The relative contribution of calcium, zinc and oxidation-based cross-links to the stiffness of<i>Arion subfuscus</i>glue

Braun, Mélanie; Menges, M.; Opoku, Freda; Smith, Andrew M.

doi:10.1242/jeb.077149

Cited by 37 publications

(68 citation statements)

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“…Previous work focused on the factors that make gastropod adhesive gels much stiffer than other forms of mucus (Smith et al, 1999a;Smith and Morin, 2002;Pawlicki et al, 2004;Werneke et al, 2007;Bradshaw et al, 2011;Braun et al, 2013). There are two main types of cross-links: direct metal crosslinks involving calcium, magnesium and possibly iron (Werneke et al, 2007;Braun et al, 2013), and cross-links that derive from metal-catalyzed oxidation (Bradshaw et al, 2011;Braun et al, 2013). There is indirect evidence that the latter are imine bonds created when amino acids, such as lysine, are oxidized to create carbonyls, which are susceptible to nucleophilic attack from primary amines (Braun et al, 2013).…”

Section: Introductionmentioning

confidence: 99%

“…There are two main types of cross-links: direct metal crosslinks involving calcium, magnesium and possibly iron (Werneke et al, 2007;Braun et al, 2013), and cross-links that derive from metal-catalyzed oxidation (Bradshaw et al, 2011;Braun et al, 2013). There is indirect evidence that the latter are imine bonds created when amino acids, such as lysine, are oxidized to create carbonyls, which are susceptible to nucleophilic attack from primary amines (Braun et al, 2013). The result would be labile bonds that link the higher molecular weight proteins of the glue into a network (Braun et al, 2013).…”

Section: Introductionmentioning

confidence: 99%

“…There is indirect evidence that the latter are imine bonds created when amino acids, such as lysine, are oxidized to create carbonyls, which are susceptible to nucleophilic attack from primary amines (Braun et al, 2013). The result would be labile bonds that link the higher molecular weight proteins of the glue into a network (Braun et al, 2013). Metals also act directly; when metals are removed, the glue loses all of its integrity and strength (Werneke et al, 2007;Braun, et al, 2013).…”

Section: Introductionmentioning

confidence: 99%

“…The result would be labile bonds that link the higher molecular weight proteins of the glue into a network (Braun et al, 2013). Metals also act directly; when metals are removed, the glue loses all of its integrity and strength (Werneke et al, 2007;Braun, et al, 2013). Direct metal cross-links may link the proteins together (Werneke et al, 2007), but they may also link the negatively charged polysaccharides.…”

Section: Introductionmentioning

confidence: 99%

“…They may also be reinforced with metal ions. Calcium and sulfate are the most common ions that are bound within A. subfuscus glue, and the calcium balances the negative charge of the sulfate roughly stoichiometrically (Braun et al, 2013). Thus, calcium and other divalent metals may link sulfated polysaccharides electrostatically or by coordinate bonds.…”

Section: Introductionmentioning

confidence: 99%

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Double network gels and the toughness of terrestrial slug glue

Wilks

Rabice

Garbacz

et al. 2015

Journal of Experimental Biology

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The terrestrial slug Arion subfuscus produces a defensive secretion that is sticky and tough, despite being a dilute gel. It is unusual in having high stiffness for a gel, yet retaining the high extensibility typical of mucus. In tensile tests, it sustains an average peak stress of 101 kPa, and fails at an average strain of 9.5. This gives the gel toughness; it requires much greater strain energy to fracture than most gels. This toughness may arise from a double-network type mechanism. In this mechanism, two separate, interpenetrating networks of polymers with different properties combine to give toughness that can be several orders of magnitude greater than either network individually. Native gel electrophoresis suggests that A. subfuscus glue consists of two networks: a network of negatively charged proteins ranging in M r from 40×10 3 to 220×10 3 that can be dissociated by hydroxylamine and a network of heparan sulfate-like proteoglycans. The two networks are not tightly linked, though proteins of M r 40×10 3 and 165×10 3 may associate with the carbohydrates. Targeted disruption of either network separately, using enzymatic hydrolysis, disulfide bond breakage or imine bond disruption completely disrupted the glue, resulting in no measurable toughness. Thus, the two networks separately provide little toughness, but together they work synergistically to create a tough material, as predicted in the double-network mechanism.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Double network gels and the toughness of terrestrial slug glue

