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The massive reserves of osmotic energy existing in estuary will be highly desired as promising energy source that avails to solve the problem of energy shortage and environment deterioration. The ion transport membrane is core component optimized through composite membrane heterostructure to maximize the osmotic energy harvesting but suffer from gaps and resistance increase, which limit their practical applications. Here we demonstrate mono-component heterogeneous regenerated bacterial cellulose (RBC) membranes fabricated by subtle regenerated technique through Ionic Liquids (ILs). Such membranes obtain heterogeneous nature by the difference in fiber intertwining states due to the different treatment conditions on both sides. It achieves osmotic energy conversion with maximum power density of 0.70 W·m -2 at 100-fold, which provides ingenious strategy for excellent performance and low-cost osmotic energy harvesting. By minimizing pores and maximizing the surface charges, energy barriers can be lowered, ion permeable and selective transport channels for energy harvesting device can be increased, as supported by the numerical simulation. This is the first time the construction strategy for mono-component heterogeneous membrane mediated by ILs for osmotic energy harvesting is proposed, which averts gaps between the layers of different materials effectively and provides theoretical guidance for subsequent in-depth research on mono-component ion-selective heterogeneous membrane., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier B.V.)

Flexible wearable devices are garnering significant interest, with conductive hydrogels emerging as a particularly notable category. While many of these hydrogels offer impressive conductivity, they often lack the innate ability to adhere autonomously to human skin. The ideal hydrogel should possess both superior adhesion properties and a wide responsive range. This study introduces a novel double-network conductive hydrogel, synthesized from lignosulfonate sodium and ionic liquid using a one-pot method. The gel's mechanical robustness (fracture elongation of ∼3500 % and tensile strength of ∼130 kPa) and exceptional conductivity sensing performance arise from the synergistic effects of electrostatic interactions, dynamic hydrogen bonding, and a three-dimensional network structure. Additionally, the phenolic hydroxyl and sulfonic groups from lignosulfonate sodium imbue the hydrogel with adhesive qualities, allowing it to easily bond with varied material surfaces. This hydrogel excels in human physiological signal detection and wireless monitoring, demonstrating a rapid response time (149 ms) and high sensitivity (a maximum gauge factor of 10.9 for strains between 400 and 600 %). Given these properties, the flexible, self-adhesive, and conductive hydrogel showcases immense promise for future applications in wearable devices and wireless transmission sensing., Competing Interests: Declaration of competing interest There are no conflicts of interest to declare., (Copyright © 2023 Elsevier B.V. All rights reserved.)

To further our understanding of the change in association between lignin and carbohydrates after kraft pulping, isotope-labeled kraft pulp (KP) was prepared using 13 C and D double-isotope-labeled wheat straw, and it was subjected to enzymatic hydrolysis and ionic liquid treatment to explore the linkages between lignin and carbohydrate complexes in wheat straw. Isotope abundance determination showed that 13 C and D abundances in the experimental groups were substantially higher than those in the control group, indicating that the injected exogenous coniferin-[α- 13 C], coniferin-[γ- 13 C], and d-glucose-[6-D 2 ] were effectively absorbed and metabolized during wheat internode growth. Solid-state CP/MAS 13 C-NMR spectroscopy showed that lignin was mainly linked to polysaccharides via acetal, benzyl ether, and benzyl ester bonds. Kraft pulp (KP) from the labeled wheat straw was degraded by cellulase. The obtained residue was fractionated using the ionic liquid DMSO/TBAH to separate the cellulose-lignin complex (KP-CLC) and xylan-lignin complex (KP-XLC). X-ray diffractometer determination showed that the KP-CLC regenerated cellulose type II from type I after the ionic liquid conversion. The 13 C-NMR spectrum of Ac-En-KP-CLC showed that the cellulose-lignin complex structure was chemically bonded between the lignin and cellulose through acetal and benzyl ether bonds. The 13 C-NMR spectrum of En-KP-XLC showed a lignin-hemicellulose complex structure, wherein lignin and xylan were chemically bonded by benzyl ether and acetal bonds. These results indicate that the cross-linking between lignin and carbohydrates exists in lignocellulosic fibers even after kraft pulping.

Cellulose is a promising feedstock for the production of sustainable materials. To fully utilize its potential, exploring efficient cellulose solvents is a paramount prerequisite. In this study, ten superbase amino acid ionic liquids (SAAILs) are synthesized using 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) with different amino acid anions via a simple neutralization method. The properties of these SAAILs, such as viscosity and glass transition temperature, varied with their cation and anion structures. The ability of the SAAILs to dissolve cellulose is related to their Kamlet-Taft parameters, particularly hydrogen bond basicity (β). The main driving force for cellulose dissolution in SAAILs is thought to be hydrogen bonding interactions between SAAILs and cellulose hydroxyl groups. Four SAAILs composed of DBN or DBU cations and proline, or aspartic acid anions are identified as promising solvents for preparing regenerated cellulose films (RCFs). The RCF prepared from [DBN]Proline(Pro) showed a favorable combination of high tensile strength (76.9 MPa), high Young's modulus (5201.2 MPa), good transparency (≈70% at 550 nm), and smooth surface morphology. These halogen- and metal-free SAAILs show the potential to provide a new avenue for cellulose processing., (© 2023 Wiley-VCH GmbH.)

Cellulose acetate (CA) is one of the most important cellulose plastics that has demonstrated extensive applications in many areas. In search of a more sustainable and efficient way to prepare CA, we synthesized a novel ionic liquid, [DBUC 8 ]Cl, based on the commonly used catalyst DBU (1,8-diazabicyclo[5.4.0]undecyquin-7-ene) in a simple manner. [DBUC 8 ]Cl can dissolve cellulose more efficiently than the same type of imidazolyl ionic liquid, owing to the stronger alkalinity of DBU. It is noteworthy that highly substituted CA (DS = 2.82) was successfully synthesized via transesterification with alkenyl ester under mild conditions (80 °C, 40 min) without the addition of a catalyst in this solvent, which is superior to most of the reported work. Furthermore, we confirmed that the synthesized CA had good thermoplasticity, and a transparent cellulose acetate film (CAF) was obtained by hot pressing with a small amount of glycerol. Therefore, we propose a new DBU-derived ionic liquid, which may serve as a versatile platform system for producing cellulose-derived bioplastics more sustainably and efficiently., Competing Interests: Declaration of competing interest The authors declare no competing financial interest in this study., (Copyright © 2023. Published by Elsevier B.V.)

