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  • 1
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    American Association for the Advancement of Science (AAAS)
    Publication Date: 2000-11-10
    Description: Magnesium is a key determinant in CaCO3 mineralization; however, macroscopic observations have failed to provide a clear physical understanding of how magnesium modifies carbonate growth. Atomic force microscopy was used to resolve the mechanism of calcite inhibition by magnesium through molecular-scale determination of the thermodynamic and kinetic controls of magnesium on calcite formation. Comparison of directly measured step velocities to standard impurity models demonstrated that enhanced mineral solubility through magnesium incorporation inhibited calcite growth. Terrace width measurements on calcite growth spirals were consistent with a decrease in effective supersaturation due to magnesium incorporation. Ca(1-x)Mg(x)CO3 solubilities determined from microscopic observations of step dynamics can thus be linked to macroscopic measurements.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Davis, K J -- Dove, P M -- De Yoreo, J J -- New York, N.Y. -- Science. 2000 Nov 10;290(5494):1134-7.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Department of Geological Sciences, Virginia Polytechnic Institute and State University, Blacksburg, VA 24061, USA.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/11073446" target="_blank"〉PubMed〈/a〉
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 2
    Publication Date: 2013-08-24
    Description: Recent experimental observations of the onset of calcium carbonate (CaCO3) mineralization suggest the emergence of a population of clusters that are stable rather than unstable as predicted by classical nucleation theory. This study uses molecular dynamics simulations to probe the structure, dynamics, and energetics of hydrated CaCO3 clusters and lattice gas simulations to explore the behavior of cluster populations before nucleation. Our results predict formation of a dense liquid phase through liquid-liquid separation within the concentration range in which clusters are observed. Coalescence and solidification of nanoscale droplets results in formation of a solid phase, the structure of which is consistent with amorphous CaCO3. The presence of a liquid-liquid binodal enables a diverse set of experimental observations to be reconciled within the context of established phase-separation mechanisms.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Wallace, Adam F -- Hedges, Lester O -- Fernandez-Martinez, Alejandro -- Raiteri, Paolo -- Gale, Julian D -- Waychunas, Glenn A -- Whitelam, Stephen -- Banfield, Jillian F -- De Yoreo, James J -- New York, N.Y. -- Science. 2013 Aug 23;341(6148):885-9. doi: 10.1126/science.1230915.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Earth Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA. afw@udel.edu〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/23970697" target="_blank"〉PubMed〈/a〉
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 3
    Publication Date: 2014-09-06
    Description: Mechanisms of nucleation from electrolyte solutions have been debated for more than a century. Recent discoveries of amorphous precursors and evidence for cluster aggregation and liquid-liquid separation contradict common assumptions of classical nucleation theory. Using in situ transmission electron microscopy (TEM) to explore calcium carbonate (CaCO3) nucleation in a cell that enables reagent mixing, we demonstrate that multiple nucleation pathways are simultaneously operative, including formation both directly from solution and indirectly through transformation of amorphous and crystalline precursors. However, an amorphous-to-calcite transformation is not observed. The behavior of amorphous calcium carbonate upon dissolution suggests that it encompasses a spectrum of structures, including liquids and solids. These observations of competing direct and indirect pathways are consistent with classical predictions, whereas the behavior of amorphous particles hints at an underlying commonality among recently proposed precursor-based mechanisms.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Nielsen, Michael H -- Aloni, Shaul -- De Yoreo, James J -- New York, N.Y. -- Science. 2014 Sep 5;345(6201):1158-62. doi: 10.1126/science.1254051.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Department of Materials Science and Engineering, University of California, Berkeley, CA 94720, USA. Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA. ; Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA. ; Physical Sciences Division, Pacific Northwest National Laboratory, Richland, WA 99352, USA. Department of Materials Science and Engineering, University of Washington, Seattle, WA 98195, USA.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/25190792" target="_blank"〉PubMed〈/a〉
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 4
    Publication Date: 1998-10-23
    Description: The complexity of biomineralized structures suggests the potential of organic constituents for controlling energetic factors during crystal synthesis. Atomic force microscopy was used to investigate the thermodynamic controls on carbonate growth and to measure the dependence of step speed on step length and the dependence of critical step length on supersaturation in precisely controlled solutions. These data were used to test the classic Gibbs-Thomson relationship and provided the step edge free energies and free energy barriers to one-dimension nucleation for calcite. Addition of aspartic acid, a common component in biomineralizing systems, dramatically affected growth morphology and altered the magnitude of the surface energy.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Teng -- Dove -- Orme -- De Yoreo JJ -- New York, N.Y. -- Science. 1998 Oct 23;282(5389):724-7.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉H. H. Teng and P. M. Dove, School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, GA 30332, USA. C. A. Orme and J. J. De Yoreo, Department of Chemistry and Materials Science, Lawrence Livermore National Laboratory, Liverm.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/9784126" target="_blank"〉PubMed〈/a〉
