A review of the synthesis and applications of renewable, biocompatible, and biodegradable hydrogels made from cellulose, chitin, and some of their derivatives indicates increased attention due to their excellent processability, high absorbency, porosity, bioactivity, and abundant active groups.

Over the past ten years, a next-generation approach to combat bacterial contamination has emerged: one which employs nanostructure geometry to deliver lethal mechanical forces causing bacterial cell death. In this review, we first discuss advances in both colloidal and topographical nanostructures shown to exhibit such "mechano-bactericidal" mechanisms of action. Next, we highlight work from pioneering research groups in this area of antibacterials. Finally, we provide suggestions for unexplored research topics that would benefit the field of mechano-bactericidal nanostructures. Traditionally, antibacterial materials are loaded with antibacterial agents with the expectation that these agents will be released in a timely fashion to reach their intended bacterial metabolic target at a sufficient concentration. Such antibacterial approaches, generally categorized as chemical-based, face design drawbacks as compounds diffuse in all directions, leach into the environment, and require replenishing. In contrast, due to their mechanisms of action, mechano-bactericidal nanostructures can benefit from sustainable opportunities. Namely, mechano-bactericidal efficacy needs not replenishing since they are not consumed metabolically, nor are they designed to release or leach compounds. For this same reason, however, their action is limited to the bacterial cells that have made direct contact with mechano-bactericidal nanostructures. As suspended colloids, mechano-bactericidal nanostructures such as carbon nanotubes and graphene nanosheets can pierce or slice bacterial membranes. Alternatively, surface topography such as mechano-bactericidal nanopillars and nanospikes can inflict critical membrane damage to microorganisms perched upon them, leading to subsequent cell lysis and death. Despite the infancy of this area of research, materials constructed from these nanostructures show remarkable antibacterial potential worthy of further investigation.

Chitin is a promising natural polymer to produce functional materials due to the attractive combination of abundance, price, favorable biological properties, and biodegradability. However, multiple literature examples often confuse processing of chitosan, the deacetylated version of chitin, due to chitosan’s much higher solubility in traditional solvents. Nonetheless, despite current challenges to solubilize natural chitin, there is still a large body of literature demonstrating multiple ways to manipulate this polymer into materials of desired forms and properties. Here we review one such area where chitin promises both technological superiority and potential for commercial success, the use of chitin in biomedical research. We discuss techniques which have been utilized to process chitin and to prepare chitin-based functional materials, particularly in the production of fibers, films, beads, and hydrogels. Emphasis is given to the most recent methods and a compilation of a compelling collection of examples based on current research and existing products. These examples demonstrate the suitability of chitin for production of surgical sutures, wound care materials, tissue engineering biomaterials, and other various biomedical applications.

Physical and/or covalently linked (chemical) hydrogels were prepared from chitin and cellulose extracted with ionic liquid from shrimp shells and wood biomass, respectively, and compared with hydrogels prepared from commercially available biopolymers, practical grade chitin, and microcrystalline cellulose. The highly porous aerogels were formed by initial dissolution of the biopolymers in NaOH/urea aqueous systems using freeze/thaw cycles, followed by thermal treatment (with or without epichlorohydrin as a cross-linker) and supercritical CO2 drying. The ionic-liquid-extracted cellulose pulp and chitin, as well as practical grade chitin could form both stable physical and chemical hydrogels, whereas biopolymers of lower apparent molecular weight such as microcrystalline cellulose required a covalent cross-linker for hydrogel formation and commercially available pure chitin was not suitable for the preparation of hydrogels of either type. Hydrogels prepared from the ionic-liquid-extracted biopolymers exhibited properties substantially different from those made from the commercially available biopolymers. Loading of an active ingredient into the hydrogel and its subsequent release was demonstrated using indigo carmine and revealed that the release rate was controlled mainly by the biopolymer concentration of the gel network.

Biocompatible porous and non-porous chitin films were prepared using ionic liquids and their potential for drug delivery demonstrated using caffeine as a model drug.

