Feng Xueyan, Zhu Sunsheng, Yue Kan, Su Hao, Guo Kai, Wesdemiotis Chrys, Zhang Wen-Bin, Cheng Stephen Z D, Li Yiwen
Department of Polymer Science, College of Polymer Science and Polymer Engineering, The University of Akron, Akron, Ohio 44325-3909, United States.
Department of Chemistry, The University of Akron, Akron, Ohio 44325-3601, United States.
ACS Macro Lett. 2014 Sep 16;3(9):900-905. doi: 10.1021/mz500422g. Epub 2014 Aug 29.
Head diversification of shape amphiphiles not only broadens the scope of supramolecular engineering for new self-organizing materials but also facilitates their potential applications in high technologies. In this letter, T azido-functionalized polyhedral oligomeric silsesquioxane (POSS) nanoparticle was used to construct new shape amphiphiles via sequential "click" chemistry for addressing two issues: (1) new symmetry of T POSS head could enrich the self-assembly behaviors of shape amphiphiles, and (2) copper-catalyzed azide-alkyne cycloaddition (CuAAC)-based head functionalization strategy allows the introduction of diverse functionalities onto POSS heads, including bulky ligands (i.e., isobutyl POSS) and UV-attenuating ones (i.e., ferrocene and 4-cyano-4'-biphenyl). This study expands the library of POSS-based shape amphiphiles with numerous possibilities for head manipulations, offering an important step toward new shape amphiphiles beyond traditional hydrophobic/hydrophilic nature for potential applications in giant molecule-based nanoscience and technology.
形状两亲物头部的多样化不仅拓宽了新型自组装材料超分子工程的范围，还促进了它们在高科技领域的潜在应用。在本信函中，叠氮基官能化的多面体低聚倍半硅氧烷（POSS）纳米颗粒通过连续的“点击”化学用于构建新型形状两亲物，以解决两个问题：（1）T POSS头部的新对称性可以丰富形状两亲物的自组装行为，（2）基于铜催化的叠氮化物-炔烃环加成（CuAAC）的头部功能化策略允许在POSS头部引入多种功能，包括体积较大的配体（即异丁基POSS）和紫外线衰减配体（即二茂铁和4-氰基-4'-联苯）。本研究扩展了基于POSS的形状两亲物库，为头部操作提供了众多可能性，朝着超越传统疏水/亲水性质的新型形状两亲物迈出了重要一步，有望应用于基于大分子的纳米科学和技术领域。
