丝素蛋白溶液的仿生纺丝研究
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摘要
本文简要介绍了仿生纺蜘蛛丝技术的研究现状,总结了人工纺丝的技术路线和所得纤维的基本性能。同时,我们从以下二个角度进行了思考,即:转基因蜘蛛丝蛋白水溶液或再生蚕丝素蛋白水溶液中丝素蛋白分子的构象结构与蜘蛛或蚕腺体内是否相同?是否需要“仿生制备纺丝液”?为了对以上问题进行解答,本文以家蚕的丝素蛋白质为模型对模仿生物体成丝过程的仿生纺丝技术进行了一些探索性的研究。我们制备了高浓度的再生蚕丝素蛋白水溶液,并首次研究了它的流变性能及剪切作用下的构象变化,同时还对它的存放稳定性进行了研究。为了弄清楚拉伸对再生丝素蛋白水溶液结构变化的影响,我们运用静电纺丝方法对再生丝素蛋白水溶液进行了纺丝试验,以寻找丝素蛋白转化为纤维的条件。结果发现静电纺所得纤维的结构是介于无定型和蚕丝之间的,尽管静电纺丝有非常高的拉伸倍数,但所得纤维还是达不到如蚕丝般的结构。为此,我们对再生丝素蛋白水溶液与蚕腺体内丝素蛋白水溶液进行了对比分析,发现浓再生丝素蛋白水溶液与蚕腺体内丝素蛋白水溶液的性能是有差别的,从而提出了“仿生纺丝”之前,首先要“仿生制备纺丝液”的新观点。
本文摸索出了制备高浓度再生丝素蛋白水溶液的方法,并研究了浓再生丝素蛋白水溶液的流变性能和在剪切作用下的构象结构变化,结果发现:(1)再生丝素蛋白水溶液的流变性能和常规聚合物浓溶液的流变性能差别很大。首先,它的切力变稀现象随溶液的浓度的增加而变弱;其次,溶液粘度非常小。(2)再生丝素蛋白浓水溶液的零切粘度随浓度的增加而增加,在35%左右达到最大值,浓度再提高粘度下降。但在粘度下降条件下仍然观察不到各向异性现象。(3)高浓度的再生丝素蛋白水溶液经过剪切作用后呈现出各向异性的性质,相同浓度下,剪切作用越大,再生丝素蛋白水溶液越容易实现由各向同性到各向异性的转变;相同剪切作用时,再生丝素蛋白水溶液的浓度越高,经剪切作用后,溶液的各向异性的性质越明显。(4)再生丝素蛋白水溶液经剪切作用后,丝素蛋白分予构象发生了由无规线团/α螺旋结构到β—折叠结构的转变。再生丝素蛋白水溶液的流变性能和常规聚合物浓溶液的流变性能差别很大。
东平大李博士论文
摘要
经过对高浓度再生丝素蛋白水溶液流动稳定性的研究发现,丝素蛋白水溶液是
一种不稳定的体系,存在存放流动稳定性问题。随着溶液浓度和存放温度的升高,
溶液的流动稳定性迅速下降,最终使体系发生凝胶化。其中当溶液浓度小于27%
时,浓度对流动稳定性的影响较大,浓度越低流动稳定性越好。而当浓度高于27
%后,溶液的流动稳定性迅速下降,浓度的影响也大大降低。丝素蛋白水溶液对环
境温度非常敏感,当温度低于25℃时,溶液的凝胶化速度较慢;而当温度升高
后,溶液的凝胶化速度迅速加快,在60℃时只需半小时就凝胶化。蚕吐丝时,其
中部丝腺内丝素蛋白水溶液的浓度在30%左右,温度为25℃左右的春天和秋天,
这一吐丝条件也是充分利用了丝素蛋白的流动稳定性。在制备丝素蛋白纺丝水溶液
时,应先把最初的转基因或再生丝素蛋白稀水溶液存放在低温下,然后在纺丝前进
行浓缩,这样就可以得到稳定的丝素蛋白纺丝用水溶液。
为了弄清楚拉伸对再生丝素蛋白水溶液结构变化的影响,我们运用静电纺丝方
法,对再生丝素蛋白水溶液进行了纺丝试验,发现可以从丝素蛋白水溶液中制得念
珠状的、圆形的或带状的超细丝纤维,纤维的直径在100 nm到900nm之间,平均
为7O0nm。当纺丝液浓度为28%、电压为ZKV、喷射距离为11 cm时,可制得具
有光滑表面的圆形丝纤维。拉曼光谱检测的结果发现,所得的静电纺丝纤维中已含
有p折叠结构。DSC和X光衍射结果表明静电纺丝纤维不是无定型结构,但也不
是和天然蚕丝一样的p一折叠结构。通过计算发现,静电纺丝时纤维经历了非常高
的拉伸比,并和蚕吐丝的条件相当,但即使这样也无法得到与蚕丝相同的结构;而
静电纺丝纤维大的比表面积和蚕以慢的吐丝速度都是起到使溶液中的水分挥发的作
用。试验表明,只有当溶液的浓度足够高,使丝素蛋白分子之间形成有效的缠结;
并对丝素蛋白水溶液加以足够高的拉伸力,使丝素蛋白分子拉伸取向;同时保证溶
液中的水分快速有效地挥发,才有可能形成丝纤维。但要使该纤维结构与蚕丝相同
尚需其他条件配合。
通过对再生蚕丝素蛋白水溶液与天然蚕腺体内丝素蛋白水溶液的性能对比分析
发现,再生蚕丝素蛋白水溶液和天然蚕腺体内丝素蛋白水溶液的性能差别非常大。
再生蚕丝蛋白分子量与蚕腺体内丝素蛋白分子量相差不大,但蚕腺体内丝素蛋白水
溶液的零切粘度要比再生丝素蛋白水溶液高得多,尽管它们的浓度相当。这说明蚕
毯
In this thesis, the development of biomimetic spider and silkworm silk has been briefly introduced. The processes and properties of resultant man-made silk fiber have also been summarized. It is found two key issues are not discussed yet. Whether the conformation of silk fibroin in regenerated solution or in the silkworm gland is the same or not? Whether it is necessary to prepare the spinning solution by a biomimetic process? In our work, silk fibroin of silkworm is selected as a model system because there is still not enough spider silk protein that can be supplied to do spinning and on the other side, the composition of silkworm fibroin is very similar to spider protein. In order to answer the above questions, the concentrated regenerated silk fibroin aqueous solution was prepared first, it's structure and properties of rheology and flow stability were studied. After that, the electrospin process was applied on regenerated concentrated silk fibroin aqueous solution in order to find out the conditions to form silk fiber from