Martel A, Burghammer M, Davies R J, Riekel C
European Synchrotron Radiation Facility, Grenoble Cedex, France.
Biomacromolecules. 2007 Nov;8(11):3548-56. doi: 10.1021/bm700935w. Epub 2007 Oct 20.
The thermal behavior up to degradation of Bombyx mori silk has been studied by scanning synchrotron radiation microdiffraction, gel electrophoresis, and mechanical testing. The diffraction patterns from single baves can be separated into scattering from anisotropic crystalline beta-sheet domains and random short-range order. In contrast to dragline silk, scattering from oriented, short-range-order fibroin is not observed. The sheath of sericin proteins can be selectively probed by a microbeam and shows also principally random short-range-order domains with a small crystalline beta-sheet fraction. Microdiffraction experiments on single baves from 100 to 573 K show an increase in lattice expansion along the [010] chain-stacking direction above 200-250 K, which could be due to an increase in side-chain mobility. Degradation of the crystalline fraction commences at approximately 500 K, and the fibers have become amorphous at about 570 K with an onset of carbonization. Gel electrophoresis shows that the degradation of FibH molecules starts already at about 350 K, while FibL molecules start degrading at about 400 K. The mechanical properties of single baves such as strain-to-failure and tensile strength also start degrading at about 400 K, while the initial modulus increases up to about 475 K. It is proposed that this is due to the development of cross-linking in the short-range-order chain fraction.
通过扫描同步辐射微衍射、凝胶电泳和力学测试研究了家蚕丝直至降解的热行为。单根丝条的衍射图谱可分为来自各向异性结晶β-折叠结构域的散射和随机短程有序散射。与拖丝不同,未观察到来自取向短程有序丝素蛋白的散射。丝胶蛋白鞘可用微束进行选择性探测,其主要也显示出具有少量结晶β-折叠部分的随机短程有序结构域。对100至573K的单根丝条进行的微衍射实验表明,在200 - 250K以上,沿[010]链堆积方向的晶格膨胀增加,这可能是由于侧链流动性增加所致。结晶部分的降解在约500K开始,纤维在约570K时变为非晶态并开始碳化。凝胶电泳表明,FibH分子的降解在约350K时就已开始,而FibL分子在约400K时开始降解。单根丝条的力学性能,如断裂应变和拉伸强度,也在约400K时开始降解,而初始模量在约475K之前增加。据推测,这是由于短程有序链部分中交联的发展所致。
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