呼吸图法制备基于准聚轮烷的响应性薄膜

doi:10.6023/A21030105

摘要/Abstract

响应性薄膜能够响应外界的刺激来改变自身的结构或性能, 是智能材料的重要组成部分. 本工作以1,4-二乙氧基柱[5]芳烃(1,4-diethoxypillar[5]arene, DEP5A)和聚己内酯-b-聚乙二醇-b-聚己内酯(PCL-b-PEG-b-PCL)构建的准聚轮烷(polypseudorotaxane, PPR)为原料, 利用呼吸图法制备出了蜂窝状多孔及球状组装体的疏水薄膜. 研究发现溶剂、浓度、柱芳烃物质的量比和成膜气氛等因素对薄膜表面形貌均能产生较大的影响. 通过制膜条件的优化, 在水汽氛围中制备出了表面具有规则蜂窝状结构的多孔薄膜, 在乙醇氛围下制备出了表面为规整的褶皱球状组装体的薄膜. 研究表明, 上述两种具有规则表面形貌的PPR薄膜对竞争性客体1,4-二溴丁烷都具有响应性, 表现出薄膜表面形貌的变化及亲疏水性的变化. 此类响应性薄膜在微量液体无损转移、功能性涂层和智能薄膜等方面具有潜在的应用前景.

关键词: 准聚轮烷, 柱芳烃, 呼吸图法, 响应性薄膜, 疏水性

Stimuli-responsive film is an essential part of smart materials for its manipulation of structures or performances in response to external stimulations, which is crucial to the exploitation of actuators, sensors, and soft robotics. Herein, a novel polypseudorotaxane (PPR) with competitive guest-responsiveness was leveraged to fabricate polymer films with diverse surface morphologies via breath figure (BF) method under water or ethanol atmosphere. PPR was constructed based on the selective recognition of 1,4-diethoxypillar[5]arene (DEP5A) to the PCL block of polycaprolactone-block-poly(ethylene glycol)-block-polycaprolactone (PCL-b-PEG-b-PCL) in CHCl₃. The morphologies of such polymer films were observed by scanning electron microscopy (SEM). Specifically, ordered honeycomb porous films with an average pore size of approximately 2.15 μm and sphere films with an average diameter of approximately 3.34 μm were fabricated via BF method under water atmosphere and ethanol atmosphere, respectively. The influences of solvent, concentration, and the equivalent ratio of DEP5A to PCL- b-PEG-b-PCL on the nanostructures of films were investigated. It was found that the films with ordered microstructures were obtained using PPR (15.0 equiv. of DEP5A to PCL-b-PEG-b-PCL, 5.0 mg?mL^-1 of PCL-b-PEG-b-PCL) solution under a constant relative humidity of 90% or ethanol atmosphere at 25 ℃. These films showed hydrophobic (water contact angle over 130°) due to their hierarchical structures. Furthermore, the obtained films were immersed in competitive guest-containing solution (20.0 μL DBrBu+10.0 mL ethanol) to manipulate their structures and hydrophobicity. The competitive guest, 1,4-dibromobutane (DBrBu), showed stronger affinity than PCL block to DEP5A. DEP5A would be detached from the PCL block and form pseudorotaxane with DBrBu after immersing the films in competitive guest-containing solution. With the immersion time increasing, PPR were destroyed progressively, resulting in the formation of cuboid-crystal films and the decrement of water contact angle. This result provided a facile strategy to fabricate a smart film with controllable wettability and to explore the potential application prospects in the non-destructive transfer of trace liquids, functional coatings and smart film materials.

Key words: polypseudorotaxane, pillararene, breath figure method, responsive film, hydrophobicity

引用此文

董锦辉, 李进杰, 王赫, 刘彬秀, 彭博, 陈健壮, 林绍梁. 呼吸图法制备基于准聚轮烷的响应性薄膜[J]. 化学学报, 2021, 79(6): 803-808.