silk fibroin aqueous solution. It is found a kind of silk fiber can be got, but the structure of this kind silk fiber is between amorphous film and nature silk. The difference between the structure and properties of silk fibroin in regenerated aqueous solution and in vivo was further studied. The main conclusions are as follows.Viscous, transparent, homogeneous and spinnable silk fibroin aqueous solutions with high silk fibroin content were first prepared. The rheological behaviors of solutions with different concentration were studied by HAAKE RS150 rheometer. There is a rapid initial shear thinning at low shear rates (<10 s-1) for regenerated silk fibroin aqueous solutions with low concentration. However, the shear-thinning phenomenon becomes not obvious with the increase of the solution concentration, which is different from ordinary polymer solution. With the increase of concentration, the macromolecule chain become more and more compacted, the entanglements in solution increase not very quickly. As a result, the viscosity of solution is not very high.The zero shear viscosity is increasing with the concentration of regenerated silk fibroin aqueous solution and reaches max in 35%, then decreases. But all these solutions are isotropic. Only with shear the solution becomes anisotropic. With the increase of
concentration, the birefringent or anisotropic phenomenon becomes easier under the same shear rate. Similarly, with the same concentration, the anisotropic phenomenon becomes more and more obvious with the increase of shear rate. Raman spectroscopy analysis showed that the structure of silk fibroin has changed from random coil and/or a helix into β-sheet by shear.The study on the flow stability of regenerated silk fibroin aqueous solutions with different concentrations under different temperatures indicates that the flow stability decreases quickly with the increase of solution concentration and temperature. X-ray diffraction, Fourier transform infrared (FTIR) and Raman spectroscopy analysis show that silk fibroin in regenerated aqueous solution is mainly in random coil conformation. However, it turns into a helix and p-sheet conformation after gelation, and both silk I and silk II structure appears accordingly. The key concentration and key temperature for the flow stability of regenerated silk fibroin aqueous solution are about 27wt% and 25°C, respectively. Silkworms in the nature may possibly make full use of this rule. The investigation implies that the original dilute regenerated or recombinant silk fibroin aqueous solution should be stored under low temperature and concentrated just before spinning.By using electrospinning technique, beaded, cylinder shaped or ribbon like ultra-fine silk fibroin fibers are obtained from regenerated concentrated silk fibroin aqueous solution under different processing conditions. These fibers have an average diameter of 700 nm. It is found that the morphology and the secondary structure of the as-spun silk fibroin fibers are strongly influenced by the
