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Anti-cooperative Self-Assembly with Maintained Emission Regulated by Conformational and Steric Effects.

ABSTRACT: Herein, we present a strategy to enable a maintained emissive behavior in the self-assembled state by enforcing an anti-cooperative self-assembly involving weak intermolecular dye interactions. To achieve this goal, we designed a conformationally flexible monomer unit 1 with a central 1,3-substituted (diphenyl)urea hydrogen bonding synthon that is tethered to two BODIPY dyes featuring sterically bulky trialkoxybenzene substituents at the meso-position. The competition between attractive forces (H-bonding and aromatic interactions) and destabilizing effects (steric and competing conformational effects) limits the assembly, halting the supramolecular growth at the stage of small oligomers. Given the presence of weak dye-dye interactions, the emission properties of molecularly dissolved 1 are negligibly affected upon aggregation. Our findings contribute to broadening the scope of emissive supramolecular assemblies and controlled supramolecular polymerization.

SUBMITTER: Helmers I

PROVIDER: S-EPMC9311066 | biostudies-literature | 2022 Apr

REPOSITORIES: biostudies-literature

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Anti-cooperative Self-Assembly with Maintained Emission Regulated by Conformational and Steric Effects.

Helmers Ingo I Hossain Muhammad Saddam MS Bäumer Nils N Wesarg Paul P Soberats Bartolome B Shimizu Linda S LS Fernández Gustavo G

Angewandte Chemie (International ed. in English) 20220302 17

Herein, we present a strategy to enable a maintained emissive behavior in the self-assembled state by enforcing an anti-cooperative self-assembly involving weak intermolecular dye interactions. To achieve this goal, we designed a conformationally flexible monomer unit 1 with a central 1,3-substituted (diphenyl)urea hydrogen bonding synthon that is tethered to two BODIPY dyes featuring sterically bulky trialkoxybenzene substituents at the meso-position. The competition between attractive forces ( ...[more]

PMID: 35112463

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Project description:The cell-dependent polymerization of intercellular fibronectin fibrils can stimulate cells to self-assemble into multicellular structures. The local physical cues that support fibronectin-mediated cellular self-assembly are largely unknown. Here, fibronectin matrix analogs were used as synthetic adhesive substrates to model cell-matrix fibronectin fibrils having different integrin-binding specificity, affinity, and/or density. We utilized this model to quantitatively assess the relationship between adhesive forces derived from cell-substrate interactions and the ability of fibronectin fibril assembly to induce cellular self-assembly. Results indicate that the strength of initial, rather than mature, cell-substrate attachments correlates with the ability of substrates to support fibronectin-mediated cellular self-assembly. The cellular response to soluble fibronectin was bimodal and independent of the integrin-binding specificity of the substrate; increasing soluble fibronectin levels above a critical threshold increased aggregate cohesion on permissive substrates. Once aggregates formed, continuous fibronectin polymerization was necessary to maintain cohesion. During self-assembly, soluble fibronectin decreased cell-substrate adhesion strength and induced aggregate cohesion via a Rho-dependent mechanism, suggesting that the balance of contractile forces derived from fibronectin fibrils within cell-cell versus cell-substrate adhesions controls self-assembly and aggregate cohesion. Thus, initial cell-substrate attachment strength may provide a quantitative basis with which to build predictive models of fibronectin-mediated microtissue fabrication on a variety of substrates.Statement of significanceCellular self-assembly is a process by which cells and extracellular matrix (ECM) proteins spontaneously organize into three-dimensional (3D) tissues in the absence of external forces. Cellular self-assembly can be initiated in vitro, and represents a potential tool for tissue engineers to organize cells into modular building blocks for artificial tissue fabrication. Fibronectin is an ECM protein that plays a key role in tissue formation during embryonic development. Additionally, the cell-mediated process of converting soluble fibronectin into insoluble, ECM-associated fibrils has been shown to initiate cellular self-assembly in vitro. In this study, we examine the relationship between the strength of cell-substrate adhesions and the ability of fibronectin fibril assembly to induce cellular self-assembly. Our results indicate that substrate composition and density play cooperative roles with cell-mediated fibronectin matrix assembly to control the transition of cells from 2D monolayers into 3D multicellular aggregates. Results of this study provide a quantitative approach to build predictive models of cellular self-assembly, as well as a simple cell-culture platform to produce biomimetic units for modular tissue engineering.

Dataset Information

Anti-cooperative Self-Assembly with Maintained Emission Regulated by Conformational and Steric Effects.

Publications

Anti-cooperative Self-Assembly with Maintained Emission Regulated by Conformational and Steric Effects.

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