Lignin precursor labeled with 13 C (coniferin- 13 Cα), carbohydrate precursor labeled with D (6,6-D 2 -glucose) were put into cambium tissue stripped from a growing poplar. The tissue was further cultured in vitro for 18d. Then, the isotopic abundance was determined. The results showed that the labeled precursors could be normally involved in the formation of new xylem. The labeled new xylem tissue was fractionated by ionic liquid DMSO/TBAH system to obtain two components: glucan-lignin complex (GL) and xylan-lignin complex (XL). The X-ray diffraction (XRD) results indicated that the crystalline form of cellulose in the GL component was transformed from type I to type II after the ionic liquid separation. Then the GL and XL were purified and modified by enzymatic and chemical methods, and their structures were elucidated by nuclear magnetic resonance (NMR) spectroscopy. The results showed that lignin subunits in the cultured tissues were mainly connected by β-5 and β-O-4 linkages, of which the β-O-4 substructure unit predominated. Lignin and carbohydrates were mainly connected by acetal bonds, ether bonds, and ester bonds. Combined with the carbohydrate composition and XRD analysis results, the GL components also confirmed the existence of acetal bonds, ester bonds and ether bonds between lignin and cellulose., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier B.V.)

Due to the poor enzyme thermal stability, the efficient conversion of high crystallinity cellulose into glucose in aqueous phase over 50 °C is challenging. Herein, an enzyme-induced MOFs encapsulation of β-glucosidase (β-G) strategy was proposed for the first time. By using various methods, including SEM, XRD, XPS, NMR, FTIR and BET, the successful preparation of a porous channel-type flower-like enzyme complex (β-G@MOFs) was confirmed. The prepared enzyme complex (β-G@MOFs) materials showed improved thermal stability (from 50 °C to 100 °C in the aqueous phase) and excellent resistance to ionic liquids (the reaction temperature was as high as 110 °C) compared to the free enzyme (β-G). Not only the catalytic hydrolysis of cellulose by single enzyme (β-G) in ionic liquid was realized, but also the high-temperature continuous reaction performance of the enzyme was significantly improved. Benefiting from the significantly improved heat resistance, the β-G@MOFs exhibited 32.1 times and 34.2 times higher enzymatic hydrolysis rate compared to β-G for cellobiose and cellulose substrates, respectively. Besides, the catalytic activity of β-G@MOFs was retained up to 86 % after five cycles at 110 °C. This was remarkable because the fixation of the enzyme by the MOFs ensured that the folded structure of the enzyme would not expand at high temperatures, allowing the native conformation of the encapsulated protein well-maintained. Furthermore, we believe that this structural stability was caused by the confinement of flower-like porous MOFs., (© 2022 Wiley-VCH GmbH.)

In this work, nitrogen and phosphorus dual-doped alkali lignin-based carbon microspheres (MLCM) were prepared by pre-oxidation and carbonization of ionic liquid ([Mmim]DMP) -lignin solution and used as green-based supercapacitor electrode materials. Compared with the directly carbonized alkali lignin carbon (LC), MLCM had a spherical structure with higher specific surface area (938.1 m 2 /g) and pore volume (0.64 cm 3 /g). Moreover, MLCM materials showed superior electrochemical performance. In the 1 mol/L H 2 SO 4 electrolyte system, MLCM presented the highest specific capacitance of 338.2F/g at a current density of 0.8 A/g. Furthermore, MLCM was used as a positive and negative electrode material to assemble a symmetrical supercapacitor. The resultant device maintained excellent cycle stability after 5000 times of charging and discharging process at 2 A/g. Overall, the facile, green and sustainable synthesis strategy of heteroatom-doped porous carbon microspheres developed in this work opens a new avenue for the fabrication of high-performance carbon electrode materials, especially based on abundant and renewable lignin., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Cellulose conversion into 5-hydroxymethylfurfural (5-HMF) is difficult because of the strong hydrogen bonding existed in cellulose chains. Brønsted/Lewis (B/L) biacidic functionalized ionic liquids (ILs) have great advantages in acid-catalyzed tandem reactions, but the catalytic effect of ILs differs considerably depending on B/L acid ratios. Therefore, this work designed a series of reactions with different proportions of biacidic ILs for the preparation of 5-HMF from cellulose. The tandem reaction is often performed in the presence of a solvent, and the activity of the catalyst is also affected by the solvent. Therefore, in this work, the solvation model density(SMD) model was introduced into the quantum chemical calculation method for molecular design to predict the catalytic effect and explore the catalytic mechanism. The calculation results and experiments jointly showed that [(HSO 3 -P) 2 im]Cl·ZnCl 2 had the highest efficiency, with a 5-HMF yield of 65.66%. This study facilitates the directional optimization design of the catalyst., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Lignocellulosic biomass is mainly composed of polysaccharides and lignin. The complexity and diversity of the plant cell wall polymers makes it difficult to isolate the components in pure form for characterization. Many current approaches to analyzing the structure of lignocellulose, which involve sequential extraction and characterization of the resulting fractions, are time-consuming and labor-intensive. The present study describes a new and facile system for rationally derivatizing and dissolving coarsely ground plant cell wall materials. Using ionic liquids (EmimAc) and dichloroacetyl chloride as a solvent/reagent produced mildly acetylated whole cell walls without significant degradation. The acetylated products were soluble in DMSO- d 6 from which they can be characterized by solution-state two-dimensional nuclear magnetic resonance (2D NMR) spectrometry. A distinct advantage of the procedure is that it realizes the dissolution of whole lignocellulosic materials without requiring harsh ball milling, thereby allowing the acquisition of high-resolution 2D NMR spectra to revealing structural details of the main components (lignin and polysaccharides). The method is therefore beneficial to understanding the composition and structure of biomass aimed at its improved utilization.

Lignocellulosic hydrogels are valuable bio-products that have been considered widely in recent investigations. Also, application of low value recycled fibers for high value added products can be of much interest. In this respect, current research has focused on producing hydrogel from recycled old corrugated container (OCC) resources, using 1-butyl-3-methyl-imidazolium chloride ionic liquid (IL) as a green solvent. The results indicated that the IL successfully dissolved OCC fibers, allowing the production of lignocellulosic hydrogel. Considering total water absorption amount as a main criterion for evaluation of hydrogels, the fabricated hydrogel showed promising results (up to 4700% water absorption). X-ray diffraction analysis confirmed obvious reduction in cellulose material crystallinity and crystallite size as a result of the process. Field emission scanning electron microscopy also demonstrated the microstructure of the hydrogel, pore size and shape in the hydrogel, which well supported the laboratory research results. Furthermore, the effect of processing parameters showed that specimens washed with distilled water as the anti-solvent resulted in the highest water absorption. Infrared spectroscopy can be used to suggest the presence of more lignin content in the hydrogel washed with ethanol. Moreover, the best water re-absorption results were observed for the hydrogel washed with distilled water., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

