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@ARTICLE{Wolf:18198,
author = {Wolf, S. and Leiterer, J. and Pipich, V. and Barrea, R. and
Emmerling, F. and Tremel, W.},
title = {{S}trong stabilization of liquid amorphous calcium
carbonate by ovalbumin: gaining insight into the mechanism
of 'polymer-induced liquid precursor' processes},
journal = {Journal of the American Chemical Society},
volume = {133},
issn = {0002-7863},
address = {Washington, DC},
publisher = {American Chemical Society},
reportid = {PreJuSER-18198},
pages = {12642 - 12649},
year = {2011},
note = {We thank Simone Rolf and Ralf Bienert (BAM) for technical
support at the beamline. We are much obliged to Frederic
Mann and Ute Schlossmacher for assistance in IG labeling and
fruitful discussions. We are grateful to the Deutsche
Forschungsgemeinschaft (DFG) for support within the priority
program No. 1415: "Kristalline Nichtgleichgewichtsphasen".
S.E.W.gratefully acknowledges the Konrad Adenauer Foundation
for a doctoral fellowship. We thank the BioCAT team at the
Advanced Photon Source for excellent support during XAS
experiments, and we are grateful to Dr. David Gore for his
careful revision of the English style. Use of the Advanced
Photon Source, an Office of Science User Facility operated
for the U.S. Department of Energy (DOE), Office of Science
by Argonne National Laboratory, was supported by the U.S.
DOE under Contract No. DE-AC02-06CH11357. BioCAT is a
National Institutes of Health-supported Research Center
RR-08630.},
abstract = {The impact of the ovo proteins ovalbumin and
lysozyme--present in the first stage of egg shell
formation--on the homogeneous formation of the liquid
amorphous calcium carbonate (LACC) precursor, was studied by
a combination of complementing methods: in situ WAXS, SANS,
XANES, TEM, and immunogold labeling. Lysozyme (pI = 9.3)
destabilizes the LACC emulsion whereas the glycoprotein
ovalbumin (pI = 4.7) extends the lifespan of the emulsified
state remarkably. In the light of the presented data: (a)
Ovalbumin is shown to behave commensurable to the
'polymer-induced liquid precursor' (PILP) process proposed
by Gower et al. Ovalbumin can be assumed to take a key role
during eggshell formation where it serves as an effective
stabilization agent for transient precursors and prevents
undirected mineralization of the eggshell. (b) It is further
shown that the emulsified LACC carries a negative surface
charge and is electrostatically stabilized. (c) We propose
that the liquid amorphous calcium carbonate is affected by
polymers by depletion stabilization and de-emulsification
rather than 'induced' by acidic proteins and polymers during
a so-called polymer-induced liquid-precursor process. The
original PILP coating effect, first reported by Gower et
al., appears to be a result of a de-emulsification process
of a stabilized LACC phase. The behavior of the liquid
amorphous carbonate phase and the polymer-induced
liquid-precursor phase itself can be well described by
colloid chemical terms: electrostatic and depletion
stabilization and de-emulsification by depletion
destabilization.},
keywords = {Animals / Calcium Carbonate: chemistry / Calcium Carbonate:
metabolism / Chickens / Crystallization / Egg Shell:
chemistry / Egg Shell: metabolism / Emulsions: chemistry /
Emulsions: metabolism / Muramidase: chemistry / Muramidase:
metabolism / Ovalbumin: chemistry / Ovalbumin: metabolism /
Emulsions (NLM Chemicals) / Calcium Carbonate (NLM
Chemicals) / Ovalbumin (NLM Chemicals) / Muramidase (NLM
Chemicals) / J (WoSType)},
cin = {ICS-1 / JCNS (München) ; Jülich Centre for Neutron
Science JCNS (München) ; JCNS-FRM-II / JCNS-1 / JCNS-2},
ddc = {540},
cid = {I:(DE-Juel1)ICS-1-20110106 /
I:(DE-Juel1)JCNS-FRM-II-20110218 /
I:(DE-Juel1)JCNS-1-20110106 / I:(DE-Juel1)JCNS-2-20110106},
pnm = {BioSoft: Makromolekulare Systeme und biologische
Informationsverarbeitung / Großgeräte für die Forschung
mit Photonen, Neutronen und Ionen (PNI)},
pid = {G:(DE-Juel1)FUEK505 / G:(DE-Juel1)FUEK415},
experiment = {EXP:(DE-MLZ)KWS1-20140101},
shelfmark = {Chemistry, Multidisciplinary},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:21736300},
pmc = {pmc:PMC3170880},
UT = {WOS:000294740000061},
doi = {10.1021/ja202622g},
url = {https://juser.fz-juelich.de/record/18198},
}