Cellulose Solvent Research Articles

Cellulose aerogels functionalized with polypyrrole and silver nanoparticles: In-situ synthesis, characterization and antibacterial activity

Green porous and lightweight cellulose aerogels have been considered as promising candidates to substitute some petrochemical host materials to support various nanomaterials. In this work, waste wheat straw was collected as feedstock to fabricate cellulose hydrogels, and a green inexpensive NaOH/polyethylene glycol solution was used as cellulose solvent. Prior to freeze-drying treatment, the cellulose hydrogels were integrated with polypyrrole and silver nanoparticles by easily-operated in-situ oxidative polymerization of pyrrole using silver ions as oxidizing agent. The tri-component hybrid aerogels were characterized by scanning electron microscope, transmission electron microscope, energy dispersive X-ray spectroscopy, selected area electron diffraction, X-ray photoelectron spectroscopy, and X-ray diffraction. Moreover, the antibacterial activity of the hybrid aerogels against Escherichia coli (Gram-negative), Staphylococcus aureus (Gram-positive) and Listeria monocytogenes (intracellular bacteria) was qualitatively and quantitatively investigated by parallel streak method and determination of minimal inhibitory concentration, respectively. This work provides an example of combining cellulose aerogels with nanomaterials, and helps to develop novel forms of cellulose-based functional materials.

Using the β-glucosidase catalyzed reaction product glucose to improve the ionic liquid tolerance of β-glucosidases.

BackgroundPretreating biomass with ionic liquids (IL) increases enzyme accessibility and cellulose is typically recovered through precipitation with an anti-solvent. An industrially feasible pretreatment and hydrolysis process requires robust cellulases that are stable and active in the presence of either small amounts of ILs co-precipitated with recovered cellulose or for saccharifications in the presence of IL. β-glucosidase (BG) hydrolyzes cellobiose into two molecules of glucose (Glc) and is the last step of biomass hydrolysis. These enzymes are prone not only to product inhibition by glucose but also to inactivation by ILs. With increasing interest in IL-based pretreatment methods, there is increasing focus toward a search for Glc-tolerant and IL-tolerant BG.ResultsWe identified a BG belonging to the GH1 family, H0HC94, encoded in Agrobacterium tumefaciens 5A, and cloned and overexpressed the protein in Escherichia coli. H0HC94 exhibited high enzymatic activity with β-glycosidic substrates (248 µmol/min/mg on pNPGlc and 262 µmol/min/mg on cellobiose) and tolerant to Glc (apparent Ki = 686 mM). Further evidence of Glc-based stabilization came from the increase in melting temperature of H0HC94, with increasing Glc concentrations. The half-life of H0HC94 also increased between 2- and 20-fold in the presence of increasing concentrations of Glc. In the presence of 0.9 M of different [C2mim]-based ionic liquids, the specific activity of H0HC94 decreased by around 20–30 %. However, the addition of 100 mM glucose to the IL-enzyme mix resulted in a more stable enzyme as evidenced by the slight recovery of H0HC94 melting temperature and up to tenfold increase in half-life. This higher stability came at a cost of 2–10 % decrease in specific activity. The steady-state kinetic analyses for a subset of the ionic liquids tested indicate that the enzyme undergoes uncompetitive inhibition by glucose and ionic liquid, indicating the possibility of binding of the ionic liquid and glucose to the enzyme–substrate complex.ConclusionsH0HC94 is a Glc-stabilized BG that is also tolerant up to 0.9 M concentrations of different IL’s and indicates the possibilities of using an IL–Glc-based cellulose solvent that displays enzyme-compatibility.Electronic supplementary materialThe online version of this article (doi:10.1186/s13068-016-0484-3) contains supplementary material, which is available to authorized users.

Employing ionic liquids to deposit cellulose on PET fibers

Several ionic liquids are excellent solvents for cellulose. Starting from that finishing of PET fabrics with cellulose dissolved in ionic liquids like 1-ethyl-3-methyl imidazolium acetate, diethylphosphate and chloride, or the chloride of butyl-methyl imidazolium has been investigated. Finishing has been carried out from solutions of different concentrations, using microcrystalline cellulose or cotton and by employing different cross-linkers. Viscosity of solutions has been investigated for different ionic liquids, concentrations, cellulose sources, linkers and temperatures. Since ionic liquids exhibit no vapor pressure, simple pad-dry-cure processes are excluded. Before drying the ionic liquid has to be removed by a rinsing step. Accordingly rinsing with fresh ionic liquid followed by water or the direct rinsing with water have been tested. The amount of cellulose deposited has been investigated by gravimetry, zinc chloride iodine test as well as reactive dyeing. Results concerning wettability, water up-take, surface resistance, wear-resistance or washing stability are presented.

