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Molecular Recognition in Poly(epsilon-caprolactone)-Based Thermoplastic Elastomers

机译:基于聚ε-己内酯的热塑性弹性体的分子识别

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The molecular recognition properties of the hydrogen bonding segments in biodegradable thermoplastic elastomers were explored,aiming at the further functionalization of these potentially interesting biomaterials.A poly(epsilon-caprolactone)-based poly(urea) 2 was synthesized and characterized in terms of mechanical properties,processibility and histocompatibility.Comparison of the data with those obtained from the structurally related poly(urethane urea) 1 revealed that the difference in hard segment structure does not significantly affect the potency for application as a biomaterial.Nevertheless,the small differences in hard block composition had a strong effect on the molecular recognition properties of the hydrogen bonding segments.High selectivity was found for poly(urea) 2 in which bisureidobutylene-functionalized azobenzene dye 3 was selectively incorporated while bisureidopentylene-functionalized azobenzene dye 4 was completely released.In contrast,the incorporation of both dyes in poly-(urethane urea) 1 led in both cases to their gradual release in time.Thermal analysis of the polymers in combination with variable temperature infrared experiments indicated that the hard blocks in 1 showed a sharp melting point,whereas those in 2 showed a very broad melting trajectory.This suggests a more precise organization of the hydrogen bonding segments in the hard blocks of poly(urea) 2 compared to poly(urethane urea) 1 and explains the results from the molecular recognition experiments.Preliminary results revealed that a bisureidobutylene-functionalized GRGDS peptide showed more supramolecular interaction with the PCL-based poly(urea),containing the bisureidobutylene recognition unit,as compared to HMW PCL,lacking this recognition unit.
机译:针对这些潜在有趣的生物材料的进一步功能化,探索了可生物降解的热塑性弹性体中氢键链段的分子识别特性。合成了一种基于聚ε-己内酯的聚脲2,并根据机械性能进行了表征数据,与结构相关的聚氨基甲酸酯尿素1的数据比较表明,硬链段结构的差异并不会显着影响作为生物材料的应用潜力。组成对氢键链段的分子识别性能有很强的影响。发现对聚(脲)2具有高选择性,在该聚脲中选择性地掺入了双脲基丁烯官能化的偶氮苯染料3而完全释放了双脲基戊二烯官能化的偶氮苯染料4。 ,两种染料的结合聚(氨基甲酸酯尿素)1中的1导致这两种情况都随着时间的推移逐渐释放。聚合物的热分析与可变温度红外实验相结合,表明1中的硬嵌段具有明显的熔点,而2中的硬嵌段具有较高的熔点。较宽的熔化轨迹,这表明与聚脲脲1相比,聚脲2的硬嵌段中氢键链段的组织更精确,并解释了分子识别实验的结果。初步结果表明,双脲基丁烯与HMW PCL相比,功能强大的GRGDS肽与含双脲基丁烯识别单元的PCL基聚脲表现出更多的超分子相互作用,而缺少该识别单元。

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