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Abstract This work investigates the influence of dielectrophoretic forces on the structural features and the resulting aggregates of a chromogenic model system, peptide‐diacetylene (D3GV‐DA) amphiphiles. Here, we systematically investigate how non‐uniform electric fields impact the (i) peptide‐directed supramolecular assembly stage and (ii) topochemical photopolymerization stage of polydiacetylenes (PDAs) in a quadrupole‐based dielectrophoresis (DEP) device, as well as the (iii) manipulation of D3GV‐DA aggregates in a light‐induced DEP (LiDEP) platform. The conformation‐dependent chromatic phases of peptide‐PDAs are utilized to probe the chain‐level effect of DEP exposure after the supramolecular assembly or after the topochemical photopolymerization stage. Steady‐state spectroscopic and microscopy analyses show that structural features such as the chirality and morphologies of peptidic 1‐D nanostructures are mostly conserved upon DEP exposure, but applying mild, non‐uniform fields at the self‐assembly stage is sufficient for fine‐tuning the chromatic phase ratio in peptide‐PDAs and manipulating their aggregates via LiDEP. Overall, this work provides insights into how non‐uniform electric fields offer a controllable approach to fine‐tune or preserve the molecularly preset assembly order of DEP‐responsive supramolecular or biopolymeric assemblies, as well as manipulate their aggregates using light projections, which have future implications for the precision fabrication of macromolecular systems with hierarchical structure‐dependent function.
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Mechanoactivated amorphization and photopolymerization of styryldipyryliums
Abstract Conventional topochemical photopolymerization reactions occur exclusively in precisely-engineered photoactive crystalline states, which often produces high-insoluble polymers. To mitigate this, here, we report the mechanoactivation of photostable styryldipyrylium-based monomers, which results in their amorphization-enabled solid-state photopolymerization and produces soluble and processable amorphous polymers. A combination of solid-state nuclear magnetic resonance, X-ray diffraction, and absorption/fluorescence spectroscopy reveals the crucial role of a mechanically-disordered monomer phase in yielding polymers via photo-induced [2 + 2] cycloaddition reaction. Hence, mechanoactivation and amorphization can expand the scope of topochemical polymerization conditions to open up opportunities for generating polymers that are otherwise difficult to synthesize and analyze.
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- Award ID(s):
- 2142887
- PAR ID:
- 10513171
- Publisher / Repository:
- Nature Publishing Group
- Date Published:
- Journal Name:
- Communications Materials
- Volume:
- 5
- Issue:
- 1
- ISSN:
- 2662-4443
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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