Jinhui Dong, Jinjie Li, He Wang, Binxiu Liu, Bo Peng, Jianzhuang Chen, Shaoliang Lin. Fabrication of Polypseudorotaxane-Based Responsive Film via Breath Figure Method[J]. Acta Chimica Sinica, 2021, 79(6): 803-808.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 7

图1. PCL-b-PEG-b-PCL与DEP5A通过主客体作用在氯仿中形成准聚轮烷并在(a)水汽氛围中形成蜂窝状多孔薄膜和在(b)乙醇氛围中形成球状组装体薄膜的示意图

Figure 1. Cartoon representation of the construction of PPR based on the host-guest interaction between PCL-b-PEG-b-PCL and DEP5A in CHCl3 and the PPR solution was used to fabricate (a) honeycomb porous films under water vapor atmosphere and (b) sphere films under ethanol vapor atmosphere

图2. 用(a) PCL-b-PEG-b-PCL (5.0 mg/mL)和(b) PPR (5.0 mg/mL PCL-b-PEG-b-PCL, 15.0 equiv. of DEP5A)在相同条件下(氯仿中, 90% RH, 25 ℃)制备得到的薄膜的SEM图. 图a2及图b2分别为图a1及图b1的放大图. 图b1的插入图为白光下薄膜的衍射图

Figure 2. SEM images of the films fabricated under 90% RH at 25 ℃ using chloroform as the solvent. (a) PCL-b-PEG-b-PCL (5.0 mg/mL) and (b) PPR (5.0 mg/mL PCL-b-PEG-b-PCL, 15.0 equiv. of DEP5A). (a2) and (b2) are the magnified pictures of (a1) and (b1), respectively. The inserted pictures of Figure 2b1 is the photograph of the diffraction of the film under white light

图3. 10 μL水滴(亚甲基蓝染色)滴在PPR蜂窝状多孔薄膜上在倾斜角为(a) 0°和(b) 90°时的照片

Figure 3. Photographs of 10 μL water droplets (dyed by methylene blue) on PPR honeycomb porous film at (a) 0° and (b) 90°

图4. 用(a) PCL-b-PEG-b-PCL(5.0 mg/mL)和(b) PPR (5.0 mg/mL PCL-b-PEG-b-PCL, 15.0 equiv. of DEP5A)在相同条件下(氯仿中, 乙醇氛围, 25 ℃制备得到的薄膜的SEM图. 图a2及图b2分别为图a1及图b1的放大图

Figure 4. SEM images of the films fabricated under ethanol atmosphere at 25 ℃ using chloroform as the solvent. (a) PCL-b-PEG-b-PCL (5.0 mg/mL) and (b) PPR (5.0 mg/mL PCL-b-PEG-b-PCL, 15.0 equiv. of DEP5A). (a2) and (b2) are the magnified pictures of (a1) and (b1), respectively

图5. PPR超分子薄膜竞争性客体响应实验流程示意图. (1)将薄膜放入含竞争性客体DBrBu的乙醇溶液中(20.0 μL DBrBu+10.0 mL乙醇)一定时间; (2)将薄膜取出并泡进乙醇溶液中30 s以去除多余游离的DBrBu分子; (3)将薄膜取出, 并放置在常温下等待乙醇挥发, 最终得到由片状组装体组成的薄膜

Figure 5. Schematic illustration of the process of competitive guest response experiment of PPR supramolecular films. (1) The films were immersed in DBrBu-containing ethanol solution (20.0 μL DBrBu+10.0 mL ethanol) for different times; (2) the films were taken out and immersed in ethanol solution to remove excess DBrBu; (3) the films were taken out and dried under room temperature

图6. PPR蜂窝状多孔薄膜和球状组装体薄膜浸泡在含DBrBu的乙醇溶液不同时间后表面形貌的SEM图及水接触角

Figure 6. The SEM images and the water contact angles of PPR honeycomb porous films and sphere films after being immersed in DBrBu-containing ethanol solution for different times

图7. (a) 蜂窝状多孔薄膜和(b) 球状组装体薄膜浸泡在含DBrBu的乙醇溶液不同时间后薄膜的水接触角变化图

Figure 7. The water contact angle curves of (a) honeycomb porous films and (b) sphere films after being immersed in DBrBu-containing ethanol solution for different times

