Synthesis and characterization of ionic block copolymer templated calcium phosphate nanocomposites

M. Kanapathipillai, Y. Yusufoglu, A. Rawal, Y. Y. Hu, Chieh-Tsung Lo, P. Thiyagarajan, Y. E. Kalay, M. Akinc, S. Mallapragada, K. Schmidt-Rohr

Research output: Contribution to journalArticle

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Abstract

Self-assembling thermo-reversibly gelling anionic and zwitterionic pentablock copolymers were used as templates for precipitation of calcium phosphate nanostructures, controlling their size and ordered structural arrangement. Calcium and phosphate ions were dissolved in a block-copolymer micellar dispersion at low temperatures. Aging at ambient temperature produced inorganic nanoparticles, presumably nucleated by ionic interactions. The self-assembled nanocomposites were characterized by small-angle X-ray and neutron scattering (SAXS/SANS), nuclear magnetic resonance (NMR), thermogravimetric analysis (TGA), and transmission electron microscopy (TEM). 1H-31P NMR with 1H spin diffusion from polymer to phosphate proved the formation of nanocomposites, with inorganic particle sizes from ∼2 nm, characterized by 1H-31P dipolar couplings, to > 100 nm. TEM analysis showed polymer micelles surrounded by calcium phosphate. SAXS attested that a significant fraction of the calcium phosphate was templated by the polymer micelles. SANS data indicated that the order of the polymer was enhanced by the inorganic phase. The nanocomposite gels exhibited higher moduli than the neat polymer gels. The calcium phosphate was characterized by TGA, X-ray diffraction, high-resolution TEM, and various NMR techniques. An unusual crystalline phase with >2 chemically and >3 magnetically inequivalent HPO42- ions was observed with the zwitterionic copolymer, highlighting the influence of the polymer on the calcium phosphate crystallization. The inorganic fraction of the nanocomposite was around 30 wt % of the dried hydrogel. Thus, a significant fraction of calcium phosphate has been templated by the tailored self-assembling ionic block copolymers, providing a bottom-up approach to nanocomposite synthesis.

Original languageEnglish
Pages (from-to)5922-5932
Number of pages11
JournalChemistry of Materials
Volume20
Issue number18
DOIs
Publication statusPublished - 2008 Sep 23

Fingerprint

Calcium phosphate
Block copolymers
Nanocomposites
Polymers
Nuclear magnetic resonance
Micelles
Thermogravimetric analysis
Phosphates
Gels
Copolymers
Transmission electron microscopy
Ions
Neutron scattering
High resolution transmission electron microscopy
X ray scattering
Hydrogel
Hydrogels
Crystallization
calcium phosphate
Calcium

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

Cite this

Kanapathipillai, M., Yusufoglu, Y., Rawal, A., Hu, Y. Y., Lo, C-T., Thiyagarajan, P., ... Schmidt-Rohr, K. (2008). Synthesis and characterization of ionic block copolymer templated calcium phosphate nanocomposites. Chemistry of Materials, 20(18), 5922-5932. https://doi.org/10.1021/cm703441n
Kanapathipillai, M. ; Yusufoglu, Y. ; Rawal, A. ; Hu, Y. Y. ; Lo, Chieh-Tsung ; Thiyagarajan, P. ; Kalay, Y. E. ; Akinc, M. ; Mallapragada, S. ; Schmidt-Rohr, K. / Synthesis and characterization of ionic block copolymer templated calcium phosphate nanocomposites. In: Chemistry of Materials. 2008 ; Vol. 20, No. 18. pp. 5922-5932.
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abstract = "Self-assembling thermo-reversibly gelling anionic and zwitterionic pentablock copolymers were used as templates for precipitation of calcium phosphate nanostructures, controlling their size and ordered structural arrangement. Calcium and phosphate ions were dissolved in a block-copolymer micellar dispersion at low temperatures. Aging at ambient temperature produced inorganic nanoparticles, presumably nucleated by ionic interactions. The self-assembled nanocomposites were characterized by small-angle X-ray and neutron scattering (SAXS/SANS), nuclear magnetic resonance (NMR), thermogravimetric analysis (TGA), and transmission electron microscopy (TEM). 1H-31P NMR with 1H spin diffusion from polymer to phosphate proved the formation of nanocomposites, with inorganic particle sizes from ∼2 nm, characterized by 1H-31P dipolar couplings, to > 100 nm. TEM analysis showed polymer micelles surrounded by calcium phosphate. SAXS attested that a significant fraction of the calcium phosphate was templated by the polymer micelles. SANS data indicated that the order of the polymer was enhanced by the inorganic phase. The nanocomposite gels exhibited higher moduli than the neat polymer gels. The calcium phosphate was characterized by TGA, X-ray diffraction, high-resolution TEM, and various NMR techniques. An unusual crystalline phase with >2 chemically and >3 magnetically inequivalent HPO42- ions was observed with the zwitterionic copolymer, highlighting the influence of the polymer on the calcium phosphate crystallization. The inorganic fraction of the nanocomposite was around 30 wt {\%} of the dried hydrogel. Thus, a significant fraction of calcium phosphate has been templated by the tailored self-assembling ionic block copolymers, providing a bottom-up approach to nanocomposite synthesis.",
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Kanapathipillai, M, Yusufoglu, Y, Rawal, A, Hu, YY, Lo, C-T, Thiyagarajan, P, Kalay, YE, Akinc, M, Mallapragada, S & Schmidt-Rohr, K 2008, 'Synthesis and characterization of ionic block copolymer templated calcium phosphate nanocomposites', Chemistry of Materials, vol. 20, no. 18, pp. 5922-5932. https://doi.org/10.1021/cm703441n