A novel mind-set, termed lignin-first biorefinery, is bewitching to synchronously boost lignin output for entirely lignocellulosic utilization. A lignin-first fractionation, using a food-additive derived ionic liquid (1-ethyl-3-methylimidazolium acesulfamate, emimAce) and mild alkaline pretreatments, was formed for the purposely isolating poplar lignin, whilst delivering a cellulose-rich substrate that can be easily available for enzymatic digestion. The emimAce-driven lignin, alkali-soluble lignin and hemicellulose, and accessible cellulose were sequentially gained. We introduce a lignin-first approach to extract the amorphous fractions, destroy the robust architecture, and reform cellulose-I to II, thereby advancing the cellulose bioconversion from 15.4 to 90.5%. A harvest of 70.7% lignin, 52.1% hemicellulose, and 330.1 mg/g glucose was fulfilled from raw poplar. A structural ''beginning-to-end'' analysis of lignin inferred that emimAce ions are expected to interact with lignin β-aryl-ether due to their aromatic character. It was reasonable to derive benefits from lignin-first technique that can substantially augment the domain of biorefinering., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

An alternative transesterification with vinyl laurate (VL) was applied for chemical modification of hemicelluloses (HC) to prepare functional packaging films. Successful transesterification was confirmed by FT-IR and NMR. Semitransparent laurated HC (LHs) films were prepared by solvent casting method. SEM indicated the ordered honeycomb-patterned surface and the dense cross section of LHs films. The LHs films exhibited excellent hydrophobicity with water contact angle about 120° and the enhanced mechanical properties with tensile strength and elongation at break as 33.94 ± 3.09 MPa and 22.41 ± 2.87%, respectively. The water vapor permeability (WVP) and oxygen permeability (OP) values of LHs films ranged from 1.59 ± 0.07 to 2.23 ± 0.11 (10 -10 ·g/m·s·Pa) and 1.21 ± 0.04 to 4.24 ± 0.30 (cm 3 ·μm/m 2 ·d·kPa), respectively. Moreover, the films had acceptable antioxidant activity. In terms of these properties, the shelf life of green chilies could be largely extended to 15 days after packing with LHs films., (Copyright © 2019. Published by Elsevier Ltd.)

This study evaluated the solubility of low-processed wood fibers produced from a low temperature acid hydrotropic fractionation (AHF) in an ionic liquid (IL) 1,5-diazabicyclo[4.3.0]non-5-enium acetate (DBNH[OAc]. Unbleached wood fibers produced from AHF using p-Toluenesulfonic acid (p-TsOH) with or without post-treatments with lignin and hemicelluloses content up to 15% and 25%, respectively, were dissolved directly into the IL DBNH[OAc]. Post-AHF treatments using dilute alkaline and glycerol swelled the cellulose and partially removed residual lignin resulting in improved dissolution. Semi-quantitative 2D HSQC NMR analyses revealed that the undissolved wood fiber residues were enriched with G units and condensed S units (S cond ), demonstrating, as expected, that G units and condensed lignin substructures have a negative effect on dissolution in DBNH[OAc]. Therefore, AHF with rapid fractionation at low temperatures offers a promising advantage over existing high temperature pulp dissolving fiber (PDF) processes in terms of reducing energy input, lowering lignin content as well as reducing lignin condensation for producing man-made cellulosic fibers (MMCF)., (Published by Elsevier B.V.)

To overcome the natural recalcitrance of cellulose for glucose production in aqueous media catalyzed by enzyme, in this study, a dissolution pretreatment strategy was developed by using in situ formed CO 2 -based reversible ionic compounds (RICs)/DMSO mixed organic electrolytes under mild conditions. The influences of the constitution of RICs, CO 2 pressure, dissolution pretreatment time on the physic-chemical structure of cellulose were investigated systematically by FTIR, XRD, SEM, AFM towards in-depth understanding of the correlations between the pretreatment conditions, micro-scale structure and enzymatic saccharification of cellulose. The results showed that the tetramethyl guanidine (TMG) based RICs solvent system [TMGH] 2 + [O 2 COCH 2 CH 2 OCO 2 ] 2- /DMSO (X RICs  = 0.1, X RICs : the mole fraction of the formed RICs in the mixture) presented the best performance, which was evidenced by 100% glucose yield after the dissolution-regeneration pretreatment strategy under mild conditions (T = 60 °C, Pco 2  = 2.0 MPa, t = 2 h). Furthermore, the solvent system have good recyclability and usability., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

It has been well known that laccases can directly or indirectly catalyze oxidation of a broad species of phenols, amines and many other electron donor substrates. However, laccases as biocatalyst in "green" ionic liquids (ILs) media instead of conventional solvents are less known and regarded as an innovative research direction. The presence of ILs can either inhibit or stimulate laccase activity, strongly depending on water-miscibility and kosmotropic natures of ILs. In addition, enzyme source, mediator, pH as well as water content are very important factors which influence laccase activity and stability. Therefore, elucidation of mechanisms underlying the interactions between laccases and ILs will facilitate to screen ILs with excellent laccase compatibility. Strategies based on molecular evolution, enzyme immobilization and/or ILs modification greatly increase the tolerance of laccases against specific ILs. The use of ILs can spread the laccase applications in fields of biosynthesis, biodegradation, biosensor and biofuel cells. This article summarizes the recent progress, trends and problems in this field and focuses, in particular, on the stimulation of laccase activity in aqueous ILs media., (Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.)

A new functional biopolymer was synthesized through an ionic liquid-mediated homogeneous grafting of cinnamic anhydride to xylans. The ionic liquid used was 1-allyl-3-methylimidazolium chloride (AMIMCl) ionic liquid. Xylans with degrees of substitution (DS) between 0.11 and 0.57 were accessible in a completely homogeneous system by changing catalysts (NaOH, KOH and LiOH), time, reaction temperature, and cinnamic anhydride/xylan molar ratio. The chemical structure and the thermal stability of the derivatives were characterized by Fourier transform infrared spectroscopy (FT-IR), 13 C-NMR spectroscopy, and thermogravimetry. The thermal stability of the derivatives was reduced compared with the original xylan. Possible applications of the cinnamic anhydride-acylated xylan derivatives include wet-end papermaking, organic-inorganic composite films, and hydrogels., Competing Interests: The authors declare no conflict of interest.

Water-miscible alkylimidazolium ionic liquids (ILs) are "green" co-solvents for laccase catalysis, but generally inhibit enzyme activity. Here, we present novel insights into inhibition mechanisms by a combination of enzyme kinetics analysis and molecular simulation. Alkylimidazolium cations competitively bound to the T I Cu active pocket in the laccase through hydrophobic interactions. Cations with shorter alkyl chains (C₂~C₆) entered the channel inside the pocket, exhibiting a high compatibility with laccase (competitive inhibition constant K ic = 3.36~3.83 mM). Under the same conditions, [Omim]Cl (K ic = 2.15 mM) and [Dmim]Cl (K ic = 0.18 mM) with longer alkyl chains bound with Leu296 or Leu297 near the pocket edge and Leu429 around T I Cu, which resulted in stronger inhibition. Complexation with alkylimidazolium cations shifted the pH optima of laccase to the right by 0.5 unit, and might, thereby, lead to invalidation of the Hofmeister series of anions. EtSO₄ - showed higher biocompatibility than did Ac - or Cl - , probably due to its binding near the T I Cu and its hindering the entry of alkylimidazolium cations. In addition, all tested ILs accelerated the scavenging of 2, 2'-azino-bis-(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS) radicals, which, however, did not play a determining role in the inhibition of laccase., Competing Interests: The authors declare no conflict of interest. The founding sponsors had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, and in the decision to publish the results.

