Topochemical polymerization in phenylalanine anchored chiral diacetylenes for chiroptical properties and tunable thermo-, halo-, solvatochromism

Maulik, Antarlina; Miglani, Chirag; Mavlankar, Nimisha A.; Joseph, Jojo P.; Chandran, Vysakh C; Pal, Asish

doi:10.1039/d2nj05708e

Cited by 4 publications

(2 citation statements)

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“…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.…”

Section: Introductionmentioning

confidence: 99%

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

Miglani,

Ralhan,

Banoo

et al. 2024

ACS Polym. Au

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The precise sequence of a protein's primary structure is essential in determining its folding pathways. To emulate the complexity of these biomolecules, functional block copolymers consisting of segmented triblocks with distinct functionalities positioned in a sequence-specific manner are designed to control the polymer chain compaction. Triblock polymers P-b-C-b-F and P-b-F-b-C and random diblock copolymer P-b-C-r-F consist of a hydrophilic poly(ethylene oxide) (PEO) block and a hydrophobic block with coumarin (C) and ferrocene (F) moieties that are grafted in a sequence-specific or random manner onto the hydrophilic block. External stimuli such as UV B light, redox, and chemical cues influence the functional hydrophobic block to alter the packing parameters that are monitored with spectroscopic and scattering techniques. Interestingly, the positioning of the stimuli-responsive moiety within the hydrophobic block of P-b-C-b-F, P-b-F-b-C, and P-b-C-r-F affects the extent of the hydrophobic−hydrophilic balance in block copolymers that renders orthogonal control in stimuli-responsive transformation of self-assembled vesicles to micelles.

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Section: Introductionmentioning

confidence: 99%

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

Miglani,

Ralhan,

Banoo

et al. 2024

ACS Polym. Au

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“…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 .…”

Section: Introductionmentioning

confidence: 99%

Selective Chirality-Driven Photopolymerization of Diacetylene Crystals

Baillargeon,

Boivin,

Vaillancourt

et al. 2024

Crystal Growth & Design

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Crystal engineering of two diacetylene monomers was achieved by branching two chiral groups [R = PhC*MeNH(CO2)CH2] exhibiting an enantiopure configuration of S,S-(DA2) and an achiral R,S-meso-isomer (DA4). The X-ray structures of DA2 and DA4 reveal the presence of supramolecular arrangements driven by intermolecular H-bonding. A significant intermolecular closer proximity in DA4 than that in DA2 is depicted, ultimately resulting in a slow thermal (days) and swift (min) photochemical polymerization of DA4 to form PDA5, whereas DA2 is unreactive. DFT computations indicate that in both cases the lowest energy-excited state is the charge-transfer state [CT; PhC*MeNH(CO2) → π*(−CC–CC−)]. Therefore, this outcome illustrates a drastic selectivity via a settle change in a carbon configuration. Analysis demonstrates that PDA5 is nonemissive and that its coloration arises from a π → π* excitation of the polymer backbone (DFT computations).

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

et al. 2023

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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.

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Topochemical polymerization in phenylalanine anchored chiral diacetylenes for chiroptical properties and tunable thermo-, halo-, solvatochromism

Abstract: Chiral polymers always have an edge over their achiral analogues owing to the effective utilization of the asymmetry to mimic nature in multiple ways. Chirality in tandem with conjugation in...

Cited by 4 publications

References 51 publications

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

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

Selective Chirality-Driven Photopolymerization of Diacetylene Crystals

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

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