An investigation of mercerization in decayed oak wood by a white rot fungus (Lentinula edodes)

The crystal transformation of cellulose I to cellulose II during alkali swelling was investigated in decayed oak wood that was used for shiitake mushroom cultivation and the results were compared with those of sound wood using X-ray diffraction analysis and ultraviolet microscopy. During mercerization, the sapwood cellulose of decayed wood was easily transformed into Na-cellulose I and then Na-cellulose I was easily converted into cellulose II after washing and drying. The sapwood cellulose of sound wood was converted more slowly to Na-cellulose I and very little Na-cellulose was converted to cellulose II. Na-cellulose I of sound wood can be reconverted to cellulose I during washing and drying. Therefore, it could be concluded that lignin prevented the alkali swelling of wood cellulose and the transformation from cellulose I to cellulose II. The decay of crystalline cellulose might cause an increase in the susceptibility of alkali swelling, so that the degree of mercerization may be also affected.     

Influence of carboxyl group on the acid hydrolysis of cellulose

Cellulose isolated from wood is more susceptible than cotton cellulose to homogeneous hydrolysis in phosphoric acid. The influence of carboxyl group introduction at the C6 position on the hydrolysis rate of cellulose in 82.5% phosphoric acid was studied as a model of the oxidation of cellulose during pulping. The rate constant of hydrolysis for dissolving pulp was larger than that of cotton cellulose at temperatures of 25°–35°C. Mercerized cotton cellulose was partially oxidized regioselectively at the C6 position by a free radical system using 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO). The oxidized cellulose was obtained at a range of 1.7–12.7 mEq carboxyl content per 100 g of cellulose. The hydrolysis rate of the oxidized cellulose samples accelerated with increasing carboxyl content in the samples.Part of this work was presented at the 5th Annual Meeting of the Cellulose Society of Japan, Kyoto, July 1998     

解结晶对纤维素吸附纤维素酶的影响

为探讨解结晶处理提高酶水解效率的机理,对比研究了高结晶度的微晶纤维素(MCC)和低结晶度的解结晶微晶纤维素(D-MCC)对纤维素酶的吸附过程。结果发现:酶吸附平衡后,样品的XPS和FT-IR分析表明纤维素酶通过酶蛋白的氨基(—NH_2)与纤维素分子链上的羟基(—OH)之间以氢键(C—OH…NH)力吸附在MCC上;相同条件下得到的MCC和D-MCC吸附率曲线的差异表明,底物结构的改善比提高温度更能提高酶吸附率;比较纤维素酶对MCC和D-MCC在35℃下的吸附动力学可知,通过降低底物的结晶度可促进酶吸附,刚性结构的MCC更满足准一级动力学的假设,D-MCC表面结构相对松散,其吸附过程需进一步分析,以得到更适合的动力学方程。     

Analysis on residue formation during wood liquefaction with polyhydric alcohol

Liquefactions of cellulose powder, steamed lignin, alkali lignin, and their mixtures were carried out to analyze the reaction process of wood using polyhydric alcohol. The liquefaction of wood proceeded immediately and wood components were converted to N,N-dimethylformamide (DMF)-soluble components. After that, the condensation reaction occurred with increasing reaction time. However, none of cellulose powder, steamed lignin, and alkali lignin condensed by themselves during their liquefaction. The mixture of cellulose and lignin was also liquefied, and condensed after a long reaction time. The results of analysis showed that the behavior of the mixture resembled that of wood with respect to molecular weight distribution and the main functional groups. Lignin was converted to DMF-soluble compounds in the initial stage of wood liquefaction, followed by cellulose gradually being converted into soluble compounds. After that, condensation reactions took place among some parts of depolymerized and degraded compounds from cellulose and lignin, and were converted into DMF-insoluble compounds. It was concluded that the rate-determining step of wood liquefaction was the depolymerization of cellulose. Furthermore, it was suggested that the condensation reaction was due to the mutual reaction among depolymerized cellulose and degraded aromatic derivatives from lignin or due to the nucleophilic displacement reaction of cellulose by phenoxide ion.Part of this report was presented at the 52nd Annual Meeting of the Japan Wood Research Society, Gifu, April 2002     

