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Intra- and intermolecular self-assembly of a 20-nm-wide supramolecular hexagonal grid.

ABSTRACT: For the past three decades, the coordination-driven self-assembly of three-dimensional structures has undergone rapid progress; however, parallel efforts to create large discrete two-dimensional architectures-as opposed to polymers-have met with limited success. The synthesis of metallo-supramolecular systems with well-defined shapes and sizes in the range of 10-100?nm remains challenging. Here we report the construction of a series of giant supramolecular hexagonal grids, with diameters on the order of 20?nm and molecular weights greater than 65?kDa, through a combination of intra- and intermolecular metal-mediated self-assembly steps. The hexagonal intermediates and the resulting self-assembled grid architectures were imaged at submolecular resolution by scanning tunnelling microscopy. Characterization (including by scanning tunnelling spectroscopy) enabled the unambiguous atomic-scale determination of fourteen hexagonal grid isomers.

SUBMITTER: Zhang Z

PROVIDER: S-EPMC7375338 | biostudies-literature | 2020 May

REPOSITORIES: biostudies-literature

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Intra- and intermolecular self-assembly of a 20-nm-wide supramolecular hexagonal grid.

Zhang Zhe Z Li Yiming Y Song Bo B Zhang Yuan Y Jiang Xin X Wang Ming M Tumbleson Ryan R Liu Changlin C Wang Pingshan P Hao Xin-Qi XQ Rojas Tomas T Ngo Anh T AT Sessler Jonathan L JL Newkome George R GR Hla Saw Wai SW Li Xiaopeng X

Nature chemistry 20200413 5

For the past three decades, the coordination-driven self-assembly of three-dimensional structures has undergone rapid progress; however, parallel efforts to create large discrete two-dimensional architectures-as opposed to polymers-have met with limited success. The synthesis of metallo-supramolecular systems with well-defined shapes and sizes in the range of 10-100 nm remains challenging. Here we report the construction of a series of giant supramolecular hexagonal grids, with diameters on the ...[more]

PMID: 32284575

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Project description:Anfinsen's famous experiment showed that the restoration of catalytic activity of a completely unfolded ribonuclease A is only possible when the correct order of events is followed during the refolding process. Inspired by this work, the effect of structural constraints induced by covalent cross-links on the folding of a synthetic polymer chain via hydrogen-bonding interactions is investigated. Hereto, methacrylate-based monomers comprising either benzene-1,3,5-tricarboxamide (BTA)-based or coumarin-based pendants are copolymerized with n-butyl methacrylate in various ratios via reversible addition-fragmentation chain-transfer (RAFT) polymerization. To assess whether the folding and single-chain polymeric nanoparticle (SCPN) formation depend on the order of events, we compare two folding pathways. In the one case, we first covalently cross-link the coumarin pendants within the polymers in a solvent that prevents hydrogen bonding, after which hydrogen bonding is activated, inducing folding of the polymer. In the other case, we induce hydrogen-bonding interactions between tethered BTAs prior to covalent cross-linking of the coumarin pendants. A combination of circular dichroism (CD) spectroscopy, UV-vis spectroscopy, size-exclusion chromatography (SEC), and dynamic light scattering (DLS) is employed to understand the effect of the structural constraints on the folding behavior of these synthetic polymers. The results show that like in ribonuclease A, the order of events matters greatly and determines the outcome. Importantly, a hydrogen-bond-promoting solvent prevents the formation of SCPNs upon covalent cross-linking and results in multichain aggregates. In contrast, covalently cross-linking the polymer when no hydrogen bonds are present followed by inducing hydrogen bonding favors the formation of SCPNs above the UCST of the methacrylate-based polymer. To our surprise, the two systems show a fundamentally different response to changes in temperature, indicating that also in synthetic polymers differences in the folding pathway induce differences in the properties of the resultant nanostructures.

Dataset Information

Intra- and intermolecular self-assembly of a 20-nm-wide supramolecular hexagonal grid.

Publications

Intra- and intermolecular self-assembly of a 20-nm-wide supramolecular hexagonal grid.

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