Fabrication of a model cellulose surface from straw with an aqueous sodium hydroxide/thiourea solution

Model cellulose surfaces were prepared with both microcrystalline cellulose and cellulose isolated from wheat straw with different molecular weights. A sodium hydroxide/thiourea aqueous solution, instead of any organic solvents, worked as the solvent for dissolving cellulose, and model cellulose films were prepared by a two‐step method: first, the cellulose solution was deposited onto the surface of the substrate with the spin‐coating method, and second, the as‐prepared film was washed with deionized water to remove the impurities and was formed with a flattened surface. Atomic force microscopy was used to measure the morphology, surface roughness, and thickness of the cellulose thin films. X‐ray photoelectron spectroscopy and energy‐dispersive X‐ray spectrometry were used to characterize the surface chemical information of the films. The results revealed that model cellulose surfaces could form from both kinds of cellulose. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Progress of dissolution of cellulose with imidazolium ionic liquid

Cellulose is the most abundant renewable bio-material. Due to its hydrogen-bonded supramolecular structure,cellulose is insoluble in water and most common organic liquids,which limits its application. The emergence of ionic liquids provides a broad platform to the application of cellulose. The recent developments concerning imidazolium ionic liquids as cellulose solvents as well as the dissolution mechanism are reviewed. Ionic liquids,containing Cl^－,CH₃CHOO^－ and (MeO)RPO₂^－ anions,appear to be the most effective solvents. A series of alkyl imidazolium ionic liquids containing alkyl phosphate was prepared by a one-pot procedure. Such ionic liquids have good thermal stability and are capable of solubilizing cellulose under mild conditions. The structure of imidazolium cation has an influence on the solubility as well. Future development of imidazolium ionic liquids is discussed.     

纤维素在离子液体AmimCl中的均相苯甲酰化反应

酱油渣中可以提取到纤维素等生物资源,但由于纤维素不溶于水和一般溶剂,难以进行衍生化应用,因此常常遭到浪费。而离子液体对纤维素呈现出较好的溶解性,可作为纤维素衍生化的良好溶剂。本文利用提取过油脂和半纤维素的酱油渣为原料进一步提取纤维素,并对以离子液体为溶剂,无催化剂条件下纤维素的均相苯甲酰化进行了研究。重点考察了离子液体种类对均相苯甲酰化的产率和取代率的影响,反应温度、时间、苯甲酰氯与葡萄糖单元摩尔比对均相苯甲酰化的取代率的影响。研究结果发现以离子液体AminCl（1-烯丙基-3甲基咪唑氯盐）为溶剂时有最优的产率。在最优反应条件为温度80℃、时间90min、苯甲酰氯与葡萄糖单元摩尔比4：1时,可得到最高取代率0.72。     

Application of optical microscopy as a screening technique for cellulose and lignin solvent systems

Rapid and facile screening techniques to determine the effectiveness of solvents for cellulose or biomass dissolution can advance biomass processing research. Here, we report the use of a simple optical microscopy method to screen potential cellulose and lignin solvents. The described methodology was used to screen the dissolution of cellulose and lignin in two imidazolium‐based ionic liquids (ILs), two phosphonium‐based ILs, as well as a N,N‐dimethylacetamide/lithium chloride (DMAc/LiCl) solution in less time than other techniques. The imidazolium‐based ILs and the DMAc/LiCl were found to dissolve both cellulose and lignin. Also, it was observed that one of the phosphonium‐based ILs dissolved lignin and not cellulose, demonstrating a potential for biomass fractionation applications. © 2011 Canadian Society for Chemical Engineering     

Calculation of alcohol‐acetone‐cellulose acetate ternary phase diagram and their relevance to membrane formation

