论文标题
聚合物结构在聚(N-异丙基丙烯酰胺)分散体中的水限制中的作用
The role of polymer structure on water confinement in poly(N-isopropylacrylamide) dispersions
论文作者
论文摘要
聚(N-异丙基丙烯酰胺)(PNIPAM)是一种合成聚合物,以其热响应特性进行了广泛研究。然而,最近的工作还报道了在浓缩的PNIPAM悬浮液中,低温(蛋白质样)动力学过渡的证据,与聚合物结构无关,即线性链和微凝胶。在这项工作中,我们通过对两个系统的广泛差异扫描量热法(DSC)测量进行了水聚合物的相互作用,以了解不同拓扑结构对溶液行为的影响,尤其是在结晶和熔化过程中。此外,我们在水和氘代水中比较了侵蚀和氘化的微凝胶。 DSC的结果与动态光散射实验相辅相成,这证实选择性同位素替代对溶液行为有所不同。我们的发现突出了聚合物结构在溶液行为上起着重要的作用:实际上,微凝胶证明是更有效的限制剂,能够避免在线性链方面更广泛的浓度范围内水结晶。总体而言,目前的数据对于解释PNIPAM分散体的未来低温研究将是有价值的,特别是通过中子散射实验。
Poly(N-isopropylacrylamide) (PNIPAM) is a synthetic polymer that is widely studied for its thermoresponsive character. However, recent works also reported evidence of a low temperature (protein-like) dynamical transition around 225 K in concentrated PNIPAM suspensions, independently of the polymer architecture, i.e., both for linear chains and for microgels. In this work, we investigate water-polymer interactions by extensive differential scanning calorimetry (DSC) measurements of both systems, in order to understand the effect of the different topological structures on the solution behaviour, in particular regarding crystallization and melting processes. In addition, we compare protiated and deuterated microgels, in both water and deuterated water. The DSC results are complemented by dynamic light scattering experiments, which confirm that the selective isotopic substitution differently affects the solution behaviour. Our findings highlight the important role played by the polymer architecture on the solution behaviour: indeed, microgels turn out to be more efficient confining agents, able to avoid water crystallization in a wider concentration range with respect to linear chains. Altogether, the present data will be valuable to interpret future low-temperature investigations of PNIPAM dispersions, particularly by neutron scattering experiments.