Impact of selected solvent systems on the pore and solid structure of cellulose aerogels.

The impact of selected cellulose solvent systems based on the principal constituents tetrabutylammonium fluoride (TBAF), 1-ethyl-3-methyl-1H-imidazolium-acetate, N-methylmorpholine-N-oxide, or calcium thiocyanate octahydrate (CTO) on the properties of cellulose II aerogels prepared from these solvent systems has been investigated as a means towards tailoring cellulose aerogel properties with respect to specific applications. Cotton linters were used as representative plant cellulose. Cellulose was coagulated from solutions with comparable cellulose content, and dried with supercritical carbon dioxide after solvent exchange. The resulting bulk aerogels were comprehensively morphologically and mechanically tested to relate structure and mechanical properties. Different solvent systems caused considerable differences in the properties of the bulk samples, such as internal surface area (nitrogen sorption), morphology, porosity (He pycnometry, thermoporosimetry), and mechanical stability (compression testing). The results of SAXS, WAXS, and solid-state 13C NMR spectroscopy suggest that this is due to different mechanisms of cellulose self-assembling on the supramolecular and nanostructural level, respectively, as reflected by the broad ranges of cellulose crystallinity, fibril diameter, fractal dimension and skeletal density. Both solid state NMR and WAXS experiments confirmed the sole existence of the cellulose II allomorph for all aerogels, with crystallinity reaching a maximum of 46–50 % for CTO-derived aerogels. Generally, higher fibril diameter, degree of crystallinity, hence increased skeletal density were associated with good preservation of shape and dimension throughout conversion of lyogels to aerogels, and enhanced mechanical stability, but somewhat reduced specific surface area. Amorphous, yet highly rigid aerogels derived from TBAF/DMSO mixtures deviated from this trend, most likely due to their particular homogeneous and nanostructured morphology.Electronic supplementary materialThe online version of this article (doi:10.1007/s10570-016-0896-z) contains supplementary material, which is available to authorized users.

Solvent Pretreatments of Lignocellulosic Materials to Enhance Biogas Production: A Review

Biogas production via anaerobic digestion is a constantly growing technology all around the world. Lignocellulosic materials (LMs) present several features that make them particularly attractive among the organic substrates commonly employed in anaerobic bioreactors. However, their recalcitrance to biological conversion still hinders their application for commercial production of biogas and requires a pretreatment step to improve their microbial degradability. Among the several pretreatments proposed for LMs, cellulose solvents and organosolv pretreatments are arising as the most effective in disrupting the bonds among cellulose, hemicellulose, and lignin, thus increasing the accessible surface area of the biodegradable matter for microbes. Here, the solvents that have been employed as pretreatment to enhance the biogas production yields from the anaerobic digestion of LMs are reviewed, examining the dissolution mechanisms involved, as well as the main advantages and drawbacks for their full-scale applica...

ChemInform Abstract: Organic Solvent Effects in Biomass Conversion Reactions

AbstractReview: 257 refs.

Improvement of Solid-State Biogas Production from Wood by Concentrated Phosphoric Acid Pretreatment

Cellulose solvent- and organic solvent-based lignocellulose fractionation (COSLIF) has been repeatedly shown to be a cost-effective and promising process to modify the structure of different lignocelluloses. It has been repeatedly reported to improve enzymatic hydrolysis and ethanol production from different lignocelluloses. In this study, COSLIF was used to improve biomethane production from pine (softwood), poplar (soft hardwood), and berry (hard hardwood) via solid state anaerobic digestion (SSAD). Feed to inoculum (F/I) ratio, which plays a major role in SSAD, was set to 3, 4, and 5. After the pretreatment, 39, 33, and 24% higher methane yield from pine was achieved for F/I ratios of 3, 4, and 5, respectively. However, the methane yield from the hardwoods was not improved by the pretreatment, which was related to overloading of the digester. Compositional analysis showed considerable reduction in hemicellulose and lignin content by the pretreatment. Structural changes in the woods, before and after the pretreatment, were examined by X-ray diffractometer and scanning electron microscopy. The results showed that the crystallinity of cellulose was decreased and accessible surface area was drastically increased by the pretreatment.

