skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

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

Abstract

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.

Authors:
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)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1408130
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Biomacromolecules
Additional Journal Information:
Journal Volume: 18; Journal Issue: 10; Journal ID: ISSN 1525-7797
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; mineralization; nanoparticles; phosphates; phase transitions; nanorods; calcium phosphate; polyaspartic acid; biomineralization; oriented attachment

Citation Formats

Krogstad, Daniel V., Wang, Dongbo, and Lin-Gibson, Sheng. Polyaspartic Acid Concentration Controls the Rate of Calcium Phosphate Nanorod Formation in High Concentration Systems. United States: N. p., 2017. Web. doi:10.1021/acs.biomac.7b00772.
Krogstad, Daniel V., Wang, Dongbo, & Lin-Gibson, Sheng. Polyaspartic Acid Concentration Controls the Rate of Calcium Phosphate Nanorod Formation in High Concentration Systems. United States. https://doi.org/10.1021/acs.biomac.7b00772
Krogstad, Daniel V., Wang, Dongbo, and Lin-Gibson, Sheng. 2017. "Polyaspartic Acid Concentration Controls the Rate of Calcium Phosphate Nanorod Formation in High Concentration Systems". United States. https://doi.org/10.1021/acs.biomac.7b00772. https://www.osti.gov/servlets/purl/1408130.
@article{osti_1408130,
title = {Polyaspartic Acid Concentration Controls the Rate of Calcium Phosphate Nanorod Formation in High Concentration Systems},
author = {Krogstad, Daniel V. and Wang, Dongbo and Lin-Gibson, Sheng},
abstractNote = {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.},
doi = {10.1021/acs.biomac.7b00772},
url = {https://www.osti.gov/biblio/1408130}, journal = {Biomacromolecules},
issn = {1525-7797},
number = 10,
volume = 18,
place = {United States},
year = {Tue Aug 22 00:00:00 EDT 2017},
month = {Tue Aug 22 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 13 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

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


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


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


Works referencing / citing this record:

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


pH-Responsive Polypeptide-Based Smart Nano-Carriers for Theranostic Applications
journal, August 2019