State Key Laboratory of Chemical Engineering, Department of Chemistry, Zhejiang University , Hangzhou 310027, P. R. China.
J Am Chem Soc. 2014 Nov 5;136(44):15497-500. doi: 10.1021/ja5093503. Epub 2014 Oct 23.
Oligo(ethylene glycol) (OEG)-decorated supramolecular assemblies are distinguished by their neutral character and macroscopic temperature-sensitive phase transition behavior. OEG functionalization is an emerging strategy to obtain thermoresponsive macrocyclic amphiphiles, although known methods organize the hydrophilic and hydrophobic segments by covalent bonding. Coordination-driven self-assembly offers an alternative route for organizing OEG-functionalized precursors into nanoscopic architectures, resulting in well-defined metallacycle cores surrounded by hydrophilic scaffolds to impart overall amphiphilic character. Here a tri(ethylene glycol)-functionalized thermosensitive amphiphilic metallacycle was prepared with high efficiency by means of the directional-bonding approach. The ensembles thus formed showed good lower critical solution temperature behavior with a highly sensitive phase separation and excellent reversibility. Moreover, the clouding point decreased with increasing metallacycle concentration and addition of K(+).
聚乙二醇(OEG)修饰的超分子组装体以其中性特征和宏观温度敏感相转变行为而著称。OEG 功能化是获得温度响应性大环两亲物的一种新兴策略,尽管已知的方法通过共价键将亲水性和疏水性片段组织在一起。配位驱动的自组装为将 OEG 功能化的前体组织成纳米结构提供了另一种途径,从而形成由亲水性支架围绕的具有良好定义的金属环核,赋予整体两亲性特征。在这里,通过定向键合方法高效制备了三(乙二醇)功能化的热敏感两亲金属环。由此形成的聚集体表现出良好的低临界溶液温度行为,具有高度敏感的相分离和优异的可逆性。此外,浊点随着金属环浓度的增加和 K(+)的加入而降低。