Homogenous Carboxymethylation of Cellulose in the New Alkaline Solvent LiOH/Urea Aqueous Solution

In this work, the carboxymethylation of cellulose in a new alkaline cellulose solvent, LiOH/urea aqueous solution, was investigated. Carboxymethyl cellulose (CMC) samples were characterized with FT-IR, NMR, HPLC, and viscosity measurements. Water-soluble CMC with DS = 0.36∼0.65 was prepared, from both Avicel cellulose and cotton linters in the LiOH/urea system. The total DS of CMC could be controlled by varying the molar ratio of reagents and the reaction temperature. The results from structure analysis by HPLC after complete depolymerization showed that the mole fractions of the different carboxymethylated repeating units as well as those of unmodified glucose follow a simple statistic pattern. A distribution of the carboxymethyl groups of the AGU was determined to be in the order O-6 > O-2 > O-3 position at the level.     

纤维素的均相化学反应

本文回顾了近10多年来的纤维素均相反应发展过程,研究了PF/DMSO、LiCl/DMAc、N₂O₄/DMF、苯/DMSO、LiCl/DMI和水等溶剂体系的纤维素均相反应条件(如酯化反应、交联反应、醚化反应、接枝共聚等),并总结了纤维素均相衍生化的分析方法,讨论了各种方法的优缺点以及发展前景.     

纤维素苯基氨基甲酸酯的均相合成及其手性拆分性能评价

认识多糖类手性拆分材料的结构性能关系对于构建新型高效手性固定相具有重要指导意义。该文中,以1-烯丙基-3-甲基咪唑氯离子液体为介质,合成了系列不同结构的纤维素苯基氨基甲酸酯,进而考察了取代度、取代基团种类和位置对产物手性拆分性能的影响。结果表明,随着取代度的增加,纤维素苯基氨基甲酸酯对于绝大部分手性分子的拆分效果提高;苯环上取代基团的种类和位置对纤维素苯基氨基甲酸酯手性拆分性能影响显著,弱吸电子基团氯基和给电子基团甲基在合适的位置能显著增强纤维素苯基氨基甲酸酯的手性拆分性能;纤维素3-甲基-4-氯苯基氨基甲酸酯、3,5-二氯苯基氨基甲酸酯和2-甲基-5-氯苯基氨基甲酸酯对一些手性分子的拆分效果优于纤维素3,5-二甲基苯基氨基甲酸酯。     

Radiation preparation and swelling behavior of sodium carboxymethyl cellulose hydrogels

Sodium carboxymethyl cellulose (CMC) is a kind of degraded polymer under γ-irradiation. However, in this work, it has been found that CMC crosslinks partially to form hydrogel by radiation technique at more than 20% CMC aqueous solution. The gel fraction increases with the dose. The crosslinking reaction of CMC is promoted in the presence of N₂ or N₂O due to the increase of free radicals on CMC backbone, but gel fraction of CMC hydrogel is not high (<40%). Some important values related to this kind of new CMC hydrogel synthesized under different conditions, such as radiation yield of crosslinking G(x), gelation dose R_g, number average molecular weight of network M_c were calculated according to the Charlesby–Pinner equation. The results indicated that although crosslinked CMC hydrogel could be prepared by radiation method, the rate of radiation degradation of CMC was faster than that of radiation crosslinking due to the character of CMC itself. Swelling dynamics of CMC hydrogel and its swelling behavior at different conditions, such as acidic, basic, inorganic salt as well as temperature were also investigated. Strong acidity, strong basicity, small amount of inorganic salts and lower temperature can reduce swelling ratio.     

Dispersion of cellulose nanocrystals in polar organic solvents

In an attempt to prepare stable dispersions of cellulose nanocrystals in dipolar aprotic solvents, dilute aqueous suspensions of cellulose nanocrystals were prepared by sulfuric acid hydrolysis of cotton. The aqueous suspensions were freeze-dried, and then sonicated in the solvent of interest. Dispersions of 1 and 3% w/v concentration were prepared in polar organic solvents DMSO and DMF. The dispersions showed flow birefringence. The redispersion was incomplete, and there was some evidence for aggregation in the suspensions. A small amount of water appeared to be critical to suspension stability. Birefringent cellulose films were prepared from the dispersions by drying under vacuum and at ambient conditions.     

An optical glucose biosensor based on entrapped-glucose oxidase in silicate xerogel hybridised with hydroxyethyl carboxymethyl cellulose

An optical glucose biosensor was fabricated by entrapping glucose oxidase (GOx) within the xerogel that was derived from tetraethylorthosilicate and hybridised with hydroxyethyl carboxymethyl cellulose polymer. The entrapped-GOx was mainly characterised with its long-lasting apparent biocatalytic activity as compared to that being entrapped in only sol-gel matrix. The biocatalytic activity of the entrapped-enzyme has extended its shelf lifetime up to 3 years. This long-term stability was closely correlated with the reduction in the shrinkage process of the hybrid gel being used. In conjunction with an optical oxygen transducer, the entrapped-GOx was assembled as an optical glucose biosensor comprised a sample flow system with which the dissolved oxygen in the sample could be precisely controlled and varied. The analytical working range was tuneable within 9.0 μM-100 mM range depending on the dissolved oxygen concentration in the test solution. The time taken to reach a 95% steady signal was 6-9 min at flow rate of 1.0 mL min⁻¹. The glucose biosensor has been satisfactorily applied to the determination of glucose contents of urine samples.     

Carboxymethylation of Bacterial Cellulose

The carboxymethylation of bacterial cellulose (BC) was studied under typical heterogeneous reaction conditions. It was found that the BC possesses a significantly lower reactivity compared to wood cellulose converted under comparable conditions. Moreover, water-solubility of carboxymethyl cellulose (CMC) obtained from BC appears at rather high degree of substitution of about 1.5 although a nearly statistical functionalization pattern was analyzed by HPLC. Obviously, the nano-structure of BC is important for the reactivity and the properties of the synthesized CMC like water-solubility.     

Homogeneous tritylation of cellulose in 1-butyl-3-methylimidazolium chloride

1-Alkyl-3-methylimidazolium-based ionic liquids, having chloride as a counter ion, were studied for cellulose solubility; and the influence of different alkyl chain lengths was also investigated. The alkyl chain length was incrementally varied from ethyl to decyl to determine structure-dissolution properties; a distinct odd-even effect was observed for short chain lengths. In addition, the tritylation of cellulose was performed in 1-butyl-3-methylimidazolium chloride using pyridine as base. The influences of reaction time and the ratio of trityl chloride per cellulose monomer unit on the degree of substitution were investigated in detail by elemental analysis and 1H NMR spectroscopy. A DS of around 1 was obtained after 3 h reaction time using a six fold excess of trityl chloride.     

Thermal behavior of polystyrene synthesized in the presence of carboxymethyl cellulose

Summary Study of the decomposition kinetics is an important tool for the development of polymer recycling in industrial scale. In this work, parameters such as activation energy, frequency factor and reaction order, were measured under dynamic conditions. Flynn-Wall-Ozawa, Van Krevelen, Horowitz-Metzger, Coats-Redfern, Madhusudanan and Vyazovkin methods were used to determine the kinetic parameters. The analysis of the results obtained by the Coats-Redfern method shows that the thermal degradation process of LDPE and HDPE corresponds to a phase boundary controlled reaction (mechanism R2). This method shows that the reaction order values of LDPE and HDPE are about 0.7 and 0.6, respectively.     

4.2 Chemical characteristics of cellulose acetate

The chemical structure of cellulose acetates (CA), different synthesis paths, analysis strategies and the correlation of these structural features with properties, especially with the solubility are summarized. Alternative paths, in particular homogeneous procedures, for the synthesis of CA are described focusing on the application of new media and the in situ activation of acetic acid. The preparation of selectively substituted CA is reviewed including the defined hydrolysis under acidic or basic conditions. Strategies for the structure analysis by means of ¹H- and ¹³C-NMR spectroscopy and by means of chromatographic methods are discussed. In addition, the preparation and the application of a variety of mixed CA ethers and esters are described.     

