skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Visualization of the effect of additives on the nanostructures of individual bio-inspired calcite crystals

Abstract

Soluble additives provide a versatile strategy for controlling crystallization processes, enabling selection of properties including crystal sizes, morphologies, and structures. Here, the additive species can also be incorporated within the crystal lattice, leading for example to enhanced mechanical properties. However, while many techniques are available for analyzing particle shape and structure, it remains challenging to characterize the structural inhomogeneities and defects introduced into individual crystals by these additives, where these govern many important material properties. Here, we exploit Bragg coherent diffraction imaging to visualize the effects of soluble additives on the internal structures of individual crystals on the nanoscale. Investigation of bio-inspired calcite crystals grown in the presence of lysine or magnesium ions reveals that while a single dislocation is observed in calcite crystals grown in the presence of lysine, magnesium ions generate complex strain patterns. Indeed, in addition to the expected homogeneous solid solution of Mg ions in the calcite lattice, we observe two zones comprising alternating lattice contractions and relaxation, where comparable alternating layers of high magnesium calcite have been observed in many magnesium calcite biominerals. Such insight into the structures of nanocomposite crystals will ultimately enable us to understand and control their properties.

Authors:
ORCiD logo [1];  [2];  [3]; ORCiD logo [1]; ORCiD logo [1];  [4];  [5]; ORCiD logo [3];  [6]; ORCiD logo [1]
  1. Univ. of Leeds, Leeds (United Kingdom)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  3. Univ. of St. Andrews, St. Andrews (United Kingdom)
  4. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
  5. Diamond Light Source, Didcot (United Kingdom)
  6. Univ. College London, London (United Kingdom); Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States); Brookhaven National Lab. (BNL), Upton, NY (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Engineering and Physical Sciences Research Council (EPSRC); European Research Council (ERC)
OSTI Identifier:
1503407
Alternate Identifier(s):
OSTI ID: 1497380; OSTI ID: 1561087
Report Number(s):
BNL-211305-2019-JAAM
Journal ID: ISSN 2041-6520; CSHCBM
Grant/Contract Number:  
AC02-76SF00515; EP/H005374/1; EP/M003027/1; EP/N002423/1; 614290 “EXONMR”; SC0012704; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 10; Journal Issue: 4; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats

Ihli, Johannes, Clark, Jesse N., Kanwal, Nasima, Kim, Yi -Yeoun, Holden, Mark A., Harder, Ross J., Tang, Chiu C., Ashbrook, Sharon E., Robinson, Ian K., and Meldrum, Fiona C. Visualization of the effect of additives on the nanostructures of individual bio-inspired calcite crystals. United States: N. p., 2018. Web. doi:10.1039/c8sc03733g.
Ihli, Johannes, Clark, Jesse N., Kanwal, Nasima, Kim, Yi -Yeoun, Holden, Mark A., Harder, Ross J., Tang, Chiu C., Ashbrook, Sharon E., Robinson, Ian K., & Meldrum, Fiona C. Visualization of the effect of additives on the nanostructures of individual bio-inspired calcite crystals. United States. doi:10.1039/c8sc03733g.
Ihli, Johannes, Clark, Jesse N., Kanwal, Nasima, Kim, Yi -Yeoun, Holden, Mark A., Harder, Ross J., Tang, Chiu C., Ashbrook, Sharon E., Robinson, Ian K., and Meldrum, Fiona C. Fri . "Visualization of the effect of additives on the nanostructures of individual bio-inspired calcite crystals". United States. doi:10.1039/c8sc03733g. https://www.osti.gov/servlets/purl/1503407.
@article{osti_1503407,
title = {Visualization of the effect of additives on the nanostructures of individual bio-inspired calcite crystals},
author = {Ihli, Johannes and Clark, Jesse N. and Kanwal, Nasima and Kim, Yi -Yeoun and Holden, Mark A. and Harder, Ross J. and Tang, Chiu C. and Ashbrook, Sharon E. and Robinson, Ian K. and Meldrum, Fiona C.},
abstractNote = {Soluble additives provide a versatile strategy for controlling crystallization processes, enabling selection of properties including crystal sizes, morphologies, and structures. Here, the additive species can also be incorporated within the crystal lattice, leading for example to enhanced mechanical properties. However, while many techniques are available for analyzing particle shape and structure, it remains challenging to characterize the structural inhomogeneities and defects introduced into individual crystals by these additives, where these govern many important material properties. Here, we exploit Bragg coherent diffraction imaging to visualize the effects of soluble additives on the internal structures of individual crystals on the nanoscale. Investigation of bio-inspired calcite crystals grown in the presence of lysine or magnesium ions reveals that while a single dislocation is observed in calcite crystals grown in the presence of lysine, magnesium ions generate complex strain patterns. Indeed, in addition to the expected homogeneous solid solution of Mg ions in the calcite lattice, we observe two zones comprising alternating lattice contractions and relaxation, where comparable alternating layers of high magnesium calcite have been observed in many magnesium calcite biominerals. Such insight into the structures of nanocomposite crystals will ultimately enable us to understand and control their properties.},
doi = {10.1039/c8sc03733g},
journal = {Chemical Science},
number = 4,
volume = 10,
place = {United States},
year = {2018},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Intercalation of Sea Urchin Proteins in Calcite: Study of a Crystalline Composite Material
journal, November 1990


