Citation:
. CCS Chemistry:POSS树枝状聚合物自组装:刚柔相济、始可有成[J]. CCS Chemistry,
;2020, 2(0): 1093-1104.
doi:
10.31635/ccschem.020.202000238
-
中国科学院化学研究所吴德成研究员、王星副研究员课题组提出了一种POSS树枝状聚合物的快速合成方法以及组装形貌的自适应调控策略。基于刚性内核的疏水区域自增大空间效应和柔性链段的自调节优化性能,POSS树枝状聚合物在溶液中展现出了丰富多彩的组装形貌。
自然界中存在着丰富多彩的生命组装体(如DNA双螺旋结构、蛋白质聚集与折叠结构等),在多重相互作用的驱动下可以将有机和/或无机结构单元进行层级化、模块化、智能化地精准构建和优化重组。随着现代科学技术的进步,尤其信息、电子、生命、材料、纳米等研究领域的快速发展,自组装技术引起了科学家的研究兴趣。利用和发展大分子自组装技术模拟自然界生命体的复杂结构并发挥特殊功能,对于探索和发现自然具有重要的研究意义。
两亲性树枝状大分子具有明确和稳定的结构,在分层自组装领域引起了广泛关注,已在超分子化学、转基因技术、药物输送、催化等方面有诸多应用。然而,结构精细的树枝状聚合物的合成和纯化步骤繁琐、实验条件苛刻,限制了进一步的发展。根据核壳结构和内核刚度,树枝状聚合物可分为刚性和柔性,前者倾向于形成大小均匀且形状固定的晶体或刚性3D晶格,后者具有各种可互换的的链构象,可形成一系列异构聚集体。其中,同时集成高刚度和有限变形自由度即“刚柔并济”的树枝状大分子,实现精确控制组装结构的分层自主装是目前此类研究面临的挑战之一。
多面体笼型低聚倍半硅氧烷(PolyhedralOligomeric Silsesquioxanes, POSS)是一类结构规整的有机-无机杂化纳米粒子,具有三维多面体结构,拥有Si-O-Si键构成的无机笼状刚性内核和多个有机官能团顶点。通过物理共混或化学共聚的方法将其引入到聚合物材料中,能够得到具有特殊结构和功能的有机-无机杂化材料。这些POSS基元的纳米粒子彼此之间不能相互渗透、不可穿透、不可压缩,具有规整的拓扑结构、均匀的纳米尺寸、确定的空间对称性等“刚性”特征,同时它们纳米基元之间又拥有较多的“柔性”链段可进行组装重排,这就提供了更多通过微调其拓扑结构实现组装形貌可控构筑的可能性。
中国科学院化学研究所吴德成研究员、王星副研究员课题组提出了一种高效快速构建POSS树枝状聚合物的普适化方法并实现了“刚柔相济、始可有成”调控组装形貌新策略。在这一设计中,基于设计合成的AB7型单体,按照新型的1→7支化点生长方式与具有不同拓扑结构的中心内核通过交替的酯化反应和点击化学反应,制备得到具有多种拓扑结构和均匀尺寸的POSS树枝状聚合物(Cx-G1,图1)和两亲性树枝状聚合物(Cx-POSSm-PEGn)。
图1 四种拓扑结构的POSS树枝状聚合物
在溶液组装过程中,刚性的POSS内核对疏水区域具有显著的自增大空间效应,POSS基元之间的柔性链段和外壳的PEG链段提供了组装体自适应调整和重排能力。在无需任何特殊控制的情况下,“刚柔相济”的特性促使这一类POSS树枝状聚合物在溶液中组装得到一系列特殊的组装形貌(如多腔室胶束、雪人型囊泡、环型囊泡等)。特别的是,当POSS内核的立体空间结构与PEG外壳链段长度相匹配时,POSS基元的强相分离能力和PEG柔性链段的自调节优化性能进一步触发组装体自发地进行层级自组装,实现组装形貌和尺寸的原位演变(图2)。
图2 多腔室胶束组装体及形貌尺寸演变
综上所述,该研究工作发展了一种快速制备POSS树枝状聚合物的合成方法以及组装形貌的自适应调控策略。基于刚性内核的疏水区域自增大空间效应和柔性链段的自调节优化性能,POSS树枝状聚合物在溶液中展现出了丰富多彩的组装形貌。在未来的工作中,通过进一步调节树枝状共聚物的刚性内核结构和尺寸、刺激响应性的外壳种类以及多样化的核壳连接位置,利用超分子相互作用、结晶诱导组装、分子纳米粒子可控堆积等技术手段,有望实现在微纳米尺度下对组装体的精确调控,以期获得种类更加多样化、结构更加可控化、性能更加智能化的先进功能材料。“刚柔相济、始可有成”,彰显自然之美与生命之力的真正融合。
此项研究得到了国家自然科学基金和中科院青促会的资助,中国科学院化学研究所王星副研究员是该论文第一作者,郑州大学杨艳宇副教授、中国科学技术大学尤业字教授和化学所吴德成研究员是论文的共同通讯作者。该工作以Research Article的形式发表在CCS Chemistry上,并在官网“Just Published”栏目上线。
文章详情:
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Xing Wang, Peiyuan Gao, Juan Wang, YanyuYang*, Yezi You* & Decheng Wu*
Link:https://doi.org/10.31635/ccschem.020.202000238
Citation:CCS Chem. 2020, 2, 1093–1104
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