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Blind predictions of octanol/water partition coefficients and pKa at 298.15 K for 22 drug-like compounds were made for the SAMPL7 challenge. Octanol/water partition coefficients were predicted from solvation free energies computed using electronic structure calculations with the SM12, SM8 and SMD solvation models. Within these calculations we compared the use of gas- and solution-phase optimized geometries of the solute. Based on these calculations we found that in general the use of solution phase-optimized geometries increases the affinity of the solutes for water as compared to octanol, with the use of gas-phase optimized geometries resulting in the better agreement with experiment. The pKa is computed using the direct approach, scaled solvent-accessible surface model, and the inclusion of an explicit water molecule, where the latter two methods have previously been shown to offer improved predictions as compared to the direct approach. We find that the use of an explicit water molecule provides superior predictions, and that the predicted macroscopic pKa is sensitive to the employed microstates., (© 2022. The Author(s), under exclusive licence to Springer Nature Switzerland AG.)

Pure deep eutectic solvents (DESs) system of choline chloride (ChCl)/Lactic acid (Lac) were demonstrated to be an effective strategy for extraction of lignin. In this study, two kinds of different promising solid acid (SA) with DESs were designed to promote the pretreatment of lignocellulose. The SA of phosphotungstic acid (H 3 O 40 PW 12 ) and iron bromide (FeBr 3 ) were introduced into DESs to extract poplar wood lignin and evaluate the antioxidant activity. It was found that 82.2% and 80.9% of lignin were obtained from poplar wood under H 3 O 40 PW 12 -ChCl/Lac acid and FeBr 3 -choline ChCl/Lac system with 4 h and 8 h, respectively. The lignin fractions with a high purity (>89%), low molecular weight (Mw 1800-2000 g/mol). Besides, the antioxidant activities of lignin fractions were better than butyl hydroxyanisole (BHA). Therefore, DES lignin has prominent antioxidant activity and could developed a potential natural cosmetics and food packaging., (Copyright © 2021 Elsevier B.V. All rights reserved.)

This study investigated the process intensification strategies for the pretreatment of Radiata Pine with the green deep eutectic solvent (DES) system composed of benzyltrimethylammonium chloride/formic acid (BTMAC/FA). The results showed that DES pretreatment drastically improved the delignification and hemicelluloses-removal capacity. The conducted process acceptably remained most of the cellulose in pretreated biomass (88.3%-91.8%). Benefiting from the overcoming of recalcitrance, the enzymatic digestibility of pretreated residues reached 92.4%. The efficient conversion was mainly ascribed to the lignin and hemicelluloses co-extraction. Meanwhile, the lignin yield and enzymatic saccharification was still largely maintained after five reuses. Further structural characteristics of lignin nanoparticles revealed that the lignin possessed high purity (95.19-97.51%), medium molecular weight (9600 to 6495 g/mol), and low polydispersity (ca 2.0), which was attributed to cleavage of ether bonds in lignin as well as linkages between lignin and hemicelluloses. Overall, this study illustrated that DES pretreatment was promising to achieve an efficient fractionation of woody biomass into fermentable glucose and high-quality lignin., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Developing green and simple methods for the preparation of cellulose nanofibrils (CNFs) is of great significance. Herein, a green deep eutectic solvent (DES) system based on choline chloride (ChCl) and citric acid (CA) is employed to pretreat cellulose fibers for the preparation of CNFs. The effect of the pretreatment temperature on the chemo-physical properties of the CNFs is comprehensively investigated. A high CNFs yield of up to 84.19% can be achieved under optimized conditions. The optimal CNFs show a narrow diameter distribution and length up to several microns, high crystallinity and thermal stability, as well as excellent dispersibility in water. Furthermore, semi-transparent and flexible cellulose nanopaper (CNP) was fabricated through a facile vacuum filtration process. The optimal CNP shows high tensile strength (175.15 MPa) and toughness (7.51 MJ/m 3 ). Therefore, this work provides a sustainable and facile approach to fabricate CNFs and CNP, which can be potentially used for various high-tech applications., (Copyright © 2021. Published by Elsevier Ltd.)

