Protein–polysaccharide composites have been known to show a wide range of applications in biomedical and green chemical fields. These composites have been fabricated into a variety of forms, such as films, fibers, particles, and gels, dependent upon their specific applications. Post treatments of these composites, such as enhancing chemical and physical changes, have been shown to favorably alter their structure and properties, allowing for specificity of medical treatments. Protein–polysaccharide composite materials introduce many opportunities to improve biological functions and contemporary technological functions. Current applications involving the replication of artificial tissues in tissue regeneration, wound therapy, effective drug delivery systems, and food colloids have benefited from protein–polysaccharide composite materials. Although there is limited research on the development of protein–polysaccharide composites, studies have proven their effectiveness and advantages amongst multiple fields. This review aims to provide insight on the elements of protein–polysaccharide complexes, how they are formed, and how they can be applied in modern material science and engineering.

Natural biomacromolecules such as structural proteins and polysaccharides are composed of the basic building blocks of life: amino acids and carbohydrates. Understanding their molecular structure, self-assembly and interaction in solvents such as ionic liquids (ILs) is critical for unleashing a flora of new materials, revolutionizing the way we fabricate multi-structural and multi-functional systems with tunable physicochemical properties. Ionic liquids are superior to organic solvents because they do not produce unwanted by-products and are considered green substitutes because of their reusability. In addition, they will significantly improve the miscibility of biopolymers with other materials while maintaining the mechanical properties of the biopolymer in the final product. Understanding and controlling the physicochemical properties of biopolymers in ionic liquids matrices will be crucial for progress leading to the ability to fabricate robust multi-level structural 1D fiber materials. It will also help to predict the relationship between fiber conformation and protein secondary structures or carbohydrate crystallinity, thus creating potential applications for cell growth signaling, ionic conductivity, liquid diffusion and thermal conductivity, and several applications in biomedicine and environmental science. This will also enable the regeneration of biopolymer composite fiber materials with useful functionalities and customizable options critical for additive manufacturing. The specific capabilities of these fiber materials have been shown to vary based on their fabrication methods including electrospinning and post-treatments. This review serves to provide basic knowledge of these commonly utilized protein and polysaccharide biopolymers and their fiber fabrication methods from various ionic liquids, as well as the effect of post-treatments on these fiber materials and their applications in biomedical and pharmaceutical research, wound healing, environmental filters and sustainable and green chemistry research.

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.

Electrospinning is a widely used technique to draw recalcitrant biopolymer solutions into micro to nanoscale materials in a simple and economical way. The first focus of this research involved using ionic liquids as a non-volatile solvent for natural insoluble biopolymers such as silk and cellulose (or cellulose derivatives). Compared to traditional organic solvents, ionic liquids can dissolve biopolymers without altering the molecular weight of the biopolymer. In this study, 1-ethyl-3-methylimidizolium acetate (EMIMAc) ionic liquid was used and the regenerated films were coagulated in baths of EtOH or water. The second focus of this research explored the dissolution of IL-regenerated composites into organic solvents and their electrospun composite nanomaterials. Various ratios of silk-cellulose bio-composite films regenerated from ionic liquids were used as the raw materials and sequentially dissolved/dispersed into a Formic Acid-CaCl2 solution in order to initiate the electrospinning of silk-cellulose nanomaterials. Because of the variability of ionic liquids, the nanomaterials produced using this technique have unique and tunable properties such as large surface area to volume ratios and low structural defects. FTIR and SEM results suggest that the structure and morphology of the final nanosized samples becomes more globular when the biopolymer composition ratio has increased cellulose content. TGA results demonstrated that the electrospun materials have better thermal stability than the original films. This two-step electrospinning method, using ionic liquid as a non-volatile solvent to first dissolve and mix raw natural materials, may lead to extensive research into its biomedical and pharmaceutical applications in the future.