Synthesis and characterization of ionic block copolymer templated calcium phosphate nanocomposites. / Kanapathipillai, M.; Yusufoglu, Y.; Rawal, A.; Hu, Y. Y.; Lo, Chieh-Tsung; Thiyagarajan, P.; Kalay, Y. E.; Akinc, M.; Mallapragada, S.; Schmidt-Rohr, K.

In: Chemistry of Materials, Vol. 20, No. 18, 23.09.2008, p. 5922-5932.

Research output: Contribution to journalArticle

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T1 - Synthesis and characterization of ionic block copolymer templated calcium phosphate nanocomposites

AU - Kanapathipillai, M.

AU - Yusufoglu, Y.

AU - Rawal, A.

AU - Hu, Y. Y.

AU - Lo, Chieh-Tsung

AU - Thiyagarajan, P.

AU - Kalay, Y. E.

AU - Akinc, M.

AU - Mallapragada, S.

AU - Schmidt-Rohr, K.

PY - 2008/9/23

Y1 - 2008/9/23

N2 - Self-assembling thermo-reversibly gelling anionic and zwitterionic pentablock copolymers were used as templates for precipitation of calcium phosphate nanostructures, controlling their size and ordered structural arrangement. Calcium and phosphate ions were dissolved in a block-copolymer micellar dispersion at low temperatures. Aging at ambient temperature produced inorganic nanoparticles, presumably nucleated by ionic interactions. The self-assembled nanocomposites were characterized by small-angle X-ray and neutron scattering (SAXS/SANS), nuclear magnetic resonance (NMR), thermogravimetric analysis (TGA), and transmission electron microscopy (TEM). 1H-31P NMR with 1H spin diffusion from polymer to phosphate proved the formation of nanocomposites, with inorganic particle sizes from ∼2 nm, characterized by 1H-31P dipolar couplings, to > 100 nm. TEM analysis showed polymer micelles surrounded by calcium phosphate. SAXS attested that a significant fraction of the calcium phosphate was templated by the polymer micelles. SANS data indicated that the order of the polymer was enhanced by the inorganic phase. The nanocomposite gels exhibited higher moduli than the neat polymer gels. The calcium phosphate was characterized by TGA, X-ray diffraction, high-resolution TEM, and various NMR techniques. An unusual crystalline phase with >2 chemically and >3 magnetically inequivalent HPO42- ions was observed with the zwitterionic copolymer, highlighting the influence of the polymer on the calcium phosphate crystallization. The inorganic fraction of the nanocomposite was around 30 wt % of the dried hydrogel. Thus, a significant fraction of calcium phosphate has been templated by the tailored self-assembling ionic block copolymers, providing a bottom-up approach to nanocomposite synthesis.

AB - Self-assembling thermo-reversibly gelling anionic and zwitterionic pentablock copolymers were used as templates for precipitation of calcium phosphate nanostructures, controlling their size and ordered structural arrangement. Calcium and phosphate ions were dissolved in a block-copolymer micellar dispersion at low temperatures. Aging at ambient temperature produced inorganic nanoparticles, presumably nucleated by ionic interactions. The self-assembled nanocomposites were characterized by small-angle X-ray and neutron scattering (SAXS/SANS), nuclear magnetic resonance (NMR), thermogravimetric analysis (TGA), and transmission electron microscopy (TEM). 1H-31P NMR with 1H spin diffusion from polymer to phosphate proved the formation of nanocomposites, with inorganic particle sizes from ∼2 nm, characterized by 1H-31P dipolar couplings, to > 100 nm. TEM analysis showed polymer micelles surrounded by calcium phosphate. SAXS attested that a significant fraction of the calcium phosphate was templated by the polymer micelles. SANS data indicated that the order of the polymer was enhanced by the inorganic phase. The nanocomposite gels exhibited higher moduli than the neat polymer gels. The calcium phosphate was characterized by TGA, X-ray diffraction, high-resolution TEM, and various NMR techniques. An unusual crystalline phase with >2 chemically and >3 magnetically inequivalent HPO42- ions was observed with the zwitterionic copolymer, highlighting the influence of the polymer on the calcium phosphate crystallization. The inorganic fraction of the nanocomposite was around 30 wt % of the dried hydrogel. Thus, a significant fraction of calcium phosphate has been templated by the tailored self-assembling ionic block copolymers, providing a bottom-up approach to nanocomposite synthesis.

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