A facile and environmentally-friendly strategy for increasing antioxidant activity is a crucial issue for value-added lignin and lignin-carbohydrate complex (LCC) as alternative antioxidants. However, the antioxidant activities of lignin and LCC by the traditional solid-liquid extraction (SLE) methods were restricted by the relatively lower solubility induced from high molecular weight (Mw), and the less functional groups including, phenolic hydroxyl and carboxyl. To improve the antioxidantion of lignin and LCC, lithium chloride/dimethyl sulfoxide (LiCl/DMSO) solvent fractionation (LDSF) was conducted to increase the functional groups and reduce Mw, in which LiCl/DMSO acted triple roles as solvent, acid, and metal chloride catalyst for the depolymerization reaction synchronously. The β-O-4' linkages were cleaved to release the phenolic hydroxyl, resulting in decreasing Mw; the hydroxyl of the side-chain of lignin was oxidized into carboxyl. Thus, the lignin (LD-RL) and LCC (LD-LCC) samples from LDSF had a higher syringyl (S)/guaiacyl (G) ratio, phenolic hydroxyl, and carboxyl contents, but less Mw than control groups from SLE. Consequently, they presented more excellent scavenging rates toward DPPH and ABTS radicals, up to 90%. This work provided panoramic perspectives and basics of the green and convenient approach to isolate and modify lignin and LCC for great antioxidantion with LDSF., (Copyright © 2021. Published by Elsevier B.V.)

A facile, catalyst-free synthesis of a norbornylated cellulosic material (NC) with a high degree of substitution (2.9) is presented by direct reaction of trimethylsilyl cellulose with norbornene acid chloride. The resulting NC is highly soluble in organic solvents and its reactive double bonds were exploited for the copper-free inverse-electron demand Diels-Alder (iEDDA) "click" reaction with 3,6-di(pyridin-2-yl)-1,2,4,5-tetrazine. Reaction kinetics are comparable to the well-known Huisgen type 1,3-dipolar cycloaddition of azide with alkynes, while avoiding toxic catalysts.

Two molecules, 7-(diethylamino)coumarin-3-carbohydrazide (DCCH) and fluorescein-5-thiosemicarbazide (FTSC) were investigated in different solvents, under varying pH conditions regarding their spectroscopic properties for the usage as a Förster Resonance Energy Transfer (FRET) pair to study the molecular interaction between cellulosic surfaces. All the relevant spectroscopic properties to determine the Förster distance were measured and the performance as a FRET system was checked. From the results, it is clear that the environmental conditions need to be accurately controlled as both, but especially the FTSC dyes are sensitive to changes. For high enough concentrations positive FRET systems were observed in DMF, DMSO, H2O, THF and alkaline DMF. However due to the low quantum yield of the unmodified DCCH throughout the investigated parameter range and the strong environmental dependency of FTSC, both dyes are not preferable for being used in a FRET system for studying interaction between cellulosic surfaces., Competing Interests: The authors have declared that no competing interests exist.

This review deals with two overlapping issues, namely polymer chemistry and deep eutectic solvents (DESs). With regard to polymers, specific aspects of synthetic polymers, polymerization processes producing such polymers, and natural cellulose-based nanopolymers are evaluated. As for DESs, their compliance with green chemistry requirements, their basic properties and involvement in polymer chemistry are discussed. In addition to reviewing the state-of-the-art for selected kinds of polymers, the paper reveals further possibilities in the employment of DESs in polymer chemistry. As an example, the significance of DES polarity and polymer polarity to control polymerization processes, modify polymer properties, and synthesize polymers with a specific structure and behavior, is emphasized.

