Veloso-Fernández Antonio, Laza José Manuel, Ruiz-Rubio Leire, Martín Ane, Benito-Vicente Asier, Martín Cesar, Vilas-Vilela José Luis
Grupo de Química Macromolecular (LABQUIMAC), Departamento de Química Física, Facultad de Ciencia y Tecnología, Universidad del País Vasco UPV/EHU, CSIC, 48940 Leioa, Spain.
BCMaterials, Basque Center for Materials, Applications and Nanostructures, UPV/EHU Science Park, 48940 Leioa, Spain.
Materials (Basel). 2024 Sep 28;17(19):4770. doi: 10.3390/ma17194770.
Cytotoxicity is a critical parameter for materials intended for biological applications, such as food packaging. Shape-memory polyurethanes (SMPUs) have garnered significant interest due to their versatile properties and adaptability in synthesis. However, their suitability for biological applications is limited by the use of aromatic isocyanates, such as methylene diphenyl 4,4'-diisocyanate (MDI) and toluene diisocyanate (TDI), which are commonly used in SMPU synthesis but can generate carcinogenic compounds upon degradation. In this study, thermo-responsive shape-memory polyurethanes (SMPUs) were synthesized using poly(tetramethylene ether) glycol (PTMG) and castor oil (CO) as a chain extender with four different isocyanates-aromatic (MDI and TDI), aliphatic (hexamethylene diisocyanate [HDI] and isophorone diisocyanate [IPDI])-to evaluate their impact on polyurethane cytotoxicity. Cytotoxicity assays were conducted on the synthesized SMPU samples before and after exposure to light-induced degradation. The results showed that prior to degradation, all samples exhibited cell proliferation rates above 90%. However, after degradation, the SMPUs containing aromatic isocyanates demonstrated a drastic reduction in cell proliferation to values below 10%, whereas the samples with aliphatic isocyanates maintained cell proliferation above 70%. Subsequently, the influence of polyol chain length was assessed using PTMG, with molecular weights of 1000, 650, and 250 g·mol. The results indicated that the SMPUs with longer chain lengths exhibited higher cell proliferation rates both before and after degradation. The thermal and mechanical properties of the SMPUs were further characterized using thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and thermomechanical analysis (TMA), providing comprehensive insights into the behavior of these materials.
细胞毒性是用于生物应用(如食品包装)的材料的一个关键参数。形状记忆聚氨酯(SMPU)因其多样的性能和合成中的适应性而备受关注。然而,它们在生物应用中的适用性受到芳香族异氰酸酯使用的限制,如二苯基甲烷二异氰酸酯(MDI)和甲苯二异氰酸酯(TDI),这些在SMPU合成中常用,但在降解时会产生致癌化合物。在本研究中,使用聚四亚甲基醚二醇(PTMG)和蓖麻油(CO)作为扩链剂,与四种不同的异氰酸酯——芳香族(MDI和TDI)、脂肪族(六亚甲基二异氰酸酯 [HDI] 和异佛尔酮二异氰酸酯 [IPDI])合成了热响应形状记忆聚氨酯(SMPU),以评估它们对聚氨酯细胞毒性的影响。对合成的SMPU样品在光诱导降解前后进行了细胞毒性测定。结果表明,在降解之前,所有样品的细胞增殖率均高于90%。然而,降解后,含有芳香族异氰酸酯的SMPU的细胞增殖急剧下降至10%以下,而含有脂肪族异氰酸酯的样品的细胞增殖率保持在70%以上。随后,使用分子量为1000、650和250 g·mol的PTMG评估多元醇链长的影响。结果表明,链长较长的SMPU在降解前后均表现出较高的细胞增殖率。使用热重分析(TGA)、差示扫描量热法(DSC)、动态力学分析(DMA)和热机械分析(TMA)进一步表征了SMPU的热性能和力学性能,从而全面了解这些材料的行为。