ABSTRACT Alcohol‐acetone‐cellulose acetate phase diagrams incorporated with methanol, ethanol, and isopropanol as nonsolvents are calculated according to a new form of the Flory–Huggins equation. Nonsolvent–cellulose acetate interaction parameters are measured by swelling experiments. Concentration‐dependent nonsolvent–solvent interaction parameters are obtained by vapor–liquid equilibrium and the Wilson equation. It is shown that alcohol is a week coagulant compared with water, and water > methanol > ethanol > isopropanol for cellulose acetate. The phase diagrams characteristic of acetone‐cellulose acetate combined with water, methanol, ethanol, and isopropanol as nonsolvents is different, which leads to the different morphological structure of a cellulose acetate membrane. The structure of a water coagulated membrane has large macrovoids from liquid–liquid phase separation. A methanol coagulated membrane has a honeycomb‐like structure from spinodal microphase separation. An ethanol or isopropanol coagulated membrane has a thicker, dense top layer from the delay time phase separation. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1650–1657, 2001     

Enzymatic ring‐opening polymerization (ROP) of polylactones: roles of non‐aqueous solvents

Aliphatic polyesters such as polylactides (PLAs) and other polylactones are thermoplastic, biodegradable and biocompatible polymers with the potential to replace petro‐chemical‐based synthetic polymers. A benign route for synthesizing these polyesters is through the enzyme‐catalyzed ring‐opening polymerization (ROP) reaction; this type of enzymatic process is very sensitive to reaction conditions such as solvents, water content and temperature. This review systematically evaluates the crucial roles of different solvents (such as solvent‐free/in bulk, organic solvents, supercritical fluids, ionic liquids, and aqueous biphasic systems) on the degree of polymerization and polydispersity. In general, many studies suggest that hydrophobic organic solvents with minimum water contents lead to efficient enzymatic polymerization and subsequently high molecular weights of polyesters; the selection of solvents is also limited by the reaction temperature, e.g. the ROP of lactide is often conducted at above 100 °C, therefore, the solvent typically needs to have its boiling point above this temperature. The use of supercritical fluids could be limited by its scaling‐up potential, while ionic liquids have exhibited many advantages including their low‐volatility, high thermal stability, controllable enzyme‐compatibility, and a wide range of choices. However, the fundamental and mechanistic understanding of the specific roles of ionic liquids in enzymatic ROP reactions is still lacking. Furthermore, the lipase specificity towards l ‐ and d ‐lactide is also surveyed, followed by the discussion of engineered lipases with improved enantioselectivity and thermal stability. In addition, the preparation of polyester‐derived materials such as polyester‐grafted cellulose by the enzymatic ROP method is briefly reviewed. © 2017 Society of Chemical Industry     

Enhancing In Vitro Bioactivity of Melt‐Derived 45S5 Bioglass® by Comminution in a Stirred Media Mill

45S5 Bioglass^® (45S5 BG) is a frequently applied Type A bioactive material, capable of forming an inherent bond to bone and soft tissue. Currently, applied melt‐derived bioactive glass powders (BG) exhibit particle sizes between a few to several hundred micrometers. Recent studies on nanometer‐sized bioactive glasses (nBGs), produced by bottom‐up methods like sol–gel processing or flame spray pyrolysis, have indicated their great potential for several biomedical applications. In this study, the feasibility of top‐down processing starting from bulk 45S5 BG by wet comminution in a stirred media mill was investigated. The products were assessed by in vitro hydroxycarbonate apatite (HCAp) formation in simulated body fluid, which is a marker for bioactive behavior. The study reveals the paramount influence of the used solvent for a successful top‐down processing: In comparison with the as‐received material bioactivity is lost for powders processed in water, preserved for comminution in ethanol and increased for powders processed using the alcohols n‐butanol, n‐pentanol, and n‐hexanol. It was also found that only for the latter solvents, the chemical composition of the glass is maintained during comminution. Flake‐like, slightly porous particles with specific surface areas of ~25–30 m²/g are obtained. Thus, the presented comminution approach offers a convenient technique to process 45S5 BG with enhanced bioactivity.     

