Abstract:The
addition of water to dihydrolevoglucosenone (Cyrene) creates
a solvent mixture with highly unusual properties and the ability to
specifically and efficiently solubilize a wide range of organic compounds,
notably, aspirin, ibuprofen, salicylic acid, ferulic acid, caffeine,
and mandelic acid. The observed solubility enhancement (up to 100-fold)
can be explained only by the existence of microenvironments mainly
centered on Cyrene’s geminal diol. Surprisingly, the latter
acts as a reversible hydrotrope and reg… Show more
“…The cellulose acetate (CA) membrane produced using 3 as solvent and cast from a gel at RT or from a hot gel (Figure 4.1a, b) display finger‐like layer through the membrane due to the instantaneous solvent‐nonsolvent de‐mixing during the phase inversion. During the de‐mixing between the solvent (Cyrene) and nonsolvent (water) a mixture of pure water, pure Cyrene and a geminal diol can coexist [85] and are involved in the formation of the porous structures. A Cg−Cy membrane exhibits a completely different morphology when cast from a solution at room temperature (Figure 4.1c); mostly a sponge‐like structure with large macro‐voids, probably due to the air bubbles which did not collapse during the degassing [86] .…”
This study explores a binary solvent system composed of biobased Cyrene and its derivative Cygnet 0.0 for application in membrane technology and in biocatalytic synthesis of polyesters. Cygnet‐Cyrene blends could represent viable replacements for toxic polar aprotic solvents. The use of a 50 wt % Cygnet‐Cyrene mixture makes a practical difference in the production of flat sheet membranes by nonsolvent‐induced phase separation. New polymeric membranes from cellulose acetate, polysulfone, and polyimide are manufactured by using Cyrene, Cygnet 0.0, and their blend. The resultant membranes have different morphology when the solvent/mixture and temperature of the casting solution change. Moreover, Cyrene, Cygnet 0.0, and Cygnet‐Cyrene are also explored for substituting diphenyl ether for the biocatalytic synthesis of polyesters. The results indicate that Cygnet 0.0 is a very promising candidate for the enzymatic synthesis of high molecular weight polyesters.
“…The cellulose acetate (CA) membrane produced using 3 as solvent and cast from a gel at RT or from a hot gel (Figure 4.1a, b) display finger‐like layer through the membrane due to the instantaneous solvent‐nonsolvent de‐mixing during the phase inversion. During the de‐mixing between the solvent (Cyrene) and nonsolvent (water) a mixture of pure water, pure Cyrene and a geminal diol can coexist [85] and are involved in the formation of the porous structures. A Cg−Cy membrane exhibits a completely different morphology when cast from a solution at room temperature (Figure 4.1c); mostly a sponge‐like structure with large macro‐voids, probably due to the air bubbles which did not collapse during the degassing [86] .…”
This study explores a binary solvent system composed of biobased Cyrene and its derivative Cygnet 0.0 for application in membrane technology and in biocatalytic synthesis of polyesters. Cygnet‐Cyrene blends could represent viable replacements for toxic polar aprotic solvents. The use of a 50 wt % Cygnet‐Cyrene mixture makes a practical difference in the production of flat sheet membranes by nonsolvent‐induced phase separation. New polymeric membranes from cellulose acetate, polysulfone, and polyimide are manufactured by using Cyrene, Cygnet 0.0, and their blend. The resultant membranes have different morphology when the solvent/mixture and temperature of the casting solution change. Moreover, Cyrene, Cygnet 0.0, and Cygnet‐Cyrene are also explored for substituting diphenyl ether for the biocatalytic synthesis of polyesters. The results indicate that Cygnet 0.0 is a very promising candidate for the enzymatic synthesis of high molecular weight polyesters.
“…Owing to its sustainable character, Cyrene has sparked a great deal of interest in the scientific community. [2][3][4][5][6][7][8][9][10][11] In fact, and rather surprisingly considering its novelty, a demonstration plant able to produce 50 tons per year of Cyrene was opened by the Circa group in early 2019, 12 and plans to build a plant to produce 1000 tons of Cyrene per year in France were announced in early 2020. 13 Mixing with water may greatly expand the potential of Cyrene as a green solvent.…”
Cyrene, a recently introduced bio-based green solvent, behaves as a hydrotrope, greatly increasing the aqueous solubility of hydrophobic substances in water. Moreover, water, when present in small quantities, has also been shown to increase the solubility of hydrophobic substances in Cyrene. Albeit of large practical importance, the understanding of the solvation ability of water/Cyrene mixtures is hampered by a lack of fundamental knowledge of their solvation mechanisms, which is further complicated by a chemical equilibrium established between the ketone form of Cyrene and water, yielding the diol form of Cyrene. In this work, COSMO-RS is used to rationalize the co-solvency effect of water on Cyrene.It is shown here that COSMO-RS can accurately predict the solubility of hydrophobic substances in water/Cyrene mixtures, in the entire composition range from pure water to pure Cyrene. The predictions of the model show that the ketone form of Cyrene controls its hydrotropic ability, supporting the concept of cooperative hydrotropy. Using COSMO-RS to assess molecular contacts probability, it is also shown that water, when added in small quantities to Cyrene, acts as a co-solvent by preferentially interacting with the solute as a hydrogen bond acceptor, effectively doubling the hydrogen bond donning ability of the solute and, thus, maximizing the interactions with Cyrene. In turn, this leads to a solubility increase of hydrophobic substances in wet Cyrene.
“…The chemical and physical properties and technical applications of II have now been studied extensively (Camp 2018 ), such that its strengths and limitations as a solvent are better known. In addition, evidence has become available of its toxicological and ecotoxicological promise leading to initial regulatory approval (Camp 2018 ; De bruyn et al 2019 ). Scheme 1 Solvents derivable from biomass via levoglucosenone or glycerol …”
Section: Solvents and Sustainabilitymentioning
confidence: 99%
“…Dihydrolevoglucosenone readily equilibrates with water to form the geminal diol, [(1 S ,5 R )-6,8-dioxabicyclo[3.2.1]octan-4,4-diol ( III )] (De bruyn et al 2019 ). It can also be sensitive to inorganic bases which under some conditions leads to the formation of a solid dimer ( IV ) (RN 2044679-62-9) (Wilson et al 2016 ), rendering solvent recovery and reuse problematic (Wilson et al 2019 ).…”
Solvents are important in most industrial and domestic applications. The impact of solvent losses and emissions drives efforts to minimise them or to avoid them completely. Since the 1990s, this has become a major focus of green chemistry, giving rise to the idea of the ‘green’ solvent. This concept has generated a substantial chemical literature and has led to the development of so-called neoteric solvents. A critical overview of published material establishes that few new materials have yet found widespread use as solvents. The search for less-impacting solvents is inefficient if carried out without due regard, even at the research stage, to the particular circumstances under which solvents are to be used on the industrial scale. Wider sustainability questions, particularly the use of non-fossil sources of organic carbon in solvent manufacture, are more important than intrinsic ‘greenness’. While solvency is universal, a universal solvent, an alkahest, is an unattainable ideal.
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