ABC型准聚轮烷的构建及其响应性薄膜

doi:10.6023/A24040123

摘要/Abstract

响应性薄膜的表面微观结构和浸润性会随着外界环境的改变发生自适应性变化, 在高端制造和生物医药等领域研究意义重大. 本研究利用1,4-二乙氧基柱[5]芳烃(DEP5A)对聚乙烯嵌段聚乙二醇嵌段聚己内酯(PE-b-PEG-b-PCL)中聚乙烯和聚己内酯链段的选择性识别作用, 通过DEP5A和PE-b-PEG-b-PCL共组装, 构建了ABC型准聚轮烷; 再采用静电喷雾和呼吸图法相结合的制膜新技术, 制备得到由多孔纳米片堆叠而成的准聚轮烷薄膜. 研究发现该薄膜的微结构和浸润性可通过改变柱芳烃含量、聚合物浓度和制膜湿度等实验条件来调控. 此外, 通过乙醇或竞争客体分子1,4-二溴丁烷的引入, 可方便且精准地调控准聚轮烷薄膜的微结构和浸润性. 这种响应性薄膜在催化剂载体和智能涂层等方面应用潜力巨大.

关键词: 准聚轮烷, 静电喷雾, 呼吸图法, 刺激响应性, 浸润性调控

The surface microstructure and wettability of responsive membranes will change adaptively with changes in the external environment, which is significant in fields such as high-end manufacturing and biomedicine. However, it is still very challenging to precisely control the response of such films in an extensive range. Due to their incorporation of non-covalent bonds, polypseudorotaxanes exhibit distinctive reversibility and stimuli-responsiveness, rendering them a pivotal avenue in advancing smart materials, especially responsive membranes. Polypseudorotaxane membranes have the characteristics of easy control of structure and properties and multiple responses, which are of great significance in theoretical research and practical applications. This study capitalizes on the selective recognition property of 1,4-diethoxy pillar[5]arene (DEP5A) towards the polyethylene (PE) and polycaprolactone (PCL) segments within the polyethylene block polyethylene glycol block polycaprolactone (PE-b-PEG-b-PCL) copolymer, obtaining ABC-type polypseudorotaxane with competitive guest responsiveness. The successful assembly and competitive guest responsiveness to 1,4-dibromobutane is validated through ¹H NMR spectroscopy. Additionally, a polypseudorotaxane membrane consisting of porous nanosheets and featuring superhydrophobicity is fabricated utilizing a novel technique combining electrospraying and the breath figure method. Notably, the polypseudorotaxane forms porous nanosheets during the membrane fabrication process, which then stack into a thin membrane. In addition, the polypseudorotaxane membrane's regular microstructure and superhydrophobicity can be achieved by controlling the molar ratio of DEP5A to polymer, polymer concentration, and relative humidity. Furthermore, the polypseudorotaxane membrane exhibits responsiveness to solvents and competing guest molecules, thus giving rise to different microstructure and hydrophobicity. Such responsive membranes hold immense promise for diverse applications, including catalyst supports and smart coatings.

Key words: polypseudorotaxane, electrospraying, breath figure method, stimuli-responsiveness, tunable wettability

引用此文

尹晓璇, 李进杰, 禚可欣, 牟蔚鑫, 黄灵丽, 陈健壮, 林绍梁. ABC型准聚轮烷的构建及其响应性薄膜[J]. 化学学报, 2024, 82(7): 790-796.

Xiaoxuan Yin, Jinjie Li, Kexin Zhuo, Weixin Mou, Lingli Huang, Jianzhuang Chen, Shaoliang Lin. Construction of ABC-Type Polypseudorotaxane and Its Responsive Membrane[J]. Acta Chimica Sinica, 2024, 82(7): 790-796.

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图/表 6

图1. ABC型准聚轮烷构建及其竞争客体响应过程和利用静电喷雾与呼吸图法相结合制备响应性PPR薄膜过程示意图

Figure 1. The construction of ABC-type polypseudorotaxane and its competitive guest response process and the schematic diagram of the process of preparing PPR membranes by combining electrospraying and breath figure method

图2. PPR的构建与竞争客体响应性. (a)加入不同物质的量比DEP5A后PE-b-PEG-b-PCL(5.0 mg?mL?1)的核磁共振氢谱图(600 MHz, CDCl3, 20 ℃), (b)加入不同物质的量比DBrBu后PPR (40 equiv. DEP5A)的核磁共振氢谱图(600 MHz, CDCl3, 20 ℃)

Figure 2. Construction and competitive guest responsiveness of PPR. (a) Partial 1H NMR spectra (600 MHz, CDCl3, 20 ℃) of PE-b-PEG- b-PCL (5 mg?mL?1) upon the addition of DEP5A, (b) partial 1H NMR spectra (600 MHz, CDCl3, 20 ℃) of PPR (40 equiv. DEP5A) upon the addition of DBrBu

图3. 相对湿度对PPR薄膜浸润性和表面孔径的影响. (a) PPR薄膜接触角与相对湿度的曲线图, (b) PPR薄膜表面纳米片孔径与相对湿度曲线图

Figure 3. Effect of RH on wettability and surface pore size of PPR membranes. (a) Change curve of contact angle with RH, (b) the relationship between the pore diameter of membrane surface and RH

图4. PPR薄膜响应性实验流程示意图

Figure 4. Schematic illustration of responsing experiments on PPR membranes

图5. 在乙醇中浸泡不同时间的PPR薄膜的SEM图. (a1) 0 s, (b1) 30 s, (c1) 10 min, (d1) 2 h, 图(a2~d2)和(a3~d3)分别为(a1~d1)的放大图, (a1~d1)的插图为对应的接触角数据

Figure 5. SEM images of PPR membranes after soaking in ethanol for different times. (a1) 0 s, (b1) 30 s, (c1) 10 min, (d1) 2 h. (a2~d2) and (a3~d3) are enlarged views of (a1~d1), respectively. The insets (a1~d1) are contact angle data

图6. 在竞争客体中浸泡不同时间的PPR薄膜的SEM图. (a1) 0 s, (b1) 5 s, (c1) 10 min, 图(a2~c2)分别为(a1~c1)的放大图, (a1~c1)的插图为对应的接触角数据

Figure 6. SEM images of PPR membranes after soaking in competitive guest for different times. (a1) 0 s, (b1) 5 s and (c1) 10 min. (a2~c2) are enlarged views of (a1~c1), respectively. The insets (a1~c1) are contact angle data

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