参考文献 44

[1]	Zhang, A.; Bai, H.; Li, L. Chem. Rev. 2015, 115, 9801. doi: 10.1021/acs.chemrev.5b00069
[2]	Yabu, H.; Jia, R.; Matsuo, Y.; Ijiro, K.; Yamamoto, S.; Nishino, F.; Takaki, T.; Kuwahara, M.; Shimomura, M. Adv. Mater. 2008, 20, 4200.
[3]	Lan, P.; Li, J.; Gong, J.; Li, L. Acta Chim. Sinica 2012, 70, 45. (in Chinese) doi: 10.6023/A1107291
	(兰平, 李剑, 龚剑亮, 李磊, 化学学报, 2012, 70, 45.) doi: 10.6023/A1107291
[4]	Geng, F.; Chen, J.; Zhao, Q.; Li, J.; Ma, Z. Acta Chim. Sinica 2011, 69, 2741. (in Chinese)
	(耿风华, 陈健壮, 赵巧玲, 李剑, 马志, 化学学报, 2011, 69, 2741.)
[5]	Yang, X.-Y.; Chen, L.-H.; Li, Y.; Su, B.-L. Chem. Soc. Rev. 2017, 46, 481. doi: 10.1039/C6CS00829A
[6]	Wu, Y.; Shah, D. U.; Wang, B.; Liu, J.; Ren, X.; Ramage, M. H.; Scherman, O. A. Adv. Mater. 2018, 30, 1707169. doi: 10.1002/adma.201707169
[7]	Yang, Y.; Li, X.; Zheng, X.; Chen, Z.; Zhou, Q.; Chen, Y. Adv. Mater. 2018, 30, 1704912. doi: 10.1002/adma.v30.9
[8]	Xu, Y. Y.; Wang, W.; Chen, J. Z.; Lin, S. L. Chin. J. Org. Chem. 2018, 38, 2161. (in Chinese) doi: 10.6023/cjoc201803037
	(徐悦莹, 王伟, 陈健壮, 林绍梁, 有机化学, 2018, 38, 2161.) doi: 10.6023/cjoc201803037
[9]	Heng, L.; Guo, T.; Wang, B.; Fan, L.-Z.; Jiang, L. J. Mater. Chem. A 2015, 3, 23699. doi: 10.1039/C5TA06786C
[10]	Li, C.; Zhang, Y.; Ju, J.; Cheng, F.; Liu, M.; Jiang, L.; Yu, Y. Adv. Funct. Mater. 2012, 22, 760. doi: 10.1002/adfm.201101922
[11]	Chen, Y.; Li, F.; Cao, W.; Li, T. J. Mater. Chem. A 2015, 3, 16934. doi: 10.1039/C5TA04065E
[12]	Ma, J.; Yan, H.; Quan, J.; Bi, J.; Li, H. ACS Appl. Mater. Interfaces 2019, 11, 1665. doi: 10.1021/acsami.8b18202
[13]	Ding, J.; Zhang, A.; Li, L. Soft Matter 2013, 9, 506. doi: 10.1039/C2SM27093E
[14]	Li, H.; Yang, Y.; Xu, F.; Liang, T.; Wen, H.; Tian, W. Chem. Commun. 2019, 55, 271. doi: 10.1039/C8CC08085B
[15]	Wang, X.-H.; Song, N.; Hou, W.; Wang, C.-Y.; Wang, Y.; Tang, J.; Yang, Y.-W. Adv. Mater. 2019, 31, 1903962. doi: 10.1002/adma.v31.37
[16]	Li, X.-S.; Li, Y.-F.; Wu, J.-R.; Lou, X.-Y.; Han, J.; Qin, J.; Yang, Y.-W. J. Mater. Chem. A 2020, 8, 3651. doi: 10.1039/C9TA13776A
[17]	Chen, J.; Meng, G.; Zhu, Q.; Zhang, S.; Chen, P. J. Mater. Chem. C 2019, 38, 11747.
[18]	Catalan, A.; Tiburcio, J. Chem. Commun. 2016, 52, 9526. doi: 10.1039/C6CC04619C
[19]	Steck, J.; Yang, J.; Suo, Z. ACS Macro Lett. 2019, 8, 754. doi: 10.1021/acsmacrolett.9b00325
[20]	Wu, C.-H.; Lu, C.-S.; Chen, W.-L.; Tung, S.-H.; Jeng, R.-J. Macromol. Mater. Eng. 2018, 303, 1700433. doi: 10.1002/mame.v303.2
[21]	Li, J.; Han, Y.; Chen, C. F. Chin. J. Org. Chem. 2020, 40, 3714. (in Chinese) doi: 10.6023/cjoc202005007
	(李晶, 韩莹, 陈传峰, 有机化学, 2020, 40, 3714.) doi: 10.6023/cjoc202005007
[22]	Bertrand, A.; Bousquet, A.; Lartigau-Dagron, C.; Billon, L. Chem. Commun. 2016, 52, 9562. doi: 10.1039/C6CC04760B
[23]	Wu, X.; Duan, Q. P.; Ni, M. F.; Hu, X. Y.; Wang, L. Y. Chin. J. Org. Chem. 2014, 34, 437. (in Chinese)