Group IIIA halometallate ionic liquids (ILs) present fascinating properties for the field of catalysis, particularly through the ability to tune their Lewis acidity solely by changing the metal complex speciation. In this Review, we present a critical perspective on the use of Group IIIA halide-derived ILs in catalysis, focusing on the effect of speciation of the metal-containing ions on various acid-catalyzed reactions, some of which are applied industrially. We summarize all applications of Group IIIA halometallates in catalysis (where they are notably well-represented in reactions of importance in petroleum refining and processing), compare the authors' investigations or assumptions with regard to chemical speciation, and present examples of how the tunability of these materials is used to overcome their initially perceived drawbacks. Further, advances in the field of halometallate ILs such as the role of the cations in the IL, IL analogues, and heterogenization strategies are discussed. High selectivity, reactivity, and stability are the cornerstones of the ideal catalyst, and the journey of catalysis research toward the ideal catalyst will be possible only with rational catalyst design and innovative thinking.

BackgroundBiomass pretreatment using certain ionic liquids (ILs) is very efficient, generally producing a substrate that is amenable to saccharification with fermentable sugar yields approaching theoretical limits. Although promising, several challenges must be addressed before an IL pretreatment technology can become commercially viable. One of the most significant challenges is the affordable and scalable recovery and recycle of the IL itself. Pervaporation (PV) is a highly selective and scalable membrane separation process for quantitatively recovering volatile solutes or solvents directly from non-volatile solvents that could prove more versatile for IL dehydration.ResultsWe evaluated a commercially available PV system for IL dehydration and recycling as part of an integrated IL pretreatment process using 1-ethyl-3-methylimidazolium acetate ([C2C1Im][OAc]) that has been proven to be very effective as a biomass pretreatment solvent. Separation factors as high as 1500 were observed. We demonstrate that >99.9 wt% [C2C1Im][OAc] can be recovered from aqueous solution (≤20 wt% IL) and recycled five times. A preliminary technoeconomic analysis validated the promising role of PV in improving overall biorefinery process economics, especially in the case where other IL recovery technologies might lead to significant losses.ConclusionsThese findings establish the foundation for further development of PV as an effective method of recovering and recycling ILs using a commercially viable process technology.Electronic supplementary materialThe online version of this article (doi:10.1186/s13068-017-0842-9) contains supplementary material, which is available to authorized users.

In the design of stronger chitin fibers reinforced with poly­(lactic acid) (PLA), an ionic-liquid-based (IL-based) approach was developed in which both polymers were codissolved in an 1-ethyl-3-methylimidazolium acetate ([C2mim]­[OAc]) and wet-jet spun into composite fibers. Chitin, directly extracted from shrimp shell, had a solubility in the IL of 2.75 wt %, while PLA of MW 700 000 g/mol had a solubility of 49 wt %. Keeping the IL saturated in chitin, homogeneous solutions of chitin and PLA could be obtained up to 27 wt % (relative to the IL) PLA. Spinning dopes were prepared by maintaining the chitin concentration relative to the IL at 1.75 wt % and adding PLA in chitin to PLA weight ratios of 1:0.1 through 1:1 (PLA concentrations of 0.175–1.75 wt % relative to the IL). Homogeneous chitin/PLA fibers could be spun when the chitin to PLA ratio was between 1:0.1 and 1:0.3. The tensile strength and plasticity of the fibers depended on the chitin to PLA ratio with the highest plasticity (8.8% vs 3.0% for pure chitin fibers), strength (112 vs 71 MPa), and stiffness (5.9 vs 4.2 GPa) observed for fibers with a chitin to PLA ratio of 1:0.3. Studies of the fracturing surface of the fibers indicated that fracturing occurred through an initial disruption of the interactions between polymer chains, followed by complete fiber breakage. The work not only demonstrates that homogeneous composite fibers can be spun using a biopolymer and PLA additive, but also suggests a versatile platform for preparation of multiple biopolymer–PLA materials using solution processing methods.