PNIPAm温敏纳米纤维膜：交联作用下的形貌稳定性和响应行为

doi:10.3866/PKU.WHXB202304037

物理化学学报 >> 2024, Vol. 40 >> Issue (4): 2304037.doi: 10.3866/PKU.WHXB202304037

PNIPAm温敏纳米纤维膜：交联作用下的形貌稳定性和响应行为

田晓靖¹^,², 黄至纯³, 张青松¹^,⁴^,*(), 王旭⁵, 杨宁¹^,², 邓南平³

¹ 天津工业大学材料科学与工程学院, 天津 300387
² 分离膜与膜过程国家重点实验室, 天津 300387
³ 天津工业大学纺织科学与工程学院, 天津 300387
⁴ 烟台南山学院, 山东烟台 265706
⁵ 李宁(中国)体育用品有限公司, 北京 100000

收稿日期:2023-04-20 修回日期:2023-06-19 录用日期:2023-06-23 发布日期:2023-06-30
通讯作者: Email: zqs8011@163.com; Tel.: +86-18622036882 (张青松)
基金资助:
国家自然科学基金(52173060); 中国纺织工业联合会科技指导性项目(2018034); 山东省自然科学基金(ZR2022ME095); 天津工业大学纤维研究基金(TGF-21-B5); 天津工业大学医工结合科研计划课题(2021YGJHLX03)

PNIPAm Thermo-Responsive Nanofibers Mats: Morphological Stability and Response Behavior under Cross-Linking

Xiaojing Tian¹^,², Zhichun Huang³, Qingsong Zhang¹^,⁴^,*(), Xu Wang⁵, Ning Yang¹^,², Nanping Deng³

¹ School of Materials Science and Engineering, Tiangong University, Tianjin 300387, China
² State Key Laboratory of Separation Membranes and Membrane Processes, Tianjin 300387, China
³ School of Textile Science and Engineering, Tiangong University, Tianjin 300387, China
⁴ Yantai Nanshan University, Yantai 265706, Shandong Province, China
⁵ Lining (China) Sports Goods, Co., Ltd., Beijing 100000, China

Received:2023-04-20 Revised:2023-06-19 Accepted:2023-06-23 Published:2023-06-30
Contact: Email: zqs8011@163.com; Tel.: +86-18622036882 (Qingsong Zhang)
Supported by:
the National Natural Science Foundation of China(52173060); Science and Technology Guidance Projects of China National Textile and Apparel Council(2018034); Natural Science Foundation of Shandong Province(ZR2022ME095); Fiber Research Foundation of Tiangong University(TGF-21-B5); Research Plan of Combining Medicine with Engineering of Tiangong University(2021YGJHLX03)

摘要/Abstract

摘要：

聚N-异丙基丙烯酰胺(PNIPAm)交联温敏纳米纤维膜作为一种相变温度易于控制的新兴响应性材料，克服了传统PNIPAm块状水凝胶的生产成本高、响应速率慢和PNIPAm非交联温敏纳米纤维耐水性差的缺点，受到广泛研究并应用于智能开关、温度致动器、水油分离、药物、细胞控制释放和伤口敷料等领域。形貌稳定性和快速响应性是温敏纳米纤维膜在重复体积变化过程中最大的挑战，同时也作为评价PNIPAm温敏纳米纤维膜的实用性最重要指标引起了人们广泛的关注。本文全面综述了PNIPAm温敏纳米纤维膜近二十年来国内外的突破性进展和非交联作用下PNIPAm温敏纳米纤维膜的形貌变化和响应性，重点综合分析了物理和化学交联中交联反应类型、交联度、交联时间和交联分子量对PNIPAm温敏纳米纤维膜的形貌稳定性和响应行为的影响，为之后纤维膜的交联处理提供了理论支持，并对PNIPAm温敏纳米纤维膜的发展及应用前景进行了展望。

关键词: 聚N-异丙基丙烯酰胺, 纳米纤维膜, 形貌稳定性, 响应性, 耐水性

Abstract:

