丝素蛋白的磷酸化及其仿生矿化膜的制备
|
摘要
为制备功能性丝素基仿生矿化材料,将丝素蛋白通过三聚磷酸钠(STP)磷酸化,从而在仿生矿化过程中促进钙离子吸附,利于更多的钙磷酸盐的形成和沉积。探究了体系中pH值和三聚磷酸钠用量对丝素磷酸化的影响,分析了磷酸化对丝素蛋白二级结构、热性能、粒径及膜力学性能的影响;以磷酸化丝素为原料制备冻干丝素膜,采用交替矿化法,在其表面沉积形成羟基磷灰石(HA);借助扫描电子显微镜和能量色散X射线光谱仪,评价了矿化膜表面结构形态和钙、磷元素含量变化。结果表明:在pH值为10和STP质量为0.24 g条件下,磷转移量达到67.1%,且磷酸化丝素膜对阳离子有较好的吸附效果,力学性能较空白样略有下降;经交替仿生矿化处理后,磷酸化丝素膜表面沉积的羟基磷灰石较空白样结构更规整。
In order to prepare the silk fibroin-based bionic mineralization materials, silk fibroin(SF) was phosphorylated by sodium tripolyphosphate(STP), which can promote the adsorption of calcium ions, and facilitates the formation and deposition of calcium phosphate. The effects of two factors on the phosphorylated silk fibroin were explored by controlling pH and the amount of sodium tripolyphosphate. The secondary structure, thermal stability, particle size, mechanical properties were analyzed. Phosphorylated silk fibroin was freeze-dried to form a membrane, hydroxyapatite(HA) was formed on the surface by alternating mineralization method, and the surface morphology and content of calcium and phosphorus were evaluated by scanning electron microscopy and energy dispersive spectro-metery. The results show that the phosphorylated conditions is pH 10 and the 0.24 g of STP, phosphorus transfer rate reaches 67.1%, and the adsorption capacity of cationic dyes on the phosphorylated silk fibroin is better, and mechanical properties is slightly lower than the blank. Hydroxyapatite deposited on the surface of the phosphorylated silk fibroin membrane is more regular than the blank sample after alternating bionic mineralization.
In order to prepare the silk fibroin-based bionic mineralization materials, silk fibroin(SF) was phosphorylated by sodium tripolyphosphate(STP), which can promote the adsorption of calcium ions, and facilitates the formation and deposition of calcium phosphate. The effects of two factors on the phosphorylated silk fibroin were explored by controlling pH and the amount of sodium tripolyphosphate. The secondary structure, thermal stability, particle size, mechanical properties were analyzed. Phosphorylated silk fibroin was freeze-dried to form a membrane, hydroxyapatite(HA) was formed on the surface by alternating mineralization method, and the surface morphology and content of calcium and phosphorus were evaluated by scanning electron microscopy and energy dispersive spectro-metery. The results show that the phosphorylated conditions is pH 10 and the 0.24 g of STP, phosphorus transfer rate reaches 67.1%, and the adsorption capacity of cationic dyes on the phosphorylated silk fibroin is better, and mechanical properties is slightly lower than the blank. Hydroxyapatite deposited on the surface of the phosphorylated silk fibroin membrane is more regular than the blank sample after alternating bionic mineralization.
引文
[1] 周步光, 张宇慧, 王平,等. 丝素/丙烯酰胺/丙烯酸吸水复合材料的紫外光辐照法制备[J]. 纺织学报, 2017, 38(5):25-30.ZHOU Buguang, ZHANG Yuhui, WANG Ping, et.al. Preparation of water-absorbing composite of silk fibroin/acrylamide/acrylic acid using UV irradiation[J]. Journal of Textile Research, 2017, 38(5):25-30.
[2] ZHOU B G, HE M, WANG P, et al. Synthesis of silk fibroin-g-PAA composite using H2O2-HRP and characterization of the in situ biomimetic mineralization behavior[J]. Materials Science & Engineering C: Materials for Biological Applications, 2017, 81:291-302.
