Sun Hui, Liu Danqing, Du Jianzhong
Department of Polymeric Materials , School of Materials Science and Engineering , Tongji University , 4800 Caoan Road , Shanghai 201804 , China . Email:
Department of Orthopedics , Shanghai Tenth People's Hospital , Tongji University School of Medicine , Shanghai 200072 , China.
Chem Sci. 2018 Nov 21;10(3):657-664. doi: 10.1039/c8sc03995j. eCollection 2019 Jan 21.
Asymmetric nanoparticles such as nanobowls have promising potential in many fields due to their interior asymmetric cavities and specific concave structure. However, the fabrication of nanobowls and control over their openings and interior holes are still challenging. Herein we demonstrate a versatile strategy for preparing nanobowls with precisely controlled openings and interior holes based on the synergy of hydrogen bonding and π-π interaction of homopolymers. We designed and synthesized a series of amphiphilic homopolymers with an amino alcohol moiety and azobenzene pendant (poly(2-hydroxy-3-((4-(phenyldiazenyl)phenyl)amino)propyl methacrylate) (PHAzoMA)). The homopolymers can self-assemble into nanobowls due to the heterogeneous shrinkage of the preformed spheres. Upon increasing the molecular weight of the homopolymers from 10.1 to 76.9 kg mol, the sizes of the openings of nanobowls can be precisely controlled from 242 to 423 nm with a linear relationship as a result of the enhancement of the hydrogen bonding and π-π interaction between homopolymer chains. Overall, we have prepared finely controlled nanobowls by the synergy of non-covalent interactions such as hydrogen bonding and π-π interaction of polymers, which opens a new avenue for the preparation of asymmetric nanoparticles.
诸如纳米碗之类的不对称纳米粒子由于其内部不对称的空腔和特定的凹面结构，在许多领域具有广阔的应用潜力。然而，纳米碗的制备以及对其开口和内部孔洞的控制仍然具有挑战性。在此，我们展示了一种基于均聚物的氢键和π-π相互作用协同效应来制备具有精确控制开口和内部孔洞的纳米碗的通用策略。我们设计并合成了一系列带有氨基醇部分和偶氮苯侧基的两亲性均聚物（聚（甲基丙烯酸2-羟基-3-（（4-（苯基重氮基）苯基）氨基）丙酯）（PHAzoMA））。由于预制球体的异质收缩，这些均聚物能够自组装成纳米碗。随着均聚物分子量从10.1增至76.9 kg/mol，纳米碗开口尺寸可从242精确控制到423 nm，这是由于均聚物链间氢键和π-π相互作用增强，二者呈线性关系。总体而言，我们通过聚合物的氢键和π-π相互作用等非共价相互作用的协同效应制备了精细可控的纳米碗，这为制备不对称纳米粒子开辟了一条新途径。