Three-dimensional coordinates of individual atoms in materials revealed by electron tomography
journal, September 2015

  • Xu, Rui; Chen, Chien-Chun; Wu, Li
  • Nature Materials, Vol. 14, Issue 11
  • DOI: 10.1038/nmat4426

Rapid Screening of Calcium Carbonate Precipitation in the Presence of Amino Acids: Kinetics, Structure, and Composition
journal, August 2016

  • Green, David C.; Ihli, Johannes; Kim, Yi-Yeoun
  • Crystal Growth & Design, Vol. 16, Issue 9
  • DOI: 10.1021/acs.cgd.6b00741

Thermodynamics of Calcite Growth: Baseline for Understanding Biomineral Formation
journal, October 1998


Evaluation of strengthening mechanisms in calcite single crystals from mollusk shells
journal, February 2013


One-pot synthesis of an inorganic heterostructure: uniform occlusion of magnetite nanoparticles within calcite single crystals
journal, January 2014

  • Kulak, Alexander N.; Semsarilar, Mona; Kim, Yi-Yeoun
  • Chem. Sci., Vol. 5, Issue 2
  • DOI: 10.1039/C3SC52615A

Solid state 17 O NMR—an introduction to the background principles and applications to inorganic materials
journal, January 2006

  • Ashbrook, Sharon E.; Smith, Mark E.
  • Chem. Soc. Rev., Vol. 35, Issue 8
  • DOI: 10.1039/B514051J

Biologically Induced Reduction in Symmetry: A Study of Crystal Texture of Calcitic Sponge Spicules
journal, October 1995

  • Aizenberg, Joanna; Hanson, Jonathan; Koetzle, Thomas F.
  • Chemistry - A European Journal, Vol. 1, Issue 7
  • DOI: 10.1002/chem.19950010705

Elucidating Mechanisms of Diffusion-Based Calcium Carbonate Synthesis Leads to Controlled Mesocrystal Formation
journal, November 2012

  • Ihli, Johannes; Bots, Pieter; Kulak, Alexander
  • Advanced Functional Materials, Vol. 23, Issue 15
  • DOI: 10.1002/adfm.201201742

Nanoparticles Incorporated inside Single-Crystals: Enhanced Fluorescent Properties
journal, October 2016


Residual Strain and Stress in Biocrystals
journal, May 2018


The effect of magnesium substitution on the hardness of synthetic and biogenic calcite
journal, September 2012

  • Kunitake, Miki E.; Baker, Shefford P.; Estroff, Lara A.
  • MRS Communications, Vol. 2, Issue 3
  • DOI: 10.1557/mrc.2012.20

New type of compositional zoning in calcite: Insights into crystal-growth mechanisms
journal, January 1990


The incorporation of Mg2+ and Sr2+ into calcite overgrowths: influences of growth rate and solution composition
journal, February 1983


Dyeing crystals since 2000
journal, January 2016


Bio-Inspired Synthesis and Mechanical Properties of Calcite-Polymer Particle Composites
journal, March 2010

  • Kim, Yi-Yeoun; Ribeiro, Luis; Maillot, Fabien
  • Advanced Materials, Vol. 22, Issue 18
  • DOI: 10.1002/adma.200903743

Liquid chromatographic determination of d- and l-amino acids by derivatization with o-phthaldialdehyde and chiral thiols
journal, April 1994


