title: Giant surfactants provide a versatile platform for sub-10-nm nanostructure engineering.
abstract: The engineering of structures across different length scales is central to the design of novel materials with controlled macroscopic properties. Herein, we introduce a unique class of self-assembling materials, which are built upon shape- and volume-persistent molecular nanoparticles and other structural motifs, such as polymers, and can be viewed as a size-amplified version of the corresponding small-molecule counterparts. Among them, "giant surfactants" with precise molecular structures have been synthesized by "clicking" compact and polar molecular nanoparticles to flexible polymer tails of various composition and architecture at specific sites. Capturing the structural features of small-molecule surfactants but possessing much larger sizes, giant surfactants bridge the gap between small-molecule surfactants and block copolymers and demonstrate a duality of both materials in terms of their self-assembly behaviors. The controlled structural variations of these giant surfactants through precision synthesis further reveal that their self-assemblies are remarkably sensitive to primary chemical structures, leading to highly diverse, thermodynamically stable nanostructures with feature sizes around 10 nm or smaller in the bulk, thin-film, and solution states, as dictated by the collective physical interactions and geometric constraints. The results suggest that this class of materials provides a versatile platform for engineering nanostructures with sub-10-nm feature sizes. These findings are not only scientifically intriguing in understanding the chemical and physical principles of the self-assembly, but also technologically relevant, such as in nanopatterning technology and microelectronics.
authors.affiliation: Department of Polymer Science, College of Polymer Science and Polymer Engineering, University of Akron, Akron, OH 44325-3909, USA.
authors.forename: Xinfei
authors.initials: X
authors.lastname: Yu
authors.forename: Kan
authors.initials: K
authors.lastname: Yue
authors.forename: I-Fan
authors.initials: IF
authors.lastname: Hsieh
authors.forename: Yiwen
authors.initials: Y
authors.lastname: Li
authors.forename: Xue-Hui
authors.initials: XH
authors.lastname: Dong
authors.forename: Chang
authors.initials: C
authors.lastname: Liu
authors.forename: Yu
authors.initials: Y
authors.lastname: Xin
authors.forename: Hsiao-Fang
authors.initials: HF
authors.lastname: Wang
authors.forename: An-Chang
authors.initials: AC
authors.lastname: Shi
authors.forename: George R
authors.initials: GR
authors.lastname: Newkome
authors.forename: Rong-Ming
authors.initials: RM
authors.lastname: Ho
authors.forename: Er-Qiang
authors.initials: EQ
authors.lastname: Chen
authors.forename: Wen-Bin
authors.initials: WB
authors.lastname: Zhang
authors.forename: Stephen Z D
authors.initials: SZ
authors.lastname: Cheng
mesh_terms: D003102:Colloids / Q000737:chemistry; D004581:Electronics / Q000379:methods; D053758:Nanoparticles / Q000737:chemistry*; D049329:Nanostructures; D036103:Nanotechnology / Q000379:methods*; D013499:Surface Properties; D013501:Surface-Active Agents / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D003102:Colloids; D013501:Surface-Active Agents
keywords: colloidal particles; giant molecules; hybrid materials; microphase separation; shape amphiphiles