Microstructure characterization and thermal stability of new silk fibroin composite films

LI Yingying; DENG Qianqian; LIU Hao; LIU Qichun; GU Zhenggui; WANG Fang

doi:10.11949/0438-1157.20191317

您当前的位置：

首页 >

文章列表页 >

Microstructure characterization and thermal stability of new silk fibroin composite films

Material science and engineering\, nanotechnology | 更新时间：2026-07-24

- Microstructure characterization and thermal stability of new silk fibroin composite films
- CIESC Journal Vol. 71, Issue 1, Pages: 388-396(2020)
- 作者机构：
  
  1. 南京师范大学分析测试中心，江苏南京210023
  2. 南京师范大学化学与材料科学学院，江苏南京210023
- 作者简介：
- 基金信息：
- DOI：10.11949/0438-1157.20191317
  CLC： TQ 317
- Received：04 November 2019，
  
  Revised：2019-11-18，
  
  Online First：12 August 2020，
  
  Published：05 January 2020
- 稿件说明：
移动端阅览
李莹莹, 邓谦谦, 刘浩, 刘其春, 顾正桂, 王昉. 新型丝素复合膜的微结构表征及热稳定性[J]. 化工学报, 2020, 71(1): 388-396

LI Yingying, DENG Qianqian, LIU Hao, LIU Qichun, GU Zhenggui, WANG Fang. Microstructure characterization and thermal stability of new silk fibroin composite films[J]. CIESC Journal, 2020, 71(1): 388-396
李莹莹, 邓谦谦, 刘浩, 刘其春, 顾正桂, 王昉. 新型丝素复合膜的微结构表征及热稳定性[J]. 化工学报, 2020, 71(1): 388-396 DOI： 10.11949/0438-1157.20191317.

LI Yingying, DENG Qianqian, LIU Hao, LIU Qichun, GU Zhenggui, WANG Fang. Microstructure characterization and thermal stability of new silk fibroin composite films[J]. CIESC Journal, 2020, 71(1): 388-396 DOI： 10.11949/0438-1157.20191317.

摘要

基于丝素的高分子复合材料可以广泛地应用于组织工程、生物医药和半导体材料等领域。通过物理-共混技术制备了一种新型生物高分子丝素/聚乳酸复合膜。利用扫描电镜、傅里叶红外光谱、拉曼光谱、X射线衍射和热分析技术对其形貌、结构和相态组分以及热稳定性进行了表征，探究了不同比例复合膜的微结构、相互作用机理和热稳定性。结果表明：随着丝素含量的增加，复合膜中的β-折叠含量增多，α-螺旋和无规卷曲含量减少，玻璃化转变温度提高；由于丝素与聚乳酸间的相互作用，提高了复合膜的热稳定性。

Abstract

Silk fibroin-based polymer composites can be widely used in the fields of tissue engineering

biomedicine

and semiconductor materials. In this study

a novel silk fibroin/polylactic acid biocomposite film was prepared by physical-blending technique. Scanning electron microscope(SEM)

Fourier transform infrared analysis(FTIR)

Raman spectroscopy

X-ray diffraction (XRD) and thermal analysis were used to characterize the morphology

structure

phase components and thermal stability of the composite films with different proportions

and to explore their microstructure

interaction mechanism and thermal stability. The results showed that with the increase of silk fibroin content

the content of β-sheet increased

the content of α-helix and random coils decreased

and the glass transition temperature increased. Due to the interaction between silk fibroin and polylactic acid

which improved the thermal stability of the composite film.

关键词

Keywords

references

Yu S , Yang W , Chen S , et al . Floxuridine-loaded silk fibroin nanospheres [J ] . RSC Advances , 2014 , 4 ( 35 ): 18171 .

Mitropoulos A N , Marelli B , Ghezzi C E , et al . Transparent, nanostructured silk fibroin hydrogels with tunable mechanical properties [J ] . ACS Biomater . Sci. Eng ., 2015 , 1 ( 10 ): 964 - 970 .

Koh L D , Cheng Y , Teng C P , et al . Structures, mechanical properties and applications of silk fibroin materials [J ] . Prog. Polym. Sci ., 2015 , 46 : 86 - 110 .

李莹莹 , 王昉 , 刘其春 , 等 . 丝素蛋白及其复合材料的研究进展 [J ] . 材料工程 , 2018 , 46 ( 8 ): 18 - 30 .

Li Y Y , Wang F , Liu Q C , et al . Research progress of silk fibroin and its composites [J ] . Materials Engineering , 2018 , 46 ( 8 ): 18 - 30 .

Pritchard E M , Dennis P B , Omenetto F , et al . Physical and chemical aspects of stabilization of compounds in silk [J ] . Biopolymers , 2012 , 97 ( 6 ): 479 - 498 .

Zhu H L , Feng X X , Zhang H P , et al . Structural characteristics and properties of silk fibroin/poly (lactic acid) blend films [J ] . Biomater . Sci . Polym . Ed ., 2009 , 20 ( 9 ): 1259 - 1274 .

