Self-assembly of three-component bolaform giant surfactants with branched architectures
Bo Hou,
Xiaojin Yan,
Jinlin He,
Wen-Bin Zhang,
Yu Shao
Affiliations
Bo Hou
Key Laboratory of Polymer Chemistry & Physics of Ministry of Education, Center for Soft Matter Science and Engineering, College of Chemistry and Molecular Engineering, Beijing National Laboratory for Molecular Sciences, Peking University, Beijing 100871, PR China
Xiaojin Yan
College of Chemistry, Chemical Engineering and Materials Science, State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, Soochow University, Suzhou 215123, PR China
Jinlin He
College of Chemistry, Chemical Engineering and Materials Science, State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, Soochow University, Suzhou 215123, PR China
Wen-Bin Zhang
Key Laboratory of Polymer Chemistry & Physics of Ministry of Education, Center for Soft Matter Science and Engineering, College of Chemistry and Molecular Engineering, Beijing National Laboratory for Molecular Sciences, Peking University, Beijing 100871, PR China; Corresponding authors.
Yu Shao
Key Laboratory of Polymer Chemistry & Physics of Ministry of Education, Center for Soft Matter Science and Engineering, College of Chemistry and Molecular Engineering, Beijing National Laboratory for Molecular Sciences, Peking University, Beijing 100871, PR China; Corresponding authors.
Branched architecture profoundly influences the physical properties of polymers, making it an important topic in the field of polymer science. Herein, we report a facile synthetic strategy to introduce one site-specific side chain at the junction point to fabricate a series of bolaform giant surfactants with branched architecture. By tuning the volume fraction and the ratio between the linking chain and side chain, various phases have been identified, including three-phase-four-layer lamellae, graphene-like honeycombs, tetragonally packed cylinders, and two-phase lamellae. Notably, the lattice dimension of obtained columnar structures is ∼12 nm, corresponding to sub-10 nm cylinder diameters. As revealed by temperature-dependent small-angle X-ray scattering profiles, a branched architecture significantly decreases the order-disorder transition temperature by ∼90 °C. We also use semi-quantitative calculations to analyze the thermodynamic properties of the observed phases and build rational connections between phase behaviors and the corresponding branching ratios. This study shed light on fine-tuning the macromolecular assembly via molecular topology engineering.
