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Title: Direct observation of mineral–organic composite formation reveals occlusion mechanism

Journal Article · · Nature Communications
DOI:https://doi.org/10.1038/ncomms10187· OSTI ID:1249368
 [1]; ORCiD logo [2];  [3];  [4];  [5];  [2];  [6];  [6];  [3];  [2];  [7]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  2. Univ. of Leeds, Leeds (United Kingdom)
  3. Univ. of Sheffield, Sheffield (United Kingdom)
  4. Stanford Univ., Stanford, CA (United States)
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Zhejiang Univ., Hangzhou (China)
  6. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  7. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Manipulation of inorganic materials with organic macromolecules enables organisms to create biominerals such as bones and seashells, where occlusion of biomacro-molecules within individual crystals generates superior mechanical properties. Current understanding of this process comes from entrapment of micron-size particles in cooling melts. Here, by studying micelle incorporation in calcite with atomic force microscopy and micromechanical simulations, we show that different mechanisms govern nanoscale occlusion. By simultaneously visualizing the micelles and propagating step edges, we demonstrate that the micelles experience significant compression during occlusion, which is accompanied by cavity formation. This generates local lattice strain, leading to enhanced mechanical properties. These results give new insight into the formation of occlusions in natural and synthetic crystals, and will facilitate the synthesis of multifunctional nanocomposite crystals.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
AC05-76RL01830; AC02-05CH11231; AC52-07NA27344
OSTI ID:
1249368
Alternate ID(s):
OSTI ID: 1379025; OSTI ID: 1474347; OSTI ID: 1526977
Report Number(s):
PNNL-SA-114998; LLNL-JRNL-673292; ncomms10187
Journal Information:
Nature Communications, Vol. 7; ISSN 2041-1723
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 125 works
Citation information provided by
Web of Science

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Cited By (25)

Encapsulation of Plant Viral Particles in Calcite Crystals journal March 2018
Site-Selective In Situ Grown Calcium Carbonate Micromodels with Tunable Geometry, Porosity, and Wettability journal May 2016
Amino Acid Assisted Incorporation of Dye Molecules within Calcite Crystals journal June 2018
Spatially Controlled Occlusion of Polymer‐Stabilized Gold Nanoparticles within ZnO journal February 2019
Super‐Resolution Microscopy Reveals Shape and Distribution of Dislocations in Single‐Crystal Nanocomposites journal November 2019
The Effect of Additives on the Early Stages of Growth of Calcite Single Crystals journal August 2017
Amino Acid Assisted Incorporation of Dye Molecules within Calcite Crystals journal June 2018
Spatially Controlled Occlusion of Polymer-Stabilized Gold Nanoparticles within ZnO journal February 2019
How Many Phosphoric Acid Units Are Required to Ensure Uniform Occlusion of Sterically Stabilized Nanoparticles within Calcite? journal June 2019
Super‐Resolution Microscopy Reveals Shape and Distribution of Dislocations in Single‐Crystal Nanocomposites journal November 2019
Incorporation of osteopontin peptide into kidney stone-related calcium oxalate monohydrate crystals: a quantitative study journal December 2018
3D visualization of additive occlusion and tunable full-spectrum fluorescence in calcite journal November 2016
Tuning hardness in calcite by incorporation of amino acids journal May 2016
Hydroxyl-rich macromolecules enable the bio-inspired synthesis of single crystal nanocomposites journal December 2019
The role of phosphorylation and dephosphorylation of shell matrix proteins in shell formation: an in vivo and in vitro study journal January 2018
Anionic block copolymer vesicles act as Trojan horses to enable efficient occlusion of guest species into host calcite crystals journal January 2018
Bionic synthesis of a magnetic calcite skeletal structure through living foraminifera journal January 2019
Efficient occlusion of oil droplets within calcite crystals journal January 2019
Ptychographic X-ray tomography reveals additive zoning in nanocomposite single crystals journal January 2020
Encapsulation of Multiple Microalgal Cells via a Combination of Biomimetic Mineralization and LbL Coating journal February 2018
The Effect of Additives on the Early Stages of Growth of Calcite Single Crystals journal August 2017
How Many Phosphoric Acid Units Are Required to Ensure Uniform Occlusion of Sterically Stabilized Nanoparticles within Calcite? journal May 2019
Ptychographic X-ray tomography reveals additive zoning in nanocomposite single crystals text January 2020
Influence of Surfactants on Sodium Chloride Crystallization in Confinement journal April 2017
Occlusion of Sulfate-Based Diblock Copolymer Nanoparticles within Calcite: Effect of Varying the Surface Density of Anionic Stabilizer Chains journal August 2016

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