稀酸预处理改善玉米秸秆酶水解性能的机制探讨

为了探讨在稀酸预处理提高玉米秸秆在纤维素酶酶解阶段提高纤维素转化率的机制,利用一系列的检测方法:FT-IR、XRD、SEM和比表面积分析仪分析了预处理前后玉米秸秆在形态学和物理化学性质方面的变化.在经过稀酸预处理后的玉米秸秆在纤维素酶酶解阶段其纤维素转化率有较大的提高,经过170℃,60 min,固液比1∶15(g∶mL),1.00 g/mL酸质量浓度的条件预处理后,从31.88％提高到95.74％.XRD结果显示预处理后玉米秸秆的结晶度有所增加,从原料的37.8％增加到58.7％,但是当预处理强度增加到一定程度后,结晶度没有较大的变化,基本维持在58％.玉米秸秆的表面结构在稀酸预处理后,原来的光滑表面变得粗糙、多孔,这样的表面有利于纤维素酶与玉米秸秆的接触,预处理后玉米秸秆的比表面积有很大程度的增加,经过170℃,60 min,固液比1∶15,1.00g/mL酸质量浓度的条件预处理后,玉米秸秆的比表面积从0.329 m2/g增加到2.878 m2/g,这都有利于改善纤维素酶对纤维素的作用,增加纤维素转化率.     

三肽纤维素酯的制备及应用研究

以微晶纤维素为原料,芴甲氧羰基-L-脯氨酸(FMOC-L-Pro-OH)、芴甲氧羰基-L-缬氨酰-L-苯丙氨酸(FMOC-L-Val-L-Phe-OH)和3,5-二硝基苯甲酸为衍生化试剂,经酰氯化、酯化、肽链的延长和氨基的修饰等反应,合成了末端氨基被修饰的三肽纤维素酯(TPC)。通过实验证实三肽若要与纤维素成酯,必须采用先酯化后肽链延长的方式,其中关键步骤为酯化反应,其反应条件为:纤维素在LiCl/DMAc溶液中的质量浓度为20 g/L,温度100℃,n(酰氯)∶n(纤维素中羟基总量)为3∶1,反应时间20 h。再通过肽链延长、氨基修饰反应,最终可得到取代度为2.15的三肽纤维素酯。经过FT-IR、TG、XRD和元素分析等多种分析手段测试可知,3,5-二硝基苯甲酸对肽链末端进行了成功的修饰,该反应路径可行。酯化反应的产物根据沉淀析出液不同,内部氢键产生也不相同,可得到功能不同的三肽纤维素酯。TPC的应用实验结果表明,以甲醇为沉淀析出液的纤维素酯,是良好的肠溶包衣材料,具有遮光性强崩解迅速的特点,但其生理毒性有待进一步研究;以水为沉淀析出液的纤维素酯,被制成手性涂敷柱后,综合了刷型固定相与纤维素固定相的两大优势,拆分能力强大高效,耐化学性极佳,适用范围比以往涂敷柱更广泛,尤其适用于四氢呋喃流动相体系。     

互花米草化学性质和纤维形态分析

对不同生长时期的互花米草的化学性质和纤维形态进行测定与分析,结果表明:随生长期的增长,互花米草综纤维素与木质素含量逐渐增加,而各种抽出物含量呈减少趋势,成熟的互花米草综纤维素含量与马尾松木材相近.秆部位的综纤维素和木质素含量最高;互花米草原料pH值呈中性或弱碱性,秆部位酸碱缓冲容量最低,梢部位则较高;互花米草秆部位的表皮和叶部位二氧化硅含量较高.互花米草纤维属于中等长度纤维,纤维大小等级为细.     