本文摸索出了制备高浓度再生丝素蛋白水溶液的方法,并研究了浓再生丝素蛋白水溶液的流变性能和在剪切作用下的构象结构变化,结果发现:(1)再生丝素蛋白水溶液的流变性能和常规聚合物浓溶液的流变性能差别很大。首先,它的切力变稀现象随溶液的浓度的增加而变弱;其次,溶液粘度非常小。(2)再生丝素蛋白浓水溶液的零切粘度随浓度的增加而增加,在35%左右达到最大值,浓度再提高粘度下降。但在粘度下降条件下仍然观察不到各向异性现象。(3)高浓度的再生丝素蛋白水溶液经过剪切作用后呈现出各向异性的性质,相同浓度下,剪切作用越大,再生丝素蛋白水溶液越容易实现由各向同性到各向异性的转变;相同剪切作用时,再生丝素蛋白水溶液的浓度越高,经剪切作用后,溶液的各向异性的性质越明显。(4)再生丝素蛋白水溶液经剪切作用后,丝素蛋白分予构象发生了由无规线团/α螺旋结构到β—折叠结构的转变。再生丝素蛋白水溶液的流变性能和常规聚合物浓溶液的流变性能差别很大。
东平大李博士论文
摘要
经过对高浓度再生丝素蛋白水溶液流动稳定性的研究发现,丝素蛋白水溶液是
一种不稳定的体系,存在存放流动稳定性问题。随着溶液浓度和存放温度的升高,
溶液的流动稳定性迅速下降,最终使体系发生凝胶化。其中当溶液浓度小于27%
时,浓度对流动稳定性的影响较大,浓度越低流动稳定性越好。而当浓度高于27
%后,溶液的流动稳定性迅速下降,浓度的影响也大大降低。丝素蛋白水溶液对环
境温度非常敏感,当温度低于25℃时,溶液的凝胶化速度较慢;而当温度升高
后,溶液的凝胶化速度迅速加快,在60℃时只需半小时就凝胶化。蚕吐丝时,其
中部丝腺内丝素蛋白水溶液的浓度在30%左右,温度为25℃左右的春天和秋天,
这一吐丝条件也是充分利用了丝素蛋白的流动稳定性。在制备丝素蛋白纺丝水溶液
时,应先把最初的转基因或再生丝素蛋白稀水溶液存放在低温下,然后在纺丝前进
行浓缩,这样就可以得到稳定的丝素蛋白纺丝用水溶液。
为了弄清楚拉伸对再生丝素蛋白水溶液结构变化的影响,我们运用静电纺丝方
法,对再生丝素蛋白水溶液进行了纺丝试验,发现可以从丝素蛋白水溶液中制得念
珠状的、圆形的或带状的超细丝纤维,纤维的直径在100 nm到900nm之间,平均
为7O0nm。当纺丝液浓度为28%、电压为ZKV、喷射距离为11 cm时,可制得具
有光滑表面的圆形丝纤维。拉曼光谱检测的结果发现,所得的静电纺丝纤维中已含
有p折叠结构。DSC和X光衍射结果表明静电纺丝纤维不是无定型结构,但也不
是和天然蚕丝一样的p一折叠结构。通过计算发现,静电纺丝时纤维经历了非常高
的拉伸比,并和蚕吐丝的条件相当,但即使这样也无法得到与蚕丝相同的结构;而
静电纺丝纤维大的比表面积和蚕以慢的吐丝速度都是起到使溶液中的水分挥发的作
用。试验表明,只有当溶液的浓度足够高,使丝素蛋白分子之间形成有效的缠结;
并对丝素蛋白水溶液加以足够高的拉伸力,使丝素蛋白分子拉伸取向;同时保证溶
液中的水分快速有效地挥发,才有可能形成丝纤维。但要使该纤维结构与蚕丝相同
尚需其他条件配合。
通过对再生蚕丝素蛋白水溶液与天然蚕腺体内丝素蛋白水溶液的性能对比分析
发现,再生蚕丝素蛋白水溶液和天然蚕腺体内丝素蛋白水溶液的性能差别非常大。
再生蚕丝蛋白分子量与蚕腺体内丝素蛋白分子量相差不大,但蚕腺体内丝素蛋白水
溶液的零切粘度要比再生丝素蛋白水溶液高得多,尽管它们的浓度相当。这说明蚕
毯
In this thesis, the development of biomimetic spider and silkworm silk has been briefly introduced. The processes and properties of resultant man-made silk fiber have also been summarized. It is found two key issues are not discussed yet. Whether the conformation of silk fibroin in regenerated solution or in the silkworm gland is the same or not? Whether it is necessary to prepare the spinning solution by a biomimetic process? In our work, silk fibroin of silkworm is selected as a model system because there is still not enough spider silk protein that can be supplied to do spinning and on the other side, the composition of silkworm fibroin is very similar to spider protein. In order to answer the above questions, the concentrated regenerated silk fibroin aqueous solution was prepared first, it's structure and properties of rheology and flow stability were studied. After that, the electrospin process was applied on regenerated concentrated silk fibroin aqueous solution in order to find out the conditions to form silk fiber from silk fibroin aqueous solution. It is found a kind of silk fiber can be got, but the structure of this kind silk fiber is between amorphous film and nature silk. The difference between the structure and properties of silk fibroin in regenerated aqueous solution and in vivo was further studied. The main conclusions are as follows.Viscous, transparent, homogeneous and spinnable silk fibroin aqueous solutions with high silk fibroin content were first prepared. The rheological behaviors of solutions