柞蚕丝素/CMCS共混膜、柞蚕丝素/HAP复合膜的制备与研究
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摘要
目前桑蚕丝素蛋白用作多种形式生物材料已有很多报道,并且成果显著。研究证明柞蚕丝素与桑蚕丝素相比在分子形态和结晶结构上没有太大区别,此外柞蚕丝素的氨基酸构成中含有RGD三肽序列,可以增强细胞的活性,在生物材料方面具有一定优势。本文以LiSCN为溶剂溶解柞蚕丝,透析后得到柞蚕丝素溶液,分别采用简单共混在40℃下制得柞蚕丝素(TSF)/羧甲基壳聚糖(CMCS)共混膜和共沉淀法在室温20℃下制得柞蚕丝素(TSF)/羟基磷灰石(HAP)复合膜,分别适用于组织工程支架培养皮肤上皮细胞和骨细胞的膜材料。本课题对制得的两种TSF共混膜的基本应用性能进行了测试,并对其内部结构进行分析。通过衍射、红外光谱、扫描电镜、热分析等的测试结果表明,40℃下形成的TSF/CMCS共混膜中丝素分子的内部构象以β-折叠为主。少量的CMCS可以与丝素分子形成氢键进而诱导共混膜的结晶,在95/5时结晶度最大。当CMCS的比例增加到15%时,CMCS开始过量,共混膜的结晶度显著下降。在共混比例达到45/55时,TSF与CMCS出现分相现象。共混膜的含水率、透湿性、溶失率和力学性能方面的测试结果表现出与内部结构变化规律的一致性。对TSF/HAP复合膜的研究结果表明,20℃下形成的TSF/HAP复合膜中丝素分子的内部构象以α-螺旋为主。研究表明当HAP的加入量少于12%时,复合膜中的HAP并没有出现团聚现象。当HAP的含量达到12%时,HAP出现了明显的团聚现象,复合膜的结晶度显著下降,含水率下降,透湿性下降,强力下降。另外,本文对TSF/HAP复合膜进行了乙醇化处理,结果表明随着乙醇处理时间的延长复合膜的含水率下降、透湿性下降,β-折叠含量增加,热稳定性增加。
So far, various forms of silk fibroin biomaterials have been reported and remarkable achievements have been acquired. Researches have shown that the molecular conformation and crystal structure of tussah silk fibroin (TSF) were similar with that of silk fibroin (SF). Besides, TSF aminoacid contain a large number of RGD three peptide sequence which could contribute to the activity of cells. This property made TSF have some advantages uesd as biomaterials. In this paper, tussah silk was dissolved with LiSCN solution and then dialyzed in the flowing water to obtain TSF aqueous solution. TSF/CMCS (tussah silk fibroin & carboxymethyl chitosan) blend membranes were made by the mixture of TSF and CMCS solution at 40℃. And the TSF/HAP (tussah silk fibroin & hydroxylapatite) composite membranes were made by co-precipitation at 20℃. This two kinds of membranes were respectively applied as membranes biomaterial of tissue engineering scaffolds to culture skin epithelial cells and bone cells. The basic application performance of this two kinds of blend membranes were tested and their internal structure were analysised. The test results of scanning electron microscopy, X-ray diffraction, infrared spectroscopy, DSC showed that the TSF/CMCS membranes were predominantly inβ-sheet structure and TSF/HAP composite membranes were predominantly inα-helix and amorphous structure. Researches showed that small mount of CMCS could induce the crystallization of tussah silk fibroin and the crystallinity of the blend membranes come to its maximum at the ratio of 95/5 (TSF/CMCS). When the CMCS contents come to 15%, its crystallinity had a outstanding decrease. At the ratio of 45/55 (TSF/CMCS), TSF and CMCS appeared phase separation phenomenon. The changes of moisture content, moisture permeability, dissolving loss and mechanical properties of the TSF/CMCS blend membranes showing consistent with its structural. The physical tests of TSF/HAP composite membranes showed that HAP did not appeared to agglomeration until HAP contnts exceeded 12% and the corresponding properties decreased at the same time. In addition, TSF/HAP composite membranes were treated with ethanol solution. And the internal structure test results of TSF/HAP composite membranes showed that the moisture content, thermal stability increased and proportion ofβ-sheet structure added with the prolonging of the treating time.
So far, various forms of silk fibroin biomaterials have been reported and remarkable achievements have been acquired. Researches have shown that the molecular conformation and crystal structure of tussah silk fibroin (TSF) were similar with that of silk fibroin (SF). Besides, TSF aminoacid contain a large number of RGD three peptide sequence which could contribute to the activity of cells. This property made TSF have some advantages uesd as biomaterials. In this paper, tussah silk was dissolved with LiSCN solution and then dialyzed in the flowing water to obtain TSF aqueous solution. TSF/CMCS (tussah silk fibroin & carboxymethyl chitosan) blend membranes were made by the mixture of TSF and CMCS solution at 40℃. And the TSF/HAP (tussah silk fibroin & hydroxylapatite) composite membranes were made by co-precipitation at 20℃. This two kinds of membranes were respectively applied as membranes biomaterial of tissue engineering scaffolds to culture skin epithelial cells and bone cells. The basic application performance of this two kinds of blend membranes were tested and their internal structure were analysised. The test results of scanning electron microscopy, X-ray diffraction, infrared spectroscopy, DSC showed that the TSF/CMCS membranes were predominantly inβ-sheet structure and TSF/HAP composite membranes were predominantly inα-helix and amorphous structure. Researches showed that small mount of CMCS could induce the crystallization of tussah silk fibroin and the crystallinity of the blend membranes come to its maximum at the ratio of 95/5 (TSF/CMCS). When the CMCS contents come to 15%, its crystallinity had a outstanding decrease. At the ratio of 45/55 (TSF/CMCS), TSF and CMCS appeared phase separation phenomenon. The changes of moisture content, moisture permeability, dissolving loss and mechanical properties of the TSF/CMCS blend membranes showing consistent with its structural. The physical tests of TSF/HAP composite membranes showed that HAP did not appeared to agglomeration until HAP contnts exceeded 12% and the corresponding properties decreased at the same time. In addition, TSF/HAP composite membranes were treated with ethanol solution. And the internal structure test results of TSF/HAP composite membranes showed that the moisture content, thermal stability increased and proportion ofβ-sheet structure added with the prolonging of the treating time.