[3] 卢神州, 李明忠, 秦建彬. 丝素膜表面磷酸化研究[J]. 丝绸, 2006(10):296-299.LU Shenzhou, LI Mingzhong, QIN Jianbin. Study on the surface phosphorylation of silk fibroin membrane[J]. Journal of Silk, 2006(10):296-299.
[4] 张瑾莉, 任小元, 张琪,等. 仿生矿化法制备HA/SF/Ti复合材料的研究进展[J]. 丝绸, 2014, 51(3):19-24.ZHANG Jinli, REN Xiaoyuan, ZHANG Qi, et al. Research on the preparation of HA/SF/Ti composites by bionic mineralization[J]. Journal of Silk, 2014, 51(3): 19-24.
[5] 刘天一. 大豆分离蛋白的磷酸化改性功能性质的研究[J]. 食品与发酵工业, 2004, 30(6):118-121.LIU Tianyi. Study on functional properties of soybean protein isolates by phosphorylated modification[J]. Journal of Food and Fermentation Industries, 2004, 30(6):118-121.
[6] JAISWAL A K, CHHABRA H, SONI V P, et al. Enhanced mechanical strength and biocompatibility of electrospun polycaprolactone-gelatin scaffold with surface deposited nano-hydroxyapatite[J]. Materials Science & Engineering C: Materials for Biological Applications, 2013, 33(4):2376-2385.
[7] 梁茂林. 应用磷钼蓝比色法快速测定磷铜合金中磷含量的研究[J]. 山东化工, 2016, 45(18):60-61.LIANG Maolin. Rapid determination of phosphorus content in phosphor bronze by phosphomolybdate blue colorimetric method[J]. Shandong Chemical Industry, 2016, 45(18):60-61.
[8] TRAGOONWICHIAN S, KOTHARY P, SIRIVIRIYANUN A, et al. Silicon-compound coating for preparation of water repellent cotton fabric by admicellar polymerization[J]. Colloids & Surfaces A:Physicochemical & Engineering Aspects, 2011, 384(1):381-387.
[9] 王伟. CaCO3和SiO2改性丝素/聚乙烯醇共混膜的制备与性能研究[D]. 天津:天津工业大学,2010:15-27.WANG Wei. Preparation and properties of CaCO3 and SiO2 modified silk fibroin / PVA blends[D]. Tianjin:Tianjin Polytechnic University, 2010:15-27
[10] 孟陆丽, 程谦伟, 李军生,等. 丝素蛋白的磷酸化改性研究[J]. 食品科技, 2009(7):221-224.MENG Luli, CHENG Qianwei, LI Junsheng, et al. Research on phosphorylation of silk fibroin[J]. Journal of Food Science and Technology, 2009(7):221-224.
[11] 洪言情, 王平, 朱雪珂,等. 基于酶法交联的再生纳米弹性蛋白膜构建[J]. 功能材料, 2016, 47(10):10076-10080.HONG Yanqing, WANG Ping, ZHU Xueke, et al. Construction of regenerated nano-elastase membrane based on enzymatic crosslinking[J].Journal of Functional Materials, 2016, 47(10):10076-10080.
[12] HONG Y Q, ZHU X K, WANG P, et al. Tyrosinase-mediated construction of a silk fibroin/elastin nanofiber bioscaffold[J]. Applied Biochemistry & Bio-technology, 2016, 178(7):1363-1376.
[13] 陈俊高, 迟玉杰, 王喜波,等. 提高大豆分离蛋白乳化性的工艺优化及性质分析[J]. 食品与发酵工业, 2010(11):67-72.CHEN Jungao, CHI Yujie, WANG Xibo, et al. Process optimization and property analysis of improving emulsification of soy protein isolate[J]. Journal of Food and Fermentation Industries, 2010(11):67-72.
[14] HUX, CEBE P, KAPLAN D. Effect of water on thermal properties of silk fibroin[J]. Thermochimica Acta, 2007, 461(1):137-144.
[2] ZHOU B G, HE M, WANG P, et al. Synthesis of silk fibroin-g-PAA composite using H2O2-HRP and characterization of the in situ biomimetic mineralization behavior[J]. Materials Science & Engineering C: Materials for Biological Applications, 2017, 81:291-302.
