Modification of a Single Atom Affects the Physical Properties of Double Fluorinated Fmoc-Phe Derivatives
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 o...
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MDPI AG
2021-09-01
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| Series: | International Journal of Molecular Sciences |
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| Online Access: | https://www.mdpi.com/1422-0067/22/17/9634 |
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| author | 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 |
| author_facet | 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 |
| author_sort | Moran Aviv |
| collection | DOAJ |
| description | 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. |
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| issn | 1661-6596 1422-0067 |
| language | English |
| last_indexed | 2024-03-10T08:10:08Z |
| publishDate | 2021-09-01 |
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| series | International Journal of Molecular Sciences |
| spelling | doaj.art-d26d0dde8dc44b138920d2928b19bb752023-11-22T10:46:35ZengMDPI AGInternational Journal of Molecular Sciences1661-65961422-00672021-09-012217963410.3390/ijms22179634Modification of a Single Atom Affects the Physical Properties of Double Fluorinated Fmoc-Phe DerivativesMoran Aviv0Dana Cohen-Gerassi1Asuka A. Orr2Rajkumar Misra3Zohar A. Arnon4Linda J. W. Shimon5Yosi Shacham-Diamand6Phanourios Tamamis7Lihi Adler-Abramovich8Department of Oral Biology, The Goldschleger School of Dental Medicine, Sackler Faculty of Medicine, Tel Aviv University, Tel Aviv 6997801, IsraelDepartment of Oral Biology, The Goldschleger School of Dental Medicine, Sackler Faculty of Medicine, Tel Aviv University, Tel Aviv 6997801, IsraelArtie McFerrin Department of Chemical Engineering, Texas A&M University, College Station, TX 77843-3122, USADepartment of Oral Biology, The Goldschleger School of Dental Medicine, Sackler Faculty of Medicine, Tel Aviv University, Tel Aviv 6997801, IsraelDepartment of Oral Biology, The Goldschleger School of Dental Medicine, Sackler Faculty of Medicine, Tel Aviv University, Tel Aviv 6997801, IsraelDepartment of Chemical Research Support, Weizmann Institute of Science, Rehovot 76132701, IsraelDepartment of Materials Science and Engineering, Iby and Aladar Fleischman Faculty of Engineering, Tel Aviv University, Tel Aviv 6997801, IsraelArtie McFerrin Department of Chemical Engineering, Texas A&M University, College Station, TX 77843-3122, USADepartment of Oral Biology, The Goldschleger School of Dental Medicine, Sackler Faculty of Medicine, Tel Aviv University, Tel Aviv 6997801, IsraelSupramolecular 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.https://www.mdpi.com/1422-0067/22/17/9634self-assemblylow-molecular-weight hydrogelatorphase-transitionmolecular-dynamics |
| spellingShingle | 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 Modification of a Single Atom Affects the Physical Properties of Double Fluorinated Fmoc-Phe Derivatives International Journal of Molecular Sciences self-assembly low-molecular-weight hydrogelator phase-transition molecular-dynamics |
| title | Modification of a Single Atom Affects the Physical Properties of Double Fluorinated Fmoc-Phe Derivatives |
| title_full | Modification of a Single Atom Affects the Physical Properties of Double Fluorinated Fmoc-Phe Derivatives |
| title_fullStr | Modification of a Single Atom Affects the Physical Properties of Double Fluorinated Fmoc-Phe Derivatives |
| title_full_unstemmed | Modification of a Single Atom Affects the Physical Properties of Double Fluorinated Fmoc-Phe Derivatives |
| title_short | Modification of a Single Atom Affects the Physical Properties of Double Fluorinated Fmoc-Phe Derivatives |
| title_sort | modification of a single atom affects the physical properties of double fluorinated fmoc phe derivatives |
| topic | self-assembly low-molecular-weight hydrogelator phase-transition molecular-dynamics |
| url | https://www.mdpi.com/1422-0067/22/17/9634 |
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