Multiple length-scale control of Boc-protected diphenylalanine aggregates through solvent composition
Year: 2024
Authors: Catalini S., Bagni F., Cicchi S., Di Donato M., Iagatti A., Lapini A., Foggi P., Petrillo C., Di Michele A., Paolantoni M., Schiro G., Comez L., Paciaroni A.
Autors Affiliation: Univ Perugia, Dipartimento Fis & Geol, Via Pascoli, I-06123 Perugia, PG, Italy; CNR INO, Largo Fermi 6, I-50125 Florence, FI, Italy; European Lab Nonlinear Spect, Via Nello Carrara 1, I-50019 Sesto Fiorentino, FI, Italy; Univ Firenze, Dipartimento Chim Ugo Schiff, Via Lastruccia 3-13, I-50019 Sesto Fiorentino, FI, Italy; CNR ICCOM, Via Madonna Piano 10, I-50019 Sesto Fiorentino, FI, Italy; Univ Parma, Dipartimento Sci Chim Vita & Sostenibil Ambientale, Parco Area Sci 17-A, I-43124 Parma, PR, Italy; Univ Perugia, Dipartimento Chim Biol & Biotecnol, Via Elce Sotto 8, I-06123 Perugia, PG, Italy; Univ Grenoble Alpes, CNRS, CEA, IBS, F-38000 Grenoble, France; Univ Perugia, Ist Officina Materiali IOM, CNR, Dipartimento Fis & Geol, Via Pascoli, I-06123 Perugia, PG, Italy.
Abstract: Diphenylalanine and its variants are among the most studied building blocks in materials science due to their ability to form extended architectures with a wide range of morphologies. Given this propensity to self-assemble into very different shapes, controlling the aggregation process of the basic units is very challenging. Using a selection of techniques, this work investigates the critical role of solvation in influencing the association of Boc-protected diphenylalanine. The results indicate that the balance of solvents, specifically acetonitrile-water, significantly impacts the self-assembly process. Indeed, a change in acetonitrile content from 2% to 10% in water solutions drives the formation of different morphologies of the aggregates, spanning from spheres to plates. In a pure organic solvent a single orthorhombic crystalline phase is observed, whereas the presence of water reveals the coexistence of two phases: orthorhombic and hexagonal. The fraction of hexagonal phase relies on the solvent composition, while the peptides always adopt turn conformations, promoting the plane-to-plane stacking of aromatic rings. The architectural growth is driven by aromatic stacking and hydrophobic interactions; the development of different morphologies is dependent on the extent of the aggregate-solvent interface. Interestingly, we find a morphology re-entrant behaviour induced by finely tuning the acetonitrile content, thereby linking aggregate morphology with molecular characteristics. The selection of suitable building blocks and solvation conditions is crucial in steering the nature of aggregates toward creating smart biomaterials with enhanced properties. Self-aggregation of Boc-protected diphenylalanine towards the formation of architectures with morphology and structure highly dependent on the acetonitrile-water percentage.
Journal/Review: MATERIALS ADVANCES
Volume: 5 (9) Pages from: 3802 to: 3811
More Information: S. C. and A. P. thank the research project FSE-REACT EU financed by National Social Fund-National Operative Research Program and Innovation 2014-2020 (D. M. 1062/2021), personal Grant number 23-G-15445-3. S. C., P. F., C. P., A. D. M., M. P., L. C. and A. P. thank the European Union-NextGenerationEU project under the Italian Ministry of University and Research (MUR) National Innovation Ecosystem grant ECS00000041-VITALITY-CUP: J97G22000170005 and B43C22000470005. S. C. and G. S. thank A. Royant and S. Engilberge of the FIP2-BM07 beamline of the European Synchrotron Radiation Facility (ESRF) (Grenoble) for providing their internal beamtime and support for XRD measurements. L. C., A. I., and A. L. thank Ministero dell’Istruzione dell’Universita e della Ricerca Italiano LANTERN (PRIN2022-20225NPY8P).KeyWords: Preferential Solvation; Clustering Conditions; Circular-dichroism; Self-assemblies; Peptide; Morphology; Nanostructures; Transition; Molecules; ResidueDOI: 10.1039/d4ma00018hConnecting to view paper tab on IsiWeb: Click here