Alkali Can Accelerate The Cellulose Dissolution In Aqueous 1-Ethyl-3-Methylimidazole Acetate (EmimAc/10% Water)

Abstract Ionic liquids are potential and successful cellulose solvent but still suffer technical and economic issues in the cellulose commercialization. In this work, a relative low-viscosity aqueous 1-ethyl-3-methylimidazole acetate (EmimAc with 10% water) was used instead of EmimAc to dissolve cellulose; the results showed that adding NaOH to water can significantly accelerate cellulose dissolution and the cellulose solubility increased with the NaOH concentration in the EmimAc/10% water solution. NaOH can weaken the strong interaction between water and EmimAc because it can bond preferentially with water by hydrogen bonding and therefore release Ac - from Ac - -water cluster; which can enhance the reaction between Emim + and Ac - and therefore improve the cellulose dissolution. Unfortunately, the NaOH introduction inevitably cause a cellulose degradation via peeling reaction.

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Insight into Cellulose Dissolution with the Tetrabutylphosphonium Chloride–Water Mixture using Molecular Dynamics Simulations

Polymers ◽

10.3390/polym12030627 ◽

2020 ◽

Vol 12 (3) ◽

pp. 627 ◽

Cited By ~ 2

Author(s):

Brad Crawford ◽

Ahmed E. Ismail

Keyword(s):

Molecular Dynamics ◽

Hydrogen Bonding ◽

Molecular Dynamics Simulations ◽

Water Solution ◽

Water Concentration ◽

High Water ◽

Water Mixture ◽

Cellulose Dissolution ◽

Working Together ◽

Dynamics Simulations

All-atom molecular dynamics simulations are utilized to determine the properties and mechanisms of cellulose dissolution using the ionic liquid tetrabutylphosphonium chloride (TBPCl)–water mixture, from 63.1 to 100 mol % water. The hydrogen bonding between small and large cellulose bundles with 18 and 88 strands, respectively, is compared for all concentrations. The Cl, TBP, and water enable cellulose dissolution by working together to form a cooperative mechanism capable of separating the cellulose strands from the bundle. The chloride anions initiate the cellulose breakup, and water assists in delaying the cellulose strand reformation; the TBP cation then more permanently separates the cellulose strands from the bundle. The chloride anion provides a net negative pairwise energy, offsetting the net positive pairwise energy of the peeling cellulose strand. The TBP–peeling cellulose strand has a uniquely favorable and potentially net negative pairwise energy contribution in the TBPCl–water solution, which may partially explain why it is capable of dissolving cellulose at moderate temperatures and high water concentrations. The cellulose dissolution declines rapidly with increasing water concentration as hydrogen bond lifetimes of the chloride–cellulose hydroxyl hydrogens fall below the cellulose’s largest intra-strand hydrogen bonding lifetime.

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Room-Temperature Superbase-Derived Ionic Liquids with Facile Synthesis and Low Viscosity: Powerful Solvents for Cellulose Dissolution by Destroying the Cellulose Aggregate Structure

Macromolecules ◽

10.1021/acs.macromol.0c00592 ◽

2020 ◽

Vol 53 (9) ◽

pp. 3284-3295 ◽

Cited By ~ 3

Author(s):

Xin Li ◽

Haichao Li ◽

Zhe Ling ◽

Duxin Xu ◽

Tingting You ◽

...

Keyword(s):

Ionic Liquids ◽

Room Temperature ◽

Cellulose Dissolution ◽

Facile Synthesis ◽

Aggregate Structure ◽

Low Viscosity

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Synthesis, antibiotic structure–activity relationships, and cellulose dissolution studies of new room-temperature ionic liquids derived from lignin

Biotechnology for Biofuels ◽

10.1186/s13068-021-01898-x ◽

2021 ◽

Vol 14 (1) ◽

Cited By ~ 1

Author(s):

Shihong Liu ◽

Michael Gonzalez ◽

Celine Kong ◽

Scott Weir ◽

Aaron M. Socha

Keyword(s):