with different concentration were studied by HAAKE RS150 rheometer. There is a rapid initial shear thinning at low shear rates (<10 s-1) for regenerated silk fibroin aqueous solutions with low concentration. However, the shear-thinning phenomenon becomes not obvious with the increase of the solution concentration, which is different from ordinary polymer solution. With the increase of concentration, the macromolecule chain become more and more compacted, the entanglements in solution increase not very quickly. As a result, the viscosity of solution is not very high.The zero shear viscosity is increasing with the concentration of regenerated silk fibroin aqueous solution and reaches max in 35%, then decreases. But all these solutions are isotropic. Only with shear the solution becomes anisotropic. With the increase of
concentration, the birefringent or anisotropic phenomenon becomes easier under the same shear rate. Similarly, with the same concentration, the anisotropic phenomenon becomes more and more obvious with the increase of shear rate. Raman spectroscopy analysis showed that the structure of silk fibroin has changed from random coil and/or a helix into β-sheet by shear.The study on the flow stability of regenerated silk fibroin aqueous solutions with different concentrations under different temperatures indicates that the flow stability decreases quickly with the increase of solution concentration and temperature. X-ray diffraction, Fourier transform infrared (FTIR) and Raman spectroscopy analysis show that silk fibroin in regenerated aqueous solution is mainly in random coil conformation. However, it turns into a helix and p-sheet conformation after gelation, and both silk I and silk II structure appears accordingly. The key concentration and key temperature for the flow stability of regenerated silk fibroin aqueous solution are about 27wt% and 25°C, respectively. Silkworms in the nature may possibly make full use of this rule. The investigation implies that the original dilute regenerated or recombinant silk fibroin aqueous solution should be stored under low temperature and concentrated just before spinning.By using electrospinning technique, beaded, cylinder shaped or ribbon like ultra-fine silk fibroin fibers are obtained from regenerated concentrated silk fibroin aqueous solution under different processing conditions. These fibers have an average diameter of 700 nm. It is found that the morphology and the secondary structure of the as-spun silk fibroin fibers are strongly influenced by the
引文
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38 胡国良,朱良均,陈国定,闵思佳。丝素蛋白的胶凝和凝胶稳定性的研究。浙江工程学院学报,1999,16(3),172-176。
39 Andreas Seidel, Oskar Liivak, and Lynn W. Jelinski. Artificial spinning of spider silk. Macromolecules, 1998, 31:6733-6736
40 李栋高,蒋蕙钧。丝绸材料学,中国纺织出版社,1994
41 Kiyoichi Matsumoto, Hiroyuki Uejima, Regenerated protein fibers. I. research and development of a novel solvent for silk fibroin, Journal of applied polymer science, 1997,61:1949-1954