In this study, a novel biomass pretreatment process using three kinds of deep eutectic solvents (DESs) was developed to improve saccharification efficiency and lignin valorization. The major components of xylose residue including cellulose and lignin fractions were released, recovered and utilized. Pretreatment with betaine/lactic acid system at 120 °C for 2 h was found to be the optimal conditions with prominently increased enzymatic digestibility (from 55.3% to 96.8%). The efficient conversion was mainly ascribed to the significant delignification efficiency of 81.6% after betaine/lactic acid pretreatment, which caused incompact structure and corrosive surface of treated xylose residue. The recoverable lignin had high purity, low molecular weight (630-2040 g/mol) and polydispersity (1.07-1.76). Based on the comprehensive analysis, the one-pot DESs system provides us a facile and effective approach for whole components valorization of lignocellulosic materials., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The scientific community, experts in technology and marketing have been seeking cost-competitive and green solvents with good dissolving capacity for the valorisation of biomass and biowaste. Along with traditional solvents and techniques, deep eutectic solvents (DESs) and their bio-analogues, natural deep eutectic solvents (NADESs) are currently emerging as a new class of promising liquid media. In this review, a comprehensive summary of recent contribution of DESs to the processing and valorisation of various kinds of plant and animal based biomass and biowaste is provided. In the field of food industry based and agro-forest waste valorisation, through treatment of the waste, by-products, and natural materials by DESs, several types of compounds, such as flavonoids and other plant phenolics, phenolic acids, stilbenes, tannins, lignans, and lignin were obtained. Extraction of algae by DESs led to isolation mainly of proteins, carbohydrates, lipids and nucleic acids. Vegetable oils, spent oils, residues and by-products of their processing are a rich source of phenolic compounds such as phenolic acids and phenolic alcohols, secoiridoid derivatives (aglycone and ligstroside), lignans (pino and acetoxypinoresinol), flavones (luteolin and apigein), tocopherols and tocotrienols. Dietary fibre serves as a source of lignin, pectic substances, gums, resistant starch, inulin, as well as non-carbohydrate components, e.g., polyphenols, waxes, saponins, cutin, phytates, resistant proteins. Valorisation of wastes originated from animal processing by DESs means obtaining high-value chemicals including amino acids, proteins, bioactive peptides, collagen peptides, albumin etc. Through the valorisation of the mentioned waste types value-added products with potential applications in the pharmaceutical, food and cosmetic industries are produced. The paper gathered data on the used DESs, treated substances and obtained products, together with treatment conditions and the products yields. The evaluation of the state-of-the-art in the field of biowaste valorisation using DESs and NADESs led to conclusions and indication of future prospects and predicted development in this field., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Surface functionalization of cellulose nanocrystals (CNCs) is valuable option to tailor properties as well as increase opportunities for their application. In this study, the surface of CNCs was functionalized with 3-aminopropyltriethoxysilane (APTES), without using hazardous solvents and by a direct, simple and straightforward method. APTES was firstly hydrolyzed in water and then adsorbed onto CNC through hydrogen bonds, finally the chain hydrocarbon was covalently linked to the surface of CNC through SiOC bonds which formed via the condensation reaction between hydroxyl and silanol groups. The chemical modification of the CNCs surface was confirmed by ATR-IR and NMR spectroscopy. Experiments conducted by AFM and XRD showed no significant change in the CNC dimensions and crystalline structure as a result of the modification. The EDX and XPS results confirmed the exsistence of APTES onto the CNCs. Silylated CNC exhibited good thermal stability and a greater amount of residual char was formed at 500 °C compared to non-chemically modified CNC. Thus, The silylation of CNCs may offer applications in composite manufacturing, where these nanoparticles have limited dispersibility in hydrophobic polymer matrices, and as nano-adsorbers due to the presence of amino groups attached on the surface., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Deep eutectic solvents (DESs) are a potentially high-value lignin extraction methodology. DESs prepared from choline chloride (ChCl) and three hydrogen-bond donors (HBD)-lactic acid (Lac), glycerol, and urea-were evaluated for isolation of willow ( Salix matsudana cv. Zhuliu ) lignin. DESs types, mole ratio of ChCl to HBD, extraction temperature, and time on the fractionated DES-lignin yield demonstrated that the optimal DES-lignin yield (91.8 wt % based on the initial lignin in willow) with high purity of 94.5% can be reached at a ChCl-to-Lac molar ratio of 1:10, extraction temperature of 120 °C, and time of 12 h. Fourier transform infrared spectroscopy (FT-IR) , 13 C-NMR, and 31 P-NMR showed that willow lignin extracted by ChCl-Lac was mainly composed of syringyl and guaiacyl units. Serendipitously, a majority of the glucan in willow was preserved after ChCl-Lac treatment., Competing Interests: The authors declare no conflict of interest.

