Preparation of Polypseudorotaxane Composite Membrane and Its Application in Separation Field

doi:10.6023/A25030085

Abstract

The polypseudorotaxane (PPR) composite membrane exhibits unique stimuli-responsive properties and excellent functional extensibility, demonstrating significant practical application value, making them promising candidates for smart materials in environmental management, biomedical engineering and next-generation energy storage solutions. This study presents a systematic approach to design and fabricate advanced PPR composite membrane with tailored structures and desired performances. Firstly, a block-structured PPR was constructed by threading 1,4-diethoxy pillar[5]arene (DEP5A) macrocycles onto a triblock copolymer backbone of polycaprolactone block polytetrahydrofuran block polycaprolactone (PCL-b-PTHF-b-PCL) via host-guest interactions. Subsequently, through systematic optimization of the electrospraying parameters including polymer concentration, pillararene content, ambient humidity, and solvent selection, we successfully fabricated PPR wrinkled microsphere membrane with uniform surface morphology, strong hydrophobicity, and responsiveness to the competitive guest molecule 1,4-dibromobutane (DBrBu). To further enhance functionality, we developed composite membrane composed of PPR microspheres and polystyrene (PS) fibers by combining electrospinning and electrospraying techniques. The microsphere/fiber composite architecture provides abundant adsorption sites for organic pollutants, enabling the membrane to achieve remarkable performance in aqueous dye adsorption and separation experiments. The structural characteristics and performance advantages of composite membrane were systematically investigated through scanning electron microscopy, contact angle measurements, and UV-vis spectroscopy. The stimuli-responsive behavior was attributed to the host-guest interaction between DEP5A and the polymer chains, while the enhanced separation efficiency originated from the synergistic effects of the microsphere-fiber composite architecture. This research presents a novel strategy for the investigation and development of smart membrane. The advanced membrane-making technology opens up new possibilities for creating multifunctional separation membranes, smart coatings, and environmental remediation materials.

Key words: pillararene, polypseudorotaxane, electrospraying, electrospinning, composite membrane

Cite this article

Kexin Zhuo, Qiwei Ding, Weixin Mou, Yikai Yan, Jianzhuang Chen, Shaoliang Lin. Preparation of Polypseudorotaxane Composite Membrane and Its Application in Separation Field[J]. Acta Chimica Sinica, 2025, 83(6): 602-607.

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Fig. & Tab. 6

Figure 1. The construction of block structured PPR, its thermo and competitive guest response processes, and the schematic diagram of the process of preparing PPR membranes by electrospraying

Figure 2. 1H NMR spectra (600 MHz, CDCl3, 20 ℃) of PCL-b- PTHF-b-PCL (10 mg•mL-1) upon the addition of DEP5A. The enlarged view reveals the shifts of H4 in PCL block

Figure 3. Schematic illustration of competitive guest responsing experiment on PPR membrane

Figure 4. SEM images of PPR membranes soaked in competitive guests for different times (a1) 0 s, (b1) 10 min. (a2), (b2) are enlarged views of (a1), (b1), respectively. The insets (a1), (b1) are contact angle data

Figure 5. The process diagram of preparing PPR/PS composite membranes by electrospinning and electrospraying

Figure 6. Comparative photographs of the solution color and film before and after filtration of Rhodamine-containing solution using membranes. (a) PS membrane; (b) PPR/PS composite membrane; (c) UV-vis absorption spectra of the Rhodamine-containing solution and the solutions filtered through PS membrane and PPR/PS composite membrane

