Fabrication of hybrid composites based on biomineralization of phosphorylated poly(ethylene glycol) hydrogels

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Sung Eun Kim, Yong Woo Kim, Hong Jae Lee, Hyung Woo Choi, Jeong Ho Chang, Jinsub Choi, and Kyung Ja Kim Nanomaterials Application Division, Korea Institute of Ceramic Engineering and Technology, Seoul 153-801, Korea

Kwang Bo Shim Department of Ceramic Engineering, Hanyang University, Seoul 133-791, Korea

Young-Keun Jeong Hybrid Materials Solution National Core Research Center (NCRC), Pusan National University, Busan 609-735, Korea

Sang Cheon Leea) Nanomaterials Application Division, Korea Institute of Ceramic Engineering and Technology, Seoul 153-801, Korea (Received 20 February 2008; accepted 28 August 2008)

A novel route to organic-inorganic composites was described based on biomineralization of poly(ethylene glycol) (PEG)-based hydrogels. The 3-dimensional hydrogels were synthesized by radical crosslinking polymerization of poly(ethylene glycol fumarate) (PEGF) in the presence of ethylene glycol methacrylate phosphate (EGMP) as an apatite-nuclating monomer, acrylamide (AAm) as a compositionmodulating comonomer, and potassium persulfate (PPS) as a radical initiator. We used the urea-mediated solution precipitation technique for biomineralization of hydrogels. The apatite grown on the surface and interior of the hydrogel was similar to biological apatites in the composition and crystalline structure. Powder x-ray diffraction (XRD) showed that the calcium phosphate crystalline platelets on hydrogels are preferentially aligned along the crystallographic c-axis direction. Inductively-coupled plasma mass spectroscopy (ICP-MS) analysis showed that the Ca/P molar ratio of apatites grown on the hydrogel template was found to be 1.60, which is identical to that of natural bones. In vitro cell experiments showed that the cell adhesion/proliferation on the mineralized hydrogel was more pronounced than on the pure polymer hydrogel.

I. INTRODUCTION

Biomineralization, a process in which crystalline carbonate apatites grow on organic templates, is a sophisticated and elegant process that mediates bone formation in vertebrates.1,2 In recent years, efforts to control the nucleation and growth of apatites on organic polymer matrices have given rise to a wide range of technological developments such as organic-inorganic nanocarriers,3–6 nanofibers,7–9 and especially artificial bonelike composites used in tissue engineering.10,11 To date, many artificial systems have been developed to fabricate bonelike materials by mimicking the natural mineralization process.10–12 It is a)

Address all correspondence to this author. e-mail: [email protected] DOI: 10.1557/JMR.2009.0002 50

J. Mater. Res., Vol. 24, No. 1, Jan 2009

http://journals.cambridge.org

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well known that the main contributing factors for naturally-occurring biomineralization in bones are the acidic, non-collagenous proteins of the matrix that are closely associated with the collagen network.13,14 These anionic components tend to sequester inorganic cations, specifically Ca2+ ions, to induce localized supersaturation, followed by oriented nucleat