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

机译:由α,ω-碘基的PLGA-PEG-PLGA大分子单体的终结水凝胶的水解稳定性

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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 ( ~(1) H NMR, ~(13) C 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.
机译:通过开环聚合合成终止具有反应性双键的衣康酸(ITA)的可生物降解的两亲的PLGA-PEG-PLGA三嵌段共聚物。制备的α,ω-itaConyl-PLGA-PEG-PEG-PLGA遥型大分子单体在惰性气氛下通过蓝光照射在不使用终结聚合物网络的另一个交联剂的情况下共价交联。研究了α,ω-碘基-PLGA-PEG-PLGA共聚物和交联时间的ITA量对制备的明确定义的聚合物网络的溶胀行为和水解稳定性的交联时间。物理化学性质的特征是质子和碳核磁共振谱(〜(1)H NMR,〜(13)C NMR),质子核磁共振舒放,衰减总反射率傅里叶变换红外光谱(ATR-FTIR)和热重分析( TGA)。发现ITA改性PLGA-PEG-PLGA端部连接水凝胶的水解稳定性随着交联时间和附着于α,ω-itAconyl-PLGA-PEG-PLGA聚合物链的时倍数和双键量。与原始未交联的α,ω-碘基-PLGA-PEG-PLGA共聚物相比,端部连接水凝胶的水解稳定性显着增加。通过含有63mol%的ITA交联40分钟的水凝胶中的水凝胶中的质子NMR弛豫测定法测定三种水分(未结合弱和强粘合)。即使对于水凝胶在水中存活32天,NMR弛豫率也显示出水凝胶的结构塌陷,可能是由于末端连接的节点,然后在浸渍后的第15天之后的水扩散快速水解。端接α,ω-itAconyl-PLGA-PEG-PLGA水凝胶可用于医疗,生物或组织工程应用。

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