Combining template immobilization with surface imprinting technology is an effective strategy to overcome the difficulties associated with macromolecular template removal and to achieve high specific recognition ability. In this work, ionic liquid functionalized Fe 3 O 4 nanoparticles were prepared via a simple two-step modification process and were used as substrate to immobilize bovine serum albumin (BSA). The zeta potential study revealed immobilization of BSA on the nanoparticles through multiple interactions, and the immobilization capacity was about nine times higher compared with that of bare Fe 3 O 4 . Subsequently, dopamine was utilized as functional monomer to prepare BSA surface imprinted nanoparticles. Fourier transform infrared spectroscopy, thermo-gravimetric analysis and transmission electron microscopy verified the successful preparation of BSA imprinted nanoparticles with core-shell structure. The influence of imprinted layer thickness on recognition ability of imprinted nanoparticles was investigated, and the results suggested that 20nm was an optimum thickness to achieve the best recognition ability. The adsorption isotherm studies showed that the imprinted nanoparticles had a significantly higher adsorption capacity and stronger binding affinity than the non-imprinted ones. Furthermore, the selective as well as the competitive adsorption studies revealed higher selectivity and recognition ability of the imprinted nanoparticles for BSA. Therefore, the proposed strategy is an effective way to obtain protein imprinted polymers with high adsorption capacity and good recognition ability, thus would be beneficial for the further development and application of protein imprinting technology., (Copyright © 2017 Elsevier B.V. All rights reserved.)

An efficient one-pot approach for the production of levulinate ester from renewable carbohydrates is demonstrated over heteropolyanion-based ionic liquid (IL-POM) catalysts with alcohols as the promoters and solvents. The relationships between the structure, acidic strength, and solubility of the IL-POM in methanol and the catalytic performance were studied intensively. A cellulose conversion of 100 % could be achieved with a 71.4 % yield of methyl levulinate over the catalyst [PyPS] 3 PW 12 O 40 [PyPS=1-(3-sulfopropyl)pyridinium] at 150 °C for 5 h. This high efficiency is ascribed to the reasonably high activity of the ionic liquid (IL) catalyst and reaction coupling with rapid in situ esterification of the generated levulinic acid with the alcohol promoter, which allows the insolubility of cellulose encountered in biomass conversion to be overcome. Furthermore, the present process exhibits high feedstock adaptability for typical carbohydrates and handy catalyst recovery by a simple self-separation procedure through temperature control., (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Herein, the oxidative ionic liquid (IL) pretreatment for overcoming recalcitrance of lignocellulose with selective delignification was investigated, and the subsequent enzymatic hydrolysis was evaluated. IL pretreatment incorporating oxygen delignification could enhance lignin extraction with high selectivity at low carbohydrate loss. The dual-action of oxidative decomposition and dissolution by 1-butyl-3-methlimidazolium chloride (BmimCl) on biomass were synergistically acted, accounting for efficient recalcitrance removal. In addition, the mild oxidative IL treatment only slightly converted crystalline cellulose into amorphous structure, and the extensive extraction of the amorphous lignin and carbohydrate resulted to the expose of cellulose with high susceptibility. Correspondingly, the enzymatic hydrolysis of the pretreated lignocellulose was greatly enhanced. The oxidative IL treatment at mild conditions, collaborating BmimCl treatment with oxygen delignification is a promising and effective system for overcoming the robust structure of lignocellulose., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The efficient anti-Prelog asymmetric reduction of 2-octanone with Acetobacter pasteurianus GIM1.158 cells was successfully performed in a biphasic system consisting of deep eutectic solvent (DES) and water-immiscible ionic liquid (IL). Various DESs exerted different effects on the synthesis of (R)-2-octanol. Choline chloride/ethylene glycol (ChCl/EG) exhibited good biocompatibility and could moderately increase the cell membrane permeability thus leading to the better results. Adding ChCl/EG increased the optimal substrate concentration from 40 mM to 60 mM and the product e.e. kept above 99.9%. To further improve the reaction efficiency, water-immiscible ILs were introduced to the reaction system and an enhanced substrate concentration (1.5 M) was observed with C4MIM·PF6. Additionally, the cells manifested good operational stability in the reaction system. Thus, the efficient biocatalytic process with ChCl/EG and C4MIM·PF6 was promising for efficient synthesis of (R)-2-octanol.

During the manufacturing of pharmaceutical compounds, solvent mixtures are commonly used, where the addition of a cosolvent allows for the tuning of the intermolecular interactions present in the system. Here we demonstrate how a similar effect can be accomplished using a room temperature ionic liquid. The pharmaceutical compound acetaminophen is studied in 21 common ionic liquids composed of a 1-n-alkyl-3-methylimidazolium cation with 1 of 7 anions. Using the acetate anion, we predict a large enhancement in solubility of acetaminophen relative to water. We show how this is caused by a synergistic effect of favorable interactions between the ionic liquid and the phenyl, hydroxyl and amide groups of acetaminophen, demonstrating how the ionic liquid cation and anion may be chosen to preferentially solvate different functional groups of complex pharmaceutical compounds. Additionally, while the use of charge scaling in ionic liquid force fields has previously been found to have a minute effect on ionic liquid structural properties, we find it appreciably affects the computed solvation free energy of acetaminophen, which in turn affects the predicted solubility.

Room temperature ionic liquids have been proposed as replacement solvents in a wide range of industrial separation processes. Here, we focus on the use of ionic liquids as solvents for the pharmaceutical compound lidocaine. We show that the solubility of lidocaine in seven common 1-n-butyl-3-methylimidazolium based ionic liquids is greatly enhanced relative to water. The predicted solubility is greatest in [BMIM](+)[CH3CO2](-), which we find results from favorable hydrogen bonding between the lidocaine amine hydrogen and the [CH3CO2](-) oxygen, favorable electrostatic interactions between the lidocaine amide oxygen with the [BMIM](+) aromatic ring hydrogens, while lidocaine does not interfere with the association of [BMIM](+) with [CH3CO2](-). Additionally, by removing functional groups from the lidocaine scaffold while maintaining the important amide group, we found that as the van der Waals volume increases, solubility in [BMIM](+)[CH3CO2](-) relative to water increases.

