Autonomous Growth of a Spatially Localized Supramolecular Hydrogel with Autocatalytic Ability

Fores, Jennifer Rodon; Criado‐Gonzalez, Miryam; Chaumont, Alain; Carvalho, Alain; Blanck, Christian; Schmutz, Marc; Boulmedais, Fouzia; Schaaf, Pierre; Jierry, Loı̈c

doi:10.1002/ange.202005377

Cited by 7 publications

(3 citation statements)

References 53 publications

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“…[14] Hydrogels formed through enzyme-assisted self-assembly of peptides exhibited highly efficient esteraselike activity. [15] However, developing enzyme-driven dynamic catalytic switches remains challenging.…”

Section: Introductionmentioning

confidence: 99%

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Enzyme‐Driven, Switchable Catalysis Based on Dynamic Self‐Assembly of Peptides

Li,

Min,

Zhang

et al. 2023

Angew Chem Int Ed

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Covalent regulatory systems of enzymes are widely used to modulate biological enzyme activities. Inspired by the regulation of reactive‐site phosphorylation in organisms, we developed peptide‐based catecholase mimetics with switchable catalytic activity and high selectivity through the co‐assembly of nanofibers comprising peptides and copper ions (Cu2+). Through careful design and modification of the peptide backbone structure based on the change in the free energy of the system, we identified the peptide with the most effective reversible catalytic activity. Kinase/phosphatase switches were used to control the reversible transition of nanofiber formation and depolymerization, as well as to modulate the active‐site microenvironment. Notably, the self‐assembly and disassembly processes of nanofibers were simulated using coarse‐grained molecular dynamics. Furthermore, theoretical calculations confirmed the coordination of the peptide and Cu2+, forming a zipper‐like four‐ligand structure at the catalytically active center of the nanofibers. Additionally, we conducted a comprehensive analysis of the catalytic mechanism. This study opens novel avenues for designing biomimetic enzymes with ordered structures and dynamic catalytic activities.

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Section: Introductionmentioning

confidence: 99%

“…Enzyme‐driven dynamic self‐assembly has been widely used in tumor therapy and bioimaging [14] . Hydrogels formed through enzyme‐assisted self‐assembly of peptides exhibited highly efficient esterase‐like activity [15] . However, developing enzyme‐driven dynamic catalytic switches remains challenging.…”

Section: Introductionmentioning

confidence: 99%

Enzyme‐Driven, Switchable Catalysis Based on Dynamic Self‐Assembly of Peptides

Li,

Min,

Zhang

et al. 2023

Angew Chem Int Ed

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“…This opened the route to the precise localization of peptide self-assemblies, and a step that was taken in 2009 when Williams and Ulijn groups showed that peptide self-assembly can be initiated from covalently immobilized enzyme on a surface [ 10 ]. Our group further developed the localized enzyme-assisted self-assembly (LEASA approach by introducing seed-layers in addition to an enzyme-adsorbed layer to trigger the localized self-assembly growth [ 11 , 12 ], for catalytic and auto-catalytic self-assembled hydrogels [ 13 , 14 , 15 ] or self-assemblies initiated from nanoparticles surface [ 16 ] and in host materials [ 17 , 18 ]. This bottom-up approach is efficient in water and once the surface coated with an adequate enzyme, the localized self-assembled structure growth proceeds in an autonomous way [ 19 ].…”

Section: Introductionmentioning

confidence: 99%

Localized Enzyme-Assisted Self-Assembly in the Presence of Hyaluronic Acid for Hybrid Supramolecular Hydrogel Coating

et al. 2021

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Hydrogel coating is highly suitable in biomaterial design. It provides biocompatibility and avoids protein adsorption leading to inflammation and rejection of implants. Moreover, hydrogels can be loaded with biologically active compounds. In this field, hyaluronic acid has been largely studied as an additional component since this polysaccharide is naturally present in extracellular matrix. Strategies to direct hydrogelation processes exclusively from the surface using a fully biocompatible approach are rare. Herein we have applied the concept of localized enzyme-assisted self-assembly to direct supramolecular hydrogels in the presence of HA. Based on electronic and fluorescent confocal microscopy, rheological measurements and cell culture investigations, this work highlights the following aspects: (i) the possibility to control the thickness of peptide-based hydrogels at the micrometer scale (18–41 µm) through the proportion of HA (2, 5 or 10 mg/mL); (ii) the structure of the self-assembled peptide nanofibrous network is affected by the growing amount of HA which induces the collapse of nanofibers leading to large assembled microstructures underpinning the supramolecular hydrogel matrix; (iii) this changing internal architecture induces a decrease of the elastic modulus from 2 to 0.2 kPa when concentration of HA is increasing; (iv) concomitantly, the presence of HA in supramolecular hydrogel coatings is suitable for cell viability and adhesion of NIH 3T3 fibroblasts.

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Complex Cascade Reaction Networks via Cross β Amyloid Nanotubes

2020

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Biocatalytic reaction networks integrate complex cascade transformations via spatial localization of multiple enzymes confined within the cellular milieu. Inspired by natures ingenuity, we demonstrate that short peptide-based cross-b amyloid nanotubular hybrids can promote different kinds of cascade reactions, from simple two-step, to multistep, to complex convergent cascades. The compartmentalizing ability of paracrystalline cross-b phases was utilized to colocalize sarcosine oxidase (SOX) and hemin as an artificial peroxidase. Further, the catalytic potential of the amyloid nanotubes with ordered arrays of imidazoles were used as hydrolase mimic. The SOX-hemin amyloid nanohybrids featuring a single extant enzyme could integrate different logic networks to access complex digital designs with the help of three concatenated AND gates and biologically relevant stimuli as inputs.

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Autonomous Growth of a Spatially Localized Supramolecular Hydrogel with Autocatalytic Ability

Cited by 7 publications

References 53 publications

Enzyme‐Driven, Switchable Catalysis Based on Dynamic Self‐Assembly of Peptides

Enzyme‐Driven, Switchable Catalysis Based on Dynamic Self‐Assembly of Peptides

Localized Enzyme-Assisted Self-Assembly in the Presence of Hyaluronic Acid for Hybrid Supramolecular Hydrogel Coating

Complex Cascade Reaction Networks via Cross β Amyloid Nanotubes

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