王利君 , 熊杰 , 骆菁菁 , 等 . 聚乳酸-聚己内酯/丝素蛋白三元复合纳米纤维膜支架的结构与性能 [J ] . 纺织学报 , 2017 , 38 ( 5 ): 8 - 13 .

Wang L J , Xiong J , Luo J J , et al . Structure and properties of polylactic acid-polycaprolactone/ silk fibroin composite nanofibrous scaffolds [J ] . J. Text. Res ., 2017 , 38 ( 5 ): 8 - 13 .

肖红伟 , 熊杰 , 李妮 , 等 . 聚乳酸-乙醇酸共聚物/丝素共混纳米纤维多孔膜的制备及性能 [J ] . 高分子材料科学与工程 , 2011 , 27 ( 12 ): 142 - 145 .

Xiao H W , Xiong J , Li N , et al . Preparation and properties of poly（lactide-co-glycolide）/silk blend nanofibrous porous membrane [J ] . Polymer Materials Science & Engineering , 2011 , 27 ( 12 ): 142 - 145 .

Zhang C , Zhang Y P , Shao H L , et al . Hybrid silk fibers dry-spun from regenerated silk fibroin/ graphene oxide aqueous solutions [J ] . ACS Appl . Mater . Interfaces , 2016 , 8 : 3349 - 3358 .

Suzuki S , Dawson R A , Chirila T V , et al . Treatment of silk fibroin with poly(ethylene glycol) for the enhancement of corneal epithelial cell growth [J ] . Journal of Functional Biomaterials , 2015 , 6 ( 2 ): 345 - 366 .

Martin O , Averous L . Poly(lactic acid): plastication and properties of biodegradable multiphase systems [J ] . Polymer , 2001 , 42 ( 14 ): 6209 - 6219 .

Xiao H , Yang L , Ren X , et al . Kinetics and crystal structure of poly(lactic acid) crystallized nonisothermally: effect of plasticizer and nucleating agent [J ] . Polymer Composites , 2010 , 31 ( 12 ): 2057 - 2068 .

Shao J , Guo Y , Xiang S , et al . The morphology and spherulite growth of PLA stereocomplex in linear and branched PLLA/PDLA blends: effects of molecular weight and structure [J ] . Crystengcomm , 2015 , 18 ( 2 ): 274 - 282 .

倪莉 , 王璋 , 姚文华 , 等 . 丝素蛋白结构的研究(1): 探讨氯化钙溶液溶解丝素的机理 [J ] . 中国食品学报 , 2001 , 1 ( 1 ): 12 - 18 .

Ni L , Wang Z , Yao W H , et al . Study on the structure of silk fibroin protein(1): The mechanism of dissolving fibroin in calcium chloride solution [J ] . Journal of Chinese Food , 2001 , 1 ( 1 ): 12 - 18 .

Lai S M , Hsieh Y T . Preparation and properties of polylactic acid (PLA)/silica nanocomposites [J ] . J. Macromol. Sci. B , 2016 , 55 ( 3 ): 211 - 228 .

Zhou S B , Zheng X T , Yu X J , et al . Hydrogen bonding interaction of poly(D, L-lactide)/hydroxyapatite nanocomposites [J ] . Chem. Mater ., 2007 , 19 : 247 - 253 .

Zhong J , Ma M , Li W , et al . Self-assembly of regenerated silk fibroin from random coil nanostructures to antiparallel β-sheet nanostructures [J ] . Biopolymers , 2015 , 101 ( 12 ): 1181 - 1192 .

于海洋 , 王昉 , 刘其春 , 等 . 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 .

Yu H Y , Wang F , Liu Q C , et al . Structure and kinetics of thermal decomposition mechanism of novel silk fibroin films [J ] . Acta Physico-Chimica Sinica , 2017 , 33 ( 2 ): 344 - 355 .

Hu X , Kaplan D , Cebe P . Determining beta-sheet crystallinity in fibrous proteins by thermal analysis and infrared spectroscopy [J ] . Macromolecules , 2006 , 39 : 6161 - 6170 .

Wang F , Wu H , Venkataraman V , et al . Silk fibroin-poly(lactic acid) biocomposites: effect of protein-synthetic polymer interactions and miscibility on material properties and biological responses [J ] . Materials Science & Engineering C , 2019 , 104 : 109890 .

Wool R P , Bretzlaff R S , Li B Y , et al . Infrared and Raman spectroscopy of stressed polyethylene [J ] . Journal of Polymer Science , Part B (Polymer Physics) , 1986 , 24 ( 5 ): 1039 - 1066 .

Xu Y , Liang L . Surface-enhanced resonance Raman scattering of phycoerythrin adsorbed by silver hydrosols [J ] . Applied Spectroscopy , 1994 , 48 ( 9 ): 1147 - 1149 .

