Abstract
Porous ionic polymers have demonstrated great potential for high-performance separation by the merits of their unique molecular recognition, but the preparation of anion-functionalized ionic polymers for the separation of bioactive molecules with highly similar structures remains a challenge. Here, through the facile Friedel-Crafts alkylation between benzylimidazole ionic liquids (ILs) and crosslinkers, several anion-functionalized hypercrosslinked ionic porous polymers (HIPs) are reported, which are well decorated with strongly basic carboxylate anions as well as feature tubular morphology and excellent thermal stability. High adsorption capacity (103.6 mg g−1 for tocopherol homologues) and selectivity (Sβγ/α, 4.26; Sδ/α, 3.19) for bioactive compounds with high structural similarity have been realized, superior to those of commercial adsorbents, hypercrosslinked polymer without ILs, and HIPs with common ILs. This study manifests a new synthetic strategy and rational molecular design for functionalized adsorbents, as well as offers new opportunities to enable high-performance separation.
摘要
多孔离子聚合物由于其独特的分子识别能力在高效分离中表现出巨大的潜力, 但制备阴离子功能化离子聚合物用于结构高度相似生物活性物质分离仍然具有挑战. 本文通过苄基咪唑离子液体与交联剂发生简易的Friedel-Crafts烷基化反应, 报道了一类具有强碱羧酸阴离子功能化、管状形貌和高热稳定性的超交联离子多孔聚合物(HIPs).实现了对结构高度相似的生物活性化合物的高容量(生育酚同系物:103.6 mg g−1)和高选择性(Sβγ/α, 4.26; Sδ/α, 3.19)吸附分离, 其性能优于商业吸附剂、不含离子液体的超交联聚合物和含常规离子液体的HIPs. 本研究展示了功能化吸附剂新的合成策略和合理的分子设计, 为实现高效分离提供了新的机会.
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Acknowledgements
This work was financially supported by the National Natural Science Foundation of China (21908191, 21938011 and 21890764), Zhejiang Provincial Natural Science Foundation of China (LR20B060001), and the Entrepreneur Team Introduction Program of Zhejiang (2019R01006).
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Author contributions Xing H, Suo X and Huang Y proposed the idea; Suo X and Huang Y designed the samples and performed the experiments; Li Z and Pan H did the measurements; Suo X and Huang Y wrote the paper with support from Xing H and Cui X. All authors contributed to the general discussion.
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Supplementary information Experimental details and supporting data are available in the online version of the paper.
Xian Suo received her PhD degree in chemical engineering and technology from Zhejiang University in 2018. She was a postdoctoral fellow at Zhejiang University from 2018 to 2020, focusing on the design and synthesis of ultramicroporous materials for adsorptive separation. In the meanwhile, she has been working as a postdoctoral researcher in Prof. Sheng Dai’s group at the University of Tennessee, Knoxville (UTK) since 2019. She focuses on the development of functional ionic materials and their applications in advanced separation.
Yuqi Huang obtained his master’s degree in pharmaceutical engineering at the College of Chemical and Biological Engineering, Zhejiang University in 2019. His research interests focus on the design and synthesis of anionfunctionalized materials for the separation of hydrocarbons and natural active compounds.
Huabin Xing received his BSc degree in pharmaceutical engineering (2000) and MSc degree in chemical engineering (2003) from Zhejiang University, and a PhD degree in chemical engineering (2007) from Tsinghua University. Then he joined the College of Chemical and Biological Engineering, Zhejiang University, in 2007 as a postdoctoral fellow. He became a full professor in 2014, and currently serves as a Qiushi Distinguished Professor and dean of College of Chemical and Biological Engineering at Zhejiang University. His research interests focus on the preparation of functional materials for separation and energy storage. He has published over 150 journal articles, and was selected as the National Natural Science Foundation of China (NSFC) Distinguished Young Scholar and ACS I&EC 2017/2018 Class of Influential Researcher.
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Construction of Anion-functionalized Hypercrosslinked Ionic Porous Polymers for Efficient Separation of Bioactive Molecules
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Suo, X., Huang, Y., Li, Z. et al. Construction of anion-functionalized hypercrosslinked ionic porous polymers for efficient separation of bioactive molecules. Sci. China Mater. 65, 1068–1075 (2022). https://doi.org/10.1007/s40843-021-1845-3
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DOI: https://doi.org/10.1007/s40843-021-1845-3