42 Liu Y.; Yu, T.; Yao, H.; Yang, F. Journal of Applied Polymer Science 1997, 66, 405-408
43 Tsukada, M.; Freddi, G.; Gotoh, Y.; Kasai, N. Journal of Polymer Science part B-Polymer Physics 1994, 32, 1407-1412
44 H. Akai. The structure and ultrastructure of the silk gland. Experientia, 1983, 39(5): 443-472.
45 Craig, C. L., Hsu, M., Kaplan, D., Pierce, N. E. A comparision of the composition of silk proteins produced by spiders and insects. Int. J. Biol. Macromol. 1991,24:109-118
46 N.D.Lazo and Donald T. Downing. Crystalline regions of Bomyx mori silk fibroin may exhibit β-turn and p-helix conformation. Macromolecules 1999, 32,4700-4705.
47 F.VoUrath and D.P.Knight, Structure and function of the silk production pathway in the spider Nephila edulis, International J.of biological macromolecules, 1999,24:243-249.
48 Christian Jackson and John P.Obrien, Molecular weight distribution of Nephila clavipes dragline silk, Macromolecules, 1995,28:5975-5977.
49 E.K.Tillinghast,S.F.Chase and M.A.Townley, Water extraction by the major ampullate duct during silk formation in the spider,Argiope Aurantia lucas, J. Insect. Physiol., 1994,30(7):591 -596
50 Kerkam, K., Viney, C, Kaplan, D, Lombardi, S. Liquid crystallininity of natural silk secretions. Nature,1991, 349:596-598.
51 B.L.Thiel and C.Viney, Spider major ampullate silk(drag line):smart composite processing based on imperfect crystals, J. of Microscopy, 1997,185(2): 179-187.
52 J.Perez-Rigueiro, m. Elices, J.llorca, C.Viney, Tensile properties of silkworm silk obtained by forced silking, J. of applied polymer science, 2001,82:1928-1935.
53 N.D.Lazo and Donald T. Downing. Crystalline regions of Bomyx mori silk fibroin may exhibit p-turn and P-helix conformation. Macromolecules 1999, 32, 4700-4705.
54 Hayashi,C.Y. and Lewis,R.V. Evidence from flagelliform silk cDNA for the structural basis of elasticity and modular nature of spider silks. Science,2000,287:1477-1479
55 N.D.Lazo and Donald T.Downing, Crystalline regions of Bombyx mori silk fibrion may exhibit p-turn and Phelix conformations, Macromolecules, 1999,32:4700-4705.
56 Jun Magoshi, Yoshiko Magoshi, Shigeo Nakamura. Crystallization, liquid crystal, and fiber formation of silk fibroin., Journal of applied polymer science: applied polymer symposium41,187-204,1985
57 Magoshi J, Magoshi Y, Mary A. Becker, et al. Thermochimica Acta 2000;352-353:165-169.
58 李光宪,于同隐。丝蛋白纤维化机理(Ⅰ)-中部丝腺内丝蛋白大分子的有序态。科学通报,1989,21:1656-1659
59 于同隐,邵正中,桑蚕丝蛋白的结构、形态及其化学该性,高分子通报,1995.(3):154-160
60 邵正中 吴冬 李光宪等,用拉曼光谱研究蚕丝蛋白的结构与功能的关系。光散射学报,1995,7(1):2-7
61 李贵阳,周平,孙尧俊等。金属离子导致的丝素蛋白的构象转变,高等学校化学学报,2001,22(5):860-862。
62 孙玉书,刘永成,马明华,邵正中,陈新,于同隐。由分子间氢键导致的丝素构象转变的FT-IR研究。高等学校化学学报。1993,19(1),135-138
63 Viney, C. Chapter 10 silk fibers: origins, nature and consequences of structure. Materials, Elesevier Science, Oxford, 2000, 295-330
64 Christopher Viney, Smart assembly of polymer fibres: lessons from major ampullate spider silk, Smart materials technologies and biomimetics, Processing of SPIE, 1996, V2716, 292-295
65 Viney, C, Anne E, et al. optical characterization of silk secretions and fibers, Silk polymer: Materials Science and Biotechnology,1994, 121-136
66 C. Viney, liquid crystalline phase behavior of proteins and polypeptides, Protein-based materials, Birkhauser Boston, 1997, 281-311.
67 Viney, C. Light-microscopy of self-assembling biological macromolecules, ACS polymer preprints, 1992, 33(1):757
68 Flory PJ. Statistical thermodynamics of mixtures of rodlike particles. 3. The most probable distribution. Macromolecules, 1978, 11, 1126-1133.