Solid acid-enhanced ionic liquid (IL) pretreatment is of paramount importance for boosting the yield of sugars from biomass cost-effectively and environmentally friendly. To unravel the chemical and supramolecular structural changes of lignin after pretreatment, IL-acid lignin (ILAL) and subsequent residual cellulolytic enzyme lignin (RCEL) were isolated from Arundo donax Linn. The structural features were compared with those of the corresponding milled wood lignin (MWL). Results indicated that the pretreatment caused loss of β-O-4', β-β', β-1' linkages and formation of condensed structures in lignin. A preferential breakdown of G-type lignin may have occurred, evidenced by an increased S/G ratio revealed by 2D HSQC NMR analysis. It was determined that the depolymerization of β-O-4' linkage, lignin recondensation, and cleavage of ferulate-lignin ether linkages took place. Moreover, a simulation module was first developed to define morphological changes in lignin based on AFM and TEM analyses. Briefly, tree branch like aggregates was destroyed to monodisperse particles.

Pretreatment of lignocelluloses is a key step in the biorefinery for production of biofuels and valuable platform chemicals. In this work, various lignocelluloses were pretreated using cholinium ionic liquids (ILs) that are wholly composed of biomaterials, and fractionated into carbohydrate-rich materials (CRMs) and lignin-rich materials (LRMs). Cholinium ILs were found to be effective pretreatment solvents for grass lignocelluloses as well as eucalyptus, resulting in significant improvements in the glucose yields (58-75%) in subsequent enzymatic hydrolysis, while they were inefficient to make pine susceptible to biodegradation. Approximately 46% of lignin in native rice straw was fractionated as LRM after pretreatment using cholinium argininate ([Ch][Arg]). [Ch][Arg] showed excellent recyclability, and the total recovery was as high as 75% after reused for 8 cycles. Besides, rice straw pretreated by the recycled IL remained highly digestible, and good glucose yields (63-75%) were achieved after its enzymatic hydrolysis., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

With the serious "white pollution" resulted from the non-biodegradable plastic films, considerable attention has been directed toward the development of renewable and biodegradable cellulose-based film materials as substitutes of petroleum-derived materials. In this study, environmentally friendly cellulose films were successfully prepared using different celluloses (pine, cotton, bamboo, MCC) as raw materials and ionic liquid 1-ethyl-3-methylimidazolium acetate as a solvent. The SEM and AFM indicated that all cellulose films displayed a homogeneous and smooth surface. In addition, the FT-IR and XRD analysis showed the transition from cellulose I to II was occurred after the dissolution and regeneration process. Furthermore, the cellulose films prepared by cotton linters and pine possessed the most excellent thermal stability and mechanical properties, which were suggested by the highest onset temperature (285°C) and tensile stress (120 MPa), respectively. Their excellent properties of regenerated cellulose films are promising for applications in food packaging and medical materials., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

The amidine organocatalyst 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) is an effective nucleophilic catalyst. Biocomposites with tuneable properties were successfully synthesized by ring-opening graft polymerization (ROGP) of propylene carbonate (PC) onto xylan using DBU as a catalyst in the ionic liquid (IL) 1-allyl-3-methylimidazolium chloride ([Amim]Cl). The effects of reaction temperature, reaction time and the molar ratio of PC to anhydroxylose units (AXU) in xylan were investigated. The physico-chemical properties of xylan-graft-poly(propylene carbonate) (xylan-g-PPC) copolymers were characterised by FT-IR, NMR, TGA/DTG, AFM and tensile analysis. The FT-IR and NMR results indicated the successful attachment of PPC onto xylan. TGA/DTG suggested the increased thermal stability of xylan after the attachment of PPC side chains. AFM analysis revealed details about the molecular aggregation of xylan-g-PPC films. The results also showed that with the increased DS of xylan-g-PPC copolymers, the tensile strength and Young's modulus of the films decreased, while the elongation at break increased.

In this work, 28 cholinium ionic liquids (ILs), most of which are good solvents for dissolving lignin, were used for rice straw pretreatment to improve subsequent enzymatic hydrolysis. The anion exerted a significant effect on the pretreatment effectiveness of the IL as well as the subsequent enzymatic hydrolysis efficiency of rice straw residues. The presence of the basic group(s) in the anion significantly enhanced the IL pretreatment effectiveness, while the carboxyl, hydroxyl and aromatic groups had a negative impact on IL delignification. Except for amino acid-based ILs, the delignification abilities of the ILs are linearly and positively correlated with the pKa values of the conjugate acids of the anions. Of the ILs tested, amino acid-based ILs, especially basic amino acid-based ILs, are the most effective pretreatment solvents. Satisfactory reducing sugar yields (81% for glucose and 26% for xylose) were obtained in the enzymatic hydrolysis of rice straw pretreated by cholinium argininate ([Ch][Arg]) under a pretty mild pretreatment severity (60°C, 6 h). The results presented in this work may be useful for rational design of novel and green ILs for delignification of lignocellulose., (© 2014 Wiley Periodicals, Inc.)

The present study investigated the impact of regeneration process on the crystalline structure and enzymatic hydrolysis behaviors of microcrystalline cellulose (MCC) regenerated from ionic liquid 1-butyl-3-methylimidazolium chloride. The crystalline structures of these regenerated samples were analyzed by X-ray diffraction. Results suggested that almost amorphous cellulose was obtained by regenerating MCC in acetone (DRC-a), while partial cellulose II structure could be found in these regenerated samples from water and ethanol. Additionally, the enzymatic hydrolysis behaviors of MCC and its regenerated samples were comparatively studied. Results showed that above 90% of cellulose could be converted into glucose within 4h for DRC-a and regenerated cellulose without drying (WRC-w) as compared to that of MCC (9.7%). Therefore, the regeneration process could significantly influence the crystallinity and digestibility of cellulose., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Background: The use of biocatalysts has become an increasingly attractive alternative to traditional chemical methods, due to the high selectivity, mild reaction conditions and environmentally-friendly processes in nonaqueous catalysis of nucleosids. However, the extensive use of organic solvents may generally suffer from sever drawbacks such as volatileness and toxicity to the environment and lower activity of the biocatalyst. Recently, ionic liquids are considered promising solvents for nonaqueous biocatalysis of polyhydroxyl compounds as ILs are environmental-friendly., Results: In this research, we developed new IL-containing reaction systems for synthesis of long chain nucleoside ester catalyzed by Pseudomonas fluorescens whole-cells. Various ILs exerted significant but different effects on the bio-reaction. And their effects were closely related with both the anions and cations of the ILs. Use of 10% [BMI][PF6]/THF gave high reaction efficiency of arabinocytosine laurate synthesis, in which the initial rate, product yield and 5'-regioselectivity reached 2.34 mmol/L·h, 81.1% and >99%, respectively. Furthermore, SEM analysis revealed that ILs can alter the cell surface morphology, improve the permeability of cell envelopes and thus facilitate the mass transfer of substrates to the active sites of cell-bound enzymes., Conclusion: Our research demonstrated the potential of ILs as promising reaction medium for achieving highly efficient and regioselective whole-cell catalysis.

