Crystallinity Controlled 3D Printing of Self-Assembled Dipeptides

Universal molecular self-assembly provides a rich platform for printing technology in electronic¹ and photonic applications². Especially, highly ordered, crystallized self-assembled peptides nanostructures attracted attention due to the emergent versatile physical/chemical properties arising from huge variables in molecular structures. Due to the spontaneous nature of the self-assembly process geared by intermolecular interactions, the preparation method largely relies on the classical chemical process, which is not suitable to prepare freeform structures on demand. Despite tremendous efforts in the preparation of on-demand self-assembled structures³, the method for the fabrication of free-standing structures with a tailored molecular orientation in 3D space has not been fully demonstrated yet.<br/>Here, we have developed a crystallinity controllable 3D printing method encompassing the reprecipitation self-assembly pathway based on the manipulated solubility originating from the controlled evaporation of binary solvents (good and anti-solvents). As an exemplar, the 3D printing of diphenylalanine (FF) will be presented. FF, the simplest aromatic group-containing peptides which can form highly ordered crystal structures, is an intriguing building block due to its strong piezoelectricity⁴ and non-linear optical property⁵ with superior chemical/mechanical stability⁴. The method employs the guided femtoliter solution meniscus to form programmed microscale 3D architectures. The crystallinity was tunable under controlled evaporation of binary solvents (Water/HFIP) upon humidity. The computed supersaturation ratio of FF explained the effect of humidity on its crystallinity. In this talk, we will discuss the mechanism and present the free-standing alternative crystal/amorphous patterns for encrypting/transferring information based on light polarization.<br/>References:<br/>1. C-C, Liu, E. Franke, Y. Mignot, R. Xie, C. W. Yeung, J. Zhang, C. Chi, C. Zhang, R. Farrel, K. Lai, H. Tsai, N. Felix & D. Corliss. <i>Nat</i>. <i>Electronics</i>, 2018, <b>1</b>, 562-569.<br/>2. A. Handelman, N. Lapshina, B. Apter, G. Rosenman. Peptide Integrated Optics. <i>Adv</i>. <i>Mater</i>., 2017. <b>30</b>, 1705776.<br/>3. V. Nguyen, R. Zhu, K. Jenkins, R. Yang. Self-assembly of diphenylalanine peptide with controlled polarization for power generation. <i>Nat</i>. <i>Commun</i>, 2016, 7, 13566.<br/>4. V. Basavalingappa, S. Bera, B. Xue, J. O’Donnel, S. Guerin, P.-A. Cazade, H. Yuan, E. ul Haq, C. Silien, K. Tao, L. J. W. Shimon, S. A. M. Tofail, D. Thompson, S. Kolusheva, R. Yang, Y. Cao, and E. Gazit. Diphenylalanine-Derivative Peptide Assemblies with Increased Aromaticity Exhibit Metal-like Rigidity and High Piezoelectricity. <i>ACS</i> <i>Nano</i>, 2020, <b>14</b>, 6, 7025-7037.<br/>5. N. Amdursky, P. Beker, I. Koren, B. Bank-Srour, E. Mishina, S. Semin, T. Rasing, Y. Rosenberg, Z. Barkay, E. Gazit, and G. Rosenman. <i>Biomacromolecules</i>, 2011, <b>12</b>, 4, 1349-1354.