69 Emily Renuart and Christopher Viney, Biological fibrous materials:self-assembled structures and optimized properties. In structural biological materials(edited by M. Elices), Elsevier Science, Oxford, 2000, 223-267
70 Khandker S. Hossain, Eiji Ohyama, Akie Ochi, Jun Magoshi, and Norio Nemoto. Dillute-solution properties of regenerated silk fibroin. J. Phys. Chem. B 2003, 107, 8066-8073
71 Khandker S. Hossain, Akie Ochi, Eiji Ooyama, Jun Magoshi, and Norio Nemoto. Dynamic light scattering of native silk fibroin solution extracted from different parts of the middle division of the silk gland of the Bombyx mori silkworm. Biomacromolecules, 2003, 4- 350-359.
72 Jun Magoshi, Shi geo Nakamura, and Shigeo Nakamura. Physical properties and structure of silk: 10. The mechanism of fibre formation from liquid silk of silkworm Bomyx mori. Polymer communication. 1985, 26, 309-311
73 Eiaku Iizuka. Silk: an overview. Journal of applied polymer science: applied polymer symposium. 1985, 41,163-171
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4 Eiaku Iizuka. Silk: an overview. Journal of applied polymer science: applied polymer symposium. 1985, 41,163-171.
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6 Viney, C, Keven Kerkam, et al. Molecular order in silk secretions, Complex fluid, Mat.Res.Soc.Proc.Vol.248,1992
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15 F. Vollrath and D.P.Knight, Structure and function of the silk production pathway in the spider Nephila edulis, International Journal of biological macromolecules, 1999,24:243-249
16 33.D.L.Kaplan, silk, biomaterials novel materials from biological sources, 1994, 1-54.
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19 Eisaku Iizuka. Silk thread: mechanism of spinning and its mechanical properties. Journal of applied polymer science: applied polymer symposium41,173-185,1985
20 Jun Magoshi. Physical properties and structure of silk: 4. spherulites grown from aqueous solution of silk fibroin. Polymer, 1977, 18,643-645.
21 Jun Magoshi, Yoshiko Magoshi and Shi geo Nakamura, Mechanism of fiber formation of silkworm, Silk polymer: Materials Science and Biotechnology, 1994,293-310
22 于同隐 张胜 邵正中,丝素蛋白的构象转变。高等学校化学学报,1996,17(2):323-325
23 刘永成 邵正中 孙玉宇,于同隐,蚕丝蛋白的结构与功能。高分子通报,1998,3:17-23
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36 吴徽宇,金宗明,徐力群,丝素的结晶度和结构变化的研究,蚕业科学,1993,19(2),105-110
37 黄君霆,朱良均。蚕丝的纤维化机理研究,蚕桑通报,1998,29:5-7
38 胡国良,朱良均,陈国定,闵思佳。丝素蛋白的胶凝和凝胶稳定性的研究。浙江工程学院学报,1999,16(3),172-176。
39 Andreas Seidel, Oskar Liivak, and Lynn W. Jelinski. Artificial spinning of spider silk. Macromolecules, 1998, 31:6733-6736
40 李栋高,蒋蕙钧。丝绸材料学,中国纺织出版社,1994
41 Kiyoichi Matsumoto, Hiroyuki Uejima, Regenerated protein fibers. I. research and development of a novel solvent for silk fibroin, Journal of applied polymer science, 1997,61:1949-1954
42 Liu Y.; Yu, T.; Yao, H.; Yang, F. Journal of Applied Polymer Science 1997, 66, 405-408
43 Tsukada, M.; Freddi, G.; Gotoh, Y.; Kasai, N. Journal of Polymer Science part B-Polymer Physics 1994, 32, 1407-1412
44 H. Akai. The structure and ultrastructure of the silk gland. Experientia, 1983, 39(5): 443-472.
45 Craig, C. L., Hsu, M., Kaplan, D., Pierce, N. E. A comparision of the composition of silk proteins produced by spiders and insects. Int. J. Biol. Macromol. 1991,24:109-118
46 N.D.Lazo and Donald T. Downing. Crystalline regions of Bomyx mori silk fibroin may exhibit β-turn and p-helix conformation. Macromolecules 1999, 32,4700-4705.
47 F.VoUrath and D.P.Knight, Structure and function of the silk production pathway in the spider Nephila edulis, International J.of biological macromolecules, 1999,24:243-249.