A facile method is reported to prepare Maillard reaction products (MRPs) from chitosan and xylan in co-solvent ionic liquid. UV absorbance and fluorescence changes were regarded as indicators of the occurrence of Maillard reaction. FT-IR, NMR, XRD and TG were used to investigate the structure of chitosan-xylan conjugate. The results revealed that when chitosan reacted with xylan in ionic liquid, the hydrogen bonds in chitosan were destroyed, the facts resulted in the formation of chitosan-xylan MRPs. Moreover, when the mass ratio of chitosan to xylan was 1:1, the Maillard reaction proceeded easily. In addition, relatively high antioxidant property was also noted for the chitosan-xylan conjugate with mass ratio 1:1. So the obtained chitosan-xylan MRP is a promising antioxidant agent for food industry., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Pretreatment of rice straw by using renewable cholinium amino acids ionic liquids ([Ch][AA] ILs)-water mixtures and the subsequent enzymatic hydrolysis of the residues were conducted in the present work. Of the eight mixtures composed of ILs and water, most were found to be effective for rice straw pretreatment. After pretreatment with 50% ILs-water mixtures, the enzymatic digestion of the lignocellulosic biomass was enhanced significantly, thus leading to satisfactory sugar yields of >80% for glucose and approximately 50% for xylose. To better understand the ILs pretreatment mechanism, confocal laser scanning microscopy combined with immunolabeling and transmission electron microscopy were used to visualize changes in the contents and distribution of two major components--lignin and xylan. The results coupled with changes in chemical structures (infrared spectra) of the substrates indicated occurrence of extensive delignification, especially in cell corner and compound middle lumen of cell walls, which made polysaccharides more accessible to enzymes. This pretreatment process is promising for large-scale application because of the high sugar yields, easy handling, being environmentally benign and highly tolerant to moisture, and significantly reduced cost and energy consumption., (Copyright © 2013 Wiley Periodicals, Inc.)

In this study two imidazole-based ionic liquids (ILs), namely 1-butyl-3-methyl-1-imidazolium chloride ([BMIM]Cl) and 1,3-methyl imidazolium dimethyl sulfate ([DiMIM][MeSO4]), were used to dissolve ball-milled poplar wood (PW), chemi-mechanical pulp (CMP), and cotton linter (CEL). A set of comparative experiments was carried out, and physical and mechanical properties of the composite films from three different raw materials were determined by means of optical transparency (OT), scanning electron microscopy (SEM), water absorption (WA), thickness swelling (TS), water vapor permeability (WVP), and tensile strength (σb). The overall evaluation indicates the inability of [DiMIM][MeSO4] in complete dissolution of lignocellulosic materials, and sample treatment with this solvent did not lead to water soluble degradation products. However, dissolution trials using [BMIM]Cl were able to dissolve all used lignocellulosic materials by destroying inter and intramolecular hydrogen bonds between lignocelluloses. The OT, WA, TS, and σb of regenerated CEL films were much higher than those of CMP and PW composites. In addition, CEL film showed the lowest WVP compared to WF and CMP composite films. This work demonstrated a promising route for the preparation of biodegradable green cellulose composite films., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Pretreatment of rice straw by using renewable cholinium lysine ionic liquid ([Ch][Lys] IL)-water mixtures and subsequent enzymatic hydrolysis of the residues were conducted in this work. There is a clear correlation between the delignification capacity of the pretreatment solvent and its basicity. After pretreatment, surface area and pore volume of rice straw increased significantly, which substantially improved polysaccharides accessibility to enzymes and thus enhanced polysaccharides digestion. By carefully controlling the pretreatment severity (IL content, temperature and duration), loss of readily extractable xylan could be minimized. The sugar yields of 81% for glucose and 48% for xylose were achieved in the enzymatic hydrolysis of rice straw after pretreatment with 20% [Ch][Lys]-water mixture at 90 °C for 1 h. This pretreatment process is highly promising for industrial application because of high sugar yields, low energy input, short pretreatment time, and being environmentally benign and highly tolerant to moisture., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Imidazolium-based ionic liquids (ILs), including 1-butyl-3-methylimidazolium chloride (BmimCl) and 1-allyl-3-methylimidazolium chloride (AmimCl), were used to improve the refining properties of pulps under mild conditions. Results showed that the macro appearance of pulps was virtually unchanged after pretreatment with ILs under mild conditions. In addition, chemical pulps pretreated with ILs are more suitable for pretreatment than chemimechanical pulps. Pretreatment with ILs facilitates the refining process by destroying hydrogen bonds, which exist extensively in fiber. At the same refining energy input, the Canada standard freeness (CSF) of refined pulp decreased with improved fiber quality. At identical CSF values, the energy consumed during refining significantly decreased because ILs pretreatment facilitated swelling and fibrillation. The viscosity of cellulose changed slightly after IL pretreatment. However, the crystallinity index and fines content decreased, and the micro appearance of the fiber surface changed. BmimCl has a stronger swelling influence on pulp than AmimCl under optimal conditions., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Cholinium amino acid ionic liquids ([Ch][AA] ILs), which are wholly composed of renewable biomaterials, have recently been demonstrated to have very promising properties for applications in organic synthesis and biomass pretreatment. In this work, the toxicity of these ILs toward enzymes and bacteria was assessed, and the effect of the anion on these properties is discussed. The inhibitory potentials of this type of ILs to acetylcholinesterase were weaker approximately an order of magnitude than the traditional IL 1-butyl-3-methylimidazolium tetrafluoroborate. Additionally, the [Ch][AA] ILs displayed low toxicity toward the bacteria tested. Furthermore, the biodegradability of the [Ch][AA] ILs was evaluated via the closed bottle and CO(2) headspace tests using wastewater microorganisms. All the ILs were classified as 'readily biodegradable' based on their high levels of mineralization (62-87%). The presence of extra carboxyl or amide groups on the amino acid side chain rendered the ILs significantly more susceptible to microbial breakdown. In addition, for most of the [Ch][AA] ILs, low toxicity correlated with good biodegradability. The low toxicity and high biodegradability of these novel [Ch][AA] make them promising candidates for use as environmentally friendly solvents in large-scale applications.