Strong Quantum Confinement Effects and Chiral Excitons in Bio-Inspired ZnO–Amino Acid Cocrystals
journal, February 2018

  • Muhammed, Madathumpady Abubaker Habeeb; Lamers, Marlene; Baumann, Verena
  • The Journal of Physical Chemistry C, Vol. 122, Issue 11
  • DOI: 10.1021/acs.jpcc.8b01567

All-electron magnetic response with pseudopotentials: NMR chemical shifts
journal, May 2001


Chemical composition mapping with nanometre resolution by soft X-ray microscopy
journal, September 2014


Liquid-Liquid Diffusion-Assisted Crystallization: A Fast and Versatile Approach Toward High Quality Mixed Quantum Dot-Salt Crystals
journal, March 2015

  • Adam, Marcus; Wang, Zhiyu; Dubavik, Aliaksei
  • Advanced Functional Materials, Vol. 25, Issue 18
  • DOI: 10.1002/adfm.201500552

Deformation twinning and the role of amino acids and magnesium in calcite hardness from molecular simulation
journal, January 2015

  • Côté, A. S.; Darkins, R.; Duffy, D. M.
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 31
  • DOI: 10.1039/C5CP03370E

Revealing crystalline domains in a mollusc shell single-crystalline prism
journal, July 2017

  • Mastropietro, F.; Godard, P.; Burghammer, M.
  • Nature Materials, Vol. 16, Issue 9
  • DOI: 10.1038/nmat4937

Formation of chiral morphologies through selective binding of amino acids to calcite surface steps
journal, June 2001

  • Orme, C. A.; Noy, A.; Wierzbicki, A.
  • Nature, Vol. 411, Issue 6839
  • DOI: 10.1038/35081034

Effects of temperature and transport conditions on calcite growth in the presence of Mg2+: Implications for paleothermometry
journal, September 2005

  • Wasylenki, Laura E.; Dove, Patricia M.; De Yoreo, James J.
  • Geochimica et Cosmochimica Acta, Vol. 69, Issue 17
  • DOI: 10.1016/j.gca.2005.04.006

A three-dimensional view of structural changes caused by deactivation of fluid catalytic cracking catalysts
journal, October 2017


Screening the Incorporation of Amino Acids into an Inorganic Crystalline Host: the Case of Calcite
journal, June 2012

  • Borukhin, Shirly; Bloch, Leonid; Radlauer, Tzvia
  • Advanced Functional Materials, Vol. 22, Issue 20
  • DOI: 10.1002/adfm.201201079

Nanoscale chemical tomography of buried organic–inorganic interfaces in the chiton tooth
journal, January 2011


Inhibition of aragonite precipitation from supersaturated seawater; a laboratory and field study
journal, June 1978

  • Berner, R. A.; Westrich, J. T.; Graber, R.
  • American Journal of Science, Vol. 278, Issue 6
  • DOI: 10.2475/ajs.278.6.816

3D Imaging of Twin Domain Defects in Gold Nanoparticles
journal, May 2015


Spiers Memorial Lecture : Lessons from biomineralization: comparing the growth strategies of mollusc shell prismatic and nacreous layers in Atrina rigida
journal, January 2007

  • Nudelman, Fabio; Chen, Hong H.; Goldberg, Harvey A.
  • Faraday Discussions, Vol. 136
  • DOI: 10.1039/b704418f

Cold Flow as Versatile Approach for Stable and Highly Luminescent Quantum Dot–Salt Composites
journal, August 2016

  • Benad, Albrecht; Guhrenz, Chris; Bauer, Christoph
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 33
  • DOI: 10.1021/acsami.6b06452

Atomic-scale Chemical Imaging and Quantification of Metallic Alloy Structures by Energy-Dispersive X-ray Spectroscopy
journal, February 2014

  • Lu, Ping; Zhou, Lin; Kramer, M. J.
  • Scientific Reports, Vol. 4, Issue 1
  • DOI: 10.1038/srep03945

Rethinking Classical Crystal Growth Models through Molecular Scale Insights: Consequences of Kink-Limited Kinetics
journal, December 2009

  • De Yoreo, J. J.; Zepeda-Ruiz, L. A.; Friddle, R. W.
  • Crystal Growth & Design, Vol. 9, Issue 12
  • DOI: 10.1021/cg900543g

Coherent X-Ray Diffraction Imaging of Morphology and Strain in Nanomaterials
journal, July 2013


