Diffusion of 1-Ethyl-3-methyl-imidazolium Acetate in Glucose, Cellobiose, and Cellulose Solutions

Ries, Michael E.; Radhi, Asanah; Keating, Alice S.; Parker, O; Budtova, Tatiana

doi:10.1021/bm401652c

Cited by 41 publications

(65 citation statements)

References 35 publications

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“…ions to cellulose was also proposed from SAXS experiments (Behrens et al 2016). The obtained result can be compared with previous work on glucose, cellobiose and MCC dissolved in 1-ethyl-3-methyl-Imidazolium acetate, where the diffusion of both the cation and the anion species were monitored (Ries et al 2014). Ries et al demonstrated that the cations were preferentially solvating the glucose units/molecule and a value of three associated ions per AGU was estimated for the cellulose.…”

Section: Resultsmentioning

confidence: 65%

Cellulose–solvent interactions from self-diffusion NMR

Gentile

Olsson

2016

Cellulose

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Molecular self-diffusion coefficients were measured in solutions of microcrystalline cellulose (MCC) and dissolving pulp, in 40 wt% aqueous tetrabutylammonium hydroxide (TBAH), using pulsed field gradient stimulated echo NMR. From the cellulose diffusion coefficients, a weight averaged radius of hydration \R h [ w = 6.1 nm for MCC and \R h [ w = 15 nm for pulp were obtained. Water and TBA ? ions show a significantly different dependence on the cellulose concentration, revealing different molecular interactions with the polymer. Watercellulose are essentially excluded volume. TBA ? ions, on the other hand, bind to cellulose with approximately 1.2 TBA ? ions per glucose unit.

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Section: Resultsmentioning

confidence: 65%

Cellulose–solvent interactions from self-diffusion NMR

Gentile

Olsson

2016

Cellulose

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“…The calculated MSD for EMIM OAc compares well with available experimental values, and reproduces the experimentally observed difference between the cation and anion diffusion coefficients (i.e., the anion diffuses B0.9 times that of the cation). 47 The solvation of IL-cellulose systems at the molecular level has been characterized via radial distribution functions (RDFs), conformation of the o dihedral (i.e., trans-gauche, gauche-trans and gauche-gauche) and the j-c plots for the glycosidic bond. 23,25,50 The following sections discuss and compare each of these characteristics, in detail, from the context of EMIM OAc, BMIM OAc and OMIM OAc solvation of glucose and cellobiose with respect to an aqueous environment.…”

Section: Resultsmentioning

confidence: 99%

Elucidating the conformational energetics of glucose and cellobiose in ionic liquids

Bharadwaj

Schutt

Ashurst

et al. 2015

Phys. Chem. Chem. Phys.

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A major challenge for the utilization of lignocellulosic feedstocks for liquid fuels and other value added chemicals has been the recalcitrant nature of crystalline cellulose to various hydrolysis techniques. Ionic liquids (ILs) are considered to be a promising solvent for the dissolution and conversion of cellulose to simple sugars, which has the potential to facilitate the unlocking of biomass as a supplement and/or replacement for petroleum as a feedstock. Recent studies have revealed that the orientation of the hydroxymethyl group, described via the ω dihedral, and the glycosidic bond, described via the φ-ψ dihedrals, are significantly modified in the presence of ILs. In this study, we explore the energetics driving the orientational preference of the ω dihedral and the φ-ψ dihedrals for glucose and cellobiose in water and three imidazolium based ILs. It is found that interactions between the cation and the ring oxygen in glucose directly impact the conformational preference of the ω dihedral shifting the distribution towards the gauche-trans (GT) conformation and creating an increasingly unfavorable gauche-gauche (GG) conformation with increasing tail length. This discovery modifies the current hypothesis that intramolecular hydrogen bonding is responsible for the shift in the ω dihedral distribution and illuminates the importance of the cation's character. In addition, it is found that the IL's interaction with the glycosidic bond results in the modification of the observed φ-ψ dihedrals, which may have implications for hydrolysis in the presence of ILs. The molecular level information gained from this study identifies the favorable IL-sugar interactions that need to be exploited in order to enhance the utilization of lignocellulosic biomass as a ubiquitous feedstock.

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“…19,24,46 Here, this is not the case as peaks 1 and 3 move the most and do so in an upfield sense. At low mole fraction of DMSO (<0.4), peak 2 has instead a downfield movement, and Δδ is greater than that of the anion.…”

Section: Whereas In [Emim][oac]−dmso It Has Onlymentioning

confidence: 96%

“…41,46,52,53 Figure 9 shows NMR Relaxometry−Viscosity Analysis. Next, we correlate spin−lattice relaxation time T 1 with macroscopic viscosity.…”

Section: In the [Emim]mentioning

confidence: 99%

Macroscopic and Microscopic Study of 1-Ethyl-3-methyl-imidazolium Acetate–DMSO Mixtures

Radhi

Ries

et al. 2015

J. Phys. Chem. B

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Macroscopic (steady-state viscosity, density) and microscopic (NMR chemical shifts, (1)H NMR relaxation times, and diffusion) properties of the 1-ethyl-3-methylimidazolium acetate ([EMIM][OAc])-dimethyl sulfoxide (DMSO) mixture were studied in detail as a function of DMSO molar fraction at various temperatures. Temperature dependencies were used to calculate the activation energies. NMR results indicate that at low molar fraction of DMSO (<0.4), it weakly associates with the cation and in doing so disrupts the strong ion-ion association that exists in the pure ionic liquid. Stokes-Einstein equation, which linearly correlates the diffusion coefficient of a spherical molecule and macroscopic viscosity, was shown to work well for the [EMIM][OAc]-DMSO mixture. The influence of DMSO on the "anomalous" diffusion in [EMIM][OAc] ("quick" cation vs "slow" anion) was investigated; it was demonstrated that DMSO makes the cation diffusion slower. All parameters studied showed relatively small deviations from the ideal mixing rule behavior (from 20% to 50% difference between experimental and theoretically predicted results), confirming weak interactions between the components.

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Diffusion of 1-Ethyl-3-methyl-imidazolium Acetate in Glucose, Cellobiose, and Cellulose Solutions

Cited by 41 publications

References 35 publications

Cellulose–solvent interactions from self-diffusion NMR

Cellulose–solvent interactions from self-diffusion NMR

Elucidating the conformational energetics of glucose and cellobiose in ionic liquids

Macroscopic and Microscopic Study of 1-Ethyl-3-methyl-imidazolium Acetate–DMSO Mixtures

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