4.8 Article

Mechanomorphogenic Films Formed via Interfacial Assembly of Fluorinated Amino Acids

Journal

ADVANCED FUNCTIONAL MATERIALS
Volume 31, Issue 40, Pages -

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/adfm.202104223

Keywords

amino acids; films; interfacial assembly; liquid-liquid separation; perfluorocarbon

Funding

  1. NSF Faculty Early Career Development Program (CAREER) [DMR-1845053]
  2. Penn State Graduate Research Fellowship
  3. NSF [DMR-1905550]

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Nature has developed elegant strategies to organize inert building blocks into adaptive supramolecular structures, with interfacial self-assembly being one favored approach. By exploiting antithetical fluorous-water interfaces, non-canonical fluorinated amino acids can be assembled into crystalline mechanomorphogenic films, yielding self-healing materials that can change their macro-morphology in response to mechanical stimuli. These films exhibit responsive behavior to environmental factors and selective permeability, which has enabled the rapid extraction of perfluoroalkyl substances from contaminated water samples. Continued research in this area may lead to the design of adaptive molecular networks and living matter using interface-templated and fluorine-driven assembly phenomena.
Nature has evolved several elegant strategies to organize inert building blocks into adaptive supramolecular structures. Favored among these is interfacial self-assembly, where the unique environment of liquid-liquid junctions provides structural, kinetic, thermodynamic, and chemical properties that are distinct from the bulk solution. Here, antithetical fluorous-water interfaces are exploited to guide the assembly of non-canonical fluorinated amino acids into crystalline mechanomorphogenic films. That is, the nanoscale order imparted by this strategy yields self-healing materials that can alter their macro-morphology depending on exogenous mechanical stimuli. Additionally, like natural biomolecules, organofluorine amino acid films respond to changes in environmental ionic strength, pH, and temperature to adopt varied secondary and tertiary states. Complementary biophysical and biochemical studies are used to develop a model of amino acid packing to rationalize this bioresponsive behavior. Finally, these films show selective permeability, capturing fluorous compounds while allowing the free diffusion of water. These unique capabilities are leveraged in an exemplary application of the technology to extract perfluoroalkyl substances from contaminated water samples rapidly. Continued exploration of these materials will advance the understanding of how interface-templated and fluorine-driven assembly phenomenon a can be co-utilized to design adaptive molecular networks and living matter.

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