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In vitro mineralisation of well-defined polymers and surfaces

Suzuki, Shuko (2007) In vitro mineralisation of well-defined polymers and surfaces. PhD thesis, Queensland University of Technology.

Abstract

Currently, many polymeric biomaterials do not possess the most desirable surface properties for direct bone bonding due to the lack of suitable surface functionalities. The incorporation of negatively charged groups has been shown to enhance calcium phosphate formation in vitro and bone bonding ability in vivo. However, there are some conflicting literature reports that highlight the complicated nature of the mineralisation process as well as the sometimes apparent contradictory effect of the negatively charged groups. Surface modification using well-defined polymers offer a more precise control of the chain structures. The aims of this study were to synthesise well-defined polymers containing phosphate and carboxylic acid groups, and perform various surface modification techniques. The influence of the polymer structure on mineralisation was examined using a series of specially synthesised phosphate-containing polymers. The mineralisation ability of the fabricated surfaces was also tested.

Soluble poly(monoacryloxyethyl phosphate) (PMAEP) and poly(2-(methacryloyloxy)ethyl phosphate) (PMOEP) were synthesised using reversible addition fragmentation chain transfer (RAFT)-mediated polymerisation. The polymerisation conversions were monitored by in situ Raman spectroscopy. Subsequently 31P NMR investigation revealed the presence of large amounts of diene impurities as well as free orthophosphoric acids in both the MAEP and MOEP monomers. Elemental analyses of the polymers showed loss of phosphate groups due to hydrolysis during the polymerisation. Both gel and soluble PMAEP polymers were found to contain large amounts of carboxyl groups indicating hydrolysis at the C-O-C ester linkages. Block copolymers consisting of PMAEP or PMOEP and poly(2-(acetoacetoxy) ethyl methacrylate) PAAEMA were successfully prepared for the purpose of immobilisation of these polymers onto aminated slides.

Well-defined fluorinated polymers, (poly(pentafluorostyrene) (PFS), poly(tetrafluoropropyl acrylate) (TFPA) and poly(tetrafluoropropyl methacrylate) (TFPMA)) were synthesised by RAFT-mediated polymerisation. It was found that the Mn values of PFS at higher conversions were significantly lower than those calculated from the theory, although the PDI's were low (&lt1.1). One possible explanation for this is that it may be a result of the self-initiation of FS which created more chains than the added RAFT agents. Both TFPA and TFPMA showed well-controlled RAFT polymerisations. Chain extension of the fluorinated polymers with tert-butyl acrylate (tBA) followed by hydrolysis of the tBA groups produced the amphiphilic block copolymers containing carboxylic acid groups. Block copolymers consisting of PAAEMA segments were further reacted with glycine and L-phenylalanyl glycine.

Three types of surface modifications were carried out: Layer-by-Layer (LbL) assemblies of the soluble phosphate- and carboxylic acid-containing homopolymers, coupling reactions of block copolymers consisting of phosphate and keto groups onto aminated slides, and adsorption of fluorinated homo and block copolymers containing carboxylic acid groups onto PTFE. For LbL assemblies XPS analyses revealed that the thickness of the poly(acrylic acid) (PAA) layer was found to be strongly dependent on the pH at deposition. AFM images showed that the PMAEP LbL had a patchy morphology which was due to the carboxylate groups that were not deprotonated at low pH. Successful coupling of the block copolymers consisting of phosphate and keto groups onto aminated slides was evident in the XPS results. The conformation of attached P(MOEP-b-AAEMA) was investigated by ToF-SIMS. Adsorption of the fluorinated polymers onto the PTFE film was examined using different solvents. PFS showed the best adsorption onto PTFE. The block copolymers consisting of PFS and PtBA or PAA were successfully adsorbed onto PTFE. Contact angle measurements showed that the adsorbed block copolymers reorganised quickly to form a hydrophilic surface during the investigation.

In vitro mineralisation of various phosphate-containing polymers and the fabricated surfaces were studied using the simulated body fluid (SBF) technique. The SEM/EDX investigation showed that either brushite or monetite, with a tile-like morphology, was formed on both soluble and gel PMAEP polymers after seven days in SBF. The PMOEP gel formed a similar layer as well as a secondary growth of hydroxyapatite (HAP) that exhibited a typical globular morphology. Fourier transform infrared (FTIR) spectroscopy of the PMOEP film prepared from soluble PMOEP showed large amounts of carbonated HAP formation after seven days in SBF. Carbonated HAP is the phase that most closely resembles that found in biological systems. Both the LbL surfaces and the block copolymer-attached aminated slides showed only patchy mineralisation even after 14 days in SBF. This indicates that ionic interactions of the negatively charged phosphates or carboxylates and protonated amines prevented chelation of calcium ions, which is believed to be the first step in mineralisation. The P(FS-b-AA) adsorbed PTFE film also showed only small amounts of mineral formation after 14 days in SBF. These results highlight the many features controlling the mineralisation outcomes.

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ID Code: 16593
Item Type: QUT Thesis (PhD)
Supervisor: Wentrup-Byrne, Edeline, George, Graeme, Grondahl, Lisabeth, & Monteiro, Michael
Keywords: mineralisation, polymers, polymeric biomaterials
Divisions: Past > QUT Faculties & Divisions > Faculty of Science and Technology
Past > Schools > School of Physical & Chemical Sciences
Department: Faculty of Science
Institution: Queensland University of Technology
Copyright Owner: Copyright Shuko Suzuki
Deposited On: 03 Dec 2008 04:06
Last Modified: 28 Oct 2011 19:50

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