Changes to the Disordered Phase and Apatite Crystallite
Morphology during Mineralization by an Acidic Mineral Binding Peptide
from Osteonectin
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Abstract
Noncollagenous proteins regulate
the formation of the mineral constituent
in hard tissue. The mineral formed contains apatite crystals coated
by a functional disordered calcium phosphate phase. Although the crystalline
phase of bone mineral was extensively investigated, little is known
about the disordered layer’s composition and structure, and
less is known regarding the function of noncollagenous proteins in
the context of this layer. In the current study, apatite was prepared
with an acidic peptide (ON29) derived from the bone/dentin protein
osteonectin. The mineral formed comprises needle-shaped hydroxyapatite
crystals like in dentin and a stable disordered phase coating the
apatitic crystals as shown using X-ray diffraction, transmission electron
microscopy, and solid-state NMR techniques. The peptide, embedded
between the mineral particles, reduces the overall phosphate content
in the mineral formed as inferred from inductively coupled plasma
and elemental analysis results. Magnetization transfers between disordered
phase species and apatitic phase species are observed for the first
time using 2D <sup>1</sup>H–<sup>31</sup>P heteronuclear correlation
NMR measurements. The dynamics of phosphate magnetization transfers
reveal that ON29 decreases significantly the amount of water molecules
in the disordered phase and increases slightly their content at the
ordered-disordered interface. The peptide decreases hydroxyl to disordered
phosphate transfers within the surface layer but does not influence
transfer within the bulk crystalline mineral. Overall, these results
indicate that control of crystallite morphology and properties of
the inorganic component in hard tissue by biomolecules is more involved
than just direct interaction between protein functional groups and
mineral crystal faces. Subtler mechanisms such as modulation of the
disordered phase composition and structural changes at the ordered–disordered
interface may be involved