Key Laboratory of Coastal Biology and Bioresource Utilization, Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences, Yantai 264003, China; University of Chinese Academy of Sciences, Beijing 100049, China.
College of Chemistry and Chemical Engineering, Yantai University, Yantai 264005, China.
Carbohydr Polym. 2018 Nov 1;199:583-592. doi: 10.1016/j.carbpol.2018.07.056. Epub 2018 Jul 23.
Amino functionality has been paid growing attention in chemical modification of polysaccharides due to their potential biomedical applications. Here, the preparation of novel antioxidant materials based on chitosan derivatives bearing amino-containing groups equipped with 1,2,3-triazole and 1,2,3-triazolium by Cuprous-catalyzed azide-alkyne cycloaddition and N-methylation was described for the first time. The structural characteristics of the synthesized derivatives were examined by FTIR, H NMR, and elemental analysis. The antioxidant activities of the chitosan derivatives were assessed in vitro. The results indicated that chitosan derivatives bearing 1,2,3-triazoles displayed superior antioxidant activity over pristine chitosan, especially against superoxide anion radical. Moreover, antioxidant efficiency of chitosan derivatives further enhanced after N-methylation of 1,2,3-triazole moieties with iodomethane, which is comparative to that of ascorbic acid. Notably, of all chitosan derivatives bearing 1,2,3-triazole or 1,2,3-triazolium moieties, acylhydrazine-functionalized and amino-functionalized chitosan showed the stronger antioxidant capacity than hydroxyl-modified chitosan at the test concentration. Besides, the cytotoxicities of them were also evaluated in vitro on HaCaT cells. These results suggested that amino and acylhydrazine-functionalized chitosan derivatives with 1,2,3-triazolium could be used as novel antioxidant biomaterials.
由于其在生物医学中的潜在应用，氨基功能在多糖的化学修饰中受到越来越多的关注。在此，首次描述了通过铜催化叠氮-炔环加成和 N-甲基化，在带有氨基的壳聚糖衍生物上制备新型抗氧化材料的方法，这些衍生物带有含氨基的 1,2,3-三唑和 1,2,3-三唑鎓基团。通过傅里叶变换红外光谱（FTIR）、核磁共振氢谱（H NMR）和元素分析对合成衍生物的结构特征进行了检查。体外评估了壳聚糖衍生物的抗氧化活性。结果表明，带有 1,2,3-三唑的壳聚糖衍生物的抗氧化活性优于原始壳聚糖，尤其是对超氧阴离子自由基。此外，用碘甲烷对 1,2,3-三唑进行 N-甲基化后，壳聚糖衍生物的抗氧化效率进一步提高，与抗坏血酸相当。值得注意的是，在所有带有 1,2,3-三唑或 1,2,3-三唑鎓基团的壳聚糖衍生物中，酰腙化和氨基化壳聚糖在测试浓度下的抗氧化能力强于羟基化壳聚糖。此外，还在 HaCaT 细胞上对它们的细胞毒性进行了体外评估。这些结果表明，带有 1,2,3-三唑鎓的氨基和酰腙化壳聚糖衍生物可用作新型抗氧化生物材料。
