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Innovative technologies can transform what are now considered "waste streams" into feedstocks for a range of products. Indeed, the use of biomass as a source of biopolymers and chemicals currently has a consolidated economic dimension, with well-developed and regulated markets, in which the evaluation of the manufacturing processes relies on specific criteria such as purity and yield, and respects defined regulatory parameters for the process safety. In this context, ionic liquids and deep eutectic solvents have been proposed as environmentally friendly solvents for applications related to biomass waste valorization. This mini-review draws attention to some recent advancements in the use of a series of new-solvent technologies, with an emphasis on deep eutectic solvents (DESs) as key players in the development of new processes for biomass waste valorization. This work aims to highlight the role and importance of DESs in the following three strategic areas: chitin recovery from biomass and isolation of valuable chemicals and biofuels from biomass waste streams.

Background: Biomass 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., Results: We 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 ([C 2 C 1 Im][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% [C 2 C 1 Im][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., Conclusions: These findings establish the foundation for further development of PV as an effective method of recovering and recycling ILs using a commercially viable process technology.

Liquid multi-ion systems made by combining two or more salts can exhibit charge ordering and interactions not found in the parent salts, leading to new sets of properties. This is investigated herein by examining a liquid comprised of a single cation, 1-ethyl-3-methylimidazolium ([C2mim](+)), and two anions with different properties, acetate ([OAc](-)) and bis(trifluoromethylsulfonyl)imide ([NTf2](-)). NMR and IR spectroscopy indicate that the electrostatic interactions are quite different from those in either [C2mim][OAc] or [C2mim][NTf2]. This is attributed to the ability of [OAc](-) to form complexes with the [C2mim](+) ions at greater than 1:1 stoichiometries by drawing [C2mim](+) ions away from the less basic [NTf2](-) ions. Solubility studies with molecular solvents (ethyl acetate, water) and pharmaceuticals (ibuprofen, diphenhydramine) show nonlinear trends as a function of ion content, which suggests that solubility can be tuned through changes in the ionic compositions., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The radical intermediates of the n-octanoic monoester and n-octanoic diester of astaxanthin were detected by pulsed EPR measurements carried out on the UV-produced radicals on silica-alumina artificial matrix and characterized by density functional theory (DFT) calculations. Previous Mims ENDOR for astaxanthin detected the radical cation and neutral radicals formed by proton loss from the C3 (or C3') position and from the methyl groups. Deprotonation of the astaxanthin neutral radical formed at the C3 (or C3') position resulted in a radical anion. DFT calculations for astaxanthin showed that the lowest energy neutral radical forms by proton loss at the C3 (or C3') position of the terminal ring followed by proton loss at the methyl groups of the polyene chain. Contrary to astaxanthin where proton loss can occur at either end of the symmetrical radical, for the diester of astaxanthin, this loss is prevented at the cyclohexene ends and is favored for its methyl groups. The monoester of astaxanthin, however, allows formation of the neutral radical at C3' and prevents its formation at the opposite end where the ester group is attached. At the terminal ring without the ester group attached, migration of proton from hydroxyl group to carbonyl group facilitates resonance stabilization, similarly to already published results for astaxanthin. However, cw EPR shows no evidence of a monoester radical anion formed. This study suggests the different radicals of astaxanthin and its esters that would form in a preferred environment, either hydrophobic or hydrophilic, depending on their structure.

We present evidence of hydrogen bond formation, not salt formation, as the driving force in the liquefaction of a solid pharmaceutical in the form of a neutral acid-base complex, as exemplified by the liquid formed from a mixture of the local anesthetic lidocaine with fatty acids; these complexes exist at the boundary between simple eutectics and partially ionised ionic liquids.