48 Christian Jackson and John P.Obrien, Molecular weight distribution of Nephila clavipes dragline silk, Macromolecules, 1995,28:5975-5977.
49 E.K.Tillinghast,S.F.Chase and M.A.Townley, Water extraction by the major ampullate duct during silk formation in the spider,Argiope Aurantia lucas, J. Insect. Physiol., 1994,30(7):591 -596
50 Kerkam, K., Viney, C, Kaplan, D, Lombardi, S. Liquid crystallininity of natural silk secretions. Nature,1991, 349:596-598.
51 B.L.Thiel and C.Viney, Spider major ampullate silk(drag line):smart composite processing based on imperfect crystals, J. of Microscopy, 1997,185(2): 179-187.
52 J.Perez-Rigueiro, m. Elices, J.llorca, C.Viney, Tensile properties of silkworm silk obtained by forced silking, J. of applied polymer science, 2001,82:1928-1935.
53 N.D.Lazo and Donald T. Downing. Crystalline regions of Bomyx mori silk fibroin may exhibit p-turn and P-helix conformation. Macromolecules 1999, 32, 4700-4705.
54 Hayashi,C.Y. and Lewis,R.V. Evidence from flagelliform silk cDNA for the structural basis of elasticity and modular nature of spider silks. Science,2000,287:1477-1479
55 N.D.Lazo and Donald T.Downing, Crystalline regions of Bombyx mori silk fibrion may exhibit p-turn and Phelix conformations, Macromolecules, 1999,32:4700-4705.
56 Jun Magoshi, Yoshiko Magoshi, Shigeo Nakamura. Crystallization, liquid crystal, and fiber formation of silk fibroin., Journal of applied polymer science: applied polymer symposium41,187-204,1985
57 Magoshi J, Magoshi Y, Mary A. Becker, et al. Thermochimica Acta 2000;352-353:165-169.
58 李光宪,于同隐。丝蛋白纤维化机理(Ⅰ)-中部丝腺内丝蛋白大分子的有序态。科学通报,1989,21:1656-1659
59 于同隐,邵正中,桑蚕丝蛋白的结构、形态及其化学该性,高分子通报,1995.(3):154-160
60 邵正中 吴冬 李光宪等,用拉曼光谱研究蚕丝蛋白的结构与功能的关系。光散射学报,1995,7(1):2-7
61 李贵阳,周平,孙尧俊等。金属离子导致的丝素蛋白的构象转变,高等学校化学学报,2001,22(5):860-862。
62 孙玉书,刘永成,马明华,邵正中,陈新,于同隐。由分子间氢键导致的丝素构象转变的FT-IR研究。高等学校化学学报。1993,19(1),135-138
63 Viney, C. Chapter 10 silk fibers: origins, nature and consequences of structure. Materials, Elesevier Science, Oxford, 2000, 295-330
64 Christopher Viney, Smart assembly of polymer fibres: lessons from major ampullate spider silk, Smart materials technologies and biomimetics, Processing of SPIE, 1996, V2716, 292-295
65 Viney, C, Anne E, et al. optical characterization of silk secretions and fibers, Silk polymer: Materials Science and Biotechnology,1994, 121-136
66 C. Viney, liquid crystalline phase behavior of proteins and polypeptides, Protein-based materials, Birkhauser Boston, 1997, 281-311.
67 Viney, C. Light-microscopy of self-assembling biological macromolecules, ACS polymer preprints, 1992, 33(1):757
68 Flory PJ. Statistical thermodynamics of mixtures of rodlike particles. 3. The most probable distribution. Macromolecules, 1978, 11, 1126-1133.
69 Emily Renuart and Christopher Viney, Biological fibrous materials:self-assembled structures and optimized properties. In structural biological materials(edited by M. Elices), Elsevier Science, Oxford, 2000, 223-267
70 Khandker S. Hossain, Eiji Ohyama, Akie Ochi, Jun Magoshi, and Norio Nemoto. Dillute-solution properties of regenerated silk fibroin. J. Phys. Chem. B 2003, 107, 8066-8073
71 Khandker S. Hossain, Akie Ochi, Eiji Ooyama, Jun Magoshi, and Norio Nemoto. Dynamic light scattering of native silk fibroin solution extracted from different parts of the middle division of the silk gland of the Bombyx mori silkworm. Biomacromolecules, 2003, 4- 350-359.
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