Solubility parameter based methods have long been a valuable tool for solvent formulation and selection. Of these methods, the MOdified Separation of Cohesive Energy Density (MOSCED) has recently been shown to correlate well the equilibrium solubility of multifunctional non-electrolyte solids. However, before it can be applied to a novel solute, a limited amount of reference solubility data is required to regress the necessary MOSCED parameters. Here we demonstrate for the solutes methylparaben, ethylparaben, propylparaben, butylparaben, lidocaine and ephedrine how conventional molecular simulation free energy calculations or electronic structure calculations in a continuum solvent, here the SMD or SM8 solvation model, can instead be used to generate the necessary reference data, resulting in a predictive flavor of MOSCED. Adopting the melting point temperature and enthalpy of fusion of these compounds from experiment, we are able to predict equilibrium solubilities. We find the method is able to well correlate the (mole fraction) equilibrium solubility in non-aqueous solvents over four orders of magnitude with good quantitative agreement.

The objective of this study was to investigate the effects of organosolv and hydrotropic pretreatments on improving enzymatic hydrolysis of eucalyptus. The chemical composition of the fiber surface was analyzed using X-ray photoelectron spectroscopy (XPS) to determine the surface characteristics of pretreated eucalyptus. Other than the significant decrease of surface coverage by lignin, hydrotropic pretreatment was more effective in removing the lignin and xylose from fiber cell walls than organosolv pretreatment. The restriction of acetyl and phenolic groups in pretreated substrates was typically eliminated by hydrotropic pretreatments. Moreover, fiber structure and morphology after pretreatments were more suitable for enzymatic hydrolysis. Cellulase adsorption capacity was notably improved by hydrotropic pretreatment, which indicating the better enzyme accessibility of cellulose in pretreated substrates. Eventually, higher glucose yield was obtained with hydrotropic pretreatment. In addition, the precipitated lignin as an important by-product of pretreatments was characterized by Fourier transforms infrared spectroscopy (FTIR) also., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

We present blind predictions using the solubility parameter based method MOSCED submitted for the SAMPL5 challenge on calculating cyclohexane/water distribution coefficients at 298 K. Reference data to parameterize MOSCED was generated with knowledge only of chemical structure by performing solvation free energy calculations using electronic structure calculations in the SMD continuum solvent. To maintain simplicity and use only a single method, we approximate the distribution coefficient with the partition coefficient of the neutral species. Over the final SAMPL5 set of 53 compounds, we achieved an average unsigned error of [Formula: see text] log units (ranking 15 out of 62 entries), the correlation coefficient (R) was [Formula: see text] (ranking 35), and [Formula: see text] of the predictions had the correct sign (ranking 30). While used here to predict cyclohexane/water distribution coefficients at 298 K, MOSCED is broadly applicable, allowing one to predict temperature dependent infinite dilution activity coefficients in any solvent for which parameters exist, and provides a means by which an excess Gibbs free energy model may be parameterized to predict composition dependent phase-equilibrium.