	(吴旋, 段群鹏, 倪梦飞, 胡晓玉, 王乐勇, 有机化学, 2014, 34, 437.) doi: 10.6023/cjoc201312018
[24]	Luo, L.; Nie, G.; Tian, D.; Deng, H.; Jiang, L.; Li, H. Angew. Chem. Int. Ed. 2016, 55, 12713. doi: 10.1002/anie.201603906
[25]	Tang, X.; Tang, X. Z.; You, Y.; Ren, L.; Wang, Y.; Yan, L. Acta Chim. Sinica 2012, 70, 1565. (in Chinese) doi: 10.6023/A12030006
	(唐翔, 唐先忠, 游英才, 任立轲, 王洋, 严立京, 化学学报, 2012, 70, 1565.) doi: 10.6023/A12030006
[26]	Ogoshi, T.; Yoshikoshi, K.; Aoki, T.; Yamagishi, T. Chem. Commun. 2013, 49, 8785. doi: 10.1039/c3cc44384a
[27]	Fasano, V.; Baroncini, M.; Moffa, M.; Iandolo, D.; Camposeo, A.; Credi, A.; Pisignano, D. J. Am. Chem. Soc. 2014, 136, 14245. doi: 10.1021/ja5080322
[28]	Gao, P.; Wang, P.; Geng, X.; Ye, L.; Zhang, A.; Feng, Z. Acta Chim. Sinica 2013, 71, 347. (in Chinese) doi: 10.6023/A12120998
	(高鹏, 王培境, 耿雪, 叶霖, 张爱英, 冯增国, 化学学报, 2013, 71, 347.) doi: 10.6023/A12120998
[29]	Pan, S.; Ni, M.; Mu, B.; Li, Q.; Hu, X.-Y.; Lin, C.; Chen, D.; Wang, L. Adv. Funct. Mater. 2015, 25, 3571. doi: 10.1002/adfm.v25.23
[30]	Ahn, Y.; Jang, Y.; Selvapalam, N.; Yun, G.; Kim, K. Angew. Chem. Int. Ed. 2013, 52, 3140. doi: 10.1002/anie.201209382
[31]	Ghasemi, S.; Besharati, M. Polym. Adv. Technol. 2020, 31, 3104. doi: 10.1002/pat.v31.12
[32]	Li, Y.; Ma, X.; Ma, J.; Zhang, Z.; Niu, Z.; Chen, F. Polymers 2021, 13, 316. doi: 10.3390/polym13030316
[33]	Ma, C.; Zhong, Y.; Li, J.; Chen, C.; Gong, J.; Xie, S.; Li, L.; Ma, Z. Chem. Mater. 2010, 22, 2367. doi: 10.1021/cm9036633
[34]	Du, C.; Zhang, A.; Bai, H.; Li, L. ACS Macro Lett. 2013, 2, 27. doi: 10.1021/mz300616z
[35]	Escalé, P.; Camp, W. V.; Prez, F. D.; Rubatat, L.; Billon, L.; Save, M. Polym. Chem. 2013, 4, 4710.
[36]	Zander, N. E.; Orlicki, J. A.; Karikari, A. S.; Long, T. E.; Rawlett, A. M. Chem. Mater. 2007, 19, 6145. doi: 10.1021/cm0715895
[37]	Yabu, H.; Hirai, Y.; Kojima, M.; Shimomura, M. Chem. Mater. 2009, 21, 1787. doi: 10.1021/cm803476m
[38]	Muller, M.; Zentel, R.; Maka, T.; Romanov, S. G.; Torres, C. S. Adv. Mater. 2000, 12, 1499. doi: 10.1002/(ISSN)1521-4095
[39]	Wang, W.; Du, C.; Wang, X.; He, X.; Lin, J.; Li, L.; Lin, S. Angew. Chem. Int. Ed. 2014, 53, 12116. doi: 10.1002/anie.201407230
[40]	Wang, W.; Yao, Y.; Luo, T.; Chen, L.; Lin, J.; Li, L.; Lin, S. ACS Appl. Mater. Interfaces 2017, 9, 4223. doi: 10.1021/acsami.6b14024
[41]	Wang, W.; Shen, D.; Li, X.; Yao, Y.; Lin, J.; Wang, A.; Yu, J.; Wang, Z. L.; Hong, S. W.; Lin, Z.; Lin, S. Angew. Chem. Int. Ed. 2018, 57, 2139. doi: 10.1002/anie.v57.8
[42]	Gao, F.; Yao, Y.; Wang, W.; Wang, X.; Li, L.; Zhuang, Q.; Lin, S. Macromolecules 2018, 51, 2742. doi: 10.1021/acs.macromol.8b00059
[43]	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. doi: 10.1039/D0TA04079G
[44]	Wan, L. S.; Zhu, L. W.; Ou, Y.; Xu, Z. K. Chem. Commun. 2014, 50, 4024. doi: 10.1039/C3CC49826C