Zinc ion release from novel hard tissue biomaterials

Zinc polyalkenoate cements (ZPCs) and glass polyalkenoate cements (GPCs) are used routinely in dentistry, but have potential for orthopaedic applications as they set at body temperature without shrinkage or significant heat evolution. However, the materials have drawbacks; ZPCs are biocompatible in implant studies, but a fibrous collagen capsular layer forms adjacent to the cement. GPCs are bioactive in the bone environment as a result of the release of calcium, phosphate and fluoride ions, as well as the formation of a silicious gel phase, but research has shown that aluminum ions released result in defective bone mineralisation and as a consequence the ability of these cements to chemically bond to bone is lost. Two approaches have been developed to overcome these problems. The ZPC route considers a ZnO : hydroxyapatite (HA) : poly(acrylic acid) (PAA) mixture, the HA incorporated to improve bioactivity. The GPC route employs a calcium zinc silicate glass; the zinc taking the role that aluminum plays in conventional GPCs. This study has shown that cements can be formulated by an acid base reaction between PAA and both calcium zinc silicate glasses (GPCs) and a mixture of hydroxyapatite and zinc oxide (ZPCs). The moduli of these cements are comparable to both bone and conventional acrylic cements, highlighting their potential for biomedical applications. Unfortunately, both materials have previously been shown to be toxic by cell culture methods, as a result of high zinc ion release, and so it is necessary to study ion release profiles of the cements in order to determine the magnitude of this release. Considering the ZPCs, the modulus of the cement has an inversely proportional relationship to the zinc ion release. From the data presented it is clear that increases in polymer concentration results in lower amounts of zinc ions being released, whilst molar mass of the PAA has no influence. Therefore it would appear that polymer concentration has a significant influence over ion release. Generally, the amount of Zn(2+) released decreases with increasing HA content and/or decreasing ZnO content. Considering the GPCs, the materials are all seen to release large amounts of the active ion, when compared to the commercial versions. The extent of this release increases with temperature and agitation. The release could be minimised by an increased P : L mixing ratio, and an increased PAA concentration, which would produce a more cross-linked cement matrix. Minimising the release of the active ion should improve the in vitro bioactivity of both materials. However, for a full understanding of the clinical benefits of such materials, an in vivo study would be required.