A comparative study was made of Mung bean epoxide hydrolases-catalyzed asymmetric hydrolysis of styrene oxide to (R)-1-phenyl-1,2-ethanediol in an n-hexane/buffer biphasic system containing various hydrophilic ionic liquids (ILs). Compared to the n-hexane/buffer biphasic system alone, addition of a small amount of hydrophilic ILs reduced the amount of non-enzymatic hydrolysis, and improved the reaction rate by up to 22%. The ILs with cation containing an alkanol group, namely [C(2)OHMIM][BF(4)] and [C(2)OHMIM][TfO], and the choline amino acid ILs [Ch][Arg] and [Ch][Pro] were found to be the most suitable co-solvents for the reaction, owing to their good biocompatibility with the enzyme, which led to high initial rates (0.99-1.25 μmol/min) and high product e.e.s (95%). When substrate concentration was around 30 mM, where optimal performance was observed with the IL-containing systems, the product e.e. was improved from 90% without ILs to ≥95% in the presence of ILs., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Cholinium amino acids ionic liquids ([Ch][AA] ILs), a novel type of bio-ILs that can easily be prepared from renewable biomaterials, were investigated for pretreatment of rice straw by selective extraction of lignin from this abundant lignocellulosic biomass material. Of the eight ILs examined, most were demonstrated to be excellent pretreatment solvents. Upon pretreatment using these ILs, the initial saccharification rates of rice straw residues were substantially improved as well as the extent to which polysaccharides could be digested (>90% for cellulose and >60% for xylan). Enzymatic hydrolysis of pretreated rice straw by Trichoderma reesei cellulase/xylanase furnished glucose and xylose with the yields in excess of 80% and 30%, respectively. Detailed spectroscopic characterization showed that the enhancement of polysaccharides degestibility derived mainly from delignification rather than changes in cellulose crystallinity. The yields of fermentable reducing sugars were significantly improved after individual optimization of pretreatment temperature and duration. With [Ch][Lys] as the solvent, the sugar yields of 84.0% for glucose and 42.1% for xylose were achieved after pretreatment at 90°C for 5 h. The IL [Ch][Lys] showed excellent reusability across five successive batches in pretreatment of rice straw. These bio-ILs performed as well as or better than previously investigated non-renewable ILs, and thus present a new and environmentally friendly way to pretreat lignocellulose for production of fermentable sugars and total utilization of the biomass., (Copyright © 2012 Wiley Periodicals, Inc.)

The ability to accurately and rapidly measure plant cell wall composition, relative monolignol content and lignin-hemicellulose inter-unit linkage distributions has become essential to efforts centered on reducing the recalcitrance of biomass by genetic engineering. Growing (13)C enriched transgenic plants is a viable route to achieve the high-throughput, detailed chemical analysis of whole plant cell wall before and after pretreatment and microbial or enzymatic utilization by (13)C nuclear magnetic resonance (NMR) in a perdeuterated ionic liquid solvent system not requiring component isolation. 1D (13)C whole cell wall ionic liquid NMR of natural abundant and (13)C enriched corn stover stem samples suggest that a high level of uniform labeling (>97%) can significantly reduce the total NMR experiment times up to ~220 times. Similarly, significant reduction in total NMR experiment time (~39 times) of the (13)C enriched corn stover stem samples for 2D (13)C-(1)H heteronuclear single quantum coherence NMR was found.

Background: Biocatalytic asymmetric reductions with whole cells can offer high enantioselectivity, environmentally benign processes and energy-effective operations and thus are of great interest. The application of whole cell-mediated bioreduction is often restricted if substrate and product have low water solubility and/or high toxicity to the biocatalyst. Many studies have shown that a biphasic system is often useful in this instance. Hence, we developed efficient biphasic reaction systems with biocompatible water-immiscible ionic liquids (ILs), to improve the biocatalytic anti-Prelog enantioselective reduction of acetyltrimethylsilane (ATMS) to (R)-1-trimethylsilylethanol {(R)-1-TMSE}, which is key synthon for a large number of silicon-containing drugs, using immobilized Candida parapsilosis CCTCC M203011 cells as the biocatalyst., Results: It was found that the substrate ATMS and the product 1-TMSE exerted pronounced toxicity to immobilized Candida parapsilosis CCTCC M203011 cells. The biocompatible water-immiscible ILs can be applied as a substrate reservoir and in situ extractant for the product, thus greatly enhancing the efficiency of the biocatalytic process and the operational stability of the cells as compared to the IL-free aqueous system. Various ILs exerted significant but different effects on the bioreduction and the performances of biocatalysts were closely related to the kinds and combination of cation and anion of ILs. Among all the water-immiscible ILs investigated, the best results were observed in 1-butyl-3-methylimidazolium hexafluorophosphate (C(4)mim·PF(6))/buffer biphasic system. Furthermore, it was shown that the optimum substrate concentration, volume ratio of buffer to IL, buffer pH, reaction temperature and shaking rate for the bioreduction were 120 mM, 8/1 (v/v), 6.0, 30°C and 180 r/min, respectively. Under these optimized conditions, the initial reaction rate, the maximum yield and the product e.e. were 8.1 μmol/min g(cwm), 98.6% and >99%, respectively. The efficient whole-cell biocatalytic process was shown to be feasible on a 450-mL scale. Moreover, the immobilized cells remained around 87% of their initial activity even after being used repeatedly for 8 batches in the C(4)mim·PF(6)/buffer biphasic system, exhibiting excellent operational stability., Conclusions: For the first time, we have successfully utilized immobilized Candida parapsilosis CCTCC M203011 cells, for efficiently catalyzing anti-Prelog enantioselective reduction of ATMS to enantiopure (R)-1-TMSE in the C(4)mim·PF(6)/buffer biphasic system. The substantially improved biocatalytic process appears to be effective and competitive on a preparative scale.

Hydrophilic ionic liquids (ILs) were employed as green solvents to construct an IL-containing co-solvent system for improving the asymmetric reduction of 4-(trimethylsilyl)-3-butyn-2-one by immobilized Candida parapsilosis cells. Among 14 hydrophilic ILs examined, 1-(2'-hydroxyl)ethyl-3-methylimidazolium nitrate (C(2)OHMIM·NO(3)) was considered as the most suitable IL for the bioreduction with the fastest initial reaction rate, the highest yield and the highest product e.e., which may be due to the good biocompatibility with the cells. For a better understanding of the bioreduction performed in the C(2)OHMIM·NO(3)-containing co-solvent system, the effects of several crucial variables were systematically investigated. The optimal C(2)OHMIM·NO(3) content, substrate concentration, buffer pH, co-substrate concentration and temperature were 10% (v/v), 3.0 mmol/L, 5.0, 98.1 mmol/L and 30°C, respectively. Under the optimal conditions, the initial reaction rate, the maximum yield and the product e.e. were 17.3 µmol/h g(cell), 95.2% and >99.9%, respectively, which are much better than the corresponding results previously reported. Moreover, the immobilized cells remained more than 83% of their initial activity even after being used repeatedly for 10 batches in the C(2)OHMIM·NO(3)-containing system, exhibiting excellent operational stability.