Ethnopharmacological Relevance: Mahonia bealei has a long history of medical use in traditional Chinese medicine for the treatment of inflammatory-associated diseases. Despite numerous phytochemical and pharmacological studies, there is a lack of systematic studies to understand the cellular and molecular mechanisms of the anti-inflammatory activity of this plant., Aim of Study: This study aimed to evaluate the anti-inflammatory activity of the dichloromethane fraction from M. bealei leaves (MBL-CH)., Materials and Methods: RAW 264.7 cells were pretreated with different concentrations of MBL-CH for 30min prior to treatment with 1μg/ml of lipopolysaccharide (LPS). The nuclear factor κB (NF-κB) pathway and subsequent production of inflammatory mediators, such as nitric oxide (NO), prostaglandin E2 (PGE2), and tumour necrosis factor (TNF)-α were investigated. Furthermore, the in vivo mouse model of LPS-induced acute lung injury (ALI) was employed to study the anti-inflammatory effects of MBL-CH., Results: Pre-treatment with MBL-CH significantly inhibited the LPS-stimulated secretion of NO, PGE2, and TNF-α into the culture medium, as well as the mRNA levels of inducible nitric oxide synthase (iNOS), cyclooxygenase-2 (COX-2), and TNF-α, which were associated with a reduction in the phosphorylation of IκBα, Akt, and PI3K and inhibition of the transcriptional activity of NF-κB. Furthermore, in vivo experiments revealed that MBL-CH attenuated LPS-stimulated lung inflammation in mice., Conclusion: Taken together, our findings indicate that MBL-CH attenuates LPS-stimulated inflammatory responses in macrophages by blocking NF-κB activation through interference with activation of the PI3K/Akt pathway, providing scientific evidence that the plant can be employed in traditional remedies., (Copyright © 2016 Elsevier Ireland 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.

Here, our interest is in predicting solubility in general, and we focus particularly on predicting how the solubility of particular solutes is modulated by the solvent environment. Solubility in general is extremely important, both for theoretical reasons - it provides an important probe of the balance between solute-solute and solute-solvent interactions - and for more practical reasons, such as how to control the solubility of a given solute via modulation of its environment, as in process chemistry and separations. Here, we study how the change of solvent affects the solubility of a given compound. That is, we calculate relative solubilities. We use MD simulations to calculate relative solubility and compare our calculated values with experiment as well as with results from several other methods, SMD and UNIFAC, the latter of which is commonly used in chemical engineering design. We find that straightforward solubility calculations based on molecular simulations using a general small-molecule force field outperform SMD and UNIFAC both in terms of accuracy and coverage of the relevant chemical space.

Background: Enantiopure (S)-1-(4-methoxyphenyl) ethanol {(S)-MOPE} can be employed as an important synthon for the synthesis of cycloalkyl [b] indoles with the treatment function for general allergic response. To date, the biocatalytic resolution of racemic MOPE through asymmetric oxidation in the biphasic system has remained largely unexplored. Additionally, deep eutectic solvents (DESs), as a new class of promising green solvents, have recently gained increasing attention in biocatalysis for their excellent properties and many successful examples in biocatalytic processes. In this study, the biocatalytic asymmetric oxidation of MOPE to get (S)-MOPE using Acetobacter sp. CCTCC M209061 cells was investigated in different two-phase systems, and adding DES in a biphasic system was also explored to further improve the reaction efficiency of the biocatalytic oxidation., Results: Of all the examined water-immiscible organic solvents and ionic liquids (ILs), 1-butyl-3-methylimidazolium hexafluorophoshpate ([C4MIM][PF6]) afforded the best results, and consequently was selected as the second phase of a two-phase system for the asymmetric oxidation of MOPE with immobilized Acetobacter sp. CCTCC M209061 cells. For the reaction performed in the [C4MIM][PF6]/buffer biphasic system, under the optimized conditions, the initial reaction rate, the maximum conversion and the residual substrate e.e. recorded 97.8 μmol/min, 50.5 and >99.9 % after 10 h reaction. Furthermore, adding the DES [ChCl][Gly] (10 %, v/v) to the aqueous phase, the efficiency of the biocatalytic oxidation was rose markedly. The optimal substrate concentration and the initial reaction rate were significantly increased to 80 mmol/L and 124.0 μmol/min, respectively, and the reaction time was shortened to 7 h with 51.3 % conversion. The immobilized cell still retained over 72 % of its initial activity after 9 batches of successive reuse in the [C4MIM][PF6]/[ChCl][Gly]-containing buffer system. Additionally, the efficient biocatalytic process was feasible up to a 500-mL preparative scale., Conclusion: The biocatalytic asymmetric oxidation of MOPE with Acetobacter sp. CCTCC M209061 cells was successfully conducted in the [C4MIM][PF6]-containing biphasic system with high conversion and enantioselectivity, and the reaction efficiency was further enhanced by adding [ChCl][Gly] to the reaction system. The efficient biocatalytic process was promising for the preparation of enantiopure (S)-MOPE.