Wilks

Rabice

Garbacz

et al. 2015

Journal of Experimental Biology

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Bioinspired Metal Ion Coordinated Polyelectrolyte Fibrous Nanoreactors

Malhotra

Bera

Zhai

2016

Adv Materials Inter

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improve the stability of hydrogel fibers and introduce multiple functionality to hydrogel fibers.Hydrogel fibers have similar properties to the natural macromolecules in extracellular matrix (ECM) such as large surface area, high porosity, and high content of water. They have been applied in mimicking 3D ECM [28][29][30][31][32][33][34][35][36][37] for tissue engineering, sensors, [38,39] immobilizing biocatalysts, [40] sustained releasing of proteins and drugs, [41][42][43] and wound healing. [44][45][46] Among three common ways of synthesizing fibers, self-assembly, electrospinning and phase separation, electrospinning is the most versatile, simple and cost effective technique. However, the application of electrospun hydrogel fibers (EHFs) faces challenges of low stability in aqueous solutions, liability to harsh chemical conditions and limitations in further functionalization.The EHFs of one polyelectrolyte component are water soluble, all subsequent chemical reactions have to be performed under solvent-free conditions or in non-aqueous media. To stabilize fibrous hydrogels in aqueous media, thermal or vaporphase crosslinking is required which impedes their applications. Polyelectrolyte complexes have been used to improve the stability of fibrous hydrogels in aqueous solutions. [32,[47][48][49][50][51][52][53][54] A polyelectrolyte complex is formed by mixing oppositely charged polyelectrolytes such as poly(acrylic acid) (PAA) and poly(allyl amine hydrochloric acid) or PAA and chitosan (CS) in solutions with controlled polymer ratio and pH. The electrostatic interactions between partially charged polymeric chains lead to the formation of a polymer hydrogel network without covalent crosslinkers. [47][48][49][55][56][57] However, when exposed to solutions with high salt concentration and extreme pH, the disruption of the electrostatic interactions between polycations and polyanions results in the dissolution of the fibers.Functionalizing EHFs requires a simpler and more versatile method to introduce a variety of functional materials such as nanoparticles, peptides, polymers onto the fibers for various applications. Current approaches include in situ fabrication where nanoparticles or polymers/peptides are added to polymer solutions before electrospinning, and post fabrication where nanoparticles or polymers/peptides are introduced onto fibers via reactions in solutions. Post fabrication approaches are not sufficient in obtaining uniform and controlled functionalization in large scale while the amount of nanoparticles in fibers is limited by the dispersity of nanoparticles in polymer solutions in preloading fabrication approaches. [58][59][60] Therefore, Inspired by natural metal ion/ligand interactions, stable electrospun hydrogel fibers (EHFs) are produced from polyelectrolyte complexes coordinated with various metal ions. This development provides a novel and promising approach to advance hydrogel fiber applications by creating fibers with high stability in solutions and controlled interfacial reactions. The e...

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Die Bedeutung von Metallionen für die mechanischen Eigenschaften von Biomaterialien auf Proteinbasis

et al. 2014

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Protein‐Metall‐Wechselwirkungen wurden bisher vor allem hinsichtlich ihrer Bedeutung in Stoffwechselprozessen betrachtet. Aktuelle Forschungsergebnisse zeigen, dass sie auch die mechanischen Eigenschaften von Biomaterialien verbessern können, wie z. B. Härte, Zähigkeit, Haftung und die Fähigkeit zur Selbstheilung. Die zugrundeliegenden Prinzipien werden hier anhand einiger Beispiele, wie der Beißwerkzeuge von Arthropoden, der Byssusfäden von Miesmuscheln und des Zements von Sandburg‐Würmern, besprochen. Diese neuen Erkenntnisse können auch für die Entwicklung von bio‐inspirierten Metallopolymeren mit potentiellen Anwendungen in der Industrie und Biomedizin von Bedeutung sein.

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The relative contribution of calcium, zinc and oxidation-based cross-links to the stiffness ofArion subfuscusglue

Cited by 37 publications

References 57 publications

Double network gels and the toughness of terrestrial slug glue

Double network gels and the toughness of terrestrial slug glue

Bioinspired Metal Ion Coordinated Polyelectrolyte Fibrous Nanoreactors

Die Bedeutung von Metallionen für die mechanischen Eigenschaften von Biomaterialien auf Proteinbasis

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