Impact of cyclic backbone and thioether functionality on thermoresponsive behaviors of multi-responsive Y-junction-bearing polyacrylamides

IF 4.5 3区 工程技术 Q1 CHEMISTRY, APPLIED
Ran Chen, Meng Zhang, Fujin Duan, Qingqing Wang, Jinqian Zhang, Youliang Zhao
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Abstract

Alteration of chemical composition and chain topology of polymers allows for the rational regulation of their thermoresponsive behaviors. Compared with oxyether group, thioether moiety with higher hydrophobicity and oxidation sensitivity is proposed to present some differences in phase transition. To elucidate cyclization and thioether functionality dependent thermoresponsive behaviors, two pairs of thermo/pH/oxidation-responsive linear and cyclic Y-junction-bearing polymers (YJPs) involving dual thioether groups or coexistent thioether and oxyether moieties are designed. Multi-tunable LCST behavior can be achieved upon variations of hydrogen bonding, electrostatic and hydrophobic interactions. Owing to distinct stability of supramolecular interactions, copolymer solutions prepared by direct dispersion or self-assembly are liable to present a reverse order of phase transition temperature (Tc,l) relying on the thioether functionality. Cyclization of the backbone can result in an elevated Tc,l up to about 14 °C, revealing Y-junction-induced amplification of topology effect. Tc,l is prone to decreasing upon solvent switch from water to heavy water or pH increment, while the distinct oxidation sensitivity of monothioether and dithioether groups affords oxidation-triggered LCST “on/off” behaviors. In addition, intriguing sphere-to-vesicle-to-lamella-to-vesicle, vesicle-to-lamella-to-sphere and lamella-to-nanoribbon-to-lamella transitions occur in thermo-induced self-assembly. The success of this study paves the way for exploring thioether functionality dependent physicochemical properties and multipurpose applications of complex architectural polymers.

Abstract Image

环状骨架和硫醚官能团对多反应 Y 型接点聚丙烯酰胺热致伸缩行为的影响
通过改变聚合物的化学成分和链拓扑结构,可以合理调节它们的热致伸缩行为。与氧醚基团相比,硫醚分子具有更高的疏水性和氧化敏感性,因此在相变过程中会出现一些差异。为了阐明环化和硫醚官能团依赖性热致伸缩行为,我们设计了两对热/pH/氧化反应线性和环状 Y 型接合聚合物(YJPs),其中涉及双硫醚基团或硫醚和氧醚共存基团。通过改变氢键、静电和疏水相互作用,可实现多种可调的 LCST 行为。由于超分子相互作用具有不同的稳定性,通过直接分散或自组装制备的共聚物溶液可能会出现相变温度(Tc,l)顺序相反的情况,这取决于硫醚官能度。骨架的环化可导致 Tc,l 升高至约 14 °C,这表明 Y 键诱导了拓扑效应的放大。当溶剂从水切换到重水或 pH 值增加时,Tc,l 容易降低,而单硫醚和二硫醚基团对氧化的敏感性不同,因此会出现氧化触发的 LCST "开/关 "行为。此外,在热诱导的自组装过程中,还发生了有趣的球体到囊泡到薄片到囊泡、囊泡到薄片到球体以及薄片到纳米带到薄片的转变。这项研究的成功为探索硫醚官能团的理化性质和复杂结构聚合物的多用途应用铺平了道路。
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来源期刊
Reactive & Functional Polymers
Reactive & Functional Polymers 工程技术-高分子科学
CiteScore
8.90
自引率
5.90%
发文量
259
审稿时长
27 days
期刊介绍: Reactive & Functional Polymers provides a forum to disseminate original ideas, concepts and developments in the science and technology of polymers with functional groups, which impart specific chemical reactivity or physical, chemical, structural, biological, and pharmacological functionality. The scope covers organic polymers, acting for instance as reagents, catalysts, templates, ion-exchangers, selective sorbents, chelating or antimicrobial agents, drug carriers, sensors, membranes, and hydrogels. This also includes reactive cross-linkable prepolymers and high-performance thermosetting polymers, natural or degradable polymers, conducting polymers, and porous polymers. Original research articles must contain thorough molecular and material characterization data on synthesis of the above polymers in combination with their applications. Applications include but are not limited to catalysis, water or effluent treatment, separations and recovery, electronics and information storage, energy conversion, encapsulation, or adhesion.
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