Modification of a single atom affects the physical properties of double fluorinated fmoc-phe derivatives

Moran Aviv, Dana Cohen-Gerassi, Asuka A. Orr, Rajkumar Misra, Zohar A. Arnon, Linda J.W. Shimon, Yosi Shacham-Diamand, Phanourios Tamamis, Lihi Adler-Abramovich*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

11 Scopus citations

Abstract

Supramolecular hydrogels formed by the self-assembly of amino-acid based gelators are receiving increasing attention from the fields of biomedicine and material science. Self-assembled systems exhibit well-ordered functional architectures and unique physicochemical properties. How-ever, the control over the kinetics and mechanical properties of the end-products remains puzzling. A minimal alteration of the chemical environment could cause a significant impact. In this context, we report the effects of modifying the position of a single atom on the properties and kinetics of the self-assembly process. A combination of experimental and computational methods, used to investigate double-fluorinated Fmoc-Phe derivatives, Fmoc-3,4F-Phe and Fmoc-3,5F-Phe, reveals the unique effects of modifying the position of a single fluorine on the self-assembly process, and the physical properties of the product. The presence of significant physical and morphological differ-ences between the two derivatives was verified by molecular-dynamics simulations. Analysis of the spontaneous phase-transition of both building blocks, as well as crystal X-ray diffraction to determine the molecular structure of Fmoc-3,4F-Phe, are in good agreement with known changes in the Phe fluorination pattern and highlight the effect of a single atom position on the self-assembly process. These findings prove that fluorination is an effective strategy to influence supramolecular organiza-tion on the nanoscale. Moreover, we believe that a deep understanding of the self-assembly process may provide fundamental insights that will facilitate the development of optimal amino-acid-based low-molecular-weight hydrogelators for a wide range of applications.

Original languageEnglish
Article number9634
JournalInternational Journal of Molecular Sciences
Volume22
Issue number17
DOIs
StatePublished - Sep 2021

Funding

FundersFunder number
Texas A and M University
Horizon 2020 Framework Programme948102
European Research Council
Israel Science Foundation1732/17

    Keywords

    • Low-molecular-weight hydrogelator
    • Molecular-dynamics
    • Phase-transition
    • Self-assembly

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