A translation of the structure of mussel byssal threads into synthetic materials by the utilization of histidine-rich block copolymers

Enke, Marcel; Bose, Ranjita K.; Zechel, Stefan; Vitz, Jürgen; Deubler, Robert; Garcia, Santiago J.; Zwaag, Sybrand van der; Schacher, Felix H.; Hager, Martin D.; Schubert, Ulrich S.

doi:10.1039/c8py00663f

Cited by 14 publications

(13 citation statements)

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“…6 For example, the outstanding underwater properties of marine mussel have driven a field of mussel-inspired catechol chemistry of great significance in biomaterials science and engineering. [7][8][9][10][11][12][13][14][15][16][17] Similar to mussels, ascidians are sac-like sessile marine animals that are covered with a protective membrane composed of highly crystalline cellulose nanofiber (tunicin) and proteins (tunichrome) containing 3,4,5-trihydroxyphenylalanine (TOPA) with a pyrogallol moiety (three hydroxyls bound to a benzene ring). These organisms have extraordinary biophysicochemical properties including rapid self-healing and strong adhesiveness in seawater.…”

Section: Introductionmentioning

confidence: 99%

Unraveling the gallol-driven assembly mechanism of thermoreversible supramolecular hydrogels inspired by ascidians

et al. 2020

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Section: Introductionmentioning

confidence: 99%

Unraveling the gallol-driven assembly mechanism of thermoreversible supramolecular hydrogels inspired by ascidians

et al. 2020

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“…Moreover, the preCols provide an attractive pH-based assembly trigger that can be encoded into blocks. This aspect has already demonstrated in simpler mussel-inspired self-healing materials based on imidazole chemistry [59][60][61] . In addition to their more technical potential, these extracted concepts are also extremely relevant to ongoing efforts to produce injectable biomedical scaffolds 62,63 , especially given the collagenous nature of the building blocks.…”

Section: Resultsmentioning

confidence: 87%

Collagen Pentablock Copolymers Form Smectic Liquid Crystals as Precursors for Mussel Byssus Fabrication

Jehle¹,

Priemel²,

Strauss³

et al. 2020

Preprint

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Protein-based biological materials are important role models for the design and fabrication of next generation advanced polymers. Marine mussels (Mytilus spp.) fabricate hierarchically structured collagenous fibers known as byssal threads via bottom-up supramolecular assembly of fluid protein precursors. The high degree of structural organization in byssal threads is intimately linked to their exceptional toughness and self-healing capacity. Here, we investigated the hypothesis that multidomain collagen precursor proteins, known as preCols, are stored in secretory vesicles as a colloidal liquid crystal (LC) phase prior to thread self-assembly. Using advanced electron microscopy methods, including scanning TEM and FIB-SEM, we visualized the detailed smectic preCol LC nanostructure in 3D, including various LC defects, confirming this hypothesis and providing quantitative insights into the mesophase structure. In light of these findings, we performed an in-depth comparative analysis of preCol protein sequences from multiple Mytilid species revealing that the smectic organization arises from an evolutionarily conserved ABCBA penta-block co-polymer-like primary structure based on demarcations in hydropathy and charge distribution, as well as terminal pH-responsive domains<br>that trigger fiber formation. These distilled supramolecular assembly principles provide inspiration and strategies for sustainable assembly of nanostructured polymeric materials for<br>potential applications in engineering and biomedical applications.

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“…In particular, the complex structural hierarchy inherent in the preCol functional domains has not been successfully mimicked. Nevertheless, a first synthetic approach inspired by the multidomain structure of the preCols has been recently described by Enke et al [120] utilizing block-copolymers with hard and soft segments. The soft segments featured histidine moieties, which were utilized for the design of supramolecular polymers capable for self-healing behavior (Figure 7).…”

Section: Bioinspired Metallopolymersmentioning

confidence: 99%

“…Schematic representation of the domain formation of the natural system (left) [50] and a first approach using block copolymers for the mimicking of that behavior in artificial materials (right) [120]. For this purpose, a block copolymer was synthesized featuring hard (polystyrene) and a soft (butyl acrylate with histidine ligand) domains.…”

Section: Figurementioning

confidence: 99%

“…Afterward, these block copolymers were cross-linked by the addition of zinc salts resulting in metallopolymers with self-healing behavior. Reprinted from [50], Copyright 2009, with permission from Elsevier; and reproduced from [120] with permission from the Royal Society of Chemistry. AIBN: Azobisisobutyronitrile; DBTTC: S , S -dibenzyl trithiocarbonate; P1–8: Polymers.…”

Section: Figurementioning

confidence: 99%

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Healing through Histidine: Bioinspired Pathways to Self-Healing Polymers via Imidazole–Metal Coordination

et al. 2019

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Biology offers a valuable inspiration toward the development of self-healing engineering composites and polymers. In particular, chemical level design principles extracted from proteinaceous biopolymers, especially the mussel byssus, provide inspiration for design of autonomous and intrinsic healing in synthetic polymers. The mussel byssus is an acellular tissue comprised of extremely tough protein-based fibers, produced by mussels to secure attachment on rocky surfaces. Threads exhibit self-healing response following an apparent plastic yield event, recovering initial material properties in a time-dependent fashion. Recent biochemical analysis of the structure–function relationships defining this response reveal a key role of sacrificial cross-links based on metal coordination bonds between Zn2+ ions and histidine amino acid residues. Inspired by this example, many research groups have developed self-healing polymeric materials based on histidine (imidazole)–metal chemistry. In this review, we provide a detailed overview of the current understanding of the self-healing mechanism in byssal threads, and an overview of the current state of the art in histidine- and imidazole-based synthetic polymers.

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A translation of the structure of mussel byssal threads into synthetic materials by the utilization of histidine-rich block copolymers

Abstract: The self-healing capacities of mussel-inspired metallopolymers based on block copolymers containing histidine are briefly presented.

Cited by 14 publications

References 46 publications

Unraveling the gallol-driven assembly mechanism of thermoreversible supramolecular hydrogels inspired by ascidians

Unraveling the gallol-driven assembly mechanism of thermoreversible supramolecular hydrogels inspired by ascidians

Collagen Pentablock Copolymers Form Smectic Liquid Crystals as Precursors for Mussel Byssus Fabrication

Healing through Histidine: Bioinspired Pathways to Self-Healing Polymers via Imidazole–Metal Coordination

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