All-cellulose nanocomposite was directly fabricated using nanowelding of cellulose microfibers as a starting material, in 1-butyl-3-methylimidazolium chloride (BMIMCl) as a solvent, for the first time. The average diameter of the reinforcing component (undissolved nanofibrils) in the nanocomposite made directly from cellulose microfibers (NC-microfiber) was 53 ± 16 nm. Owing to its high mechanical properties (tensile strength of 208 MPa and Young's modulus of 20 GPa), high transparency (76% at a wavelength of 800 nm), and complete barrier to air and biodegradability, the NC-microfiber is regarded as a high multiperformance material. The NC-microfiber made directly from cellulose microfibers showed similar macro-, micro-, and nanostructures and the same properties as those made from solvent-based welding of ground cellulose nanofibers (NC-nanofiber). Omitting the step of cellulose nanofiber production makes the direct production of all-cellulose nanocomposite from cellulose microfibers easier, shorter, and cheaper than using cellulose nanofibers as starting material. The direct nanowelding of macro/micrometer-sized materials is theorized to be a fundamental approach for making nanocomposites.

Liquefaction is a process for the production of biofuel or value-added biochemicals from non-food biomass. SO(3)H-, COOH-functionalized and HSO(4)-paired imidazolium ionic liquids were shown to be efficient catalysts for bagasse liquefaction in hot compressed water. Using SO(3)H-functionalized ionic liquid, 96.1% of bagasse was liquefied and 50.6% was selectively converted to low-boiling biochemicals at 543 K. The degree of liquefaction and selectivity for low-boiling products increased and the average molecular weight of the tetrahydrofuran soluble products decreased with increasing acidic strength of ionic liquids. Analysis of products and comparative characterization of raw materials and residues suggested that both catalytic liquefaction and hydrolysis processes contribute to the high conversion of bagasse. A possible liquefaction mechanism based on the generation of 3-cyclohexyl-1-propanol, one of the main products, is proposed., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Background: Whole cells are usually employed for biocatalytic reduction reactions to ensure efficient coenzyme regeneration and to avoid problems with enzyme purification and stability. The efficiency of whole cell-catalyzed bioreduction is frequently restricted by pronounced toxicity of substrate and/or product to the microbial cells and in many instances the use of two-phase reaction systems can solve such problems. Therefore, we developed new, biphasic reaction systems with biocompatible water-immiscible ionic liquids (ILs) as alternatives to conventional organic solvents, in order to improve the asymmetric reduction of 4-(trimethylsilyl)-3-butyn-2-one (TMSB) to (S)-4-(trimethylsilyl)-3-butyn-2-ol {(S)-TMSBOL}, a key intermediate for synthesis of 5-lipoxygenase inhibitors, using immobilized Candida parapsilosis CCTCC M203011 cells as the biocatalyst., Results: Various ILs exerted significant but different effects on the bioreduction. Of all the tested water-immiscible ILs, the best results were observed with 1-butyl-3-methylimidazolium hexafluorophosphate (C4MIM.PF6), which exhibited not only good biocompatibility with the cells but also excellent solvent properties for the toxic substrate and product, thus markedly improving the efficiency of the bioreduction and the operational stability of the cells as compared to the IL-free aqueous system. 2-Propanol was shown to be the most suitable co-substrate for coenzyme regeneration, and it was found that the optimum volume ratio of buffer to C4MIM.PF6, substrate concentration, buffer pH, 2-propanol concentration and reaction temperature were 4/1 (v/v), 24 mM, 5.5, 130 mM and 30 degrees C, respectively. Under these optimized conditions, the maximum yield and the product e.e. wer 97.7% and >99%, respectively, which are much higher than the corresponding values previously reported. The efficient whole-cell biocatalytic process was shown to be feasible on a 250-mL scale., Conclusion: The whole cell-catalyzed asymmetric reduction of TMSB to (S)-TMSBOL can be substantially improved by using a C4MIM.PF6/buffer biphasic system instead of a single-phase aqueous system and the resulting biocatalytic process appears to be effective and competitive on a preparative scale.

The biocatalytic enantioselective reduction of 4'-methoxyacetophenone to (S)-1-(4-methoxyphenyl)ethanol was successfully conducted in a hydrophilic IL-containing co-solvent system using immobilized Rhodotorula sp. AS2.2241 cells. Of all the tested ILs, the best results were observed with the novel IL 1-(2'-hydroxy)ethyl-3-methylimidazolium nitrate (C(2)OHMIM.NO(3)), which showed a good biocompatibility with the cells and increased the cell membrane permeability moderately, thus improving the efficiency of the bioreduction. To better understand the bioreduction, several crucial influential variables were also examined. The optimal C(2)OHMIM.NO(3) content, buffer pH, reaction temperature and substrate concentration were 5.0% (v/v), 8.5, 25 degrees C and 12 mM, respectively. Under the optimized conditions, the initial reaction rate, the maximum yield and the product e.e. were 9.8 micromol/hg(cell), 98.3% and >99%, respectively, which are much better than the results previously reported. The established biocatalytic system has proven to be highly effective for the reduction of other aryl ketones. Also, the cells exhibited excellent operational stability in the presence of C(2)OHMIM.NO(3). Moreover, the ILs can accumulate within the cells, suggesting that ILs are likely to interact with the related enzymes within the cells.

The homogeneous chemical modification of cellulose with succinic anhydride was investigated in a solvent system containing 1-butyl-3-methylimidazolium chloride ionic liquid and dimethylsulfoxide using N-bromosuccinimide (NBS) as a catalyst. The results showed that the degree of substitution of the succinylated cellulosic samples, in the range of 0.24-2.31, noticeably increased as compared with the products without any catalysts, indicating that NBS was a novel efficient catalyst for cellulose succinoylation in ionic liquids. Fourier transform infrared and solid-state cross-polarization/magic angle spinning (13)C NMR spectroscopies also provided evidence of succinoylation reaction. The results indicated that the reaction of hydroxyl groups at C-6, C-2, and C-3 positions in cellulose occurred. The thermal stability of the succinylated cellulose was found to decrease upon chemical modification.

The homogeneous chemical modification of sugarcane bagasse cellulose with succinic anhydride using 1-allyl-3-methylimidazolium chloride (AmimCl) ionic liquid as a reaction medium was studied. Parameters investigated included the molar ratio of succinic anhydride/anhydroglucose units in cellulose in a range from 2:1 to 14:1, reaction time (from 30 to 160min), and reaction temperature (between 60 and 110 degrees C). The succinylated cellulosic derivatives were prepared with a low degree of substitution (DS) ranging from 0.071 to 0.22. The results showed that the increase of reaction temperature, molar ratio of SA/AGU in cellulose, and reaction time led to an increase in DS of cellulose samples. The products were characterized by FT-IR and solid-state CP/MAS (13)C NMR spectroscopy, and thermal analysis. It was found that the crystallinity of the cellulose was completely disrupted in the ionic liquid system under the conditions given. The data also demonstrated that homogeneous modification of cellulose with succinic anhydride in AmimCl resulted in the production of cellulosic monoester. The thermal stability of the succinylated cellulose decreased upon chemical modification.