新型丝素蛋白膜的结构和热分解动力学机理

引用本文: 于海洋, 王昉, 刘其春, 马青玉, 顾正桂. 新型丝素蛋白膜的结构和热分解动力学机理[J]. 物理化学学报, 2017, 33(2): 344-355. doi: 10.3866/PKU.WHXB201611023 shu

Citation: YU Hai-Yang, WANG Fang, LIU Qi-Chun, MA Qing-Yu, GU Zheng-Gui. Structure and Kinetics of Thermal Decomposition Mechanism of Novel Silk Fibroin Films[J]. Acta Physico-Chimica Sinica, 2017, 33(2): 344-355. doi: 10.3866/PKU.WHXB201611023 shu

新型丝素蛋白膜的结构和热分解动力学机理

1.
南京师范大学分析测试中心, 南京 210023;
2.
南京师范大学化学与材料科学学院, 南京 210023;
3.
南京师范大学物理科学与技术学院, 南京 210023
基金项目:
国家自然科学基金（11474166）和江苏省高校自然科学基金（15kJB150018）资助项目

摘要: 采用氯化钙-甲酸溶解新方法，制备了氯化钙含量分别为1.50%（w，质量分数）和3.00%（w）的新型丝素蛋白膜SF-1.5和SF-3.0。运用傅里叶变换红外光谱技术和X射线衍射技术对样品的分子构象和结晶结构进行了表征。同时，利用热重技术对比研究了两种膜的热稳定性和热分解特性，依据Kissinger、Ozawa和Vyazovkin模型，考察了氯化钙含量对丝素蛋白膜热分解反应的热力学参数和动力学参数以及其机理函数的影响。结果表明，丝素蛋白膜SF-1.5中蛋白分子主要以β-折叠结构为主，丝素蛋白膜SF-3.0中蛋白分子构象主要以无规卷曲为主；SF-3.0膜在不同升温速率下的分解温度、活化能和活化焓均低于SF-1.5膜，SF-1.5膜的热稳定性优于SF-3.0膜。另外，利用Achar法和Coats-Redfern法研究发现：丝素蛋白膜在190.00-330.00℃的热分解过程遵循二维扩散（圆柱形对称）机理。

关键词:

English

Structure and Kinetics of Thermal Decomposition Mechanism of Novel Silk Fibroin Films

1.
Center of Analysis and Testing, Nanjing Normal University, Nanjing 210023, P. R. China;
2.
School of Chemistry and Materials Science, Nanjing Normal University Jiangsu, Nanjing 210023, P. R. China;
3.
School of Physics and Technology, Nanjing Normal University, Nanjing 210023, P. R. China
Received Date: 10 October 2016
Revised Date: 02 November 2016
Fund Project:
The project was supported by the National Natural Science Foundation of China (11474166) and the College of Natural Science Foundation of Jiangsu Province, China (15KJB150018).

Abstract: A new CaCl₂-formic acid dissolution method was used to prepare silk fibroin (SF) films. Films SF-1.5 and SF-3.0 were prepared using 1.50% (w, mass fraction) and 3.00% (w) CaCl₂-formic acid solutions, respectively. The molecular conformations and crystal structures of the films were characterized by Fourier transform infrared spectroscopy and X-ray diffraction. The thermal stability, thermal decomposition properties, and effect of CaCl₂ concentration on the thermodynamic parameters, kinetic parameters, and formation mechanism of the SF films were investigated using thermogravimetry techniques and the models of Kissinger, Ozawa, and Vyazovkin. The results showed that the SF-1.5 film mainly contained β-sheet structure, while the main molecular conformation in the SF-3.0 film was random coils. The decomposition temperature, activation energy, and activation enthalpy of SF-3.0 were lower than those of SF-1.5, while the thermal stability of SF-1.5 was higher than that of SF-3.0. In addition, the thermal decomposition of the SF films was studied by the Achar and Coats-Redfern methods. The mechanism of decomposition of these SF films followed the two-dimensional diffusion (cylindrical symmetry) law in the temperature range of 190.00-330.00℃.

