q. Eugenol-based optically active helical polymers: From controlled synthesis to post-polymerization modification and chiral recognition. Sci. China Mater . 2026 , DOI: 10.1007/s40843-025-3913-3..

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