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Title: Template Adaptability is Key in the Oriented Crystallization of CaCO3

Abstract

In CaCO3, biomineralization nucleation and growth of the crystals are related to the presence of carboxylate-rich proteins within a macromolecular matrix, often with organized {beta}-sheet domains. To understand the interplay between the organic template and the mineral crystal it is important to explicitly address the issue of structural adaptation of the template during mineralization. To this end we have developed a series of self-organizing surfactants (1-4) consisting of a dodecyl chain connected via a bisureido-heptylene unit to an amino acid head group. In Langmuir monolayers the spacing of these molecules in one direction is predetermined by the hydrogen-bonding distances between the bis-urea units. In the other direction, the intermolecular distance is determined by steric interactions introduced by the side groups (-R) of the amino acid moiety. Thus, by the choice of the amino acid we can systematically alter the density of the surfactant molecules in a monolayer and their ability to respond to the presence of calcium ions. The monolayer films are characterized by surface pressure-surface area (p-A) isotherms, Brewster angle microscopy, in-situ synchrotron X-ray scattering at fixed surface area, and also infrared reflection absorption spectroscopy (IRRAS) of films transferred to solid substrates. The developing crystals are studied with scanningmore » and transmission electron microscopy (SEM, TEM), selected area electron diffraction (SAED), and crystal modeling. The results demonstrate that although all compounds are active in the nucleation of calcium carbonate, habit modification is only observed when the size of the side group allows the molecules to rearrange and adapt their organization in response to the mineral phase.« less

Authors:
; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL) National Synchrotron Light Source
Sponsoring Org.:
Doe - Office Of Science
OSTI Identifier:
959770
Report Number(s):
BNL-82756-2009-JA
Journal ID: ISSN 0002-7863; JACSAT; TRN: US1005805
DOE Contract Number:
DE-AC02-98CH10886
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of the American Chemical Society; Journal Volume: 129
Country of Publication:
United States
Language:
English
Subject:
43 PARTICLE ACCELERATORS; ABSORPTION SPECTROSCOPY; AMINO ACIDS; CALCIUM CARBONATES; CALCIUM IONS; CHAINS; CRYSTALLIZATION; ELECTRON DIFFRACTION; ISOTHERMS; MICROSCOPY; MINERALIZATION; MODIFICATIONS; NUCLEATION; PROTEINS; REFLECTION; SCATTERING; SUBSTRATES; SURFACE AREA; SURFACTANTS; SYNCHROTRONS; TRANSMISSION ELECTRON MICROSCOPY; national synchrotron light source

Citation Formats

Popescu,D., Smulders, M., Pichon, B., Chebotareva, N., Kwak, S., van Asselen, O., Sijbesma, R., DiMasi, E., and Sommerdijk, N. Template Adaptability is Key in the Oriented Crystallization of CaCO3. United States: N. p., 2007. Web. doi:10.1021/ja075875t.
Popescu,D., Smulders, M., Pichon, B., Chebotareva, N., Kwak, S., van Asselen, O., Sijbesma, R., DiMasi, E., & Sommerdijk, N. Template Adaptability is Key in the Oriented Crystallization of CaCO3. United States. doi:10.1021/ja075875t.
Popescu,D., Smulders, M., Pichon, B., Chebotareva, N., Kwak, S., van Asselen, O., Sijbesma, R., DiMasi, E., and Sommerdijk, N. Mon . "Template Adaptability is Key in the Oriented Crystallization of CaCO3". United States. doi:10.1021/ja075875t.
@article{osti_959770,
title = {Template Adaptability is Key in the Oriented Crystallization of CaCO3},
author = {Popescu,D. and Smulders, M. and Pichon, B. and Chebotareva, N. and Kwak, S. and van Asselen, O. and Sijbesma, R. and DiMasi, E. and Sommerdijk, N.},
abstractNote = {In CaCO3, biomineralization nucleation and growth of the crystals are related to the presence of carboxylate-rich proteins within a macromolecular matrix, often with organized {beta}-sheet domains. To understand the interplay between the organic template and the mineral crystal it is important to explicitly address the issue of structural adaptation of the template during mineralization. To this end we have developed a series of self-organizing surfactants (1-4) consisting of a dodecyl chain connected via a bisureido-heptylene unit to an amino acid head group. In Langmuir monolayers the spacing of these molecules in one direction is predetermined by the hydrogen-bonding distances between the bis-urea units. In the other direction, the intermolecular distance is determined by steric interactions introduced by the side groups (-R) of the amino acid moiety. Thus, by the choice of the amino acid we can systematically alter the density of the surfactant molecules in a monolayer and their ability to respond to the presence of calcium ions. The monolayer films are characterized by surface pressure-surface area (p-A) isotherms, Brewster angle microscopy, in-situ synchrotron X-ray scattering at fixed surface area, and also infrared reflection absorption spectroscopy (IRRAS) of films transferred to solid substrates. The developing crystals are studied with scanning and transmission electron microscopy (SEM, TEM), selected area electron diffraction (SAED), and crystal modeling. The results demonstrate that although all compounds are active in the nucleation of calcium carbonate, habit modification is only observed when the size of the side group allows the molecules to rearrange and adapt their organization in response to the mineral phase.},
doi = {10.1021/ja075875t},
journal = {Journal of the American Chemical Society},
number = ,
volume = 129,
place = {United States},
year = {Mon Jan 01 00:00:00 EST 2007},
month = {Mon Jan 01 00:00:00 EST 2007}
}
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