Photo-cross-linked poly(D,L-lactide)-based networks. Structural characterization by HR-MAS NMR spectroscopy and hydrolytic degradation behavior

Melchels, Ferry P.W., Velders, Aldrik H., Feijen, Jan, & Grijpma, Dirk W. (2010) Photo-cross-linked poly(D,L-lactide)-based networks. Structural characterization by HR-MAS NMR spectroscopy and hydrolytic degradation behavior. Macromolecules, 43(20), pp. 8570-8579.

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To date, biodegradable networks and particularly their kinetic chain lengths have been characterized by analysis of their degradation products in solution. We characterize the network itself by NMR analysis in the solvent-swollen state under magic angle spinning conditions. The networks were prepared by photoinitiated cross-linking of poly(dl-lactide)−dimethacrylate macromers (5 kg/mol) in the presence of an unreactive diluent. Using diffusion filtering and 2D correlation spectroscopy techniques, all network components are identified. By quantification of network-bound photoinitiator fragments, an average kinetic chain length of 9 ± 2 methacrylate units is determined. The PDLLA macromer solution was also used with a dye to prepare computer-designed structures by stereolithography. For these networks structures, the average kinetic chain length is 24 ± 4 methacrylate units. In all cases the calculated molecular weights of the polymethacrylate chains after degradation are maximally 8.8 kg/mol, which is far below the threshold for renal clearance. Upon incubation in phosphate buffered saline at 37 °C, the networks show a similar mass loss profile in time as linear high-molecular-weight PDLLA (HMW PDLLA). The mechanical properties are preserved longer for the PDLLA networks than for HMW PDLLA. The initial tensile strength of 47 ± 2 MPa does not decrease significantly for the first 15 weeks, while HMW PDLLA lost 85 ± 5% of its strength within 5 weeks. The physical properties, kinetic chain length, and degradation profile of these photo-cross-linked PDLLA networks make them most suited materials for orthopedic applications and use in (bone) tissue engineering.

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15 citations in Scopus
15 citations in Web of Science®
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ID Code: 38855
Item Type: Journal Article
Refereed: Yes
Additional Information: This article is freely available from the American Chemical Society website 12 months after the publication date. See links to publisher website in this record.
Keywords: polymer network, nmr, magic angle spinning, hr-mas, hydrolytic degradation, biodegradable
DOI: 10.1021/ma1011705
ISSN: 0024-9297
Subjects: Australian and New Zealand Standard Research Classification > ENGINEERING (090000) > BIOMEDICAL ENGINEERING (090300) > Biomaterials (090301)
Divisions: Past > QUT Faculties & Divisions > Faculty of Built Environment and Engineering
Current > Institutes > Institute of Health and Biomedical Innovation
Copyright Owner: Copyright 2010 American Chemical Society
Deposited On: 24 Nov 2010 05:43
Last Modified: 21 Jun 2017 14:44

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