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 films that were blended had higher thermal stability than the pure cellulose acetate sample but presented gradual changes amongst the changing of ratios, as demonstrated by thermogravimetric analysis (TGA). This study provides the basis for the comprehension of the protein-polysaccharide composites for various biomedical applications.
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Ammonia-salt solvent promotes cellulosic biomass deconstruction under ambient pretreatment conditions to enable rapid soluble sugar production at ultra-low enzyme loadings
Here, we report a novel ammonia : ammonium salt solvent based pretreatment process that can rapidly dissolve crystalline cellulose into solution and eventually produce highly amorphous cellulose under near-ambient conditions. Pre-activating the cellulose I allomorph to its ammonia–cellulose swollen complex (or cellulose III allomorph) at ambient temperatures facilitated rapid dissolution of the pre-activated cellulose in the ammonia-salt solvent ( i.e. , ammonium thiocyanate salt dissolved in liquid ammonia) at ambient pressures. For the first time in reported literature, we used time-resolved in situ neutron scattering methods to characterize the cellulose polymorphs structural modification and understand the mechanism of crystalline cellulose dissolution into a ‘molecular’ solution in real-time using ammonia-salt solvents. We also used molecular dynamics simulations to provide insight into solvent interactions that non-covalently disrupted the cellulose hydrogen-bonding network and understand how such solvents are able to rapidly and fully dissolve pre-activated cellulose III. Importantly, the regenerated amorphous cellulose recovered after pretreatment was shown to require nearly ∼50-fold lesser cellulolytic enzyme usage compared to native crystalline cellulose I allomorph for achieving near-complete hydrolytic conversion into soluble sugars. Lastly, we provide proof-of-concept results to further showcase how such ammonia-salt solvents can pretreat and fractionate lignocellulosic biomass like corn stover under ambient processing conditions, while selectively co-extracting ∼80–85% of total lignin, to produce a highly digestible polysaccharide-enriched feedstock for biorefinery applications. Unlike conventional ammonia-based pretreatment processes ( e.g. , Ammonia Fiber Expansion or Extractive Ammonia pretreatments), the proposed ammonia-salt process can operate at near-ambient conditions to greatly reduce the pressure/temperature severity necessary for conducting effective ammonia-based pretreatments on lignocellulose.
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- NSF-PAR ID:
- 10165200
- Date Published:
- Journal Name:
- Green Chemistry
- Volume:
- 22
- Issue:
- 1
- ISSN:
- 1463-9262
- Page Range / eLocation ID:
- 204 to 218
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/C9GC03524A
