Thiol Click Modification of Cyclic Disulfide Containing Biodegradable Polyurethane Urea Elastomers
Thiol Click Modification of Cyclic Disulfide Containing Biodegradable Polyurethane Urea Elastomers
复制标题
含环二硫醚可生物降解聚氨酯脲弹性体的硫醇点击改性
DOI：
10.1021/acs.biomac.5b00192
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发表时间：
2015-05-01
影响因子：
6.2
通讯作者：
Wagner, William R.
中科院分区：
文献类型：
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作者：
Fang, Jun;Ye, Sang-Ho;Wagner, William R.
虽然巯基点击反应是一种很有吸引力的硫聚合物聚合后修饰工具，但巯基很容易氧化，限制了生物活性包膜共价固定的潜力。本研究开发了一系列含有稳定环二硫基的可生物降解聚氨酯弹性体，并对其进行了表征：以聚己内酯、二醇（PCL）、氧化dl -二硫苏糖醇（O-DTT）、赖氨酸二异氰酸酯或二异氰酸酯丁酯（BDI）为基料，经腐胺扩链，制备了三种聚（酯聚氨酯）脲(PEUU-SS)-聚合物。改变O-DTT:PCL的比例，以研究不同水平的潜在功能化。采用聚乙二醇丙烯酸酯研究了PEUU-SS聚合物的本体改性和表面改性的机理和有效性。所有合成的PEUU-SS聚合物都具有弹性，断裂强度为38 ~ 45 MPa，而PEUU-SS（LDI）聚合物比PEUU-SS（BDI）聚合物更具无定形，具有更低的模量和相对较小的永久变形。通过控制还原量，实现了PEUU-SS（LDI）聚合物的可变体积点击改性。试剂，快速反应速率发生使用一锅，两步的过程。同样，在温和的水环境下，表面的咔嗒反应也可以快速进行。此外，在电纺丝PEUU-SS（BDI）纤维片表面成功地点击了一种马伦烯修饰的亲和肽（TPS），与未修饰的膜相比，它改善了内皮祖细胞的粘附性。所描述的含有可生物降解聚氨酯的环二硫烷为心血管和其他软组织再生医学应用提供了一种选择，其中需要一种相对简单的点击化学方法设计的具有生物功能的临时弹性支架。
Although the thiol Click reaction is an attractive tool for postpolymerization modification of thiolmers, thiol groups are easily oxidized, limiting the potential for covalent immobilization of bioactive inclecules. In this study, a series of biodegradable polyurethane elastomers incorporating stable cyclic disulfide groups Was developed and characterized: Thee poly(ester urethane)urea (PEUU-SS)- polymers were based on polycaprolactone,diol (PCL), oxidized DL-dithiothreitol (O-DTT), lysine diisocyanate or butyl diisocyanate (BDI), with, chain extension by putrescine. The,ratio, of O-DTT:PCL was altered to investigate different levels of potential functionalization. PEG acrylate was employed to study the mechanism and availability of both bulk and surface click modification of PEUU-SS polymers. All synthesited-PEUU-SS polymers were elastic with breaking strengths of 38-45 MPa, while the PEUU-SS (LDI) polymers were more amorphous, possessing lower moduli and relatively small permanent deformations versus PEUU-SS(BDI) polymers. Variable bulk click modification of PEUU-SS(LDI) polymers was achieved by controlling the amount of reduction. reagent, and rapid reaction rates occurred using a one-pot, two-step process. Likewise, surface click reaction could be carried out-quiCkly-under mild, aqueous conditions. Furthermore, a malennide-modified affinity peptide (TPS) was successfully clicked on the surface of an electrospun PEUU-SS(BDI) fibrous sheet, which improved endothelial-progenitor cell adhesion versus corresponding unmodified films. The cyclic disulfide containing biodegradable polyurethanes described provide an option for cardiovascular and Other soft tissue regenerative medicine applications where a temporary, elastic scaffold with designed biofunctionality from a relatively simple click chemistry approach is desired.