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Constrained thermoresponsive polymers – new insights into fundamentals and applications
Beilstein Journal of Organic Chemistry ( IF 2.7 ) Pub Date : 2021-08-20 , DOI: 10.3762/bjoc.17.138 Patricia Flemming 1, 2 , Alexander S Münch 1 , Andreas Fery 1, 2 , Petra Uhlmann 1, 3
Beilstein Journal of Organic Chemistry ( IF 2.7 ) Pub Date : 2021-08-20 , DOI: 10.3762/bjoc.17.138 Patricia Flemming 1, 2 , Alexander S Münch 1 , Andreas Fery 1, 2 , Petra Uhlmann 1, 3
Affiliation
In the last decades, numerous stimuli-responsive polymers have been developed and investigated regarding their switching properties. In particular, thermoresponsive polymers, which form a miscibility gap with the ambient solvent with a lower or upper critical demixing point depending on the temperature, have been intensively studied in solution. For the application of such polymers in novel sensors, drug delivery systems or as multifunctional coatings, they typically have to be transferred into specific arrangements, such as micelles, polymer films or grafted nanoparticles. However, it turns out that the thermodynamic concept for the phase transition of free polymer chains fails, when thermoresponsive polymers are assembled into such sterically confined architectures. Whereas many published studies focus on synthetic aspects as well as individual applications of thermoresponsive polymers, the underlying structure–property relationships governing the thermoresponse of sterically constrained assemblies, are still poorly understood. Furthermore, the clear majority of publications deals with polymers that exhibit a lower critical solution temperature (LCST) behavior, with PNIPAAM as their main representative. In contrast, for polymer arrangements with an upper critical solution temperature (UCST), there is only limited knowledge about preparation, application and precise physical understanding of the phase transition. This review article provides an overview about the current knowledge of thermoresponsive polymers with limited mobility focusing on UCST behavior and the possibilities for influencing their thermoresponsive switching characteristics. It comprises star polymers, micelles as well as polymer chains grafted to flat substrates and particulate inorganic surfaces. The elaboration of the physicochemical interplay between the architecture of the polymer assembly and the resulting thermoresponsive switching behavior will be in the foreground of this consideration.
中文翻译:
受约束的热敏聚合物——对基本原理和应用的新见解
在过去的几十年中,已经开发并研究了许多刺激响应聚合物的开关特性。特别是热响应聚合物,它与环境溶剂形成混溶间隙,根据温度具有较低或较高的临界分层点,已在溶液中进行了深入研究。为了将此类聚合物应用于新型传感器、药物输送系统或作为多功能涂层,它们通常必须转移到特定的排列中,例如胶束、聚合物薄膜或接枝纳米颗粒。然而,事实证明,当热响应聚合物组装成这种空间受限的结构时,自由聚合物链相变的热力学概念就失效了。尽管许多已发表的研究侧重于合成方面以及热响应聚合物的个别应用,但控制空间受限组件热响应的基本结构-性能关系仍然知之甚少。此外,绝大多数出版物都涉及表现出较低临界溶解温度 (LCST) 行为的聚合物,其中 PNIPAAM 是它们的主要代表。相比之下,对于具有上限临界溶解温度 (UCST) 的聚合物排列,关于相变的制备、应用和精确物理理解的知识有限。这篇综述文章概述了流动性有限的热敏聚合物的当前知识,重点关注 UCST 行为以及影响其热敏开关特性的可能性。它包括星形聚合物、胶束以及接枝到平坦基材和颗粒无机表面的聚合物链。聚合物组装结构与由此产生的热响应转换行为之间的物理化学相互作用的详细说明将是这一考虑的重点。
更新日期:2021-08-20
中文翻译:
受约束的热敏聚合物——对基本原理和应用的新见解
在过去的几十年中,已经开发并研究了许多刺激响应聚合物的开关特性。特别是热响应聚合物,它与环境溶剂形成混溶间隙,根据温度具有较低或较高的临界分层点,已在溶液中进行了深入研究。为了将此类聚合物应用于新型传感器、药物输送系统或作为多功能涂层,它们通常必须转移到特定的排列中,例如胶束、聚合物薄膜或接枝纳米颗粒。然而,事实证明,当热响应聚合物组装成这种空间受限的结构时,自由聚合物链相变的热力学概念就失效了。尽管许多已发表的研究侧重于合成方面以及热响应聚合物的个别应用,但控制空间受限组件热响应的基本结构-性能关系仍然知之甚少。此外,绝大多数出版物都涉及表现出较低临界溶解温度 (LCST) 行为的聚合物,其中 PNIPAAM 是它们的主要代表。相比之下,对于具有上限临界溶解温度 (UCST) 的聚合物排列,关于相变的制备、应用和精确物理理解的知识有限。这篇综述文章概述了流动性有限的热敏聚合物的当前知识,重点关注 UCST 行为以及影响其热敏开关特性的可能性。它包括星形聚合物、胶束以及接枝到平坦基材和颗粒无机表面的聚合物链。聚合物组装结构与由此产生的热响应转换行为之间的物理化学相互作用的详细说明将是这一考虑的重点。