Abstract

Goals. The goal of this study was a development of biocompatible composite hydrogels, structurally similar to native bone tissue, by incorporation of ~60 wt % of calcium hydroxyapatite (HA) into a matrix of hydrogels. Also, a possibility to control swelling kinetic and equilibrium swelling degree (SDeq) of hydrogels, by altering the degree of neutralization of the precursor (DN) was examined. Methods. Composite hydrogels, based on HA and poly(methacrylic acid) (PMAA), were synthesized by free-radical polymerization with different DN. Theoretical content of HA in synthesized composites was 60 wt %. Composites were synthesized by methods of dynamic mechanical analysis and scanning electron microscopy. SDeq and swelling kinetic were examined in distilled water and simulated body fluid. Results. Morphological observations revealed uniform distribution and strong bond of spherical HA particles within the polymer matrix. Swelling analyses demonstrated that SDeq is directly proportional to DN, while rheological examinations indicated inverse proportion between DN and storage modulus, but due to the HA particles inclusion, mechanical properties of composites were significantly better compared to monophasic PMAA hydrogels. Significance. Simple method of synthesis of composite hydrogels with high content of filler nanoparticles is presented. Incorporation of HA nanoparticles significantly improved mechanical properties of hydrogels, while at the same time was demonstrated a possibility to control swelling kinetic by influencing the DN.

Highlights

  • Ako uporedimo kompozite dobijene u ovom radu sa čistim poly(methacrylic acid) (PMAA) hidrogelovima sintetisanim u radu Panić i saradnika [8], čak i najniža vrednost G’ sintetisanih kompozita (G’PMAA/HA100=55130 Pa) je 80 puta veća od vrednosti G’ čistih hidrogelova (G’PMAA=692.7 Pa)

  • Incorporation of HA nanoparticles significantly improved mechanical properties of hydrogels, while at the same time was demonstrated a possibility to control swelling kinetic by influencing the DN

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Summary

Sinteza kompozitnih hidrogelova

Nanočestični prah HA sintetisan je hidrotermalnom metodom prema već opisanom postupku [1416]. Molski odnos Ca/P u prekusorskom rastvoru bio je 1.67, što odgovara stehiometrijskom odnosu kalcijuma i fosfora u hidroksiapatitu. PMAA/HA kompozitni hidrogelovi, sa različitim stepenima neutralizacije prekursora (metakrilne kiseline), sintetisani su slobodno-radikalskom polimerizacijom, modifikacijom ranije opisanog postupka. U prvom koraku 1.25 ml metakrilne kiseline (MAA) (99.5 %) (proizvođač Merck KGaA, Darmstadt, Nemačka) rastvoreno je u određenoj količini destilovane vode (tabela 1), nakon čega je dodata određena količina natrijum-hidroksida (proizvođač Aldrich Chemical Co., Milwaukee, WI) da bi se postigao željeni stepen neutralizacije MAA. U sledećem koraku se dodaje 0.895 ml 1% rastvora umreživača N,N′-metilenbisakrilamida (MBA) (proizvođač Aldrich Chemical Co., Milwaukee, WI) i 2.3817 g prethodno sintetisanog praha HA. Na kraju postupka 0.2825 ml 1% rastvora inicijatora reakcije polimerizacije 2,2′-azobis-[2-(2imidazolin-2-il)propan] dihidrohlorida (VA-044) (99.8 %) (proizvođač Wako Pure Chemical Industries, Ltd., Osaka, Japan) se dodaje u reakcionu smešu. Teorijski udeo HA u kompozitima je bio 60 mas %

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