Given that the glycerol organosolv pretreatment (GOP) can effectively improve the hydrolyzability of various lignocellulosic substrates, physicochemical changes of the substrate before and after the pretreatment was characterized to elucidate what is responsible for it. The effect of GOP on the main components and hydrolyzability of wheat straw was revisited. Results demonstrate that the GOP should be a promising candidate for the current pretreatment. Then the composition and structure of substrates was measured at multi-dimensional scales by using various analytic equipment such as TGA, SEM, AFM, CLSM, FT-IR, XRD and solid-state CP/MAS (13)C NMR. This paper reports some new insights on the mechanism behind that, which can be beneficial for further development, optimization, and scale-up of the GOP process., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

A whole-cell based method was developed for the regioselective synthesis of arabinocytosine laurate. Among the seven kinds of bacteria strains tested in the acylation reaction, Pseudomonas fluorescens gave the highest productivity and a higher 5'-regioselectivity than 99%. Compared with pure organic solvents, the use of organic solvent mixtures greatly promoted the yield of the whole-cell catalyzed reaction, but showed little influence on the 5'-regioselectivity. Of all the tested solvent mixtures, the best reaction result was found in isopropyl ether/pyridine followed by isopentanol/pyridine. However, the whole-cells showed much lower thermostability in isopropyl ether/pyridine than in THF-pyridine. To better understand the toxic effects of the organic solvents on P. fluorescens whole-cells and growing cells were further examined. Significant influences of organic solvents on the biomass of the cells were found, which differed depending on the type of solvents used. SEM analysis visually revealed the changes in the surface morphology of whole-cells and growing cells cultured in media containing various organic solvents, in terms of surface smoothness, bulges and changed cell sizes. Results demonstrated that organic toxicity to cell structure played an important role in whole-cell mediated catalysis.

This study describes the use of microwaves (MW) for enhanced extractive-transesterification of algal lipids from dry algal biomass (Chlorella sp.). Two different single-step extractive-transesterification methods under MW irradiation were evaluated: (1) with ethanol as solvent/reactant and sodium hydroxide catalyst; and (2) with ethanol as reactant and hexane as solvent (sodium hydroxide catalyst). Biodiesel (fatty-acid-ethyl-esters, FAEE) yields from these two methods were compared with the conventional Bligh and Dyer (BD) method which followed a two-step extraction-transesterification process. The maximum lipid yields for MW, MW with hexane and BD methods were 20.1%, 20.1%, and 13.9%, respectively; while the FAEE conversion of the algal lipids were 96.2%, 94.3%, and 78.1%, respectively. The algae-biomass:ethanol molar ratio of 1:250-500 and 2.0-2.5% catalyst with reaction times around 6min were determined as optimum conditions for both methods. This study confers that the single-step non-conventional methods can contribute to higher algal lipid and FAEE yields., (Copyright © 2014 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.)

2-Methyltetrahydrofuran (MeTHF), a biomass-derived compound, is a promising medium for biocatalysis and organometallic reactions. The regioselective acylation of 8-chloroadenosine (8-Cl-Ado) and its analogs was carried out in MeTHF with immobilized Penicillium expansum lipase. The lipase displayed more than twofold higher catalytic activity and much better thermostability in MeTHF than in other organic solvents and co-solvent systems. The optimum reaction medium, enzyme dosage, molar ratio of viny ester to nucleoside and reaction temperature for the enzymatic acylation of 8-Cl-Ado were MeTHF, 25 U/mL, 7.5 and 35 °C, respectively, under which the desirable 5'-O-undecylenoyl-8-Cl-Ado was obtained with a yield of 95% and a regioselectivity of >99% in 3 h. In addition, the lipase catalyzed regioselective undecylenoylation of other purine nucleosides, producing 5'-undecylenic acid esters with moderate to high yields (63-94%) and excellent 5'-regioselectivities (94->99%). Use of biomass-derived solvents might open up novel opportunities for sustainable and greener biocatalytic processes., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