Key words:

Silk fibroin
/ Thermal decomposition mechanism
/ Thermodynamics
/ Thermogravimetry
/ Fourier transform infrared spectroscopy

1. [1]
  Nuanchai, K.; Prasong, S.; Wilaiwan, S. Biotechnology 2009, 8(4), 468. doi: 10.3923/biotech.2009.468.472
2. [2]
  Yu, S.; Yang, W.; Chen, S.; Chen, M.; Liu, Y.; Shao, Z.; Chen, X. RSC Adv. 2014, 4 (35), 18171. doi: 10.1039/C4RA02113D
3. [3]
  Chen, M.; Shao, Z.; Chen, X. J. Biomed. Mater. Res. Part A 2012, 100 (1), 203. doi: 10.1002/jbm.a.33265
4. [4]
  Koh, L. D.; Cheng, Y.; Teng, C. P.; Khina, Y. W.; Loha, X. J.; Teea, S. Y.; Lowa, M.; Ye, E.; Yua, H. D.; Zhang, Y. W.; Han, M.Y. Prog. Polym. Sci. 2015, 46, 86. doi: 10.1016/j.progpolymsci.2015.02.001
5. [5]
  Capelli, R.; Amsden, J. J.; Generali, G.; Toffanin, S.; Benfenati, V.; Muccini, M.; Kaplan, D. L.; Omenetto, F. G.; Zamboni, R. Org. Electron. 2011, 12, 1146. doi: 10.1016/j.orgel.2011.04.005
6. [6]
  Pereira, R. F. P.; Silva, M. M.; Bermudez, V. D. Z. Macromol. Mater. Eng. 2014, 300 (12), 1171. doi: 10.1002/mame.201400276
7. [7]
  Wang, C. H.; Hsieh, C. Y.; Hwang, J. C. Adv. Mater. 2011, 23, 1630. doi: 10.1002/adma.201004071
8. [8]
  Okamoto, M.; John, B. Prog. Polym. Sci. 2013, 38 (10－11), 1487. doi: 10.1016/j.progpolymsci.2013.06.001
9. [9]
  Muller, C.; Hamedi, M.; Karlsson, R.; Jansson, R.; Marcilla, R.; Hedhammar, M.; Inganas, O. Adv. Mater. 2011, 23, 898. doi: 10.1002/adma.201003601
10. [10]
  Byette, F.; Bouchard, F.; Pellerin, C.; Paquin, J.; Marcotte, I.; Mateescu, M. A. Polym. Bull. 2011, 67 (1), 159. doi: 10.1007/s00289-010-0438-z
11. [11]
  Zhou, J.; Zhang, B.; Shi, L. J.; Zhong, J.; Zhu, J.; Yan, J.; Wang, P.; Cao, C. B.; He, D. ACS Appl. Mater. Interfaces 2014, 6 (24), 21813. doi: 10.1021/am502278b
12. [12]
  Zhao, H.; Ren, X.; Zhang, Y.; Huang, L. Bio-Med. Mater. Eng. 2015, 26 (Suppl.1), 89. doi: 10.3233/BME-151293
13. [13]
  Zhang, F.; Lu, Q.; Yue, X. X.; Zuo, B. Q.; Qin, M. D.; Li, F.; Kaplan, D. L.; Zhang, X. G. Acta Biomaterialia 2014, 12, 139. doi: 10.1016/j. actbio.2014.09.045
14. [14]
  Matsumoto, K.; Uejima, H.; Iwasaki, T.; Sano, Y.; Sumino, H. J. Appl. Polym. Sci. 1996, 60, 503. doi: 10.1002/(SICI)1097
15. [15]
  Zhang, C.; Song, D.; Lu, Q.; Hu, X.; Kaplan, D. L.; Zhu, H. Biomacromolecues 2012, 13, 2148. doi:10.1021/bm300541g