Chemical composition, pretreatments and saccharification of Senna siamea (Lam.) H.S. Irwin & Barneby: An efficient biomass producing tree legume

Protocols were developed for efficient release of glucose from the biomass of Senna siamea, one of the highly efficient biomass producing tree legumes. Composition of mature, 1year and 2years coppice biomass were analysed. For the hydrolysis of the glucan, two pretreatments, cellulose solvent- and organic solvent-based lignocellulose fractionation (COSLIF) and alkali (sodium hydroxide) were used; COSLIF (85% phosphoric acid, 45min incubation at 50°C) pretreated mature biomass exhibited best result in which 88.90% glucose released after 72h of incubation with the use of 5 filter paper units (FPU) of cellulase and 10 international units (IU) of β-glucosidase per gram of glucan. Of the biomass of different particle sizes (40–200mesh) used for saccharification, 40–60mesh shown the maximum glucose release. COSLIF pretreated mature, 1year and 2years coppice biomass showed equivalent glucose release profiles.

Efficient preparation of high concentration cellulose solution with complex DMSO/ILs solvent

The development of a low-cost and efficient solvent for cellulose has been a longstanding challenge in the field of cellulose chemistry. In this paper, we further studied a highly effective cellulose solvent composed of a large amount of dimethyl sulfoxide (DMSO) and a small amount of 1-ethyl-3-methylimidazolium acetate ([C2mim][CH3COO]). The fact that DMSO/[C2mim][CH3COO] can dissolve cellulose more efficiently than pure [C2mim][CH3COO] was fully confirmed with a combination of polarized light microscope and turbidimetric measurements. 1H-NMR spectrographs and conductivity results indicated that an increased concentration of free [CH3COO]− was the main reason for this enhanced dissolution ability. Rheology results revealed that cellulose-DMSO/ionic liquids (ILs) solution had lower zero shear viscosity, structural viscosity index, and viscous flow activation energy, which would contribute to its outstanding spinning property compared to other cellulose solutions. These advantages combined with the low cost of this proposed complex cellulose solvent make it promising to promote its industrial applications.

One-pot preparation of hydrophobic cellulose nanocrystals in an ionic liquid

The facile one-pot preparation of hydrophobic cellulose nanocrystals (CNCs) from wood pulpboard in an ionic liquid is reported in the present paper. This process employed a so-called amorphous cellulose solvent system capable of dissolving the majority of the amorphous regions in cellulose while maintaining the crystalline domains essentially intact, and consisting of tetrabutylammonium acetate with dimethylacetamide. These solvents were mixed at a mass ratio of 1:9 in conjunction with acetic anhydride to prepare CNCs via surface acetylation. The rod-like morphology and nanometer-scale dimensions of the resulting CNCs were ascertained by atomic force microscopy and transmission electron microscopy. Successful surface acetylation while maintaining an intact crystalline core was confirmed by Fourier transform infrared, 13C CP/MAS NMR and X-ray photoelectron spectroscopy in addition to X-ray diffraction. Finally, the thermal stability and hydrophobic behavior of the hydrophobic CNCs were characterized using thermal gravimetric analysis and water contact-angle measurements, respectively.

Enhancing the stability of ionic liquid media for cellulose processing: acetal protection or carbene suppression?

The recyclability of an ionic liquid-based cellulose solvent is bolstered by the inclusion of a benign hydrogen-donor co-solvent,e.g.glycerol.

Solvent infusion processing of all-cellulose composite laminates using an aqueous NaOH/urea solvent system

All-cellulose composites are high performing green materials and solvent infusion processing makes their upscaled manufacturing possible. This study explored the use of aqueous 7wt.% NaOH/12wt.% urea solution as cost effective and environmentally friendly cellulose solvent for solvent infusion processing. A short dissolution time of 5min led to all-cellulose composite laminates with a tensile strength of 114±1.9MPa and a Young’s modulus of 7.8±0.5GPa. A decrease of tensile strength and Young’s modulus with increasing dissolution time from 5 to 60min was linked to changes in composite microstructure and fine structure of the reinforcing rayon fibres. It was shown that aqueous NaOH/urea solution is a promising alternative solvent, as it offers the advantages of shorter processing times and reduced solvent costs by 97%, while resulting in 25% stronger laminates, when compared to using ionic liquids.

