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具有良好机械性能、形状记忆性能、pH响应性能和生物相容性的姜黄素改性聚氨酯材料的设计与表征

Design and Characterization of Curcumin-Modified Polyurethane Material with Good Mechanical, Shape-Memory, pH-Responsive, and Biocompatible Properties.

作者信息

Wang Man, Liu Hongying, Zhao Wei, Wang Huafen, Zhuang Yuwei, Yang Jie, Liu Zhaohui, Zhu Jing, Chen Sichong, Cheng Jinghui

机构信息

High & New Technology Research Center of Henan Academy of Sciences, No. 56 Hongzhuan Road, Zhengzhou 450002, China.

West China School of Nursing, Sichuan University, Chengdu 610041, China.

出版信息

Biomolecules. 2025 Jul 24;15(8):1070. doi: 10.3390/biom15081070.

Abstract

In the context of critical challenges in curcumin-modified polyurethane synthesis-including limited curcumin bioavailability and suboptimal biodegradability/biocompatibility-a novel polyurethane material (Cur-PU) with good mechanical, shape memory, pH-responsive, and biocompatibility was synthesized via a one-pot, two-step synthetic protocol in which HO-PCL-OH served as the soft segment and curcumin was employed as the chain extender. The experimental results demonstrate that with the increase in Cur units, the crystallinity of the Cur-PU material decreases from 32.6% to 5.3% and that the intensities of the diffraction peaks at 2θ = 21.36°, 21.97°, and 23.72° in the XRD pattern gradually diminish. Concomitantly, tensile strength decreased from 35.5 MPa to 19.3 MPa, and Shore A hardness declined from 88 HA to 65 HA. These observations indicate that the sterically hindered benzene ring structure of Cur imposes restrictions on HO-PCL-OH crystallization, leading to lower crystallinity and retarded crystallization kinetics in Cur-PU. As a consequence, the material's tensile strength and hardness are diminished. Except for the Cur-PU-3 sample, all other variants exhibited exceptional shape-memory functionality, with R and R exceeding 95%, as determined by three-point bending method. Analogous to pure curcumin solutions, Cur-PU solutions demonstrated pH-responsive chromatic transitions: upon addition of hydroxide ion (OH) solutions at increasing concentrations, the solutions shifted from yellow-green to dark green and finally to orange-yellow, enabling sensitive pH detection across alkaline gradients. Hydrolytic degradation studies conducted over 15 weeks in air, UPW, and pH 6.0/8.0 phosphate buffer solutions revealed mass loss <2% for Cur-PU films. Surface morphological analysis showed progressive etching with the formation of micro-to-nano-scale pores, indicative of a surface-erosion degradation mechanism consistent with pure PCL. Biocompatibility assessments via L929 mouse fibroblast co-culture experiments demonstrated ≥90% cell viability after 72 h, while relative red blood cell hemolysis rates remained below 5%. Collectively, these findings establish Cur-PU as a biocompatible material with tunable mechanical properties, and pH responsiveness, underscoring its translational potential for biomedical applications such as drug delivery systems and tissue engineering scaffolds.

摘要

在姜黄素改性聚氨酯合成面临严峻挑战的背景下,包括姜黄素生物利用度有限以及生物降解性/生物相容性欠佳等问题,通过一锅两步合成方案合成了一种具有良好机械性能、形状记忆性能、pH响应性和生物相容性的新型聚氨酯材料(Cur-PU),其中HO-PCL-OH用作软段,姜黄素用作扩链剂。实验结果表明,随着Cur单元的增加,Cur-PU材料的结晶度从32.6%降至5.3%,X射线衍射图谱中2θ = 21.36°、21.97°和23.72°处的衍射峰强度逐渐减弱。同时,拉伸强度从35.5 MPa降至19.3 MPa,邵氏A硬度从88 HA降至65 HA。这些观察结果表明,Cur的空间位阻苯环结构对HO-PCL-OH结晶产生限制,导致Cur-PU的结晶度降低且结晶动力学迟缓。因此,材料的拉伸强度和硬度降低。除Cur-PU-3样品外,所有其他变体均表现出优异的形状记忆功能,通过三点弯曲法测定,R和R超过95%。与纯姜黄素溶液类似,Cur-PU溶液表现出pH响应的颜色转变:随着氢氧根离子(OH)溶液浓度的增加,溶液从黄绿色变为深绿色,最终变为橙黄色,能够在碱性梯度范围内进行灵敏的pH检测。在空气、超纯水和pH 6.0/8.0磷酸盐缓冲溶液中进行的为期15周的水解降解研究表明,Cur-PU薄膜的质量损失<2%。表面形态分析显示逐渐蚀刻并形成微米至纳米级的孔隙,表明其表面侵蚀降解机制与纯PCL一致。通过L929小鼠成纤维细胞共培养实验进行的生物相容性评估表明,72小时后细胞活力≥90%,而相对红细胞溶血率保持在5%以下。总体而言,这些发现确立了Cur-PU作为一种具有可调机械性能和pH响应性的生物相容性材料,凸显了其在药物递送系统和组织工程支架等生物医学应用中的转化潜力。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/357e/12383527/313ed7bcc845/biomolecules-15-01070-sch001.jpg

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