16. [16]
  Qiang, L.; Xiao, H.; Wang, X.; Kluge, J. A.; Lu, S.; Cebe, P.; Kaplan, D. L. Acta Biomaterialia 2010, 6 (4), 1380. doi: 10.1016/j.actbio.2009.10.041
17. [17]
  Rockwood, D. N.; Preda, R. C.; Yücel, T.; Wang, X.; Lovett, M.L.; Kaplan, D. L. Nat. Protoc. 2011, 6, 1612. doi: 10.1038/nprot.2011.379
18. [18]
  Wang, F.; Wolf, N.; Rocks, E. M.; Vuong, T.; Hu, X. J. Therm. Anal. Calorim. 2015, 122 (3), 1069. doi: 10.1007/s10973-015-4736-4
19. [19]
  Zhang, F.; You, X.; Dou, H.; Liu, Z.; Zuo, B. Q.; Zhang, X. G. ACS Appl. Mater. Inter. 2015, 7 (5), 3352. doi: 10.1021/am508319h
20. [20]
  Okhawilai, M.; Rangkupan, R.; Kanokpanont, S.; Damrongsakkul, S. Int. J. Biol. Macromol. 2010, 46 (5), 544. doi: 10.1016/j.ijbiomac.2010.02.008
21. [21]
  Wu, M. H.; Zhu, L.; Zhou, Z. Z.; Zhang, Y. Q. J. Nanopart. 2013, 2013, 1. doi: 10.1155/2013/901401
22. [22]
  Chen, F. S.; Ye, C. J.; Yao, Z. J. Natural Product Research and Development 2013, No. 25, 388. [陈复生, 叶崇军, 魏兆军. 天然产物的研究与开发, 2013, No. 25, 388.] doi: 10.3969/j.issn.1001-6880.2013.03.024
23. [23]
  Oshkovr, S. A.; Eshkoor, R. A.; Taher, S. T.; Ariffin, A. K.; Azhari, C. H. Compos. Struct. 2012, 94 (8), 2337. doi: 10.1016/j.compstruct.2012.03.031
24. [24]
  He, T.; Yue, K. F.; Chen, S. P.; Zhou, C. S.; Yan, N. Acta Phys. -Chim. Sin. 2016, 32 (6), 1397. [何甜, 岳可芬, 陈三平, 周春生, 晏妮. 物理化学学报, 2016, 32 (6), 1397.]doi: 10.3866/PKU.WHXB201603102
25. [25]
  Zheng, L.; Fan, B. H.; Pu, X. X.; Pan, Y.; Dong, J. X.; Guan, W. Acta Phys. -Chim. Sin. 2015, 31 (11), 2036. [郑玲, 樊本汉, 卜晓雪, 潘懿, 董家新, 关伟. 物理化学学报, 2015, 31 (11), 2036.] doi: 10.3866/PKU.WHXB201509111
26. [26]
  Li, J.; Chen, L. Z.; Wang, J. L.; Lan, G. C.; Hou, H.; Li, M. Acta Phys. -Chim. Sin. 2015, 31 (11), 2049. [李静, 陈丽珍, 王建龙, 兰贯超, 侯欢, 李满. 物理化学学报, 2015, 31 (11), 2049.] doi: 10.3866/PKU.WHXB201510092
27. [27]
  Huo, J. X.; Song, S. W.; Jin, C. W.; Ren, N.; Geng, L. N.; Zhang, J. J. Acta Phys. -Chim. Sin. 2016, 32 (4), 901. [霍建霞, 宋素伟, 靳成伟, 任宁, 耿丽娜, 张建军. 物理化学学报, 2016, 32 (4), 901.] doi: 10.3866/PKU.WHXB201602173
28. [28]
  Jin, C. W.; Wang, Y.; Su, S. L.; Zhang, J. J. Acta Phys. -Chim. Sin. 2016, 32 (9), 2232. [靳成伟, 王叶, 宿素玲, 张建军. 物理化学学报, 2016, 32 (9), 2232.] doi: 10.3866/PKU.WHXB201605263
