Degradation of cellulosic and hemicellulosic substrates using a chelator‐mediated Fenton reaction

The involvement of catechol and hydroxamate chelators, along with hydrogen peroxide and Fe³⁺, in the degradation of cellulosic and hemicellulosic substrates was examined with the purpose of improving our current knowledge of the non‐enzymatic mechanisms involved in wood biodegradation by fungi. It could be demonstrated that a catechol chelator‐mediated Fenton reaction not only clearly degraded hemicellulosic substrates but also significantly accelerated and increased the effectiveness of degradation reactions. On the other hand, when a hydroxamate chelator‐mediated Fenton reaction was used, an inhibitory effect was observed. When cellulosic substrates underwent a chelator‐mediated Fenton reaction, no significant difference in degradation was observed between catechol and hydroxamate chelator‐mediated reactions. However, a catechol‐mediated reaction did accelerate the degradation of cellulosic substrates at the beginning of reactions. In addition, it was observed that with a chelator‐mediated Fenton reaction, oxidation of cellulose proceeds depolymerization. Copyright © 2005 Society of Chemical Industry     

Kinetic modeling of hemicellulose hydrolysis in the presence of homogeneous and heterogeneous catalysts

Kinetic models were developed for the hydrolysis of O‐acetyl‐galactoglucomannan (GGM), a hemicellulose appearing in coniferous trees. Homogeneous and heterogeneous acid catalysts hydrolyze GGM at about 90°C to the monomeric sugars galactose, glucose, and mannose. In the presence of homogeneous catalysts, such as HCl, H₂SO₄, oxalic acid, and trifluoroacetic acid, the hydrolysis process shows a regular kinetic behavior, while a prominent autocatalytic effect was observed in the presence of heterogeneous cation‐exchange catalysts, Amberlyst 15 and Smopex 101. The kinetic models proposed were based on the reactivities of the nonhydrolyzed sugar units and the increase of the rate constant (for heterogeneous catalysts) as the reaction progresses and the degree of polymerization decreases. General kinetic models were derived and special cases of them were considered in detail, by deriving analytical solutions for product distributions. The kinetic parameters, describing the autocatalytic effect were determined by nonlinear regression analysis. The kinetic model described very well the overall kinetics, as well as the product distribution in the hydrolysis of water soluble GGM by homogeneous and heterogeneous catalysts. The modelling principles developed in the work can be in principle applied to hydrolysis of similar hemicelluloses as well as starch and cellulose. © 2014 American Institute of Chemical Engineers AIChE J, 60: 1066–1077, 2014     

纳滤技术在粘胶纤维生产中的应用

阐述了粘胶生产中分离废碱中半纤维素的必要性。重点介绍了纳滤技术的优点及其在分离中的应用。粘胶纤维生产车间采用的凯能科氏膜和沈阳新华膜的使用经验,对2种膜系统的工艺参数进行了详细对比,提出实际应用中出现的问题及解决办法。     

Preparation and Characterization of Hydrophobic Bagasse Hemicellulose-based Films

To improve the hydrophobicity of bagasse hemicellulose-based films, glutaraldehyde was applied when preparing films of original and cationic bagasse hemicellulose with the addition of polyvinyl alcohol and sorbitol. The results showed that the cationic modification could increase the hydrophobicity of the hemicellulose-based film, and the hydrophobicity of hemicellulose-based films crosslinked with glutaraldehyde also increased. However, cationic modification of hemicellulose decreased the stress of the hemicellulose-based film. While crosslinking with glutaraldehyde increased the stress of both the original and cationic hemicellulose-based films. Macrophotography indicated that the film formability of the original hemicellulose was better than that of cationic hemicellulose. Through SEM observation, the degree of bonding of different components of the films was found to be increased due to crosslinking with glutaraldehyde. The crosslinking reaction between glutaraldehyde and hemicellulose was further confirmed by FT-IR spectroscopy.     