Differences between Bond Lengths in Biogenic and Geological Calcite
journal, March 2010

  • Zolotoyabko, E.; Caspi, E. N.; Fieramosca, J. S.
  • Crystal Growth & Design, Vol. 10, Issue 3
  • DOI: 10.1021/cg901195t

Crystal Growth with Macromolecular Additives
journal, November 2017


General model for calcite growth kinetics in the presence of impurity ions
journal, August 2013

  • Nielsen, Laura C.; De Yoreo, James J.; DePaolo, Donald J.
  • Geochimica et Cosmochimica Acta, Vol. 115
  • DOI: 10.1016/j.gca.2013.04.001

Colouring crystals with inorganic nanoparticles
journal, January 2014

  • Kulak, Alexander N.; Yang, Pengcheng; Kim, Yi-Yeoun
  • Chem. Commun., Vol. 50, Issue 1
  • DOI: 10.1039/C3CC47904H

Quantum-dot-in-perovskite solids
journal, July 2015

  • Ning, Zhijun; Gong, Xiwen; Comin, Riccardo
  • Nature, Vol. 523, Issue 7560
  • DOI: 10.1038/nature14563

Amino Acid Assisted Incorporation of Dye Molecules within Calcite Crystals
journal, June 2018

  • Marzec, Bartosz; Green, David C.; Holden, Mark A.
  • Angewandte Chemie International Edition, Vol. 57, Issue 28
  • DOI: 10.1002/anie.201804365

Relationship between surface structure, growth mechanism, and trace element incorporation in calcite
journal, February 1995


Dyeing Crystals
journal, April 2001

  • Kahr, Bart; Gurney, Richard W.
  • Chemical Reviews, Vol. 101, Issue 4
  • DOI: 10.1021/cr980088n

Phase retrieval algorithms: a comparison
journal, January 1982


Polymer-Directed Assembly of Single Crystal Zinc Oxide/Magnetite Nanocomposites under Atmospheric and Hydrothermal Conditions
journal, October 2016


Soluble Organic Matrices of the Calcitic Prismatic Shell Layers of Two Pteriomorphid Bivalves
journal, February 2003


3D lattice distortions and defect structures in ion-implanted nano-crystals
journal, April 2017

  • Hofmann, Felix; Tarleton, Edmund; Harder, Ross J.
  • Scientific Reports, Vol. 7, Issue 1
  • DOI: 10.1038/srep45993

Coherently aligned nanoparticles within a biogenic single crystal: A biological prestressing strategy
journal, December 2017

  • Polishchuk, Iryna; Bracha, Avigail Aronhime; Bloch, Leonid
  • Science, Vol. 358, Issue 6368
  • DOI: 10.1126/science.aaj2156

Mapping Metals Incorporation of a Whole Single Catalyst Particle Using Element Specific X-ray Nanotomography
journal, January 2015

  • Meirer, Florian; Morris, Darius T.; Kalirai, Sam
  • Journal of the American Chemical Society, Vol. 137, Issue 1
  • DOI: 10.1021/ja511503d

Functionalizing Single Crystals: Incorporation of Nanoparticles Inside Gel-Grown Calcite Crystals
journal, March 2014

  • Liu, Yujing; Yuan, Wentao; Shi, Ye
  • Angewandte Chemie International Edition, Vol. 53, Issue 16
  • DOI: 10.1002/anie.201310712

The role of magnesium in the growth of calcite: An AFM study
journal, March 2010


Morphological consequences of differential Mg 2+ incorporation at structurally distinct steps on calcite
journal, May 2004

  • Davis, Kevin J.; Dove, Patricia M.; Wasylenki, Laura E.
  • American Mineralogist, Vol. 89, Issue 5-6
  • DOI: 10.2138/am-2004-5-605

Coordination of Sr and Mg in calcite and aragonite
journal, October 2007


Anisotropic lattice distortions in biogenic calcite induced by intra-crystalline organic molecules
journal, July 2006

  • Pokroy, Boaz; Fitch, Andrew N.; Marin, Frederic
  • Journal of Structural Biology, Vol. 155, Issue 1
  • DOI: 10.1016/j.jsb.2006.03.008

Evolution of dealloying induced strain in nanoporous gold crystals
journal, January 2017

  • Chen-Wiegart, Yu-chen Karen; Harder, Ross; Dunand, David C.
  • Nanoscale, Vol. 9, Issue 17
  • DOI: 10.1039/C6NR09635B