29. [29]
  Sreeram, A.; Patel, N. G.; Venkatanarayanan, R. I.; DeLuca, S.J.; Yuyab, P. A.; Krishnan, S. Polym. Test. 2014, 37 (8), 170. doi: 10.1016/j.polymertesting.2014.04.012
30. [30]
  Yang, Z.; He, Y. H. Acta Phys. -Chim. Sin. 2016, 32 (4), 921.[杨镇, 何远航. 物理化学学报, 2016, 32 (4), 921.]doi: 10.3866/PKU.WHXB201512251
31. [31]
  Xiong, W. H.; Zhang, W. C.; Yu, C. P.; Shen, R. Q.; Cheng, J.; Ye, J. H.; Qin, Z. C. Acta Phys. -Chim. Sin. 2016, 32 (8), 2093. [熊文慧, 张文超, 俞春培, 沈瑞琪, 程佳, 叶家海, 秦志春.物理化学学报, 2016, 32 (8), 2093.] doi: 10.3866/PKU.WHXB201605121
32. [32]
  Zhou, W.; Chen, X.; Shao, Z. Z. Prog. Chem. 2006, 18 (11), 1514. [周文, 陈新, 邵正中. 化学进展, 2006, 18 (11), 1514.] doi: 10.3321/j.issn:1005-281X.2006.11.014
33. [33]
  Tao, Y. Z.; Yan, Y.; Xu, W. L.; Zhou, W. H. Acta Polym. Sin. 2010, No. 1, 27. [陶咏真, 鄢芸, 徐卫林, 周文慧. 高分子学报, 2010, No. 1, 27.]
34. [34]
  Xie, M. X.; Liu, Y. Chem. J. Chin. Univ. 2003, 24 (2), 226. [谢孟峡, 刘媛. 高等学校化学学报, 2003, 24 (2), 226.]doi: 10.3321/j.issn:0251-0790.2003.02.007
35. [35]
  Paquet-Mercier, F.; Lefèvre, T.; Auger, M.; Pézolet, M. Soft Matter 2012, 9 (9), 208. doi: 10.1039/C2SM26657A
36. [36]
  Liu, T. Preparation and Characterization of Silk Fibroin-based Scaffolds with Nanofibrous Structure. Ph. D. Dissertation, Soochow University: Suzhou, 2012. [刘涛. 具备纳米结构特征SF基支架的构建及其结构性能研究[D]. 苏州: 苏州大学, 2012.]
37. [37]
  Minoura, N.; Aiba, S. I.; Higuchi, M.; Gotoh, Y.; Tsukada, M.; Imai, Y. Biochem. Biophys. Res. Commun. 1995, 208 (2), 511. doi: 10.1006/bbrc.1995.1368
38. [38]
  Cheng, X.; He, Q. J.; Zhang, A. M. Spectrosc. Spect. Anal. 2004, 24 (3), 295. [成煦, 何其佳, 张爱民. 光谱学与光谱分析, 2004, 24 (3), 295.] doi: 10.3321/j.issn:1000-0593.2004.03.011
39. [39]
  Wang, J.; Yu, F.; Qu, L.; Meng, X.; Wen, G. Biomed. Mater. 2010, 5 (4), 041002. doi: 10.1088/1748-6041/5/4/041002
40. [40]
  Feng, X. X.; Chen, J. Y.; Zhang, J. C.; Guo, Y. H. Acta Chim. Sin. 2006, 64 (22), 2281. [冯新星, 陈建勇, 张建春, 郭玉海. 化学学报, 2006, 64 (22), 2281.] doi: 10.3321/j.issn:0567-7351.2006.22.013
41. [41]
  Huang, B.; Dai, Y.; Ban, X. X.; Jiang, W.; Zhang, Z. H.; Sun, K.Y.; Lin, B. P.; Sun, Y. M. Acta Phys. -Chim. Sin. 2015, 31 (8), 1621. [黄斌, 代钰, 班鑫鑫, 蒋伟, 张兆杭, 孙开涌, 林保平, 孙岳明. 物理化学学报, 2015, 31 (8), 1621.] doi: 10.3866/PKU.WHXB201506121
