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Hydrolytic stability of end-linked hydrogels from PLGA–PEG–PLGA macromonomers terminated by α,ω-itaconyl groups

Author:
Michlovská, L., Vojtová, L., Humpa, O., Kučerík, J., Žídek, J., Jančář, J.
Source:
RSC advances 2016 v.6 no.20 pp. 16808-16816
ISSN:
2046-2069
Subject:
Fourier transform infrared spectroscopy, biodegradability, blue light, carbon, chemical bonding, composite polymers, crosslinking, hydrogels, hydrolysis, irradiation, moieties, nuclear magnetic resonance spectroscopy, polymerization, reflectance, thermogravimetry, tissue engineering
Abstract:
Biodegradable amphiphilic PLGA–PEG–PLGA triblock copolymers end-terminated with itaconic acid (ITA) having reactive double bonds were synthesized by ring opening polymerization. The prepared α,ω-itaconyl-PLGA–PEG–PLGA telechelic macromonomers were additionally covalently crosslinked under an inert atmosphere by blue light irradiation without the use of a further cross-linker resulting in end-linked polymeric networks. The effects of the ITA amount attached to the α,ω-itaconyl-PLGA–PEG–PLGA copolymers and the crosslinking time on swelling behaviours and hydrolytic stability of the prepared well-defined polymeric network were investigated. Physicochemical properties were characterized by proton and carbon nuclear magnetic resonance spectroscopy (¹H NMR, ¹³C NMR), proton nuclear magnetic resonance relaxometry, attenuated total reflectance Fourier transformed infrared spectroscopy (ATR-FTIR) and thermogravimetric analysis (TGA). It was found that the hydrolytic stability of ITA modified PLGA–PEG–PLGA end-linked hydrogels enhances with both increasing the time of crosslinking and the amount of double bonds attached to α,ω-itaconyl-PLGA–PEG–PLGA polymer chains. In comparison with the original un-crosslinked α,ω-itaconyl-PLGA–PEG–PLGA copolymer, the hydrolytic stability of the end-linked hydrogels significantly increased. Three kinds of water fractions (unbound, weakly and strongly bonded) were determined by proton NMR relaxometry in hydrogels containing 63 mol% of ITA crosslinked for 40 minutes. Even for hydrogels surviving 32 days in water the NMR relaxometry showed structural collapse of the hydrogel probably due to breaking of end-linked nodes followed by hydrolysis faster than water diffusion after day 15 of immersion. End-linked α,ω-itaconyl-PLGA–PEG–PLGA hydrogels can be used in medical, biological or tissue engineering applications.
Agid:
6402577