Giant surfactants provide a versatile platform for sub-10-nm nanostructure engineering

Xinfei Yu, Kan Yue, Fan Hsieh, Yiwen Li, Xue Hui Dong, Chang Liu, Yu Xin, Hsiao Fang Wang, An Chang Shi, George R. Newkome, Rong Ming Ho, Er Qiang Chen, Wen Bin Zhang, Stephen Z.D. Cheng

Research output: Contribution to journalArticlepeer-review

181 Citations (Scopus)


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.

Original languageEnglish
Pages (from-to)10078-10083
Number of pages6
JournalProceedings of the National Academy of Sciences of the United States of America
Issue number25
Publication statusPublished - 2013 Jun 18
Externally publishedYes


  • Colloidal particles
  • Giant molecules
  • Hybrid materials
  • Microphase separation
  • Shape amphiphiles

ASJC Scopus subject areas

  • General


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