Structure and properties of novel regenerated cellulose films prepared from cornhusk cellulose in room temperature ionic liquids

Cornhusk cellulose was regenerated using the ionic liquids viz., 1‐allyl‐3‐methylimidazolium chloride (AmimCl) and 1‐ethyl‐3‐methylimidazolium acetate (EmimAc). The cast cellulose films were characterized by FTIR, WAXD and SEM techniques. Their mechanical properties were also studied. These studies indicated that AmimCl and EmimAc are good solvents for the regeneration of cornhusk cellulose. The regenerated cornhusk cellulose (RCC) was found to be cellulose (II) with dense structure. The films cast from AmimCl exhibited good mechanical properties; the tensile modulus and strength were as high as 6 GPa and 120 MPa respectively, whereas these values for those films cast using EmimAc were found to be 4.1 GPa and 47 MPa respectively. Further, it was observed that after regeneration, the solvents could be effectively recycled. Thus a novel nonpolluting process of forming RCC films from agricultural waste was developed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Anwendung von Erdalkalidodecylsulfaten zur Reinigung von mit polycyclischen aromatischen Kohlenwasserstoffen (PAK) kontaminiertem Bodenmaterial in geschlossenen Tensid‐ und Wasserkreisläufen

Sodium dodecylsulfate solutions contaminated with polycyclic aromatic hydrocarbons (PAH), e.g. pyrene, were purified by addition of calcium or barium salt solution and precipitation of the corresponding calcium or barium dodecylsulfate. The precipitates were cleaned up using several organic solvents. Regeneration of sodium dodecylsulfate from the calcium dodecylsulfate precipitate was possible by solving the substance in an ethanol/water mixture (1:1) and precipitation of calcium hydroxide using sodium hydroxide as a precipitating agent. It was shown, that the calcium dodecylsulfate can be used directly as a tenside in a hot water solution or in an ethanol/water mixture. An extraction procedure could be developed, to remove the PAH contaminations quantitatively from the tenside solutions and concentrate them to small quantities by distillation of the organic solvents. It was demonstrated, that closed cycles of reagents in low need of energy are possible. The procedure was tested at a perylene contaminated kaolin sample.     

Extraction of phospholipids from structured dry chicken egg

Chicken egg contains a high level of phospholipids (PL) in the yolk. Recovering yolk total lipids and extracting egg PL with efficiency are important to the availability and utilization of these health‐promoting lipid products. In this study, we prepared two structured dry egg yolk materials and used two common solvents to extract and concentrate the PL. We found that drum‐dried flake‐like yolk is an ideal starting material for lipid extraction. Anhydrous ethanol can extract almost all the neutral lipids and PL. PL with purity over 90% can be prepared by cold acetone precipitation from the total lipids.     

室温离子液体的制备及物化性能研究

合成了[bm im]B r和[bm im]BF4室温离子液体,考察了其在不同溶剂中的溶解性能及导电性能,同时对离子液体在不同溶剂中的紫外吸收进行了测定。结果表明,离子液体在水、乙醇、乙酸、丙酮中可以较好的溶解,而在乙醚、苯、正己烷中不溶解;离子液体的电导率随浓度的增大和温度的升高而增大,在不同的溶剂中的电导率K不同,而且相差很大,其顺序为K(水作溶剂)>K(乙醇作溶剂)>K(乙酸作溶剂)。溶剂的极性对离子液体的紫外吸收影响较大,最大吸收波长的顺序为:λm ax(水为溶剂)<λm ax(乙醇为溶剂)<λm ax(乙酸为溶剂)。     

Swelling behavior of radiation‐polymerized polyampholytic two‐component gels: Dynamic and equilibrium swelling kinetics

Polyampholytic hydrogels, with varying degrees of crosslinking and ionic content, were prepared by radiation polymerization of p‐sodium styrene sulfonate (SSS) and vinyl benzyl trimethylammoniumchloride (VBT). These gels were investigated for their dynamic and equilibrium swelling kinetics. Dynamic swelling of these gels established that the gels containing equal amounts of SSS and VBT strictly follow Fickian diffusion. The hydrogels containing excess of SSS followed the case II type of diffusion, whereas those containing excess of VBT followed anomalous diffusion. Equilibrium swelling kinetics of these gels in aqueous system, ethanol–water mixture, at different pHs, and in the presence of solutions of biological interest was studied. It was seen that gels containing equal amounts of SSS and VBT show the lowest equilibrium swelling. Swelling of the polyampholytic gel decreased with an increase in the radiation dose imparted and the amount of crosslinking agent incorporated in the gel. The gels having an excess of VBT showed higher equilibrium swelling in comparison to those having an excess of SSS. Differential scanning calorimetry (DSC) studies showed that crosslinking of the gels decreases equilibrium swelling but increases the bonded nonfreezable water content of the gels. The organic solvents like ethanol cause abrupt collapse of the polyampholyte gels containing excess of SSS and those containing equal amounts of both the monomers at some critical ratio of water and ethanol in swelling medium. However, the deswelling in the water–ethanol mixture was gradual for gels containing an excess of VBT and the extent of deswelling was also low for these gels in comparison to other gels. The swelled gels of all compositions deswelled when they were transferred to solutions at pH in the range 2–12. Biologically important solutes like urea, glucose, and surfactants like Triton‐X tend to further swell the polymer matrices, whereas NaCl causes their deswelling. The additive effect is more prominent for polyampholyte gels containing excess of either of the monomers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 730–742, 2003     