[3] 卢神州, 李明忠, 秦建彬. 丝素膜表面磷酸化研究[J]. 丝绸, 2006(10):296-299.LU Shenzhou, LI Mingzhong, QIN Jianbin. Study on the surface phosphorylation of silk fibroin membrane[J]. Journal of Silk, 2006(10):296-299.
[4] 张瑾莉, 任小元, 张琪,等. 仿生矿化法制备HA/SF/Ti复合材料的研究进展[J]. 丝绸, 2014, 51(3):19-24.ZHANG Jinli, REN Xiaoyuan, ZHANG Qi, et al. Research on the preparation of HA/SF/Ti composites by bionic mineralization[J]. Journal of Silk, 2014, 51(3): 19-24.
[5] 刘天一. 大豆分离蛋白的磷酸化改性功能性质的研究[J]. 食品与发酵工业, 2004, 30(6):118-121.LIU Tianyi. Study on functional properties of soybean protein isolates by phosphorylated modification[J]. Journal of Food and Fermentation Industries, 2004, 30(6):118-121.
[6] JAISWAL A K, CHHABRA H, SONI V P, et al. Enhanced mechanical strength and biocompatibility of electrospun polycaprolactone-gelatin scaffold with surface deposited nano-hydroxyapatite[J]. Materials Science & Engineering C: Materials for Biological Applications, 2013, 33(4):2376-2385.
[7] 梁茂林. 应用磷钼蓝比色法快速测定磷铜合金中磷含量的研究[J]. 山东化工, 2016, 45(18):60-61.LIANG Maolin. Rapid determination of phosphorus content in phosphor bronze by phosphomolybdate blue colorimetric method[J]. Shandong Chemical Industry, 2016, 45(18):60-61.
[8] TRAGOONWICHIAN S, KOTHARY P, SIRIVIRIYANUN A, et al. Silicon-compound coating for preparation of water repellent cotton fabric by admicellar polymerization[J]. Colloids & Surfaces A:Physicochemical & Engineering Aspects, 2011, 384(1):381-387.
[9] 王伟. CaCO3和SiO2改性丝素/聚乙烯醇共混膜的制备与性能研究[D]. 天津:天津工业大学,2010:15-27.WANG Wei. Preparation and properties of CaCO3 and SiO2 modified silk fibroin / PVA blends[D]. Tianjin:Tianjin Polytechnic University, 2010:15-27
[10] 孟陆丽, 程谦伟, 李军生,等. 丝素蛋白的磷酸化改性研究[J]. 食品科技, 2009(7):221-224.MENG Luli, CHENG Qianwei, LI Junsheng, et al. Research on phosphorylation of silk fibroin[J]. Journal of Food Science and Technology, 2009(7):221-224.
[11] 洪言情, 王平, 朱雪珂,等. 基于酶法交联的再生纳米弹性蛋白膜构建[J]. 功能材料, 2016, 47(10):10076-10080.HONG Yanqing, WANG Ping, ZHU Xueke, et al. Construction of regenerated nano-elastase membrane based on enzymatic crosslinking[J].Journal of Functional Materials, 2016, 47(10):10076-10080.
[12] HONG Y Q, ZHU X K, WANG P, et al. Tyrosinase-mediated construction of a silk fibroin/elastin nanofiber bioscaffold[J]. Applied Biochemistry & Bio-technology, 2016, 178(7):1363-1376.
[13] 陈俊高, 迟玉杰, 王喜波,等. 提高大豆分离蛋白乳化性的工艺优化及性质分析[J]. 食品与发酵工业, 2010(11):67-72.CHEN Jungao, CHI Yujie, WANG Xibo, et al. Process optimization and property analysis of improving emulsification of soy protein isolate[J]. Journal of Food and Fermentation Industries, 2010(11):67-72.
[14] HUX, CEBE P, KAPLAN D. Effect of water on thermal properties of silk fibroin[J]. Thermochimica Acta, 2007, 461(1):137-144.