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 5
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    American Association for the Advancement of Science (AAAS)
    Publication Date: 2004-11-20
    Description: 〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉De Yoreo, James J -- Dove, Patricia M -- New York, N.Y. -- Science. 2004 Nov 19;306(5700):1301-2.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Chemistry and Materials Science Directorate, Lawrence Livermore National Laboratory, Livermore, CA 94551, USA. deyoreo1@llnl.gov〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/15550649" target="_blank"〉PubMed〈/a〉
    Keywords: Amino Acids/chemistry ; Calcium Carbonate/*chemistry ; Calcium Oxalate/*chemistry ; Chemistry, Physical ; Citric Acid/chemistry ; *Crystallization ; Magnesium/chemistry ; Models, Molecular ; Molecular Conformation ; Physicochemical Phenomena ; Proteins/*chemistry ; Stereoisomerism ; Thermodynamics
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 6
    Publication Date: 2012-05-26
    Description: The oriented attachment of molecular clusters and nanoparticles in solution is now recognized as an important mechanism of crystal growth in many materials, yet the alignment process and attachment mechanism have not been established. We performed high-resolution transmission electron microscopy using a fluid cell to directly observe oriented attachment of iron oxyhydroxide nanoparticles. The particles undergo continuous rotation and interaction until they find a perfect lattice match. A sudden jump to contact then occurs over less than 1 nanometer, followed by lateral atom-by-atom addition initiated at the contact point. Interface elimination proceeds at a rate consistent with the curvature dependence of the Gibbs free energy. Measured translational and rotational accelerations show that strong, highly direction-specific interactions drive crystal growth via oriented attachment.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉Li, Dongsheng -- Nielsen, Michael H -- Lee, Jonathan R I -- Frandsen, Cathrine -- Banfield, Jillian F -- De Yoreo, James J -- New York, N.Y. -- Science. 2012 May 25;336(6084):1014-8. doi: 10.1126/science.1219643.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Materials Science Division, Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA 94720, USA.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/22628650" target="_blank"〉PubMed〈/a〉
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 7
    Publication Date: 2015-08-01
    Description: Field and laboratory observations show that crystals commonly form by the addition and attachment of particles that range from multi-ion complexes to fully formed nanoparticles. The particles involved in these nonclassical pathways to crystallization are diverse, in contrast to classical models that consider only the addition of monomeric chemical species. We review progress toward understanding crystal growth by particle-attachment processes and show that multiple pathways result from the interplay of free-energy landscapes and reaction dynamics. Much remains unknown about the fundamental aspects, particularly the relationships between solution structure, interfacial forces, and particle motion. Developing a predictive description that connects molecular details to ensemble behavior will require revisiting long-standing interpretations of crystal formation in synthetic systems, biominerals, and patterns of mineralization in natural environments.〈br /〉〈span class="detail_caption"〉Notes: 〈/span〉De Yoreo, James J -- Gilbert, Pupa U P A -- Sommerdijk, Nico A J M -- Penn, R Lee -- Whitelam, Stephen -- Joester, Derk -- Zhang, Hengzhong -- Rimer, Jeffrey D -- Navrotsky, Alexandra -- Banfield, Jillian F -- Wallace, Adam F -- Michel, F Marc -- Meldrum, Fiona C -- Colfen, Helmut -- Dove, Patricia M -- New York, N.Y. -- Science. 2015 Jul 31;349(6247):aaa6760. doi: 10.1126/science.aaa6760.〈br /〉〈span class="detail_caption"〉Author address: 〈/span〉Physical Sciences Division, Pacific Northwest National Laboratory, Richland, WA 99352, USA. Department of Materials Science and Engineering, University of Washington, Seattle, WA 98195, USA. ; Departments of Physics and Chemistry, University of Wisconsin, Madison, WI 53706, USA. Radcliffe Institute for Advanced Study, Harvard University, Cambridge, MA 02138, USA. ; Laboratory of Materials and Interface Chemistry and Soft Matter CryoTEM Unit, Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, Netherlands. Institute for Complex Molecular Systems, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, Netherlands. ; Department of Chemistry, University of Minnesota, 207 Pleasant Street, SE, Minneapolis, MN 55455, USA. ; The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA. ; Department of Materials Science and Engineering, Northwestern University, Evanston, IL 60208, USA. ; Department of Earth and Planetary Science, University of California Berkeley, Berkeley, CA 94720, USA. ; Department of Chemical and Biomolecular Engineering, University of Houston, 4800 Calhoun Road, Houston, TX 77204, USA. ; Peter A. Rock Thermochemistry Laboratory, Department of Chemistry, University of California Davis, 1 Shields Avenue, Davis, CA 95616, USA. ; Department of Geological Sciences, University of Delaware, Newark, DE 19716, USA. ; Department of Geosciences, Virginia Polytechnic Institute, Blacksburg, VA 24061, USA. ; School of Chemistry, University of Leeds, Leeds LS2 9JT, West Yorkshire, England. ; Physical Chemistry, Department of Chemistry, University of Konstanz, D-78457 Constance, Germany. ; Department of Geosciences, Virginia Polytechnic Institute, Blacksburg, VA 24061, USA. dove@vt.edu.〈br /〉〈span class="detail_caption"〉Record origin:〈/span〉 〈a href="http://www.ncbi.nlm.nih.gov/pubmed/26228157" target="_blank"〉PubMed〈/a〉