半纤维素基阿维菌素载药微囊的制备及性能

目前阿维菌素以高效性、无污染和低抗药性等特点而得到广泛应用,但是其稳定性较差,易降解导致使用量较大从而造成浪费。为解决上述问题,本文以半纤维素为基体,利用原位聚合法制备阿维菌素载药微囊（HDCM）,通过制备条件、热降解性、储存稳定性和释放动力学研究,确定了HDCM的载药量、热稳定性及释放性能。结果表明,在芯壁比为1∶34（质量比）,温度为65℃,pH为3.5的制备条件下,HDCM的载药量可达66.5%,粒径较小且分散均匀。HDCM的热降解性能和恒温热稳定性能较阿维菌素原药有所提高,最高热分解温度从261℃增加到272℃,阿维菌素原药10h后降解率达到12.1%,而载药量为66.5%的HDCM降解率仅为5.2%。HDCM的释放机理满足Fick扩散,阿维菌素原药在水中的累积释放率在12h之内达到83.8%,而HDCM的累积释放率在24h之后才有所增大,12h内其释放率仅为33.7%,表明HDCM具有极好的缓释性能。     

半纤维素醚化改性及其用作造纸助剂的研究进展

介绍了半纤维素的化学组成和结构特点以及近20年来半纤维素醚化改性和用作造纸助剂的研究进展。主要阐述了使用不同醚化剂对半纤维素醚化改性,制备羧甲基半纤维素（阴离子半纤维素）、季铵化半纤维素（阳离子半纤维素）和两性离子化半纤维素及醚化改性后产品的应用研究现状,展望了半纤维素醚化改性的发展前景。     

苹果膳食纤维中半纤维素的化学组成

采用碱法和二甲亚砜法从苹果膳食纤维中提取出4种半纤维素,分别命名为半纤维素A、B、C和E,通过红外分析和电镜扫描对其化学组成和表面微观结构进行了研究。结果表明:苹果膳食纤维中半纤维素由木葡聚糖(半纤维素A)、木聚糖1(半纤维素B)和木聚糖2(半纤维素C)以及半乳甘露聚糖(半纤维素E)等组成,4种半纤维素的表面微观各不相同,木聚糖1颗粒表面呈规则的晶形外观,具有成晶性;木葡聚糖颗粒表面具有很多颗粒状结构,具有一定的成晶性;木聚糖2和半乳甘露聚糖颗粒表面呈不规则形状,不具有成晶性。     

Green and Effective Ammonium Carbonate-assisted Process for Drying Hemicellulose Obtained through Alkali Extraction of Bleached Bamboo Kraft Pulp

Hemicellulose has a wide range of applications,including that as an emulsifier for the food industry and raw material for the synthesis of bioethanol/biochemicals and biodegradable films.Hemicellulose is usually present as a spent liquor,such as the prehydrolysis liquor of the prehydrolysis kraft dissolving pulp production process and the alkali extraction liquor of the cold caustic extraction of pulp fibers.Due to its dilute nature,hemicellulose needs to be dried for practical utilization,and this is challenging.In this study,cellulose and hemicellulose in a bleached bamboo kraft pulp were separated using an alkali extraction process.Hemicellulose obtained from the extraction liquor was dried by an ammonium carbonate-assisted drying process.The effects of drying time and drying temperature were determined.Structure of the hemicellulose obtained by the ammonium carbonate-assisted drying process was similar to that of original hemicellulose,as revealed by detailed Fourier transform infrared and X-ray diffraction analyses.The novel drying method was more energy efficient and required a shorter drying time than the conventional freeze drying method,and the excellent solubility in alkaline solutions favored the chemical modification of hemicellulose.The dried hemicellulose can be used as a renewable raw material for the preparation of hydrogels and other substances such as bioethanol/biochemicals and biodegradable films.     

玉米皮半纤维素/壳聚糖/甘油复合膜制备及性质研究

以玉米皮半纤维素、壳聚糖和甘油共混制备复合膜,研究了玉米皮半纤维素、壳聚糖和甘油添加量对复合膜力学性质的影响,考察了复合膜的结晶结构、表面形貌、热稳定性、抗菌性能、降解性能、热溶解性和透光性。结果表明,当玉米皮半纤维素浓度为2.4%,壳聚糖浓度为0.6%,甘油浓度为0.4%时,做出的复合膜具有较好的抗拉强度和断裂伸长率。X-射线分析表明,半纤维素结晶结构未发生实质性变化,SEM和DSC分析表明,复合膜具有较好的表面特性和热稳定性,制得的复合膜对大肠菌群和金黄色葡萄球菌具有一定的抑菌效果,并且具有较好的降解性、热溶解性和透光性。