Synthesis, swelling, degradation and cytocompatibility of crosslinked PLLA-PEG-PLLA networks with short PLLA blocks Hui Peng a,f , Srinivas Varanasi a,b,2 , David K. Wang a,c , Idriss Blakey a,d , Firas Rasoul a,c,1 , Anne Symons b , David J.T. Hill a,e,⇑ , Andrew K. Whittaker a,f,⇑ a Australian Institute for Bioengineering and Nanotechnology, The University of Queensland, St. Lucia Q4072, Australia b School of Dentistry, The University of Queensland, St. Lucia Q4072, Australia c Functional Interfacial Materials and Membranes Laboratory, School of Chemical Engineering, The University of Queensland, St. Lucia Q4072, Australia d Centre for Advanced Imaging, The University of Queensland, St. Lucia Q4072, Australia e School of Chemistry and Molecular Biosciences, The University of Queensland, St. Lucia Q4072, Australia f ARC Centre of Excellence in Convergent Bio-Nano Science and Technology, The University of Queensland, St. Lucia Q4072, Australia article info Article history: Received 10 May 2016 Received in revised form 15 September 2016 Accepted 23 September 2016 Available online 29 September 2016 Keywords: PEG PLLA Crosslinked networks Degradation Hydrolysis Cytocompatibility abstract A series of triblock macromonomers with the general structure PLA a -PEG b -PLA a with acrylate end-groups and very short segments of PLA have been synthesized and character- ized for potential use in the treatment of periodontitis. In the proposed application aqueous solutions of the triblock macromonomers would be injected into the pockets formed around the teeth and then crosslinked via photo-induced free radical polymeriza- tion to form drug-laden hydrogels. One of the macromonomers with the structure PLA 4 -PEG 45 -PLA 4 showed optimum properties for the proposed application and was chosen for a more detailed study. In the study, the nature of the hydrogels formed by the macromonomer and by its copolymerization with PEG 16 diacrylate has been investigated, along with its swelling and degradation in PBS at 37 °C and pH 7.4. The hydrogels swell to equilibrium in water or PBS within approximately 5 h, with swelling ratios in the range 4.5–3.5 and penetrant diffusion coefficients 1.5–2.4  10 6 cm 2 s 1 in PBS, depending on the PLA 4 -PEG 45 -PLA 4 macromonomer content over the range 1.00–0.80 wt fraction. The swollen hydrogels have an open pore structure, with the diameter of the largest pores in excess of 25 lm. A detailed spectroscopic study confirmed that degradation in PBS proceeds as expected via hydrolysis of the lactide segments, and the polymer matrix completely dissolves after 22 days. The potential for control of degradation kinetics using the comacromonomer composition was also demonstrated. The cytotoxicity towards fibroblasts and osteoblasts, two important cell types involved in tissue repair and bone regeneration, has also been thoroughly evaluated. The hydrogels, and the products of hydrolytic degradation, were found to be non-cytotoxic towards these particular cells. Crown Copyright Ó 2016 Published by Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.eurpolymj.2016.09.039 0014-3057/Crown Copyright Ó 2016 Published by Elsevier Ltd. All rights reserved. ⇑ Corresponding author at: Australian Institute for Bioengineering and Nanotechnology, The University of Queensland, St. Lucia Q4072, Australia. E-mail addresses: d.hill@uq.edu.au (D.J.T. Hill), a.whittaker@uq.edu.au (A.K. Whittaker). 1 Current address: Petroleum Research Centre, Kuwait Institute for Scientific Research, PO Box 24885, Safat 13109, Kuwait. 2 Current address: TAFE Queensland, South Bank, Brisbane, Q4010, Australia. European Polymer Journal 84 (2016) 448–464 Contents lists available at ScienceDirect European Polymer Journal journal homepage: www.elsevier.com/locate/europolj