    Print ISSN: 0036-8075
    Electronic ISSN: 1095-9203
    Topics: Biology , Chemistry and Pharmacology , Computer Science , Medicine , Natural Sciences in General , Physics
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  • 8
    Publication Date: 2016-10-04
    Description: The interplay between polymers and inorganic minerals during the formation of solids is crucial for biomineralization and bio-inspired materials, and advanced material properties can be achieved with organic-inorganic composites. By studying the reaction mechanisms, basic questions on organic-inorganic interactions and their role during material formation can be answered, enabling more target-oriented strategies in future synthetic approaches. Here, we present a comprehensive study on the hydrolysis of iron( iii ) in the presence of polyaspartic acid. For the basic investigation of the formation mechanism, a titration assay was used, complemented by microscopic techniques. The polymer is shown to promote precipitation in partly hydrolyzed reaction solutions at the very early stages of the reaction by facilitating iron( iii ) hydrolysis. In unhydrolyzed solutions, no significant interactions between the polymer and the inorganic solutes can be observed. We demonstrate that the hydrolysis promotion by the polymer can be understood by facilitating oxolation in olation iron( iii ) pre-nucleation clusters. We propose that the adsorption of olation pre-nucleation clusters on the polymer chains and the resulting loss in dynamics and increased proximity of the reactants is the key to this effect. The resulting composite material obtained from the hydrolysis in the presence of the polymer was investigated with additional analytical techniques, namely, scanning and transmission electron microscopies, light microscopy, atomic force microscopy, zeta potential measurements, dynamic light scattering, and thermogravimetric analyses. It consists of elastic, polydisperse nanospheres, ca. 50-200 nm in diameter, and aggregates thereof, exhibiting a high polymer and water content.
    Print ISSN: 0021-9606
    Electronic ISSN: 1089-7690
    Topics: Chemistry and Pharmacology , Physics
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  • 9
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Journal of Applied Physics 73 (1993), S. 7780-7789 
    ISSN: 1089-7550
    Source: AIP Digital Archive
    Topics: Physics
    Notes: In electro-optic applications of the mixed crystal K(DxH1−x)2PO4 (KDP-KD*P), strain-induced refractive index variations result in beam depolarization and transmitted wave-front distortion. Here the combined linear stress-optic and electro-optic effects in crystals of KDP-KD*P oriented perpendicular to the c axis are analyzed and it is shown that while the depolarization is caused by the induced birefringence, the wave-front distortion is due to average index shifts. Furthermore, the birefringence is determined by the shear stress in the xy plane of the crystal while the average index shift depends only on the normal stresses. For depolarization losses of 0.1%–1% and wave-front distortion of 0.1–1λ, the critical range of stress is 105–106 Pa. Measured depolarization loss and wave-front distortion profiles of 5, 16, and 27 cm K(DxH1−x)2PO4 crystals for 0≤x≤0.98 are also presented. Using the analysis described above it is shows that the maximum internal stresses in these crystals are within the critical range, but that the area-averaged stresses are substantially lower. It is found that crystals from different locations along the length of a boule can have similar strain birefringence and wave-front distortion profiles indicating that the growth conditions which generate the internal strain persist throughout a significant portion of the growth history of the boule. It is also observed that the most highly strained crystals come from near the seed cap. Finally, potential sources of strain in KD*P are discussed and thermodynamic and structural arguments are given which suggest that inhomogeneities in the H/D ratio are a potential source of the strain in KD*P.
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  • 10
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Journal of Applied Physics 85 (1999), S. 3988-3992 
    ISSN: 1089-7550
    Source: AIP Digital Archive
    Topics: Physics
    Notes: Photoexcited defect clusters in the bulk of KH2PO4 crystals are investigated using a microscopic fluorescence imaging system with 1 μm spatial resolution. The observed defect cluster concentration is approximately 104–106 per mm3 depending on the crystal growth method and sector of the crystal. The intensity of the emission clusters varies widely within the image field while a nearly uniformly distributed background is present. Spectroscopic measurements provided information on the emission characteristics of the observed defect population. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
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