The lyophilized Pseudomonas fluorescens cell was an efficient alternative catalyst to enzymes for highly regioselective acylation of a polar nucleoside, 1-β-D-arabinofuranosylcytosine (ara-C). The cells showed an evident solvent dependence in the reaction. Among the tested solvents except for acetonitrile-pyridine, catalytic activity of the cells clearly increased with increasing the polarity of the organic solvents used. Among all the tested solvents both pure and binary, the best results were observed in isopropyl ether-pyridine system, in which the catalyst also showed good thermal and operational stabilities. For the biocataylsis in isopropyl ether-pyridine, the optimal isopropyl ether concentration, water content, acyl donor/ara-C ratio, biocatalyst dosage and reaction temperature were 30% (v/v), 4%, 45, 50mg/mL and 30 °C, respectively, under which the initial rate, yield and 5'-regioselectivity were 2.93 mM/h, 77.1% and 97.3%, respectively. The bacterial cells exhibited comparable 5'-regioselectivity to the expensive immobilized enzyme, which could also have environmental and cost advantages., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

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.

Regioselective enzymatic acylations of 1-beta-D-arabinofuranosylcytosine (ara-C) with vinyl laurate (VL) in binary organic solvents were explored for the preparation of 5'-O-laurate of ara-C. Among the nine kinds of enzymes, Novozym 435 showed the highest regioselectivity (>99.9%) towards the 5'-OH of ara-C. This lipase showed higher catalytic activity in hexane-pyridine than in other tested solvent mixtures. The most suitable VL to ara-C molar ratio, initial water activity, and reaction temperature were shown to be 15:1, 0.07, and 50 degrees C, respectively, under which the initial reaction rate and the maximum substrate conversion were as high as 84.0 mmol L(-1) h(-1) and 98.1%, respectively. The product of Novozym 435-catalyzed acylation was characterized by (13)C NMR and confirmed to be 5'-O-laurate of ara-C., (2010 Elsevier Ltd. All rights reserved.)

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.

Organosolv pulping of bagasse was conducted following a central composite design using a two-level factorial plan involving three pulping variables (temperature: 190-210 degrees C, time: 120-180 min, organic solvent ratio: 40-60% dimethyl formamide). Responses of pulp and handsheets properties to the process variables were analyzed using statistical software (MINITAB 14). Using values of the independent variables the variation ranges considered provided the following optimum values of the dependent variables: 82.7% (yield), 92.9 (kappa number), 1.403% (ash), 370 ml (freeness), 6290 m (breaking length), 9.4 (folding endurance), 5.955 mN m2 g(-1) (Tear index) and 2.811 kN g(-1) (Burst index) for pulps and handsheets. Results showed that acceptable physical and mechanical properties of pulps and papers similar the pulp used for bleaching could be achieved at 210 degrees C for 150 min and 50% DMF. These are the most suitable conditions for obtaining paper sheets with a high breaking length, tear and burst indices. Also bagasse could be pulped with ease to about 55.72% yield with kappa number approximately 35. The cooking temperature was a significant factor while the DMF ratio and cooking time were not as important in term of the properties of the resultant pulps and papers.

An efficient one-pot, three-component synthesis of highly substituted bicyclic pyridines containing a ring-junction nitrogen, starting from simple and readily available materials, is described. Cyclocondensation of heterocyclic ketene aminals (HKAs), triethoxymethane, and active methylene compounds by refluxing under solvent-free and catalyst-free conditions, provided bicyclic pyridines in excellent yields. [ABSTRACT FROM AUTHOR]

An unprecedented twofold interpenetrating (3,4)-connected topology of the Cu3L4-type metal–organic framework was prepared using N,N′,N″-tris(4-pyridinyl)-1,3,5-benzenetricarboxamide (L) as a trigonal three-connection node and the copper(ii) ion as a square planar four-connection node, where the framework contains remarkably large 1-D solvent channels. [ABSTRACT FROM AUTHOR]