Graft copolymerization of 2‐methacryloyloxyethyl phosphorylcholine to cellulose in homogeneous media using atom transfer radical polymerization for providing new hemocompatible coating materials

To develop new hemopurification systems based on cellulose membrane, we synthesized a graft copolymer of cellulose with poly(2‐methacryloyloxyethyl phosphorylcholine) (MPC) by a metal‐catalyzed atom transfer radical polymerization process in homogeneous media. First, cellulose was dissolved in a DMAc/LiCl solution system, and it reacted with 2‐bromoisobutyloyl bromide to produce macroinitiator (cell‐BiB). Then, MPC was polymerized to the cellulose backbone in a homogeneous DMSO/methanol mixture solution in the presence of cell‐BiB. Characterization with FT‐IR, NMR, and GPC measurements showed that there obtained a graft copolymer of cellulose backbone and poly(MPC) side chains (cell‐PMPC) with well‐defined structure, indicating a controlled/“living” radical polymerization. The proteins adsorption studies showed that cellulose membranes modified by the as‐prepared cell‐PMPC owns good protein adsorption resistance. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3306–3313, 2008     

Equilibrium sorption of C.I.Basic Red 18 by carboxymethyl cellulose membranes

The equilibrium sorption of a cationic dye, C.I.Basic Red 18, by a partially carboxymethylated cellulose membrane at pH 4.2 was investigated. The sorption isotherm was interpreted by considering a cooperative mode of binding of the dye by the polymer. The intrinsic binding constantK, the number of consecutive polymer residues occupied by a single dye moleculen, and the cooperativity parameter were determined. In the case of the polymer with high content of carboxylate groups an additional mode of dye binding was presumed.     

Preparation,swelling, and stimuli‐responsive characteristics of superabsorbent nanocomposites based on carboxymethyl cellulose and rectorite

Utilization of naturally available raw materials for the fabrication of eco‐friendly functional materials has long been desired. In this work, a series of superabsorbent nanocomposites were prepared by radical solution copolymerization of sodium carboxymethyl cellulose (CMC), partially neutralized acrylic acid (NaA), and rectorite (REC) in the presence of initiator ammonium persulfate (APS) and crosslinker N,N'‐methylene‐bis‐acrylamide (MBA). The optimal reaction variables including the mass ratio of acrylic acid (AA) to CMC, MBA concentration, and REC content were explored. FTIR spectra confirmed that NaA had been grafted onto CMC and REC participated in polymerization. REC was exfoliated and uniformly dispersed in the CMC‐g‐PNaA matrix without agglomeration as shown by XRD, TEM, and SEM analysis. The thermal stability, swelling capabilities, and rate of the nanocomposites were improved after introducing REC, and the gel strength greatly depended on the concentration of crosslinker MBA. The nanocomposite showed excellent responsive properties and reversible On–Off switching characteristics in various saline, pH, and hydrophilic organic solvent/water solutions, which provided great possibility to extend the application domain of the superabsorbent nanocomposites such as drug delivery system. Copyright © 2010 John Wiley & Sons, Ltd.     

2,4-D/CMC-g-AM/SA/FK微球的制备及其缓释性能

以丙烯酰胺(AM)为单体,制备了羧甲基纤维素钠接枝丙烯酰胺共聚物(CMC-g-AM)。以2,4-二氯苯氧乙酸(2,4-D)为模型药物,以羽毛蛋白(FK)为共混改性剂,采用挤压法制备了CMC-g-AM/海藻酸钠(SA)/羽毛蛋白载药微球。利用红外光谱、光学显微镜、激光粒度仪分别对接枝共聚物的结构、载药微球的形貌以及粒径分布进行了表征,并探讨了不同的接枝共聚物、羽毛蛋白用量、交联剂浓度和交联时间对缓释微球的载药量和缓释性能影响。结果表明,当CMC-g-AM的合成单体比AM:CMC为3:1,羽毛蛋白用量为30%,交联剂浓度为0.7 mol·L-1,交联时间为1 h,载药微球的载药量较高,为16.7%。复合微球平均粒径为1.6 mm。载药微球具有良好的缓释性能,释药曲线符合Higuchi动力学方程。     

Chromatography of inorganic ions o sulfoethyl cellulose layer in hydrochloric acid and in hydrochloric acid-ammonium thiocyanate media

Summary Chromatographic behavior of 51 inorganic ions has been systematically studied on layers of sulfoethyl (SE) cellulose, a strongly acidic exchanger, in hydrochloric acid and in acid-ammonium thiocyanate media. The sorption of most of the ions on he SE-cellulose decreases with increasing concentration of the acid and the thiocyanate. The characteristic retention of some metal ions of SE-cellulose layer can be recognized over a low concentration of the acid or the salt. Feasibilities for separations of analytical interest are also presented in both systems.     

Mercerization of primary wall cellulose and its implication for the conversion of cellulose I→cellulose II

The mercerization of homogenized primary wall cellulose extracted fromsugar beet pulp was investigated by transmission electron microscopy (TEM),X-ray diffraction together with ¹³C CP-MAS NMR, and FT-IR spectroscopy.For samples resulting from acid extraction, mercerization began at 9% NaOH, whereasfor samples purified by alkaline treatment, the mercerization started at 10%NaOH. The change in morphology when going from cellulose I to cellulose II wasspectacular, as all the microfibrillar cellulose morphology disappeared duringthe treatment. This change in morphology was very drastic as soon as the NaOHconcentrations were increased beyond 8 and 9% for the acid and alkalinepreparedsamples, respectively. On the other hand, the conversion was found to be moreprogressive in terms of increasing NaOH concentration when the transformationwas analyzed by X-ray diffraction or spectroscopy. Our observations of themercerization of isolated cellulose microfibrils are consistent with theconceptof cellulose microfibrils made of parallel chains in cellulose I and crystalsofcellulose II consisting of antiparallel chains.     

Thin-layer chromatography of inorganic ions on sulphoethyl cellulose in sulphuric acid and ammonium sulphate media

Summary Thin-layer chromatographic (TLC) behaviour of 51 inorganic ions on a strongly acidic cation-exchanger, sulphoethyl (SE) cellulose, has been studied systematically in sulphuric acid and ammonium sulphate media (0.01–0.2 mol dm⁻³). Some aspects of the adsorption behaviour of the inorganic ions on the SE-cellulose are compared with those on other cation-exchangers in the same eluent systems. The possibilities for TLC separations of analytical interest are also proposed on SE-cellulose in sulphuric acid and acid ammonium sulphate media.     

交联-羧甲基复合变性淀粉的流变与降失水性能

以马铃薯淀粉和氯乙酸为主要原料,通过交联-醚化制备了交联-羧甲基复合变性淀粉(CCMS),考察了所得CCMS糊液的流变性能和在钻井泥浆中的降滤失水性能,并对其降失水原理进行了探讨。结果表明,在质量分数为0.5%~4.0%、温度为20~60℃的实验条件下,CCMS糊液表现为假塑性流体特征,符合Ostwald-Dewaele的经验公式ηa=Kγn-1;将CCMS与中粘羧甲基纤维素(MV-CMC)进行对比实验,结果发现,在饱和盐水泥浆和4%盐水泥浆中,当其用量分别为MV-CMC质量分数的57%和75%时,就可达到钻井液用MV-CMC的增粘、降滤失水性能指标。     

Improved Cell Viability and Biocompatibility of Bacterial Cellulose through in Situ Carboxymethylation

Bacterial cellulose (BC) is a natural product with multiple properties, which has been utilized in tissue engineering. However, cell adhesion and proliferation are reported to be weaker on native BC, providing less support compared to other types of biomaterials, like collagen. To increase the biocompatibility and the medical performance of BC, in situ modification is used to add carboxymethyl group to BC. By partially changing the structure and physical properties of BC, carboxymethylation significantly increases cell affinity and viability, especially on the initial cell adhesion. Furthermore, in the in vivo implantation, the tissue reaction shows that carboxymethylation significantly increases the biocompatibility of BC, exhibiting better tissue condition and a lower inflammatory reaction which are proved through HE staining and immunohistochemistry. The data prove that in situ carboxymethylation is a simple and direct way of improving the performance of BC in medical applications.     

Separation of rhenium by thin-layer chromatography with polyethyleneimine cellulose in hydrochloric acid media

Summary The thin-layer chromatographic behavior of 49 inorganic ions on polyethyleneimine (PEI) cellulose has been investigated in hydrochloric acid media (0.01–1.0 mol dm⁻³). The sorption on the cellulose decreases with increasing acid concentration for most of the ions, but As(III), Ti(IV) and Te(VI) do not exhibit any R_f variation with the acid concentration. The R_f spectra of TI(I), Cd(II), Pb(II) and Zn(II) have a maximum. Ag(I), Bi(III), Nb(V), Ta(V), Mo(VI) and W(VI) are retained tightly on the layer, due to either insoluble salt formation or extensive hydrolysis. The extremely low R_f values of Hg(II), Pd(II), Au(III), Ru(III) and Pt(IV) are accounted for by stability of their chlorocomplexes. Re(VII) distributes chromatographically, having moderate R_f values between 0.3 and 0.6, so that the selective separation of Re(VII) from the other ions is feasible.