Carey P R . Biochemical Applications of Raman and Resonance Raman Spectroscopies [M ] . New York : Academic Press , 1982 : 71 - 96 .

Bandekar J , Krimm S . Vibrational analysis of peptides, polypeptides, and proteins: characteristic amide bands of β-turns [J ] . Proc. Natl. Acad. Sci. USA , 1979 , 76 ( 2 ): 774 - 777 .

Kister G , Cassanas G , Vert M , et al . Vibrational analysis of poly(L-lactic acid) [J ] . Journal of Raman Spectroscopy , 2010 , 26 ( 4 ): 307 - 311 .

Furukawa T , Sato H , Murakami R , et al . Raman microspectroscopy study of structure, dispersibility, and crystallinity of poly(hydroxybutyrate)/poly(L-lactic acid) blends [J ] . Polymer , 2006 , 47 ( 9 ): 3132 - 3140 .

Huang S M , Hwang J J , Liu H J , et al . Crystallization behavior of poly(L-lactic acid)/montmorillonite nanocomposites [J ] . J. Appl. Polym. Sci ., 2010 , 117 ( 1 ): 434 - 442 .

Bruckmoser K , Resch K . Effect of processing conditions on crystallization behavior and mechanical properties of poly(lactic acid) staple fibers [J ] . J . Appl . Polym . Sci ., 2015 , 132 ( 33 ). doi: 10.1002/app.42432 http://dx.doi.org/10.1002/app.42432 .

Pluta M . Morphology and properties of polylactide modified by thermal treatment, filling with layered silicates and plasticization [J ] . Polymer , 2004 , 45 ( 24 ): 8239 - 8251 .

Wu T M , Wu C Y . Biodegradable poly (lactic acid)/chitosan-modified montmorillonite nanocomposites: preparation and characterization [J ] . Polymer Degradation & Stability , 2006 , 91 ( 9 ): 2198 - 2204 .

Zhang J , Yan D X , Xu J Z , et al . Highly crystallized poly (lactic acid) under high pressure [J ] . AIP Advances , 2012 , 2 ( 4 ): 042159 .

Pal A , Katiyar V . Melt processing of biodegradable poly (lactic acid)/ functionalized chitosan nanocomposite films: mechanical modeling with improved oxygen barrier and thermal properties [J ] . J . Polym . Res ., 2017 , 24 ( 10 ): 173 .

Iannace S , Maffezzoli A , Leo G , et al . Influence of crystal and amorphous phase morphology on hydrolytic degradation of PLLA subjected to different processing conditions [J ] . Polymer , 2001 , ( 42 ): 3799 - 3807 .

Wang F , Wolf N , Rocks E M , et al . Comparative studies of regenerated water-based Mori, Thai, Eri, Muga and Tussah silk fibroin films [J ] . J. Therm. Anal. Calorim ., 2015 , 122 ( 3 ): 1069 - 1076 .

Gaur U . Advanced thermal analysis system (ATHAS) polymer heat capacity data bank [C ] // ACS Symposium . 1982 : 355 - 366 .

Sheng S J , Hu X , Wang F , et al . Mechanical and thermal property characterization of poly-L-lactide(PLLA) scaffold developed using pressure-controllable green foaming technology [J ] . Materials Science and Engineering: C, 2 015 , 49 : 612 - 622 .

刘其春 , 王昉 , 李莹莹 , 等 . 比较两种丝素膜的结构、热分解机理与热力学参数 [J ] . 中国科学: 化学 , 2019 , ( 7 ): 1014 - 1029 .

Liu Q C , Wang F , Li Y Y , et al . Comparative studies of structure, thermal decomposition mechanism and thermodynamic parameters of two kinds of silk fibroin films [J ] . Chinese Science: Chemistry , 2019 , ( 7 ): 1014 - 1029 .

Views

下载量

CSCD

Alert me when the article has been cited

提交

Tools

Publicity Resources

Crystallization and degradation behavior of poly(lactic acid)/poly(ethylene glycol) blends

Influence of shear history on morphology, microstructure and mechanical properties of micro injection molded parts

Recent advances in machine learning for modeling and control of crystallization processes

Research progress on anode materials and performance optimization of redox flow batteries

Molecular simulation study on adsorption behavior of K⁺ and NH4+ by biomass ash

Related Author

ZHANG Kuangsheng

TANG Meirong

XUE Xiaojia

LI Kai

SHAO Yan

ZHOU Jian

YUE Chongchong

LI Zhuangzhuang

Related Institution

Oil and Gas Technology Research Institute of PetroChina Changqing Oilfield Branch Company

State Key Laboratory of Chemical Engineering, College of Chemical and Biological Engineering, Zhejiang University

International Joint Research Laboratory for Micro-Nano Moulding Technology, Zhengzhou University

National Engineering & Research Center for Advanced Polymer Processing Technology, Zhengzhou University

National Engineering Research Center for Integrated Utilization of Salt Lake Resources, East China University of Science and Technology

⁰