Organic Solvent Effects in Biomass Conversion Reactions.

Transforming lignocellulosic biomass into fuels and chemicals has been intensely studied in recent years. A large amount of work has been dedicated to finding suitable solvent systems, which can improve the transformation of biomass into value-added chemicals. These efforts have been undertaken based on numerous research results that have shown that organic solvents can improve both conversion and selectivity of biomass to platform molecules. We present an overview of these organic solvent effects, which are harnessed in biomass conversion processes, including conversion of biomass to sugars, conversion of sugars to furanic compounds, and production of lignin monomers. A special emphasis is placed on comparing the solvent effects on conversion and product selectivity in water with those in organic solvents while discussing the origins of the differences that arise. We have categorized results as benefiting from two major types of effects: solvent effects on solubility of biomass components including cellulose and lignin and solvent effects on chemical thermodynamics including those affecting reactants, intermediates, products, and/or catalysts. Finally, the challenges of using organic solvents in industrial processes are discussed from the perspective of solvent cost, solvent stability, and solvent safety. We suggest that a holistic view of solvent effects, the mechanistic elucidation of these effects, and the careful consideration of the challenges associated with solvent use could assist researchers in choosing and designing improved solvent systems for targeted biomass conversion processes.

Dissolution of cellobiose in the aqueous solutions of chloride salts: Hofmeister series consideration

The effects of chloride salts on the dissolution of cellobiose in aqueous solution were investigated using calorimetry and 1H NMR. The dissolution of cellobiose in salt solutions is a typical entropy-driven process. The activity of ZnCl2 and LiCl hydrated ions is enhanced as the hydration number decreases with increasing temperature. Zn2+ and Li+ hydrates can interact with the oxygen atoms at the O5 and O6 positions of cellobiose and associate with the Cl− anions, leading to the breakage of cellobiose hydrogen bonds. We found that the solubility of cellobiose in aqueous solutions is on the order of ZnCl2 > LiCl > NaCl > H2O > KCl > NH4Cl, which is consistent with the Hofmeister series. For the first time, we recognized the specific ionic effects of the Hofmeister series on the dissolution of cellobiose in salt aqueous solutions. This finding is helpful for understanding the dissolving mechanism of cellulose in aqueous solvents with salts and providing fundamental knowledge for finding and designing new cellulose solvents.

Comparative Study of Alkali and Acidic Cellulose Solvent Pretreatment of Corn Stover for Fermentable Sugar Production

As an immerging lignocellulose pretreatment strategy, cellulose solvent-based pretreatment can break down inter- and intra-molecular hydrogen bonds and disrupt the rigid structure of cellulose. Two cellulose solvent pretreatments were examined and compared in this study: NaOH/urea and concentrated phosphoric acid. Pretreated corn stover substrates were characterized by optical microscopy, confocal laser scanning microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, and chemical analyses. It was found that both alkaline- and acid-based cellulose solvent pretreatments can disrupt cell wall structures and cause partial dissolution of the cell wall components. The results indicated that the alkaline-based cellulose solvent was more effective at removing lignin as compared with the phosphoric acid-based cellulose solvent. The initial enzymatic saccharification rate of corn stover pretreated by alkaline-based cellulose solvent was greatly enhanced; complete saccharification of the glucans was achieved within 24 h at an enzyme loading of 15 filter paper units (FPU)/g substrate. The enzymatic digestibility of corn stover pretreated by phosphoric acid was lower than that of the alkaline-based system; this was probably caused by the presence of a high concentration of lignin.

Cellulose in NaOH–water based solvents: a review

The article is a critical review of all aspects of the dissolution of cellulose in NaOH-based aqueous solutions: from the background properties of the solvent itself, to the mechanisms of cellulose fibre swelling and dissolution, solution structure and properties and influence of additives and, finally, to the properties of various materials (fibres, films, aerogels, composites and interpenetrated networks) prepared from these solutions. A historical evolution of the research on this topic is presented. The pros and cons of NaOH-based aqueous solvent for cellulose are summarised and some prospects are suggested.

