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JOURNAL OF MATERIALS SCIENCE: MATERIALS IN MEDICINE 14 (2003) 973±978 Surface modi®cation of a porous hydroxyapatite to promote bonded polymer coatings ATSUSHI MATSUDA 1 * , TSUTOMU FURUZONO 2 , DOMINIC WALSH 3 , AKIO KISHIDA 2 , JUNZO TANAKA 1 1 Biomaterials Center, National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan 2 Department of Bioengineering, National Cardiovascular Center Research Institute, 5-7-1 Fujishiro-dai, Suita, Osaka 565-8565, Japan 3 School of Chemistry, University of Bristol, Cantock Close, Bristol BS8 1TS, UK Email: [email protected] Porous hydroxyapatite (Hap) blocks were sintered at several temperatures and methyl methacrylate (MMA) grafted onto the surface in a 2-step heterogeneous system as a model example for surface modi®cation. First, sintered porous Hap was modi®ed with 2-methacryloyloxyethylene isocyanate (MOI) monomer in anhydrous dimethyl sulfoxide using di-n-butyltin (IV) dilaurate as a catalyst and hydroquinone as an inhibitor. Amount of the introduction of MOI monomer on porous Hap was 1.62 wt % at sintered temperature 800 C, 0.68 wt % at it of 1000 C, and 0.59 wt % at it of 1200 C. Scanning electron microscopy (SEM) showed that porous Hap pore size and shape before and after MOI treatment were unchanged. Second, graft polymerization with MMA through the vinyl bond on porous Hap was conducted using a,a 0 -azobis isobutyronitrile (AIBN) as an initiator. Amount of Grafted PMMA on the MOI modi®ed porous Hap was 2.84 wt % at sintered temperature of 800 C, 6.97 wt % at it of 1000 C, and 6.27 wt % at it of 1200 C. MOI-modi®ed and PMMA-grafted porous Hap were characterized using Fourier transform infrared (FT-IR) spectroscopy. The compressive strength of sintered porous Hap with grafted PMMA increased about 2.7±6.7 times compared to intact porous Hap. This 2-step surface modi®cation on porous Hap is widely applicable to graft polymerization with vinyl polymer and conjugation with a protein or an oligopeptide, such as growth factor or an adhesion molecule, to improve Hap mechanical properties and functionality. # 2003 Kluwer Acadamic Publishers 1. Introduction Hydroxyapatite (Hap) has been used in medical applications such as bone implant materials [1±3]. Porous natural corals have also been used because the macroporosity of these materials promotes osteoconduc- tivity and resorption in vivo. Walsh et al. reported synthesizing unique porous Hap with continuous cavities formed by a foaming calcium phosphate preparation [4, 5]. Porous Hap was applicable for graft cartridges in maxillofacial surgery [6] as alveolar ridge augments and as bone defect ®ller [7]. Mechanical strength, or cell adhesion and tissue migration on porous Hap, may be limited by its crystallinity, or surface composition and morphology [8±12]. The use of Hap in medical implants would greatly increase if surface modi®cation by an organic compound could improve its mechanical strength or functionality of cell adhesion or multi- plication. Composite preparation of organic materials with Hap has involved the use of coupling agents, such as silanes [13±15], zirconyl salts [16], and polyacid [17], and the introduction of a chemical linkage to octacalcium phosphate by coprecipitation [18, 19]. As is well known, organic compounds with isocyanate groups react readily with Hap surface hydroxyl groups [20]. This paper details a novel 2-step surface modi®cation with an organic compound that improves porous Hap mechanical properties and functionality. We chose poly methyl methacrylate (PMMA) as a typical example for porous Hap surface modi®cation. PMMA is a common polymer used as bone cement for ®xing total hip prostheses [15, 18, 19, 21] to give suitable mechanical properties to the material. Initially, 2-methacryloyloxy- ethylene isocyanate (MOI) possessing a vinyl polymer- izable double bond and a reactive isocyanate group at both ends of the compound is reacted with a hydroxyl group of Hap to introduce vinyl groups, applicable as initiation points for grafting PMMA onto porous Hap. We then studied reaction kinetics and the effect on porous Hap shape and microstructure. *Author to whom all correspondence should be addressed. 0957±4530 # 2003 Kluwer Academic Publishers 973

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