Stereoselective Plasmonic Interaction in Peptide‐tethered Photopolymerizable Diacetylenes Doped with Chiral Gold Nanoparticles

Abstract

Designing polymeric systems with ultra‐high optical activity is instrumental in the pursuit of smart artificial chiroptical materials, including the fundamental understanding of structure/property relations. Herein, we report a diacetylene (DA) moiety flanked by chiral D‐ and L‐FF dipeptide methyl esters that exhibits efficient topochemical photopolymerization in the solid phase to furnish polydiacetylene (PDA) with desired control over the chiroptical properties. The doping of the achiral gold nanoparticles provides plasmonic interaction with the PDAs to render asymmetric shape to the circular dichroism bands. With the judicious design of the chiral amino acid ligand appended to the AuNPs, we demonstrate the first example of selective chiral amplification mediated by stereo‐structural matching of the polymer‐plasmonic AuNP hybrid pairs. Such ordered self‐assembly aided by topochemical polymerization in peptide‐tethered PDA provides a smart strategy to produce soft responsive materials for applications in chiral photonics.

Divergent self-assembly propensity of enantiomeric phenylalanine amphiphiles that undergo pH-induced nanofiber-to-nanoglobule conversion

“…Self-assembly of phenylalanine-derived amphiphiles (PDAs) yields diverse soft (nano) materials 1,2 that elicit high utility in biomedicine 3,4 and chiral templation. 5–9 Helical fibers, chiral tubes, globules, vesicles, etc. 10–12 have been fabricated through PDA self-assembly.…”

Stimuli-Responsive Control over Self-Assembled Nanostructures in Sequence-Specific Functional Block Copolymers

“…Thus, the coassembled vesicles, influenced by orthogonal stimuli, formed self-sorted compartments, offering potential applications in mimicking interactions of artificial cell models with the extracellular matrix. In that regard, we explored chirality-driven compartmentalization in dynamic supramolecular polymers and covalent polymers, moving a step closer to imitating orthogonality in biological systems. − However, emulating the complexity of cellular systems demands the design of polymers with orthogonal stimuli-responsive moieties to achieve compartmentalization akin to biological systems. Thus, the synthesis of triblock copolymer systems further enhances the control, facilitating the development of compartmentalized structures that closely resemble the organization seen in biological systems.…”

Selective Chirality-Driven Photopolymerization of Diacetylene Crystals

“…Ideal packing requirements for DA monomers were established many years ago, mainly on the basis of crystallographic studies (Figure ). , As mentioned, the study of PDAs with asymmetric carbons has attracted some attention, but the focus was on chiroptical applications. − To the best of our knowledge, no single-crystal structure of PDA with asymmetric carbons was successfully resolved. Baughman and co-workers reported a racemic mixture of diacetylene monomers and assumed the formation of a polymer based on residual densities .…”