A new understanding concerning the influence of structural changes on the thermal behavior of cellulose

A study has been made on an attempt to further expand the current knowledge in melt processing of cellulose. The basic idea is that a few zinc compounds may remain in the regenerated cellulose by formation of a zinc-cellulose complex and hydrolysis reaction when ZnCl2 molten hydrates are used as a solvent for cellulose. The chance is that zinc compounds may act as isolation agents to destroy the hydrogen bonding and reduce the crystallinity of cellulose. Interesting results revealed that the raw cellulose and regenerated celluloses in our work showed different structures and other, but specific, thermal behavior, admitting that the melting of cellulose was not detected. The results are preliminary but demonstrate that simply destroying the hydrogen bonding and reducing the crystallinity will promote the dehydration of cellulose at a lower temperature, since the activity of the cellulose hydroxyls would be improved unexpectedly in that condition. It is expected that this study will stimulate some new ideas to make some progress in the melt processing of this material.

Theoretical Insights into the Role of Water in the Dissolution of Cellulose Using IL/Water Mixed Solvent Systems.

The use of certain ionic liquids (ILs) as pretreatment solvents for lignocellulosic biomass has gained great interest in recent years due to the IL's capacity for efficient cellulose dissolution in aqueous solution as compared to other common pretreatment techniques. A fundamental understanding on how these ILs in aqueous environments act on cellulose, particularly at lower IL concentrations with water as a cosolvent, is essential for optimizing pretreatment efficiency, lowering pretreatment cost, and improving IL recyclability. The IL 1-ethyl-3-methylimidazolium acetate ([C2C1Im][OAc]) is one of the most efficient cellulose solvents known, greatly altering cellulose structure for improved enzymatic saccharification. To understand the role of water as a cosolvent with [C2C1Im][OAc], we investigated the dissolution mechanism of microcrystalline cellulose, type Iβ, in different [C2C1Im][OAc]:water ratios at room (300 K) and pretreatment (433 K) temperatures using all atom molecular dynamics (MD) simulations. These simulations show that 80:20 ratios of [C2C1Im][OAc]:water should be considered as "the tipping point" above which [C2C1Im][OAc]:water mixtures are equally effective on decrystallization of cellulose by disrupting the interchain hydrogen bonding interactions. Simulations also reveal that the resulting decrystallized cellulose from 100% [C2C1Im][OAc] begins to repack in the presence of water but into a less crystalline, or more amorphous, form.

Understanding the dissolution of cellulose in 1-butyl-3-methylimidazolium acetate + DMAc solvent

Cellulose solvent ([C4mim][CH3COO]/DMAc) could be obtained by adding N,N-dimethylacetamide (DMAc) in 1-butyl-3-methylimidazolium acetate ([C4mim][CH3COO]). The solubilities of cellulose in [C4mim][CH3COO]/DMAc solvents were determined at 25°C. The effects of molar ratio of DMAc to [C4mim][CH3COO] on cellulose solubility and the possible dissolution mechanism of cellulose in [C4mim][CH3COO]/DMAc solvent have been studied. Moreover, the regenerated cellulose from [C4mim][CH3COO]/DMAc solvent were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). It was found that, cellulose was more readily dissolved in [C4mim][CH3COO]/DMAc solvent than in a neat [C4mim][CH3COO], which mainly attributed to the increased “free” [CH3COO]− anions and [C4mim]+ cations which result from the dissociation of [C4mim][CH3COO] by DMAc. Moreover, the regenerated cellulose from [C4mim][CH3COO]/DMAc solvent displayed good thermostability and similar molecular structure to the original cellulose.

Controlled molecular reorientation enables strong cellulose fibers regenerated from ionic liquid solutions

Cellulose is difficult to solubilize and undergoes thermal decomposition prior to melting. In recent years ionic liquids have been evaluated as solvents of cellulose. In the regeneration process the non-solvent governs the resulting material's crystallinity. Water adsorbs to amorphous cellulose, acts as plasticizer and lowers the Tg, hence the degree of crystallinity will affect the potential strain induced reorientation. We prepared regenerated cellulose fibers form ionic liquid using different non-solvents. The influence of shear forces upon cellulose chain alignment during extrusion was simulated in silica based upon rheological measurements. The regenerated fibers had different physical, morphological and mechanical properties. Molecular re-orientation in fibers induced by mechanical strain, at humidities above the Tg, resulted in much improved mechanical properties with the Young's modulus reaching 23.4 ± 0.8 GPa and the stress at break 504.6 ± 51.9 MPa, which is comparable to commercially available cellulose fibers.