Towards a molecular understanding of cellulose dissolution in ionic liquids: anion/cation effect, synergistic mechanism and physicochemical aspects

Li, Yao; Wang, Jianji; Liu, Xiaomin; Zhang, Suojiang

doi:10.1039/c7sc05392d

Cited by 214 publications

(167 citation statements)

References 116 publications

(124 reference statements)

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“…Native cellulose is a heterogeneous mixture of not less than two structural arrangements (O'Sullivan 1997). The center of the elementary fibrils (micro-fibrils) of cellulose is very crystalline (Reza et al 2019), and insoluble in water (Li et al 2018). The crystalline order of cellulose is hard to disrupt.…”

Section: Constituents Of Various Biomass Materialsmentioning

confidence: 99%

Interaction of enzymes with lignocellulosic materials: causes, mechanism and influencing factors

Baig

2020

Bioresour. Bioprocess.

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For the production of biofuel (bioethanol), enzymatic adsorption onto a lignocellulosic biomass surface is a prior condition for the enzymatic hydrolysis process to occur. Lignocellulosic substances are mainly composed of cellulose, hemicellulose and lignin. The polysaccharide matrix (cellulose and hemicellulose) is capable of producing bioethanol. Therefore, lignin is removed or its concentration is reduced from the adsorption substrates by pretreatments. Selected enzymes are used for the production of reducing sugars from cellulosic materials, which in turn are converted to bioethanol. Adsorption of enzymes onto the substrate surface is a complicated process. A large number of research have been performed on the adsorption process, but little has been done to understand the mechanism of adsorption process. This article reviews the mechanisms of adsorption of enzymes onto the biomass surfaces. A conceptual adsorption mechanism is presented which will fill the gaps in literature and help researchers and industry to use adsorption more efficiently. The process of enzymatic adsorption starts with the reciprocal interplay of enzymes and substrates and ends with the establishment of molecular and cellular binding. The kinetics of an enzymatic reaction is almost the same as that of a characteristic chemical catalytic reaction. The influencing factors discussed in detail are: surface characteristics of the participating materials, the environmental factors, such as the associated flow conditions, temperature, concentration, etc. Pretreatment of lignocellulosic materials and optimum range of shear force and temperature for getting better results of adsorption are recommended.

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Section: Constituents Of Various Biomass Materialsmentioning

confidence: 99%

Interaction of enzymes with lignocellulosic materials: causes, mechanism and influencing factors

Baig

2020

Bioresour. Bioprocess.

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“…Water preferentially solvates the F − ions at the expense of F − ···HO-Cel interactions, this leads to reformation of the cellulose-cellulose H-bonds, and eventually to solution gelation and cellulose precipitation [81]. More information on the use of NMR to probe the mechanism of cellulose dissolution can be found in a recent review article [82].…”

Section: Use Of Nmr and Theoretical Calculations To Assess Ionic Liqumentioning

confidence: 99%

Cellulose in Ionic Liquids and Alkaline Solutions: Advances in the Mechanisms of Biopolymer Dissolution and Regeneration

et al. 2019

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This review is focused on assessment of solvents for cellulose dissolution and the mechanism of regeneration of the dissolved biopolymer. The solvents of interest are imidazole-based ionic liquids, quaternary ammonium electrolytes, salts of super-bases, and their binary mixtures with molecular solvents. We briefly discuss the mechanism of cellulose dissolution and address the strategies for assessing solvent efficiency, as inferred from its physico-chemical properties. In addition to the favorable effect of lower cellulose solution rheology, microscopic solvent/solution properties, including empirical polarity, Lewis acidity, Lewis basicity, and dipolarity/polarizability are determinants of cellulose dissolution. We discuss how these microscopic properties are calculated from the UV-Vis spectra of solvatochromic probes, and their use to explain the observed solvent efficiency order. We dwell briefly on use of other techniques, in particular NMR and theoretical calculations for the same purpose. Once dissolved, cellulose is either regenerated in different physical shapes, or derivatized under homogeneous conditions. We discuss the mechanism of, and the steps involved in cellulose regeneration, via formation of mini-sheets, association into "mini-crystals", and convergence into larger crystalline and amorphous regions. We discuss the use of different techniques, including FTIR, X-ray diffraction, and theoretical calculations to probe the forces involved in cellulose regeneration.

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“…Cellulose solubility based on the basicity of the anion was experimentally and theoretically investigated in previous reports. 19,22 However, to the best of our knowledge, this is the rst attempt to evaluate in detail the slight basicity difference derived from the substituent effect on the carboxylate anion in a IL/DMSO mixed system. Furthermore, it was found that the cation structure of ILs directly inuenced the solubility of cellulose, when Emim (8) and tetrabutylammonium anisate (9) were compared.…”

Section: Solubility Of Cellulose In Ilsmentioning

confidence: 99%

“…[16][17][18] In addition, recently, the relationship between the solubility of cellulose and the molecular structure of ILs have also been investigated by both of experimental and computational methods. 19 In this study, the optimization of ILs for obtaining the cellulose esters with high DS and structural homogeneity was conducted. This was done by evaluating the substituent effect of the anion structure and the inuence of bulkiness on anionderived side reactivity and cellulose solubility.…”

Section: Introductionmentioning

confidence: 99%

Effect of anion in carboxylate-based ionic liquids on catalytic activity of transesterification with vinyl esters and the solubility of cellulose

et al. 2019

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Towards a molecular understanding of cellulose dissolution in ionic liquids: anion/cation effect, synergistic mechanism and physicochemical aspects

Abstract: This perspective summarizes mechanistic studies on cellulose dissolution in ionic liquids, highlighting the synergistic mechanism, physicochemical aspects and future research trends.

Cited by 214 publications

References 116 publications

Interaction of enzymes with lignocellulosic materials: causes, mechanism and influencing factors

Interaction of enzymes with lignocellulosic materials: causes, mechanism and influencing factors

Cellulose in Ionic Liquids and Alkaline Solutions: Advances in the Mechanisms of Biopolymer Dissolution and Regeneration

Effect of anion in carboxylate-based ionic liquids on catalytic activity of transesterification with vinyl esters and the solubility of cellulose

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