Since 2004, poly(N-isopropylacrylamide) (PNIPAm) cross-linked thermo-responsive nanofibers mats have emerged as a responsive material with a phase transition temperature that can be easily controlled. These mats overcome the limitations, such as a high production cost and slow response rate, of huge traditional PNIPAm hydrogels. They also overcome the poor water resistance of PNIPAm non-cross-linked thermo-responsive nanofibers and, thus, have been widely studied. In 2017, continuous PNIPAm thermo-responsive nanofibers in pure aqueous solvents without beads were fabricated, which began the ecological and water-based era of uniform PNIPAm nanofiber production. In this review, we comprehensively analyzed the effects of physical and chemical cross-linking reaction types, cross-linking degree, cross-linking time, and cross-linking molecular weight on the morphological stability and response behavior of PNIPAm thermo-responsive nanofibers mats, providing theoretical support for their future cross-linking treatment. Because of their high specific surface area and porosity, PNIPAm thermo-responsive nanofibers mats are vulnerable to solvent erosion before cross-linking, which damage their morphology and reduce response rates and usage times. Increased water resistance and can be utilized repeatedly, by introducing cross-linking groups to these mats, such as in drug release, cell culture, drivers, and smart switches. Chemical cross-linking are more stable than physical cross-linking and can be divided into crosslinkers, chemical reactive cross-linking, and other cross-linking. The cross-linking networks produced by a cross-linking agent are more robust; however, the resulting nanofibers mats are not applicable to the human body owing to the small, non-degradable harmful molecules, such as formaldehyde and glutaraldehyde (GA). Random 3D networks generated by physical cross-linking are easier to break but relatively safe and pollution-free. The morphological stability and response behavior of PNIPAm thermo-responsive nanofibers mats are affected by the cross-linking. The cross-linking agent content and the cross-linking time are positively correlated with the morphological stability of PNIPAm thermo-responsive nanofibers mats. This is conducive to multiple recycling but has little effect on the response rate. Greener and more reliable cross-linking methods should be investigated to realize and expand the practical applications of PNIPAm thermo-responsive nanofibers mats, with increasing focus on the effect of cross-linking on the mechanical properties of the mats. We hope this review will result in ideas for improving the development and application of PNIPAm thermo-responsive nanofibers mats.

Key words: PNIPAm, Nanofibers mat, Morphological stability, Responsiveness, Water resistance

田晓靖, 黄至纯, 张青松, 王旭, 杨宁, 邓南平. PNIPAm温敏纳米纤维膜：交联作用下的形貌稳定性和响应行为[J]. 物理化学学报, 2024, 40(4), 2304037. doi: 10.3866/PKU.WHXB202304037

Xiaojing Tian, Zhichun Huang, Qingsong Zhang, Xu Wang, Ning Yang, Nanping Deng. PNIPAm Thermo-Responsive Nanofibers Mats: Morphological Stability and Response Behavior under Cross-Linking[J]. Acta Phys. -Chim. Sin. 2024, 40(4), 2304037. doi: 10.3866/PKU.WHXB202304037

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202304037

https://www.whxb.pku.edu.cn/CN/Y2024/V40/I4/2304037

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Composition of thermo-responsive nanofibers mats	Solvent	Mean diameter of nanofibers/nm	LCST/℃	Water resistance	Application Scenarios	Ref.
PNIPAm/PS	THF	100–500	32–33	NO	–	12
PNIPAm	Water	750	32	NO	–	13
PNIPAm/ZnO	DMF	1670	–	NO	Thermo-responsive photocatalysis	25
PNIPAm/PEO	Water	250–380	32	NO	Controlled release of drugs	26

Composition of thermo-responsive nanofibers mats	Cross-linking methods	Crosslinkers	Solvent	Mean diameter of nanofibers/nm	LCST/℃	Water resistance	Application Scenarios	Ref.
p(NIPAm-co-SA)	Physical cross-linking	–	–	207	23	YES	Actuators	14
PNIPAm	–	OpePOSS	DMF : THF = 1 : 1	970 ± 120	31	YES	–	16
PNIPAm/Gelatin	In situ cross-linking	EDC-NHS	TFE : H₂O = 1 : 1	600–800	32	YES	Controlled release of drugs	38
p(PFPA-co-NIPAm)	Esteramine reaction	–	THF : DMF = 3 : 1	620 ± 160	32	YES	Cell culture	52
PNIPAm/EA/PCL	Heating cross-linking	–	TFE	614	26	YES	Controlled release of drugs	56
PCL/PNIPAm	UV cross-linking	BP、PETM	DMF/Trichloromethane	600	–	YES	Captures and Releases Cells	63
p(NIPAm-ABP)	UV cross-linking	ABP	DMF	150–250	–	YES	Actuators	64
p(NIPAm-co-MAA)/ β-CD	Esterification reaction	–	DMF	–	–	YES	Dye adsorption	66
P(NIPAm-co-NMA)/ChNWs	In situ cross-linking	–	H₂O : THF = 1 : 2	380	–	YES	Water/oil separation	69
PNIPAm/AuNRs	–	OpePOSS	DMF	–	–	YES	Smart Switch	73
P(NIPAm-ABP)/TPU	UV cross-linking	ABP	DMF	477 ± 69	29	YES	Actuators	74
p(NIPAm-co-NMA)	Self-condensation reactions	–	–	600–700	38	YES	Controlled release of drugs	76
PNIPAm-NMA-Am	Esterification reaction	–	DMF : THF = 1 : 1	200	55	YES	Controlled release of drugs	77

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PNIPAm温敏纳米纤维膜：交联作用下的形貌稳定性和响应行为

PNIPAm Thermo-Responsive Nanofibers Mats: Morphological Stability and Response Behavior under Cross-Linking

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