基于还原响应性的生物可降解不饱和聚氨酯的合成及其性能研究

谌康谧; 姚跃君; 郑鸿浩; 高长有

doi:10.11777/j.issn1000-3304.2019.18275

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基于还原响应性的生物可降解不饱和聚氨酯的合成及其性能研究

研究论文 | 更新时间：2021-01-26

- 基于还原响应性的生物可降解不饱和聚氨酯的合成及其性能研究
- Synthesis and Properties of Biodegradable Unsaturated Polyurethanes with Reductive Responsiveness
- 高分子学报 2019年50卷第6期页码：623-632
- 作者机构：
  
  教育部高分子合成与功能构造重点实验室浙江大学高分子科学与工程学系　杭州 310027
- 作者简介：
  
  E-mail: cygao@zju.edu.cn Chang-you Gao, E-mail: cygao@zju.edu.cn
- 基金信息：
  
  国家自然科学基金(基金号 51873188，21434006)资助项目()
- DOI：10.11777/j.issn1000-3304.2019.18275
  中图分类号：
- 纸质出版日期：2019-6，
  
  网络出版日期：2019-3-28，
  
  收稿日期：2018-12-25，
  
  修回日期：2019-1-19，
扫描看全文
谌康谧, 姚跃君, 郑鸿浩, 高长有. 基于还原响应性的生物可降解不饱和聚氨酯的合成及其性能研究[J]. 高分子学报, 2019,50(6):623-632.

Kang-mi Shen, Yue-jun Yao, Hong-hao Zheng, Chang-you Gao. Synthesis and Properties of Biodegradable Unsaturated Polyurethanes with Reductive Responsiveness[J]. Acta Polymerica Sinica, 2019,50(6):623-632.
谌康谧, 姚跃君, 郑鸿浩, 高长有. 基于还原响应性的生物可降解不饱和聚氨酯的合成及其性能研究[J]. 高分子学报, 2019,50(6):623-632. DOI： 10.11777/j.issn1000-3304.2019.18275.

Kang-mi Shen, Yue-jun Yao, Hong-hao Zheng, Chang-you Gao. Synthesis and Properties of Biodegradable Unsaturated Polyurethanes with Reductive Responsiveness[J]. Acta Polymerica Sinica, 2019,50(6):623-632. DOI： 10.11777/j.issn1000-3304.2019.18275.

摘要

设计合成了基于聚富马酸丙二醇酯和二硫键结构的新型不饱和聚氨酯(PPFU-SS)；为改善聚氨酯材料的力学性能，引入了聚己内酯(PCL)软段，合成了含有二硫键结构且拉伸性能得到提升的新型不饱和聚氨酯(PPFU-CO-SS)；也合成了作为对照的不含二硫键结构的不饱和聚氨酯(PPFU-Lys). 示差扫描量热仪(DSC)及热重分析(TGA)测试证明3种材料在150 ℃以下均具有良好的热稳定性. 在外力作用下，3种聚氨酯材料均表现出良好的弹性和较大的形变；引入PCL共聚后的PPFU-CO-SS的拉伸强度得到显著提高，达到了0.8 MPa. 降解实验证明，PPFU-SS及PPFU-CO-SS具有显著的还原响应性，在谷胱甘肽存在下降解速度明显加快，与不含谷胱甘肽的对照组相比存在显著性差异. PPFU-CO-SS有更强的疏水性能，其水接触角(93.5°)比PPFU-SS(73.9°)和PPFU-Lys(74.4°)高了约20°. 体外细胞培养证明，3种材料均不存在明显的细胞毒性，血管平滑肌细胞在PPFU-SS和PPFU-Lys表面、PPFU-CO-SS表面的增殖速度分别快于或相当于TCPS，说明材料具有优异的细胞相容性.

Abstract

A novel type of unsaturated polyurethanes (PPFU-SS) containing disulfide bonds was synthesized by using poly(propylene fumarate) as the soft segment and dimethyl L-cystinate dihydrochloride as the chain extender. In order to improve the mechanical properties

polycaprolactone diol (PCL) was copolymerized as the soft segment as well to obtain the novel unsaturated copolymerized polyurethanes (PPFU-CO-SS). Moreover

unsaturated polyurethane (PPFU-Lys) without disulfide bonds was synthesized and used as the control group. The chemical structures of PPFU-SS

PPFU-Lys

and PPFU-CO-SS were characterized by

H-NMR

and Raman spectroscopy

revealing that there were many carbon-carbon double bonds and disulfide bonds in PPFU-SS and PPFU-CO-SS. The thermal properties of these three types of PPFU materials were characterized by DSC and TGA

which demonstrated their good thermal stability below 150 °C. The mechanical properties of these PPFUs were analyzed by universal mechanical testing

showing that the tensile strength of PPFU-CO-SS polymer was the highest with a value of 0.8 MPa. Therefore

the copolymerization with PCL has successfully improved the mechanical property of the novel unsaturated polyurethanes. The degradation of reduction-responsive PPFU-SS and PPFU-CO-SS was significantly accelerated in glutathione solution compared with that in phosphate buffered saline

whereas the degradation of PPFU-Lys had no obvious difference in these two types of solutions. Comparatively

PPFU-CO-SS showed a stronger hydrophobicity

water contact angle (93.5°) significantly larger than those of PPFU-SS (73.9°) and PPFU-Lys (74.4°). Culture of smooth muscle cells

in vitro

demonstrated that none of PPFU-SS

PPFU-Lys

and PPFU-CO-SS had obvious cytotoxicity. The cells cultured on the PPFU-SS and PPFU-Lys surfaces showed faster proliferation rates than those cultured on TCPS

whereas the cell proliferation rate on PPFU-CO-SS was comparable to that on TCPS. In conclusion

these results demonstrated that the reduction-responsive polyurethanes possess good mechanical strength

thermal stability

degradability in response to reductants

low cytotoxicity

and cell coMPatibility

and thus hold great potential in fields of drug delivery

tissue engineering

regenerative medicine

and therapy of diseases. Furthermore

the unsaturated and high active carbon-carbon double bonds can be used to graft desired molecules

enabling the diverse functionalization and thereby applications.

关键词

还原响应性聚富马酸丙二醇酯聚氨酯生物降解性细胞相容性

Keywords

Reduction-sensitivePoly(propylene fumarate)PolyurethaneBiodegradableCell compatibility

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