Low-Viscosity Ether-Functionalized Ionic Liquids as Solvents for the Enhancement of Lignocellulosic Biomass Dissolution

Due to the substantial usage of fossil fuels, the utilization of lignocellulosic biomass as renewable sources for fuels and chemical production has been widely explored. The dissolution of lignocellulosic biomass in proper solvents is vital prior to the extraction of its important constituents, and ionic liquids (ILs) have been found to be efficient solvents for biomass dissolution. However, the high viscosity of ILs limits the dissolution process. Therefore, with the aim to enhance the dissolution of lignocellulosic biomass, a series of new ether-functionalized ILs with low viscosity values were synthesized and characterized. Their properties, such as density, viscosity and thermal stability, were analyzed and discussed in comparison with a common commercial IL, namely 1-butyl-3-methylimidazolium chloride (BMIMCl). The presence of the ether group in the new ILs reduces the viscosity of the ILs to some appreciable extent in comparison to BMIMCl. 1-2(methoxyethyl)-3-methylimidazolium chloride (MOE-MImCl), which possesses the lowest viscosity value among the other ether-functionalized ILs, demonstrates an ability to be a powerful solvent in the application of biomass dissolution via the sonication method. In addition, an optimization study employing response surface methodology (RSM) was carried out in order to obtain the optimum conditions for maximum dissolution of biomass in the solvents. Results suggested that the maximum biomass dissolution can be achieved by using 3 weight% of initial biomass loading with 40% amplitude of sonication at 32.23 min of sonication period.

Enhancement of Hydrotropic Fractionation of Poplar Wood using Autohydrolysis and Disk Refining Pretreatment: Morphology and Overall Chemical Characterization

Solid acids have been proposed as a hydrolytic agent for wood biomass dissolution. In this work, we presented an environmentally friendly physicochemical treatment to leave behind cellulose, dissolve hemicellulose, and remove lignin from poplar wood. Several pretreatments, such as autohydrolysis and disk refining, were compared to optimize and modify the process. The p-toluenesulfonic acid could extract lignin from wood with a small amount of cellulose degradation. Disk refining with subsequent acid hydrolysis (so-called physicochemical treatment) doubled the delignification efficiency. A comprehensive morphology and overall chemical composition were provided. The crystallinity index (CrI) of treated poplar was increased and the chemical structure was changed after physicochemical treatment. Optical microscopy and scanning electron microscopy analysis demonstrated physicochemical treatment affected the morphology of poplar wood by removing lignin and generating fiberization. In general, this work demonstrated this physicochemical method could be a promising fractionation technology for lignocellulosic biomass due to its advantages, such as good selectivity, in removing lignin while preserving cellulose.

A fundamental understanding of whole biomass dissolution in ionic liquid for regeneration of fiber by solution-spinning

Molecular interactions, chain alignment and entanglement of the hybrid poplar biomass in ionic liquid were investigated for fiber manufacturing.

Polyoxometalate catalysts for biomass dissolution: understanding and design

The use of polyoxometalate catalysts for selective delignification of biomass presents a possible route toward using ionic liquids (ILs) to efficiently obtain high-molecular weight biopolymers from biomass. Rapid progress in this area will depend on recognizing and using the link with already well-developed inorganic chemistry in ILs pursued outside the field of biomass processing. Here, we use crystal structures determined from single crystal X-ray diffraction to better understand the behavior of [PV2Mo10O40]5-, a polyoxometalate catalyst known for its ability to promote selective delignification of biomass in the IL 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]). The crystal structure of [C2mim]5[PV2Mo10O40]·THF shows the formation of cationic shells around the anions which are likely representative of the interactions of this catalyst with [C2mim][OAc] itself. The reaction of NH4VO3 with [C2mim][OAc] is explored to better understand the chemistry of vanadium(V), which is critical to redox catalysis of [PV2Mo10O40]5-. This reaction gives crystals of [C2mim]4[V4O12], showing that this IL forms discrete metavanadates which are obtained from aqueous solutions in a specific pH range and indicating that the basicity of [OAc]- dominates the speciation of vanadium (V) in this IL.

Relationship between lignocellulosic biomass dissolution and physicochemical properties of ionic liquids composed of 3-methylimidazolium cations and carboxylate anions

Experimental and simulation studies identify 1-allyl-3-methylimidazolium formate as an efficient biomass solvent, mainly due to strong interactions with hemicellulose.

Basicity Characterization of Imidazolyl Ionic Liquids and Their Application for Biomass Dissolution

Alkalinity determination is of crucial significance for the applications of basic ionic liquids with imidazolyl. In this work, the ionization constant pKb value and acid function H- values of ionic liquids synthesized were calculated by pH method and UV spectrum-Hammett method. The dissolution ratio of biomass in these ionic liquids was measured at different temperatures. Finally, the relationship between the alkalinity and structure of these ionic liquids was discussed, and the relationship between the alkalinity of ionic liquid and the dissolution mechanism biomass was also discussed. The results show that the basicity of carboxylate ionic liquids is determined mainly by their anions, whereas cations take some finely tuned roles. Furthermore, cations and anions are equally important and are involved in dissolution mechanisms.

Glycoside Hydrolases Degrade Polymicrobial Bacterial Biofilms in Wounds

ABSTRACT The persistent nature of chronic wounds leaves them highly susceptible to invasion by a variety of pathogens that have the ability to construct an extracellular polymeric substance (EPS). This EPS makes the bacterial population, or biofilm, up to 1,000-fold more antibiotic tolerant than planktonic cells and makes wound healing extremely difficult. Thus, compounds which have the ability to degrade biofilms, but not host tissue components, are highly sought after for clinical applications. In this study, we examined the efficacy of two glycoside hydrolases, α-amylase and cellulase, which break down complex polysaccharides, to effectively disrupt Staphylococcus aureus and Pseudomonas aeruginosa monoculture and coculture biofilms. We hypothesized that glycoside hydrolase therapy would significantly reduce EPS biomass and convert bacteria to their planktonic state, leaving them more susceptible to conventional antimicrobials. Treatment of S. aureus and P. aeruginosa biofilms, grown in vitro and in vivo, with solutions of α-amylase and cellulase resulted in significant reductions in biomass, dissolution of the biofilm, and an increase in the effectiveness of subsequent antibiotic treatments. These data suggest that glycoside hydrolase therapy represents a potential safe, effective, and new avenue of treatment for biofilm-related infections.