References 27

[1]	Kafle, S. R.; Adhikari, S.; Shrestha, R.; Ban, S.; Khatiwada, G.; Gaire, P.; Tuladhar, N.; Jiang, G.; Tiwari, A. Water Sci. Technol. 2024, 89, 2290.
[2]	Liang, B.; He, X.; Hou, J.; Li, L.; Tang, Z. Adv. Mater. 2018, 31, 1806090.
[3]	Bera, S. P.; Godhaniya, M.; Kothari, C. J. Basic Microb. 2021, 62, 245.
[4]	Zhang, M.; Yan, X.; Huang, F.; Niu, Z.; Gibson, H. W. Acc. Chem. Res. 2014, 47, 1995.
[5]	Xiao, T.; Zhou, L.; Sun, X.-Q.; Huang, F.; Lin, C.; Wang, L. Chinese Chem. Lett. 2020, 31, 1.
[6]	Wu, Y.; Shangguan, L.; Li, Q.; Cao, J.; Liu, Y.; Wang, Z.; Zhu, T.; Wang, F.; Huang, F. Angew. Chem., Int. Ed. 2021, 60, 19997.
[7]	Lu, F.; Chen, Y.; Fu, B.; Chen, S.; Wang, L. Chin. Chem. Lett. 2022, 33, 5111.
[8]	Li, J.; Wang, H.; Liu, B.; Chen, J.; Gu, J.; Lin, S. Adv. Funct. Mater. 2022, 32, 2201851.
[9]	Chen, L.; Liu, Y.; You, W.; Wang, J.; He, Z.; Mei, H.; Yang, X.; Yu, W.; Li, G.; Huang, F. Angew. Chem., Int. Ed. 2025, 64, e202417713.
[10]	Cheng, L.; Wang, W.; Bai, R.; You, W.; Liang, Y.; Yan, Z.; Zhang, R.; Yan, X.; Yu, W. Angew. Chem., Int. Ed. 2025, 64, e202422104.
[11]	Chen, J.; Li, N.; Gao, Y.; Sun, F.; He, J.; Li, Y. Soft Matter 2015, 11, 7835.
[12]	Zhang, Y. M.; Liu, Y. H.; Liu, Y. Adv. Mater. 2019, 32, 1806158.
[13]	Chen, L.; Sheng, X.; Li, G.; Huang, F. Chem. Soc. Rev. 2022, 51, 7046.
[14]	Wang, C.; Gao, B.; Xue, K.; Wang, W.; Zhao, J.; Bai, R.; Yun, T.; Fan, Z.; Yang, M.; Zhang, Z.; Zhang, Z.; Yan, X. Sci. Adv. 2025, 11, eadt8262.
[15]	Yin, X. X.; Li, J. J.; Zhuo, K. X.; Mou, W. X.; Huang, L. L.; Chen, J. Z.; Lin, S. L. Acta Chim. Sinica 2024, 82, 790 (in Chinese).
	(尹晓璇, 李进杰, 禚可欣, 牟蔚鑫, 黄灵丽, 陈健壮, 林绍梁, 化学学报, 2024, 82, 790.) doi: 10.6023/A24040123
[16]	Dong, J. H.; Li, J. J.; Wang, H.; Liu, B. X.; Peng, B.; Chen, J. Z.; Lin, S. L. Acta Chim. Sinica 2021, 79, 803 (in Chinese).
	(董锦辉, 李进杰, 王赫, 刘彬秀, 彭博, 陈健壮, 林绍梁, 化学学报, 2021, 79, 803.) doi: 10.6023/A21030105
[17]	Li, J.; Dong, J.; Cui, K.; Wang, H.; Sun, Y.; Yao, Y.; Chen, J.; Gu, J.; Lin, S. J. Mater. Chem. A 2020, 8, 10917.
[18]	Li, J.; Dong, J.; Wang, H.; Yang, X.; Chen, J.; Gu, J.; Lin, S. Adv. Mater. Interfaces 2021, 8, 2101627.
[19]	Yang, W.; Yang, C.; Jing, G.; Wang, S.; Li, J.; Zhang, X.; Liu, P.; Yu, N. AIP Adv. 2024, 14, 090701.
[20]	Huang, J. J.; Tian, Y.; Chen, L.; Liao, Y.; Tian, M.; You, X.; Wang, R. Environ. Sci. Technol. 2020, 54, 7611.
[21]	Si, Y.; Yang, J.; Wang, D.; Shi, S.; Zhi, C.; Huang, K.; Hu, J. Small 2023, 20, 2304705.
[22]	Si, Y.; Shi, S.; Hu, J. Matter 2024, 7, 1373.
[23]	He, X.; Shi, J.; Hao, Y.; He, M.; Cai, J.; Qin, X.; Wang, L.; Yu, J. Carbon Energy 2022, 4, 621.
[24]	Li, T.-T.; Sun, L.; Zhang, Y.; Shiu, B.-C.; Ren, H.-T.; Peng, H.-K.; Lin, J.-H.; Lou, C.-W. Chem. Eng. J. 2023, 472, 144820.
[25]	Cao, J.; Liang, F.; Li, H.; Li, X.; Fan, Y.; Hu, C.; Yu, J.; Xu, J.; Yin, Y.; Li, F.; Xu, D.; Feng, H.; Yang, H.; Liu, Y.; Chen, X.; Zhu, G.; Li, R. W. InfoMat 2022, 4, e12302.
[26]	Li, Y.; Xiao, S.; Zhang, X.; Jia, P.; Tian, S.; Pan, C.; Zeng, F.; Chen, D.; Chen, Y.; Tang, J.; Xiong, J. Nano Energy 2022, 98, 107347.
[27]	Ogoshi, T.; Kanai, S.; Fujinami, S.; Yamagishi, T. A.; Nakamoto, Y. J. Am. Chem. Soc. 2008, 130, 5022.

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