The novel use of ionic liquid as a solvent for biodegradable and natural organic biomaterials has increasingly sparked interest in the biomedical field. As compared to more volatile traditional solvents that rapidly degrade the protein molecular weight, the capability of polysaccharides and proteins to dissolve seamlessly in ionic liquid and form fine and tunable biomaterials after regeneration is the key interest of this study. Here, a blended system consisting of Bombyx Mori silk fibroin protein and a cellulose derivative, cellulose acetate (CA), in the ionic liquid 1-ethyl-3-methylimidazolium acetate (EMIMAc) was regenerated and underwent characterization to understand the structure and physical properties of the films. The change in the morphology of the biocomposites (by scanning electron microscope, SEM) and their secondary structure analysis (by Fourier-transform infrared spectroscopy, FTIR) showed that the samples underwent a wavering conformational change on a microscopic level, resulting in strong interactions and changes in their crystalline structures such as the CA crystalline and silk beta-pleated sheets once the different ratios were applied. Differential scanning calorimetry (DSC) results demonstrated that strong molecular interactions were generated between CA and silk chains, providing the blended films lower glass transitions than those of the pure silk or cellulose acetate. All filmsmore »
Dual-Crystallizable Silk Fibroin/Poly(L-lactic Acid) Biocomposite Films: Effect of Polymer Phases on Protein Structures in Protein-Polymer Blends
Biopolymer composites based on silk fibroin have shown widespread potential due to their brilliant applications in tissue engineering, medicine and bioelectronics. In our present work, biocomposite nanofilms with different special topologies were obtained through blending silk fibroin with crystallizable poly(L-lactic acid) (PLLA) at various mixture rates using a stirring-reflux condensation blending method. The microstructure, phase components, and miscibility of the blended films were studied through thermal analysis in combination with Fourier-transform infrared spectroscopy and Raman analysis. X-ray diffraction and scanning electron microscope were also used for advanced structural analysis. Furthermore, their conformation transition, interaction mechanism, and thermal stability were also discussed. The results showed that the hydrogen bonds and hydrophobic interactions existed between silk fibroin (SF) and PLLA polymer chains in the blended films. The secondary structures of silk fibroin and phase components of PLLA in composites vary at different ratios of silk to PLLA. The β-sheet content increased with the increase of the silk fibroin content, while the glass transition temperature was raised mainly due to the rigid amorphous phase presence in the blended system. This results in an increase in thermal stability in blended films compared to the pure silk fibroin films. This study provided detailed insights into more »
- Award ID(s):
- 1809541
- Publication Date:
- NSF-PAR ID:
- 10245300
- Journal Name:
- International Journal of Molecular Sciences
- Volume:
- 22
- Issue:
- 4
- Page Range or eLocation-ID:
- 1871
- ISSN:
- 1422-0067
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Silk fibroin (SF) is a protein polymer derived from insects, which has unique mechanical properties and tunable biodegradation rate due to its variable structures. Here, the variability of structural, thermal, and mechanical properties of two domesticated silk films (Chinese and Thailand B. Mori) regenerated from formic acid solution, as well as their original fibers, were compared and investigated using dynamic mechanical analysis (DMA) and Fourier transform infrared spectrometry (FTIR). Four relaxation events appeared clearly during the temperature region of 25 °C to 280 °C in DMA curves, and their disorder degree (fdis) and glass transition temperature (Tg) were predicted using Group Interaction Modeling (GIM). Compared with Thai (Thailand) regenerated silks, Chin (Chinese) silks possess a lower Tg, higher fdis, and better elasticity and mechanical strength. As the calcium chloride content in the initial processing solvent increases (1%–6%), the Tg of the final SF samples gradually decrease, while their fdis increase. Besides, SF with more non-crystalline structures shows high plasticity. Two α- relaxations in the glass transition region of tan δ curve were identified due to the structural transition of silk protein. These findings provide a new perspective for the design of advanced protein biomaterials with different secondary structures, and facilitatemore »
-
As the average life expectancy continues to increase, so does the need for resorbable materials designed to treat, augment, or replace components and functions of the body. Naturally occurring biopolymers such as silks are already attractive candidates due to natural abundance and high biocompatibility accompanied by physical properties which are easily modulated through blending with another polymer. In this paper, the authors report on the fabrication of biocomposite materials made from binary blends of Bombyx mori silk fibroin (SF) protein and renewably sourced low molecular weight nylon 610 and high molecular weight nylon 1010. Films were characterized using scanning electron microscopy (SEM), Fourier-transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Results of this study demonstrated that enhanced structural and thermal properties were achievable in composite films SF-N610/N1010 due to their chemical similarity and the possible formation of hydrogen bonds between nylon and silk molecular chains. This study provides useful insight into the sustainable design of functional composite materials for biomedical and green technologies.
-
Herein, we report the production of ionic polymer-metal composites (IPMCs) hybridized with cellulose nanofibrils (CNF) as a partial substitute for Nafion®. The aim is not only to reduce the production cost and enhance respective mechanical/thermal properties but also to bestow a considerable degree of biodegradability to such products. Formulations with di erent CNF/Nafion® ratios were produced in a thin-film casting process. Crack-free films were air-dried and plated by platinum (Pt) through an oxidation-reduction reaction. The produced hybrids were analyzed in terms of thermal stability, mechanical and morphological aspects to examine their performance compared to the Nafion-based IPMC prior to plating process. Results indicated that films with higher CNF loadings had improved tensile strengths and elastic moduli but reduced ductility. Thermogravimetric analysis (TGA) showed that the incorporation of CNF to the matrix reduced its thermal stability almost linearly, however, the onset of decomposition point remained above 120 C, which was far above the temperature the composite membrane is expected to be exposed to. The addition of a cross-linking agent to the formulations helped with maintaining the integrity of the membranes during the plating process, thereby improving surface conductivity. The focus of the current study was on the physical and morphological propertiesmore »
-
In this study, hexagonal boron nitride (h-BN) nanosheets and Bombyx mori silk fibroin (SF) proteins were combined and electrospun into BNSF nanofibers with different ratios. It was found that the surface morphology and crosslinking density of the nanofibers can be tuned through the mixing ratios. Fourier transform infrared spectroscopy study showed that pure SF electrospun fibers were dominated by random coils and they gradually became α-helical structures with increasing h-BN nanosheet content, which indicates that the structure of the nanofiber material is tunable. Thermal stability of electrospun BNSF nanofibers were largely improved by the good thermal stability of BN, and the strong interactions between BN and SF molecules were revealed by temperature modulated differential scanning calorimetry (TMDSC). With the addition of BN, the boundary water content also decreased, which may be due to the high hydrophobicity of BN. These results indicate that silk-based BN composite nanofibers can be potentially used in biomedical fields or green environmental research.