Development and characterization of cellulose‐based hydrogels for use as dietary bulking agents

In the last decade, cellulose‐based hydrogels have been receiving increasing attention for a number of applications because of their smart swelling behavior, biodegradability, and biocompatibility. Given the dramatic spreading of obesity and overweight in the industrialized countries and the lack of scientific consensus over currently available dietary supplements, it was recently proposed that such hydrogels might be used as orally administered bulking agents in hypocaloric diets, because the hydrogel swelling in the stomach may greatly reduce the space available for food intake, thus giving a sense of fullness. This study is focused on the synthesis of cellulose‐based hydrogels, starting from pharmaceutical and food grade cellulose derivatives, and shows that such hydrogels possess good swelling properties in water solutions mimicking the environmental conditions of the stomach and the intestine, as well as a good biocompatibility. The crosslinking agent used was a “zero‐length” crosslinker, that is, a water soluble carbodiimide, which is washed out from the gel after the synthesis and does not affect the gel compatibility, as shown by preliminary biocompatibility assays. The experimental results confirmed that cellulose‐based hydrogels might be a scientifically valid dietary adjuvant in the treatment of obesity and overweight, and provide further scientific evidence for future experiments on humans. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Recent trends in (ligno)cellulose dissolution using neoteric solvents: switchable,distillable and bio‐based ionic liquids

Recent years have witnessed the use of different ionic liquids for biomass processing, either at the level of lignocellulose pre‐treatment, to fractionate biomass in its main components, separating hemicellulose and lignin from cellulose, or directly in cellulose decrystallization by dissolving it in the ionic liquid and subsequent precipitation by adding anti‐solvents. Yet, most of the ILs employed in these strategies (e.g. imidazolium‐based solvents) are (still) expensive for such applications, and provide discussable ecological footprints. In an attempt to combine the highly useful generated knowledge with novel neoteric solvents with improved properties, economics, availability and ecology, several new trends have appeared in these areas during recent years. They comprise the use of switchable ILs, based on strong organic bases and CO₂, the application of distillable ILs, as well as the use of bio‐based and low‐cost ILs and deep‐eutectic‐solvents (DES), e.g. choline chloride‐based derivatives. Apart from other emerging uses, for all these solvents some preliminary applications in biomass processing involving pretreatments, cellulose dissolution and other applications have been successfully reported. This Minireview contextualizes these recent trends and discusses them with emphasis on future use of them in biorefineries and biomass valorization. © 2013 Society of Chemical Industry     

离子液体在植物纤维化学研究中的应用

综述了咪唑型离子液体在植物纤维原料溶解和改性方面的应用,并展望了其应用前景。离子液体与传统的植物纤维溶剂相比,具有更强的溶解能力和更好的稳定性,可以用作植物纤维原料液化和改性的高效溶剂,实现纤维素的再生和功能化。此外,离子液体还可用作植物纤维改性的添加剂。     

Cellulose derivatives and graft copolymers as blocks for functional materials

In this review, recent progresses in the synthesis of new cellulose derivatives and graft copolymers are summarized. Cellulose derivatives synthesized in new cellulose solvents, such as ionic liquids and NaOH/urea, and the regioselective synthesis of cellulose derivatives have attracted increasing attention in recent years and could be a more active field for cellulose in the future. Cellulose graft copolymers with well‐defined architectures synthesized by controlled/living radical polymerizations such as atomic transfer radical polymerization and their stimuli‐induced assembly have been investigated extensively. Stimuli‐responsive functional materials can be fabricated using either cellulose derivatives or graft copolymers, and they can be used as biosensors and carriers for controlled delivery of drugs and genes. The fabrication of functional materials with cellulosic blocks and their applications have a bright future. © 2013 Society of Chemical Industry     

