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Title: Polyaspartic Acid Concentration Controls the Rate of Calcium Phosphate Nanorod Formation in High Concentration Systems

Journal Article · · Biomacromolecules
ORCiD logo [1];  [2];  [2]
  1. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States); Univ. of Illinois at Urbana-Champaign, IL (United States)
  2. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)

Polyelectrolytes are known to greatly affect calcium phosphate (CaP) mineralization. The reaction kinetics as well as the CaP phase, morphology and aggregation state depend on the relative concentrations of the polyelectrolyte and the inorganic ions in a complex, nonlinear manner. This study examines the structural evolution and kinetics of polyaspartic acid (pAsp) directed CaP mineralization at high concentrations of polyelectrolytes, calcium, and total phosphate (19–30 mg/mL pAsp, 50–100 mM Ca2+, Ca/P = 2). Using a novel combination of characterization techniques including cryogenic transmission electron microscopy (cryo-TEM), spectrophotometry, X-ray total scattering pair distribution function analysis, and attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), it was determined that the CaP mineralization occurred over four transition steps. The steps include the formation of aggregates of pAsp stabilized CaP spherical nanoparticles (sNP), crystallization of sNP, oriented attachment of the sNP into nanorods, and further crystallization of the nanorods. The intermediate aggregate sizes and the reaction kinetics were found to be highly polymer concentration dependent while the sizes of the particles were not concentration dependent. Furthermore, this study demonstrates the complex role of pAsp in controlling the mechanism as well as the kinetics of CaP mineralization.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1408130
Journal Information:
Biomacromolecules, Vol. 18, Issue 10; ISSN 1525-7797
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
ENGLISH
Citation Metrics:
Cited by: 13 works
Citation information provided by
Web of Science

References (24)

Characterizing crystal growth by oriented aggregation journal January 2014
Kinetics of Aggregation and Crystallization of Polyaspartic Acid Stabilized Calcium Phosphate Particles at High Concentrations journal April 2015
Preparation of amorphous calcium-magnesium phosphates at pH 7 and characterization by x-ray absorption and fourier transform infrared spectroscopy journal October 1988
Mimicking the Self-Organized Microstructure of Tooth Enamel journal March 2008
Influence of polyaspartic acid and phosphophoryn on octacalcium phosphate growth kinetics journal January 2000
Amorphous calcium phosphates prepared at pH 6.5 and 6.0 journal January 1989
Crystallization by particle attachment in synthetic, biogenic, and geologic environments journal July 2015
The Role of Polycarboxylic Acids in Calcium Phosphate Mineralization journal June 2002
Effect of polyaspartic acid on hydroxyapatite deposition in silk fibroin blend films journal January 2010
Different Kinetic Pathways of Early Stage Calcium-Phosphate Cluster Aggregation Induced by Carboxylate-Containing Polymers journal September 2013
Normal Bone Anatomy and Physiology journal November 2008
The role of collagen in bone apatite formation in the presence of hydroxyapatite nucleation inhibitors journal October 2010
Transient amorphous calcium phosphate in forming enamel journal May 2009
Mimicking the Nanostructure of Bone: Comparison of Polymeric Process-Directing Agents journal December 2010
Calcium phosphate colloids with hierarchical structure controlled by polyaspartates journal March 2002
Modulation of crystal formation by bone phosphoproteins: role of glutamic acid-rich sequences in the nucleation of hydroxyapatite by bone sialoprotein journal August 1994
Fourier transform infrared spectroscopy of the solution-mediated conversion of amorphous calcium phosphate to hydroxyapatite: New correlations between X-ray diffraction and infrared data journal January 1996
Bioinspired Synthesis of Mineralized Collagen Fibrils journal August 2008
PDFgetX2: a GUI-driven program to obtain the pair distribution function from X-ray powder diffraction data journal July 2004
Controlled environment vitrification system: An improved sample preparation technique journal September 1988
Bone structure and formation: A new perspective journal November 2007
Interatomic Coulombic interactions as the driving force for oriented attachment journal January 2014
Ion-association complexes unite classical and non-classical theories for the biomimetic nucleation of calcium phosphate journal February 2013
Fourier transform infrared characterization of mineral phases formed during induction of mineralization by collagenase-released matrix vesicles in vitro. journal September 1988

Cited By (5)

Ionically crosslinked polyelectrolyte nanoparticle formation mechanisms: the significance of mixing journal January 2019
EDTA and NTA effectively tune the mineralization of calcium phosphate from bulk aqueous solution text January 2021
pH-Responsive Polypeptide-Based Smart Nano-Carriers for Theranostic Applications journal August 2019
Emerging biomedical applications of polyaspartic acid-derived biodegradable polyelectrolytes and polyelectrolyte complexes journal January 2019
Polyglutamic acid-coordinated assembly of hydroxyapatite nanoparticles for synergistic tumor-specific therapy journal January 2019