42. [42]
  Wang, Y. M.; Liu, L.; Luo, Y. F.; Jia, D. M. Acta Phys. -Chim. Sin. 2008, 24 (6), 1100. [王亚明, 刘岚, 罗远芳, 贾德民. 物理化学学报, 2008, 24 (6), 1100.] doi: 10.3866/PKU.WHXB20080633
43. [43]
  Cao, X. X.; Gao, J. G.; Du, Y. G. Polym. Mater. Sci. Eng. 2011, No. 6, 106. [曹新鑫, 高俊刚, 杜永刚. 高分子材料科学与工程, 2011, No. 6, 106.]
44. [44]
  Wang, F.; Sheng, S. J.; Huang, D.; Ma, Q. Y. Chin. J. Pharm. Anal. 2014, No. 4, 673. [王昉, 盛沈俊, 黄东, 马青玉. 药物分析杂志, 2014, No. 4, 673.]
45. [45]
  Kandelbauer, A.; Wuzella, G.; Mahendran, A.; Taudes, I.; Widsten, P. Chem. Eng. J. 2013, 152 (2－3), 556. doi: 10.1016/j.cej.2009.05.027
46. [46]
  Zhuo, L.; Kou, K.; Yao, P.; Wu, G.; Wang, Y. J. Therm. Anal. Calorim. 2015, 119 (3), 2039. doi: 10.1007/s10973-014-4360-8
47. [47]
  Xiong, Y. H.; Su, J. H.; Liu, X. P. J. Mol. Catal. 2010, 24 (5), 435. [熊亚红, 苏健鸿, 刘小平. 分子催化, 2010, 24 (5), 435.]
48. [48]
  Guo, H.; Wang, Y. B.; Ni, X. M.; Wang, J.; Han, W. L. Journal of China University of Mining & Technology 2016, 45 (3), 591.[郭慧, 王延斌, 倪小明, 王晋, 韩文龙. 中国矿业大学学报, 2016, 45 (3), 591.]
49. [49]
  Liu, W. F.; Lin, M. L. Guangzhou Chemical Industry 2004, 31(1), 6. [刘文峰, 林木良. 广东化工, 2004, 31 (1), 6.]doi: 10.3969/j.issn.1007-1865.2004.01.003
50. [50]
  Liu, S.; Chen, M.; Hu, Q.; Wang, J.; Kong, L. Bioresour. Technol. 2013, 129 (2), 381. doi: 10.1016/j.biortech.2012.11.006
51. [51]
  Hu, R. Z.; Yang, Z. Q.; Liang, Y. J. Thermochim. Acta 1988, 123(15), 135. doi: 10.1016/0040-6031(88)80017-0
52. [52]
  Zhang, J. J.; Wang, R. F.; Li, J. B.; Liu, H. M.; Yang, H. F. J. Therm. Anal. Calorim. 2000, 62 (3), 747. doi: 10.1007/s10973-004-0582-5
53. [53]
  Chen, D. Y.; Liu, R. H.; Cai, J. M. Trans. Chin. Soc. Agric. Eng. 2007, 23 (2), 188. [陈东雨, 刘荣厚, 蔡均猛. 农业工程学报, 2007, 23 (2), 188.] doi: 10.3321/j.issn:1002-6819.2007.02.037

扫一扫看文章

计量

PDF下载量: 2
文章访问数: 803
HTML全文浏览量: 76

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

新型丝素蛋白膜的结构和热分解动力学机理

English

Structure and Kinetics of Thermal Decomposition Mechanism of Novel Silk Fibroin Films

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

新型丝素蛋白膜的结构和热分解动力学机理

English

Structure and Kinetics of Thermal Decomposition Mechanism of Novel Silk Fibroin Films

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs