Modification of a Single Atom Affects the Physical Properties of Double Fluorinated Fmoc-Phe Derivatives

International Journal of Molecular Sciences

Asuka A. Orr¹  Phanourios Tamamis¹  Linda J. W. Shimon²  Yosi Shacham-Diamand³  Lihi Adler-Abramovich⁴  Rajkumar Misra⁴  Moran Aviv⁴  Zohar A. Arnon⁴  Dana Cohen-Gerassi⁴ 

[1] Artie McFerrin Department of Chemical Engineering, Texas A&M University, College Station, TX 77843-3122, USA;Department of Chemical Research Support, Weizmann Institute of Science, Rehovot 76132701, Israel;Department of Materials Science and Engineering, Iby and Aladar Fleischman Faculty of Engineering, Tel Aviv University, Tel Aviv 6997801, Israel;Department of Oral Biology, The Goldschleger School of Dental Medicine, Sackler Faculty of Medicine, Tel Aviv University, Tel Aviv 6997801, Israel;

关键词: self-assembly;    low-molecular-weight hydrogelator;    phase-transition;    molecular-dynamics;   

DOI  :  10.3390/ijms22179634

来源: DOAJ

【 摘 要 】

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. However, 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 differences 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 organization 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.

【 授权许可】

Unknown