High Abrasion Resistance with Sparse Mineralization: Copper Biomineral in Worm Jaws

Lichtenegger, Helga C.; Schöberl, Thomas; Bartl, Michael H.; Waite, Herbert; Stucky, Galen D.

doi:10.1126/science.1075433

Cited by 220 publications

(180 citation statements)

References 29 publications

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“…The properties of the bulk (D) and the atacamitecontaining material (B) were clearly below those of A and C. Additionally, the properties of B were only slightly higher than those of D, indicating that the atacamite fibers play only a minor role. The bulk properties (H Ϸ 0.7 GPa, E Ϸ 9 GPa) were comparable to those reported in previous studies (7,9).…”

Section: Results and Analysissupporting

confidence: 77%

“…Previous studies suggest that melanin forms the structural framework of the jaws, perhaps providing a scaffold onto which the other components are assembled (9). The jaws also contain small amounts of Cu and Cl (5-10%), which combine to form atacamite [Cu 2 (OH) 3 Cl] fibers (7). The fibers are found mainly in the near-tip regions of the jaw, as well as in those surrounding the venom canal.…”

mentioning

confidence: 99%

“…Current understanding of the mechanical properties of Glycera jaws has been derived principally from depth-sensing nanoindentation (7,9). In a typical series of measurements, 200 indentations, each Ϸ1 m in size, are laid down in a periodic array with a spacing of 10 m. The Cu and Cl distributions of the tested region are subsequently mapped by using either energy dispersive spectroscopy (EDS) or electron probe microscopy.…”

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confidence: 99%

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A nonmineralized approach to abrasion-resistant biomaterials

Pontin¹,

Moses

Waite

et al. 2007

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

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The tooth-like mouthparts of some animals consist of biomacromolecular scaffolds with few mineral components, making them intriguing paradigms of biostructural materials. In this study, the abrasion resistance of the jaws of one such animal, the bloodworm Glycera dibranchiata, has been evaluated by nanoindentation, nanoscratching, and wear testing. The hardest, stiffest, and most abrasion-resistant materials are found within a thin (<3 m) surface layer near the jaw tip and a thicker (10 -20 m) subsurface layer, both rich in unmineralized Cu. These results are consistent with the supposition that Cu ions are involved in the formation of intermolecular coordination complexes between proteins, creating a highly cross-linked molecular network. The intervening layer contains aligned atacamite [Cu2(OH)3Cl] fibers and exhibits hardness and stiffness (transverse to the alignment direction) that are only slightly higher than those of the bulk material but lower than those of the two Cu-rich layers. Furthermore, the atacamitecontaining layer is the least abrasion-resistant, by a factor of Ϸ3, even relative to the bulk material. These observations are broadly consistent with the behavior of engineering polymer composites with hard fiber or particulate reinforcements. The alignment of fibers parallel to the jaw surface, and the fiber proximity to the surface, are both suggestive of a natural adaptation to enhance bending stiffness and strength rather than to endow the surface regions with enhanced abrasion resistance. glycera jaw ͉ nanoindentation ͉ scratching ͉ wear

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Section: Results and Analysissupporting

confidence: 77%

mentioning

confidence: 99%

mentioning

confidence: 99%

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A nonmineralized approach to abrasion-resistant biomaterials

Pontin¹,

Moses

Waite

et al. 2007

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

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“…Mineralization 203 204 205 206 207 208 209 210 211 212 213 214 215 216 217 218 219 220 221 222 223 224 225 226 227 228 229 230 231 232 233 234 235 236 237 238 239 240 241 242 243 244 245 246 247 248 249 250 251 252 253 254 255 256 257 258 259 260 261 262 263 264 265 266 267 268 269 270 271 272 273 274 275 276 277 278 279 280 281 282 283 284 285 286 287 288 289 290 291 292 293 294 295 296 297 298 299 300 301 302 303 304could also be a defense against toxic copper, but reports of Cu + and Cu 2+ biominerals are rare; only copper sulfide in yeast (37) and copper oxalate in lichens (38) and fungi (23) are known. Atacamite (Cu2(OH)3Cl) in worms (39) does not appear to result from a biochemical defense.…”

Section: Mechanism Of Cumentioning

confidence: 99%

Formation of Metallic Copper Nanoparticles at the Soil−Root Interface

Manceau

Nagy

Marcus

et al. 2008

Environ. Sci. Technol.

222

117

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Copper is an essential element in the cellular electron-transport chain, but as a free ion it can catalyze production of damaging radicals. Thus, all life forms attempt to prevent copper toxicity. Plants diminish excess copper in two structural regions: rare hyperaccumulators bind cationic copper to organic ligands in subaerial tissues, whereas widespread metal-tolerant plants segregate copper dominantly in roots by mechanisms thought to be analogous. Here we show using synchrotron microanalyses that common wetlands plants Phragmites australis and Iris pseudoacorus can transform copper into metallic nanoparticles in and near roots with evidence of assistance by endomycorrhizal fungi when grown in contaminated soil in the natural environment. Biomolecular responses to oxidative stress, similar to reactions used to abiotically synthesize Cu0 nanostructures of controlled size and shape, likely cause the transformation. This newly identified mode of copper biomineralization by plant roots under copper stress may be common in oxygenated environments.

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“…The architecture and general composition of the jaws of Glycera species have been studied for decades (1)(2)(3)(4), but their precise chemical structure remains unclear. Lichtenegger et al (4) recently reported that Glycera jaws contain polycrystalline nanofibers of the copper hydroxychloride atacamite (Cu 2 Cl(OH) 3 ). This discovery was of particular significance as the first reported instance of a copper-based biomineral.…”

mentioning

confidence: 99%