Salt-Mediated Tuning of the Cononsolvency Response Behavior of PNIPMAM Thin Films

IF 5.1 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2024-11-08 DOI:10.1021/acs.macromol.4c02053

Julija Reitenbach, Peixi Wang, Linus F. Huber, Simon A. Wegener, Robert Cubitt, Dirk Schanzenbach, André Laschewsky, Christine M. Papadakis, Peter Müller-Buschbaum

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Abstract

The development of tuning parameters to influence the response behavior of polymer-based nanodevices is investigated by the addition of NaClO₄ or Mg(ClO₄)₂ to adjust the swelling degree of poly(N-isopropylmethacrylamide) thin films under different vapor atmospheres. By leveraging the cononsolvency effect of the polymer in a mixed vapor of water and acetone, a contraction of the preceding water-swollen films is induced. The relation between the macroscopic and the molecular processes is elucidated by static and time-resolved time-of-flight neutron reflectometry, as well as by in situ Fourier transform infrared spectroscopy. It is found that the addition of NaClO₄ strongly enhances the film thickness response for swelling and contraction, which, therefore, allows the tuning of the film toward stronger responses. Mechanistically, D₂O–amide bonds are formed during swelling and become perturbed upon vapor exchange. Thereby, the D₂O–amide interactions are reduced continuously, while acetone–amide interactions develop, accompanied by increasing amide–amide interactions during the film contraction.

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以盐为媒介调节 PNIPMAM 薄膜的凝固反应行为

通过添加 NaClO4 或 Mg（ClO4）2 来调节聚（N-异丙基甲基丙烯酰胺）薄膜在不同蒸汽环境下的溶胀度，研究了影响聚合物基纳米器件响应行为的调节参数的开发。通过利用聚合物在水和丙酮混合蒸汽中的共溶效应，诱导了之前水溶胀薄膜的收缩。静态和时间分辨飞行时间中子反射测量法以及原位傅立叶变换红外光谱法阐明了宏观和分子过程之间的关系。研究发现，NaClO4 的加入会极大地增强薄膜厚度对膨胀和收缩的响应，因此可以对薄膜进行调整，以获得更强的响应。从机理上讲，D2O-酰胺键是在膨胀过程中形成的，并在水汽交换时受到扰动。因此，在薄膜收缩过程中，D2O-酰胺的相互作用不断减弱，而丙酮-酰胺的相互作用不断发展，同时酰胺-酰胺的相互作用不断增强。

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来源期刊

Macromolecules 工程技术-高分子科学

CiteScore

9.30

自引率

16.40%

发文量

942

审稿时长

2 months

期刊介绍： Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.