For many decades, the self-assembly of amphiphilic copolymers containing polysaccharide, called glycopolymers, has been induced in water via nanoprecipitation, whereas the polymerization-induced self-assembly (PISA) approach has been less reported. Using advanced characterization techniques including static/dynamic light scattering and negative-stain/cryo TEM analyses, we studied the impact of the experimental conditions/process on the morphology of formed glyco-nanostructures. A model amphiphilic glycopolymer (Dex-g¹²-PHPMA₄₀₀) based on dextran as hydrophilic polysaccharide backbone and poly(2-hydroxypropyl methacrylate) (PHPMA) as hydrophobic grafts was prepared in water using photo-induced RAFT polymerization at 405 nm. On the one hand, our findings revealed that photo-initiated PISA (photo-PISA) at room temperature (RT) led to a mixture of spheres with a significant population of worm-like micelles (WLM), whereas the nanoprecipitation of purified Dex-g¹²-PHPMA₄₀₀ led only to spherical micelles. On the other hand, we demonstrate that the morphology of glyco-nanostructures is affected by temperature since performing photo-PISA at 60 °C led to spheres instead of WLM. Finally, our findings revealed that pre-synthesized WLM at RT underwent irreversibly an unusual morphological transition to spheres by heating to 60 °C.

中文翻译：

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含多糖的两亲共聚物的自组装：PISA与纳米沉淀，以及温度效应

数十年来，通过纳米沉淀在水中诱导了包含多糖的两亲共聚物的自组装，称为糖聚合物，而聚合诱导的自组装（PISA）方法报道较少。使用先进的表征技术，包括静态/动态光散射和负染色/低温TEM分析，我们研究了实验条件/过程对形成的糖纳米结构形态的影响。模型两亲糖聚合物（Dex-g ¹² -PHPMA ₄₀₀以葡聚糖为亲水性多糖主链，聚甲基丙烯酸2-羟丙酯（PHPMA）为疏水接枝，采用光诱导RAFT聚合在405 nm的水中制备。一方面，我们的发现表明，室温（RT）下光引发的PISA（photo-PISA）导致混合了许多蠕虫样胶束（WLM）的球体，而纯化的Dex- g ¹² -PHPMA ₄₀₀仅导致球形胶束。另一方面，我们证明糖纳米结构的形态受温度影响，因为在60°C下执行光PISA导致形成球体而不是WLM。最后，我们的发现表明，在室温下预合成的WLM通过加热到60°C不可逆地经历了异常的向球体的形态转变。