【作者】 牛睿；

【导师】 杨冬芝；

【作者基本信息】 北京化工大学 ， 材料科学与工程， 2011， 硕士

【摘要】 生物粘合剂是能够应用于生物体组织的具有一定生物相容性和粘合力的医学材料。光聚合技术制备生物粘合剂是一个较新的研究方向,近年来在国际上才有少量报道。与传统应用的代表性生物粘合剂α-氰基丙烯酸酯类和血纤维蛋白胶相比,光聚合制备生物粘合剂具有凝胶速度快、对机体损伤小、单体和树脂来源广泛的优点,特别是对于不规则损伤部位的原位修复,具有可操作性强的优势。本研究受贻贝分泌的带有邻苯二酚结构的聚酚蛋白具有超强耐水性粘结能力的启发,选择邻苯二酚结构作为所制备单体的粘附官能团,分别制备了单官能度带有邻苯二酚结构的多巴胺甲基丙烯酰胺(简称DMA)、双官能度带有邻苯二酚结构的多巴胺甲基丙烯酸酯(简称EGAMA-DOPA),采用红外、核磁对产物的结构进行了表征；研究了体系的光聚合条件,如单体和引发剂浓度、光强、溶液组成等；采用光聚合动力学测试表征了这两个生物粘合剂体系的凝胶化时间；研究了凝胶的溶胀行为、粘结强度、爆破压以及体外生物相容性。此外,制备了可光交联的壳聚糖衍生物,并以它作为DMA光聚合生物粘合剂体系的交联剂,考查其影响；同时,将所制备的DMA单体用于电纺丝无纺布膜中,提高膜的粘附力,期望在伤口敷料或多层生物修复膜中得到应用。研究得到了如下结论：1、不同组成的DMA溶液紫外光聚合体系,在光强30mw/cm2,加入0.5%引发剂2959的条件下,均能在3-15min内完成凝胶化,对于明胶片材的粘接性能最高可达3.5MPa。爆破压测试显示其对于小鼠皮的密封爆破压最高可达178mmHg。体外细胞毒性试验表明,聚合后的DMA凝胶体系对于小鼠成纤维细胞L929的毒性较小,细胞在凝胶表面贴附、分化较好。2、与DMA溶液的紫外光聚合体系相比,双官能度单体(简称EGAMA-DOPA)为液态,可直接进行无溶剂的光聚合,而且可见光聚合速率明显提高；为改善性能,采用聚乙二醇双甲基丙烯酸酯(简称PEGDMA)与其共聚,该体系的大部分样品在15min内可以完成凝胶化,PEGDMA的引入不但提高了聚合速度,使凝胶化更完全,同时还阻止了单体的游离,提高了生物相容性,使材料韧性更好。3、DMA单体加入到PEO的电纺丝溶液中,通过纺丝后光固化方法,制备了一种具有生物粘附性能的PDMA/PEO纳米纤维无纺布膜,同时这种方法为多层电纺丝膜的层间复合提供了一种新思路。更多还原

【Abstract】 Bioadhesive is well known as medical material with a certain biocompatibility and adhesion applied to biological tissue.Photopolymerization technology applied to the bioadhesive as a new research direction, few reports related to this research. When compared with other method, photopolymerization technology has a many advantages such as faster curing, less damage to organism, more widely range of sources of the monomers and resin than a-cyanoacrylate adhesives and the fibrin sealant. Especially for the irregular site of injury, this method is easier to operate.This research inspired by the mussel adhesion protein having the superior water-resistance bonding capacity. Choosing the dopamine (containing catechol groups) as the adhesive functional group, the monomer DMA with single light-sensitive functional group and EGAMA-DOPA with double light-sensitive functional groups was prepared. The structure of products was analyzed by using the FTIR and NMR; and the photopolymerization conditions of above monomer were researched, such as initiator and monomer concentration, light intensity, and solution composition etc. The gel time was characterized by series real time near infrared spectroscopy (SRTIR). And the swelling behavior of gel, bond strength, bursting pressure and in vitro biocompatibility were also studied. In addition, the modified light-sensitive chitosan was prepared and used for cross-linking DMA gels. At the same time, in order to improve the adhesion of the elecrospun membrane, we introduced the DMA into the nanofibrous membrane. The nanofibrous membranes would be further applicable for skin regeneration.The Details and conclusions are described as follows:1, The samples with different composition, each of them could complete gelation within 3-15min. The adhesive strength of the samples adhered to gelation sheets to simulate the living tissues could reached 3.5MPa. The highest burst pressure reached 178mmHg, when the samples adhered to fresh mouse skin. And good capability of the DMA gels supporting the mouse fibroblast (L929) attachment and proliferation are observed.2, Compared to the DMA, EGAMA-DOPA is a liquid. So it could be directly photocured by the visible light. In order to improve the performance of the gels, PEGDMA was introduced into the visible light curing system. As the results showed, most of the samples can be completed curing within 15min. In addition, we found the introduction of PEGDMA could not only accelerate the photopolymerzation and make the photopolymerization more completely, but also prevent the monomers dissociate, improve the biocompatibility and make the material toughness better.3, Dopamine methacrylamide/poly(ethylene oxide)(DMA/PEO) nanofibers were successfully prepared by electrospinning of aqueous DMA/PEO solution. Biocompatible nanofibrous membrane with good adhesion was produced by photocuring from the DMA/PEO nanofibers. This method provides a new idea for the preparation of the compound of multo-layer elecrospun membranes.更多还原