Bio-Inspired Band Gap Engineering of Zinc Oxide by Intracrystalline Incorporation of Amino Acids
journal, October 2013

  • Brif, Anastasia; Ankonina, Guy; Drathen, Christina
  • Advanced Materials, Vol. 26, Issue 3
  • DOI: 10.1002/adma.201303596

Tuning hardness in calcite by incorporation of amino acids
journal, May 2016

  • Kim, Yi-Yeoun; Carloni, Joseph D.; Demarchi, Beatrice
  • Nature Materials, Vol. 15, Issue 8
  • DOI: 10.1038/nmat4631

Structure and Properties of Nanocomposites Formed by the Occlusion of Block Copolymer Worms and Vesicles Within Calcite Crystals
journal, January 2016

  • Kim, Yi-Yeoun; Semsarilar, Mona; Carloni, Joseph D.
  • Advanced Functional Materials, Vol. 26, Issue 9
  • DOI: 10.1002/adfm.201504292

An artificial biomineral formed by incorporation of copolymer micelles in calcite crystals
journal, September 2011

  • Kim, Yi-Yeoun; Ganesan, Kathirvel; Yang, Pengcheng
  • Nature Materials, Vol. 10, Issue 11
  • DOI: 10.1038/nmat3103

Solution-chemistry control of Mg 2+ -calcite interaction mechanisms: Implication for biomineralization
journal, May 2016

  • Xu, Jie; Wang, Jianhua; Hong, Mina
  • American Mineralogist, Vol. 101, Issue 5
  • DOI: 10.2138/am-2016-5406

Imparting functionality to a metal–organic framework material by controlled nanoparticle encapsulation
journal, February 2012

  • Lu, Guang; Li, Shaozhou; Guo, Zhen
  • Nature Chemistry, Vol. 4, Issue 4, p. 310-316
  • DOI: 10.1038/nchem.1272

Strain-relief by single dislocation loops in calcite crystals grown on self-assembled monolayers
journal, June 2016

  • Ihli, Johannes; Clark, Jesse N.; Côté, Alexander S.
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms11878

Strain-Induced Segmentation of Magnesian Calcite Thin Films Growing on a Calcite Substrate
journal, October 2010

  • Sethmann, Ingo; Wang, Jianwei; Becker, Udo
  • Crystal Growth & Design, Vol. 10, Issue 10
  • DOI: 10.1021/cg100202h

The Effect of Additives on the Early Stages of Growth of Calcite Single Crystals
journal, August 2017

  • Kim, Yi-Yeoun; Freeman, Colin L.; Gong, Xiuqing
  • Angewandte Chemie International Edition, Vol. 56, Issue 39
  • DOI: 10.1002/anie.201706800

Additive controlled crystallization
journal, January 2011


A relationship between d104 value and composition in the calcite-disordered dolomite solid-solution series
journal, November 2010

  • Zhang, F.; Xu, H.; Konishi, H.
  • American Mineralogist, Vol. 95, Issue 11-12
  • DOI: 10.2138/am.2010.3414

Three-dimensional imaging of dislocation propagation during crystal growth and dissolution
journal, June 2015

  • Clark, Jesse N.; Ihli, Johannes; Schenk, Anna S.
  • Nature Materials, Vol. 14, Issue 8
  • DOI: 10.1038/nmat4320

The Role of Mg2+ as an Impurity in Calcite Growth
journal, November 2000


Controlling Mineral Morphologies and Structures in Biological and Synthetic Systems
journal, November 2008

  • Meldrum, Fiona C.; Cölfen, Helmut
  • Chemical Reviews, Vol. 108, Issue 11
  • DOI: 10.1021/cr8002856

    Works referencing / citing this record:

    In situ three-dimensional imaging of strain in gold nanocrystals during catalytic oxidation
    journal, January 2019

    • Suzana, Ana Flavia; Rochet, Amélie; Passos, Aline Ribeiro
    • Nanoscale Advances, Vol. 1, Issue 8
    • DOI: 10.1039/c9na00231f

    In situ three-dimensional imaging of strain in gold nanocrystals during catalytic oxidation
    journal, January 2019

    • Suzana, Ana Flavia; Rochet, Amélie; Passos, Aline Ribeiro
    • Nanoscale Advances, Vol. 1, Issue 8
    • DOI: 10.1039/c9na00231f