Chemical‐vapor‐sensitive materials based on a multiwalled carbon nanotube/hydroxyl propyl methylcellulose/cellulose composite

A type of chemical vapor‐sensing material made from multiwalled carbon nanotubes/hydroxyl propyl methyl cellulose/cellulose composite films were prepared in the room‐temperature ionic liquid 1‐butyl‐3‐methylimidazolium chloride ([BMIm]Cl). A typical negative vapor coefficient was observed when the film was placed in polar organic solvents, such as methanol and ethanol. The sensitivity of the film to vapors increased significantly with increasing temperature. Interestingly, the resistance of the films increased almost linearly with decreasing vacuum, and the changes in resistance with the vacuum show good repeatability. The surface morphology, thermostability, and stress–strain properties of the composite films were analyzed with scanning electron microscopy, thermogravimetric analysis, and an electrical universal testing machine, respectively. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41639.     

Processing of Cellulose Using Ionic Liquids

The processing of cellulose dissolved in ionic liquids (ILs) enables the development of new materials. Besides the established production of cellulosic fiber products, interesting technical applications are developed like super micro filament fibers, cellulose/chitin blend fibers, precursors for carbon fibers, and all‐cellulose composites. This review provides a detailed summary of these new developments and describes how ILs are selected for the processing of cellulose with a particular emphasis on industrial realization. State‐of‐the‐art spinning processes are reviewed and it is illustrated how uniquely selected ILs can be used not only for established fiber spinning but for the development of new cellulose‐based materials.     

两种咪唑型离子液体对纤维素的溶解及纺丝性能的比较

以1-乙基-3-甲基咪唑醋酸盐（[EMIM]Ac）和1-丁基-3-甲基咪唑氯盐（[BMIM]CI）两种咪唑型离子液体为溶剂,研究比较了它们对纤维素的溶解性能及其溶液的纺丝加工性能。结果发现：两种离子液体均能在一定条件下溶解纤维素,但[EMIM]Ac较[BMIM]Cl对纤维素具有更低的溶解温度和更快的溶解速率。从流变分析还发现：纤维素/[EMIM]Ac溶液与纤维素/[BMIMCl溶液均为切力变稀流体,相同条件下纤维素/[EMIM]Ac溶液的黏度远低于纤维素/[BMIM]Cl溶液,使其可在相对低的温度下纺丝。此外,GPC分析结果表明：纤维素在用[EMIM]Ac溶解及纺丝过程中降解程度较小,而用[BMIM]Cl进行溶解纺丝时,降解作用则较明显。对纤维结构与力学性能的分析结果进一步表明：与相同喷头拉伸比下制得的[EMIM]Ac法再生纤维素纤维相比,[BMIM]Cl法再生纤维素纤维的聚集态结构相对较完善,结晶度与取向度更高些,从而使其力学性能也相对较好。     

Effect of Solvent on Titania Particle Formation and Morphology in Thermal Hydrolysis of TiCl4

Titania powders were synthesized by the thermal hydrolysis of titanium tetrachloride with the yield of above 85% in a mixed solvent of n -propanol and water. The morphology of the precipitates was controlled by adjusting the volume ratio of n -propanol to water (RH ratio) of the mixed solvent. Precipitates obtained with an RH ratio of 0 were fine, and highly agglomerated. In contrast, an RH ratio of 3 resulted in precipitates consisting of uniform and discrete particles. According to observations of the zeta potentials of precipitates and the dielectric constants of solvents, the discrete particles obtained with an RH ratio of 3 resulted from the low zeta potential and dielectric constant. The result of Fourier transform infrared (FTIR) spectroscopy showed the chemical interaction of particle surface with the solvent alcohol, which decreased the zeta potential of precipitates with an increase of RH ratio. Adding hydroxypropyl cellulose (HPC) as a steric dispersant made it possible to reduce the size of particles to the submicrometer range. Effects of the solvent on the formation and morphology of the resulting particles were investigated.