光交联自支撑丝素蛋白水凝胶的三维快速成型  

Three-dimensional Printing of Photocrosslinked Self-supporting Silk Fibroin Hydrogels

作　　者：黄益[1,2,3] 吕玲玲 潘小鹏 孙广东 李永强[2,3] 姚菊明[1] 邵建中[2] HUANG Yi;LYU Lingling;PAN Xiaopeng;SUN Guangdong;LI Yongqiang;YAO Juming;SHAO Jianzhong(School of Materials Science and Engineering,Hangzhou 310018,China;Engineering Research Center for Eco-Dyeing and Finishing of Textiles,Ministry of Education,Zhejiang Sci-Tech University,Hangzhou 310018,China;Zhejiang Sci-Tech University Tongxiang Research Institute,Tongxiang 314500,China)

机构地区：[1]浙江理工大学材料科学与工程学院,杭州310018 [2]浙江理工大学生态染整技术教育部工程研究中心,杭州310018 [3]浙江理工大学桐乡研究院,桐乡314500

出　　处：《高等学校化学学报》2022年第4期179-186,共8页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:52103068);浙江省自然科学基金(批准号:LY21E030019);浙江理工大学桐乡研究院博士后基金(批准号:TYY202014);浙江理工大学基本科研业务费专项资金(批准号:2021Q008)资助.

摘　　要：将丝素蛋白(SF)光诱导自交联原理与挤出式三维(3D)打印相结合,开发了光交联自支撑SF水凝胶的原位成型加工技术.采用旋转流变仪、光流变测试系统和改装的挤出式3D打印设备等对SF溶液的流变性能、光交联性能和成型加工性能等进行研究.结果表明,SF溶液主要表现为黏性特征,结构强度和稳定性均较差.利用SF的光诱导自交联特性,以三联吡啶氯化钌[Ru(Ⅱ)]和过硫酸钾(KPS)为蓝光引发体系,可实现SF水凝胶的快速光交联成型.SF光交联行为符合指数函数增长模型,因“滤镜效应”,当Ru(Ⅱ)的浓度为0.05 mmol/L时,SF具有最佳的光交联性能.通过调节气压、针头孔径、移动速度及固化速率等参数,采用3D打印设备可实现从单层几何结构到多层三维网络构型SF凝胶材料的高效、精准构建,为SF的生物3D打印提供了新思路.As a biological macromolecular material degummed from silk fiber,silk fibroin(SF)is considered to be an ideal candidate for bioink components in three-dimensiona(l 3D)bioprinting because of its excellent biocompatibility,biodegradability and tunable mechanical properties.However,the conventional silk fibroin crosslinking methods cannot meet the requirements of 3D printing on the real-time forming efficiency and biocompatibility.In order to realize the 3D rapid prototyping of silk fibroin,the in-situ photocrosslinking processing technology of self-supporting silk fibroin hydrogel was proposed by combining the blue light-induced self-crosslinking method with 3D extruded printing technology.The basic rheological properties,photocrosslinking properties and moulding processability of silk fibroin solution were studied by using rotary rheometer,photorheological test system and modified 3D extrudedprinting equipment.The results showed that the silk fibroin solution(<20%,mass fraction)was mainly characterized by viscidity,and its inadequate structural strength and stability cannot meet the requirements of 3D extruded printing for material formability,shape retention and printing accuracy.Rapid photocrosslinking molding processing of silk fibroin hydrogel can be achieved by light-induced self-crosslinking in the presence of tris(2,2-bipyridyl)ruthenium(II)chloride hexahydrate[Ru(Ⅱ)]and potassium persulfate(KPS)as blue light initiators.Tyrosine residues on adja⁃cent SF macromolecular chains can be oxidized into tyrosine free radicals under the action of excited active species,and then coupled and crosslinked into di-tyrosine structure.Photocrosslinking behavior of silk fibroin under blue light irradiation conformed to exponential growth model.Due to the“filter effect”of the photosensitizer on the incident light,silk fibroin solution showed the optimized photocrosslinking performance when the dose of the photosensitizer Ru(Ⅱ)was 0.05 mmol/L.By further adjusting the parameters such as air pressure,needle aperture,m

关 键 词：光交联 丝素蛋白水凝胶 三维(3D)打印 凝胶化行为 弹性模量 

分 类 号：O636.9[理学—高分子化学]