引文
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[3]王佳培,胡建恩,白雪芳等.蚕丝素蛋白及其应用.精细与专用化妆品. 2004, 12(12): 13-18.
[4] N. Minoura, S. I. Aiba, M. Higuchi, Y. Gotoh, M. Tsukada, Y. Imai. Attachment and Growth of Fibroblast Cells on Silk Fibroin. Biochemical and Biophysical Research Communications 1995; 208(2): 511-516.
[5]李萍,王加成,秦志忠,左保齐,韦军.功能性丝素共混膜的研究现状与进展.苏州大学学报(工科版). 2004, 24(6): 4-18.
[6] Wei Tao, Mingzhong Li, Chunxia Zhao. Structure and properties of regenerated Antheraea Pernyi Silk fibroin in aqueous solution. Biological Macromolecules. 2007,40:472-478.
[7]闻荻江,王辉,朱新生,孙建平.丝素蛋白的构象和结晶性.纺织学报. 2005, 26(1): 110-112.
[8] J Magoshi, Y Magoshi, S Nakamura..Structure and molecular conformation of tussh silk films:effect of methanol [J] ,J Polym Sci,1995,33:1995-2001.
[9] M Tsukada, G Freddi,P Monti J Appl. Polym Sci,1985,41:187.
[10]陈涛.谈谈蚕丝的主要品种及性能.中国纤检. 2005, 4: 48-51.
[11]缪秋菊,左保齐,刘雷艮,刘扬.柞蚕丝素的结构性能及其应用.丝绸, 2007, 07: 51-53.
[12]梁列峰,崔彪,汪涛.蚕丝纤维的生物相容性分析.四川丝绸. 2006, 1: 19-21.
[13]黄训亭,邵正中,陈新.天然蚕丝与丝素蛋白多孔膜的生物降解性研究.化学
[14]朱良均,姚菊明,李幼禄.蚕丝蛋白的功能性生物材料[J].中国蚕业, 1996, (4):26.
[15] Minoura N, Aiba S, Gotoh Y, Tsukada M,Imai Y. Attachment and growth of fioroblast cells on silk fibroin.BIOCHEM Biopnys Res Commun, 1995, 208(2): 511-516.
[16] Pierschbacher MD,Ruosl ahti E,[J]. Nature,1984, (309), 30-33.
[17] Wu chenyu,Tian Baozhong.Properties and applications of wound protective membrance made from fibroin.TAHIRD International Silk Conference, 1996, China, Su Zhou.
[18] Gotch Y,Tsukada M, Minoura N.Chemical modification of the arihyl residue in silk fibroin:2. Reaction of 1,2-cyclohexanedione in aqueous alkaline medium International Jounal of Biological Macromolecules.1996, 19:41.
[19]应晨霞,陈建勇.丝素蛋白对粘胶织物整理初探.浙江工程学院学报. 2000, 17(3): 158-161.
[20]刘爱莲.浅谈柞蚕丝素蛋白的营养护肤功能[J]辽宁丝绸, 2003, (1): 24-26.
[21]贾艳梅.柞蚕丝素肽沐浴液的研制[J].辽宁丝绸, 2002, (3): 3-5.
[22]汝玲,黄毅萍,陈萍,齐正旺.蚕丝素蛋白的最新研究进展.化学推进剂与高分子材料. 2000, 5(4): 26-36.
[23]李亚洁,王林华等.柞蚕和家蚕丝肽抗菌作用的研究[J].辽宁丝绸, 2005, (3): 7-9.
[24]孔祥东,朱良均,闵思佳.丝素蛋白在生物生物材料领域的应用研究概况.马芳,邹凤竹.山东农业大学学报(自然科学版). 2005, 36(4): 632-636.
[25]孙启龙,狄传霞.丝素蛋白材料与组织工程支架.国外丝绸. 2007, 3:10-20.
[26] Gregory H. Altman,Frank. Diaz,Caroline Jakuba, Tara Calabro, Rebecca L.Horan, Jingsong Chen, Helen Lu, John Richmond, David L.Kaplan. Silk-based biomaterials Biomaterials, 2003, 24: 401-416.
[27] Langer R,Vacanti Jp.Tissue engineering.[J] SCIENCE, 1993 ,260 (5110):920-926.
[28] Meinel L,FajardoR, et al. Bone (online), 2005, 6, 13.
[29]冯治平,刘达玉,黄丹.用桑蚕丝素蛋白制备临苯二酚酶传感器.生物技术. 2003, 12(2), 29-30.
[30]孔祥东,朱良均,闵思佳.丝素蛋白用于生物材料的研究进展.功能高分子学报. 2001, 14 117-126.
[31]孔祥东,朱良均,闵思佳.丝素蛋白在生物材料上的研究和应用.功能材料. 2001, 32(6).
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