Citation: Wen Tang, Kan Yue, Stephen Z. D. Cheng. Molecular Topology Effects in Self-assembly of Giant Surfactants[J]. Acta Polymerica Sinica, ;2018, 0(8): 959-972. doi: 10.11777/j.issn1000-3304.2018.18102 shu

Molecular Topology Effects in Self-assembly of Giant Surfactants

South China Advanced Institute for Soft Matter Science and Technology, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640

Corresponding author: Kan Yue, kanyue@scut.edu.cn Stephen Z. D. Cheng, scheng@scut.edu.cn
Received Date: 9 April 2018
Revised Date: 22 May 2018

Self-assembly of block copolymers, which are composed of covalently connected incompatible polymer chains, can result in various ordered structures at the nanometer scale. This phenomenon, widely known as the microphase separation of block copolymers, may provide a technological platform for the development of next-generation nanopatterning techniques based on the " top-down” strategy. During the past decade, a unique class of novel amphiphilic macromolecules termed as giant surfactants have been reported, which are constructed from selected building blocks of cluster-like molecules having three-dimensional rigid conformations and nanometer sizes. By combining different " click-type” reactions, a highly efficient and modular synthetic method has been developed to prepare covalent conjugates of these molecular clusters and polymer chains. The resulting giant surfactants can be viewed as structural analogues of common block copolymers, and similarly, they also display interesting self-assembly behaviors both in solutions and in bulk. Herein, recent advances on the study of self-assembly of giant surfactants are summarized, with a particular emphasis on the molecular topology effects that can significantly change their self-assembly behaviors. As revealed by small angle X-ray scattering and transmission electron microscopy techniques, giant surfactants were able to self-assemble in bulk to form a series of highly ordered nanostructures with feature sizes below 10 nm or even 5 nm, with clearly shifted phase boundaries. More importantly, through rational molecular design to tune the molecular topology of giant surfactants, formation of some unusual nanostructures driven by molecular topological variations was achieved. Typical examples include several unconventional spherical phases, such as the Frank-Kasper A15 phase, the Frank-Kasper σ phase, and a quasicrystalline spherical phase, which were observed in multitailed giant surfactants, and a highly asymmetric lamellar phase formed by self-assembly of multiheaded giant surfactants. It is believed that these studies provide not only insights towards understanding the molecular topological effects in macromolecular self-assembly, but also experimental foundation for the development of block copolymer lithography that can afford nanostructures with sub-10-nm feature sizes.
- Microphase separation,
- Giant surfactants,
- Block copolymers,
- Molecular topology,
- Self-assembly
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