Antibacterial Activity ◽

Ionic Liquids ◽

Room Temperature ◽

Oxidation Products ◽

Cellulose Dissolution ◽

Melting Points ◽

E Coli ◽

Alkyl Chains ◽

Renewable Feedstocks ◽

Commodity Chemicals

Abstract Background Ionic liquids (ILs) are promising pretreatment solvents for lignocellulosic biomass, but are largely prepared from petroleum precursors. Benzaldehydes from depolymerized lignin, such as vanillin, syringaldehyde, and 4-methoxy benzaldehyde, represent renewable feedstocks for the synthesis of ionic liquids. We herein report syntheses of novel lignin-derived ionic liquids, with extended N-alkyl chains, and examine their melting points, cellulose dissolution capacities, and toxicity profiles against Daphnia magna and E. coli strain 1A1. The latter organism has been engineered to produce isoprenol, a drop-in biofuel and precursor for commodity chemicals. Results The new N,N-diethyl and N,N-dipropyl methyl benzylammonium ILs were liquids at room temperature, showing 75–100 °C decreased melting points as compared to their N,N,N-trimethyl benzylammonium analog. Extension of N-alkyl chains also increased antibacterial activity threefold, while ionic liquids prepared from vanillin showed 2- to 4-fold lower toxicity as compared to those prepared from syringaldehyde and 4-methoxybenzaldehyde. The trend of antibacterial activity for anions of lignin-derived ILs was found to be methanesulfonate < acetate < hydroxide. Microcrystalline cellulose dissolution, from 2 to 4 wt% after 20 min at 100 °C, was observed in all new ILs using light microscopy and IR spectroscopy. Conclusions Ionic liquids prepared from H-, S- and G-lignin oxidation products provided differential cytotoxic activity against E. coli and D. magna, suggesting these compounds could be tailored for application specificity within a biorefinery.

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Long-Chain Carboxylate Ionic Liquids Combining High Solubility and Low Viscosity for Light Hydrocarbon Separations

Industrial & Engineering Chemistry Research ◽

10.1021/acs.iecr.7b00660 ◽

2017 ◽

Vol 56 (25) ◽

pp. 7336-7344 ◽

Cited By ~ 12

Author(s):

Yi Zhang ◽

Xu Zhao ◽

Qiwei Yang ◽

Zhiguo Zhang ◽

Qilong Ren ◽

...

Keyword(s):

Ionic Liquids ◽

Light Hydrocarbon ◽

High Solubility ◽

Low Viscosity ◽

Long Chain

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Spectroscopic evidence of ‘jumping and pecking’ of cholinium and H-bond enhanced cation–cation interaction in ionic liquids

Physical Chemistry Chemical Physics ◽

10.1039/c5cp03412d ◽

2015 ◽

Vol 17 (46) ◽

pp. 30978-30982 ◽

Cited By ~ 46

Author(s):

Anne Knorr ◽

Koichi Fumino ◽

Anne-Marie Bonsa ◽

Ralf Ludwig

Keyword(s):

Hydrogen Bonding ◽

Ionic Liquids ◽

Electrostatic Interaction ◽

Spectroscopic Evidence

Spectroscopic evidence for cation–cation interaction in ionic liquids. The repulsive electrostatic interaction is overcome by hydrogen bonding between ions of like charge.

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Novel low viscosity ammonium-based ionic liquids with carboxylate anions: Synthesis, characterization, and thermophysical properties

Journal of Molecular Liquids ◽

10.1016/j.molliq.2017.01.050 ◽

2017 ◽

Vol 230 ◽

pp. 565-573 ◽

Cited By ~ 13

Author(s):

Ghassan M J Al Kaisy ◽

M. Ibrahim A Mutalib ◽

J M Leveque ◽

T V V L N Rao

Keyword(s):

Ionic Liquids ◽

Thermophysical Properties ◽

Low Viscosity ◽

Carboxylate Anions

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Computational analysis of the effect of [Tea][Ms] and [Tea][H2PO4] ionic liquids on the structure and stability of Aβ(17–42) amyloid fibrils

Physical Chemistry Chemical Physics ◽

10.1039/d0cp06434c ◽

2021 ◽

Vol 23 (11) ◽

pp. 6695-6709

Author(s):

D. Gobbo ◽

A. Cavalli ◽

P. Ballone ◽

A. Benedetto

Keyword(s):

Ionic Liquid ◽

Hydrogen Bonding ◽

Ionic Liquids ◽

Liquid Water ◽

Computational Analysis ◽

Amyloid Fibrils ◽

Aβ Peptides ◽

Structure And Stability ◽

Water Solutions ◽

Kinetics Of

Tight coordination of peptides by organic anions driven by hydrogen bonding affects the fibrillation kinetics of Aβ peptides in ionic liquid/water solutions.

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Alkoxycyanoborates: metal salts and low-viscosity ionic liquids

New Journal of Chemistry ◽

10.1039/d0nj04950f ◽

2021 ◽

Author(s):

Nils Schopper ◽

Jan A. P. Sprenger ◽

Ludwig Zapf ◽

Guido J. Reiss ◽

Nikolai V. Ignat’ev ◽

...

Keyword(s):

Ionic Liquids ◽

Metal Salts ◽

Low Viscosity ◽

Electrochemical Applications ◽

Conducting Salt

Alkoxycyanoborates including low-viscosity ionic liquids which are promising materials in particular for electrochemical applications and Li[CH3OB(CN)3], which is a potential conducting salt, are presented.

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