Mineral minimization in nature's alternative teeth

Broomell, Christopher C.; Khan, Rashda K.; Moses, Dana N.; Miserez, Ali; Pontin, Michael G.; Stucky, Galen D.; Zok, Frank W.; Waite, J. Herbert

doi:10.1098/rsif.2006.0153

Cited by 64 publications

(64 citation statements)

References 62 publications

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“…In contrast to vertebrate hard tissues, which are highly mineralized (>70% by dry mass), several marine-derived hard tissues contain significantly less mineral (<10% by dry mass) [5] but maintain comparable mechanical properties to those of their highly mineralized counterparts in vertebrates [5,6]. In addition, the marine environment has much in common with body fluids; both systems are naturally saline and experience variations of fluid flow and temperature, are prone to surface fouling via macromolecules, and exhibit cell-mediated catabolism and turnover of circulating organic solutes.…”

Section: Introductionmentioning

confidence: 99%

Marine hydroid perisarc: A chitin- and melanin-reinforced composite with DOPA–iron(III) complexes

et al. 2013

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a b s t r a c tMany marine invertebrates utilize biomacromolecules as building blocks to form their load-bearing tissues. These polymeric tissues are appealing for their unusual physical and mechanical properties, including high hardness and stiffness, toughness and low density. Here, a marine hydroid perisarc of Aglaophenia latirostris was investigated to understand how nature designs a stiff, tough and lightweight sheathing structure. Chitin, protein and a melanin-like pigment, were found to represent 10, 17 and 60 wt.% of the perisarc, respectively. Interestingly, similar to the adhesive and coating of marine mussel byssus, a DOPA (3,4-dihydroxyphenylalanine) containing protein and iron were detected in the perisarc. Resonance Raman microprobe analysis of perisarc indicates the presence of catechol-iron(III) complexes in situ, but it remains to be determined whether the DOPA-iron(III) interaction plays a cohesive role in holding the protein, chitin and melanin networks together.

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Section: Introductionmentioning

confidence: 99%

Marine hydroid perisarc: A chitin- and melanin-reinforced composite with DOPA–iron(III) complexes

et al. 2013

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“…The load-bearing properties of metallopolymers are equally important but have received less attention with few exceptions (2). This oversight needs to be rectified given how widespread metal-containing polymer networks are in biology, particularly for load-bearing exoskeletal biomaterials (3,4). The byssal cuticle of mussels in the genus Mytilus is an especially interesting case study because of its peculiar combination of hardness (100-150 MPa) and extensibility (>70% strain) (5).…”

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Strong reversible Fe ³⁺ -mediated bridging between dopa-containing protein films in water

Zeng

Hwang

Israelachvili³

et al. 2010

Proc. Natl. Acad. Sci. U.S.A.

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Metal-containing polymer networks are widespread in biology, particularly for load-bearing exoskeletal biomaterials. Mytilus byssal cuticle is an especially interesting case containing moderate levels of Fe 3þ and cuticle protein-mussel foot protein-1 (mfp-1), which has a peculiar combination of high hardness and high extensibility. Mfp-1, containing 13 mol % of dopa (3, 4-dihydroxyphenylalanine) side-chains, is highly positively charged polyelectrolyte (pI ∼ 10) and didn't show any cohesive tendencies in previous surface forces apparatus (SFA) studies. Here, we show that Fe 3þ ions can mediate unusually strong interactions between the positively charged proteins. Using an SFA, Fe 3þ was observed to impart robust bridging (W ad ≈ 4.3 mJ∕m 2 ) between two noninteracting mfp-1 films in aqueous buffer approaching the ionic strength of seawater. The Fe 3þ bridging between the mfp-1-coated surfaces is fully reversible in water, increasing with contact time and iron concentration up to 10 μM; at 100 μM, Fe 3þ bridging adhesion is abolished. Bridging is apparently due to the formation of multivalent dopa-iron complexes. Similar Fe-mediated bridging (W ad ≈ 5.7 mJ∕m 2 ) by a smaller recombinant dopa-containing analogue indicates that bridging is largely independent of molecular weight and posttranslational modifications other than dopa. The results suggest that dopa-metal interactions may provide an energetic new paradigm for engineering strong, self-healing interactions between polymers under water.byssus | metal coordination | tris-catecholato-iron (III) complex M etallopolymers are increasingly viewed as a transformative platform for the next generation of materials. This platform is related in part to their capacity for multifunctionality, but also to their wide and adjustable range of electronic, photonic, and magnetic properties (1). The load-bearing properties of metallopolymers are equally important but have received less attention with few exceptions (2). This oversight needs to be rectified given how widespread metal-containing polymer networks are in biology, particularly for load-bearing exoskeletal biomaterials (3, 4). The byssal cuticle of mussels in the genus Mytilus is an especially interesting case study because of its peculiar combination of hardness (100-150 MPa) and extensibility (>70% strain) (5). Mytilus byssal cuticle contains moderate levels of Fe 3þ and a single protein-mussel foot protein-1 (mfp-1) (6). Mfp-1 has a mass of about 108 kDa in Mytilus edulis (7) and consists largely of tan-

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“…This distinctive amino acid composition is a notable feature given the recurring presence of Gly-and His-rich proteins in load-bearing and impact-resistant tissues. [32] In such structures, the imidazole side-chain has been shown to be particularly versatile in its ability to couple with various chemical entities. This can be in the form of coordination bonds with transition metals (as in the jaws of Nereis, a predatory marine worm) [33][34][35] or as covalent cross-links with peptidyl dihydroxy phenylalanine (DOPA) in squid beaks.…”

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Microstructural and Biochemical Characterization of the Nanoporous Sucker Rings from Dosidicus gigas

et al. 2009

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Mineral minimization in nature's alternative teeth

Cited by 64 publications

References 62 publications

Marine hydroid perisarc: A chitin- and melanin-reinforced composite with DOPA–iron(III) complexes

Marine hydroid perisarc: A chitin- and melanin-reinforced composite with DOPA–iron(III) complexes

Strong reversible Fe ³⁺ -mediated bridging between dopa-containing protein films in water

Microstructural and Biochemical Characterization of the Nanoporous Sucker Rings from Dosidicus gigas

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Mineral minimization in nature's alternative teeth

Cited by 64 publications

References 62 publications

Marine hydroid perisarc: A chitin- and melanin-reinforced composite with DOPA–iron(III) complexes

Marine hydroid perisarc: A chitin- and melanin-reinforced composite with DOPA–iron(III) complexes

Strong reversible Fe 3+ -mediated bridging between dopa-containing protein films in water

Microstructural and Biochemical Characterization of the Nanoporous Sucker Rings from Dosidicus gigas

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Strong reversible Fe ³⁺ -mediated bridging between dopa-containing protein films in water