Mechanical interaction between cellulose microfibril and matrix substance in wood cell wall determined by X-ray diffraction

We investigated mechanical interactions between the cellulose microfibril and the matrix substance in wood cell walls. X-ray diffraction measurements showed that the peak positions of (200) and (004) from cellulose crystals in wood cell walls tended to shift lower and higher toward 2θ, respectively, during water desorption in wood. From our simulations, it is shown that the peak shift of (200) during water desorption is not due to changes in the scattering pattern of the amorphous substance or to lateral expansion of the cellulose crystals due to the Poisson effect in the cellulose microfibril, which is compressed in the molecular chain direction as the amorphous substance shrinks. This suggests that the cellulose microfibril expands transversely during water desorption in the wood cell wall, and that there is a mechanical interaction between the cellulose microfibril and the matrix substance.     

的催化作用

采用以多元羧酸为酯化剂，无机盐为催化剂的交联体系。这一体系是水溶的、无毒害的纤维素交联反应的非甲醛系试剂的交联体系。作者采用傅立叶转换红外光谱(ITIR)分析了多元羧酸与纤维素交联反应过程中催化剂次磷酸盐(NaH2PO2)的作用机理。结果表明：催化剂NaH2PO2对多元羧酸与纤维素酯化反应的两个过程都有催化作用，其两个过程为：1)多元羧酸脱水形成五元环酸酐中间体，NaH2PO2可以降低五元环酸酐中间体形成的温度，加速五元环酸酐的形成；2)五元环酸酐与纤维素亲核取代形成酯，NaH2PO2提高了酯化产物转化率，具有明显的催化作用。     

Mechanism of mercerization revealed by X-ray diffraction

We studied the crystalline conversion of cellulose fiber from cellulose I to cellulose II (mercerization) by X-ray diffraction, focusing on the putative chain-polarity conversion from parallel to antiparallel. The structural change of Na-cellulose was examined during stepwise changes in NaOH concentration. Either Na-cellulose I or Na-cellulose II was formed depending on the initial NaOH concentration. Once formed, both structures were stable and did not inter-convert to each other when the NaOH concentration was changed. Such stability indicates that the parallel-to-antiparallel conversion is not likely to take place in the crystalline region of Na-cellulose. Regeneration of cellulose II from both forms of alkali cellulose proceeded with the formation of 0.44 nm lattice plane corresponding to the sheet of (1 ¯1 0) plane of cellulose II, showing that the molecular stacking due to van der Waals' interaction is the driving force of the formation of cellulose II. A mechanism was proposed whereby the geometry of the cellulose molecule allows close fitting of the hydrophobic faces only in the antiparallel arrangement, thus driving formation of the antiparallel structure of cellulose II.This study was presented in part at the 47th Annual Meeting of the Japan Wood Research Society, Kochi, April 1997; and at the 6th Annual Meeting of the Cellulose Society of Japan, Tokyo, June 1999     

Improved method for evaluation of cellulose degradation

 Use of a fundamental concept, henceforth referred to as the scission fraction of cellulose unit (SFCU), was suggested to clarify the cleavage reactivity of cellulose during oxygen delignification (OD). According to the SFCU theory, the cleavage activity of pulp cellulose remains relatively undisturbed provided the experimental conditions are maintained regardless of pulp origin. SCFU is a universal variable for evaluating how processes and additives affect the degree of pulp cellulose degradation. Specifically in this study, the effects of the protector additives MgSO₄ and phenol on the oxygen delignification (OD) process were investigated. Both phenol and MgSO₄ retard the cleavage rate of the cellulose chain, but the retarding effect of MgSO₄ is greater than that of phenol. Phenol alone cannot significantly improve the selectivity of the OD process, whereas MgSO₄ can decrease the cleavage rate of cellulose and increase the selectivity of OD. Moreover, synergistic selectivity enhancement for pulp using a combination of MgSO₄ and phenol was observed. The protective effect of various chemical protectors was additive, whereas the retarding effect on delignification was not. Received: December 21, 2001 / Accepted: July 22, 2002 Acknowledgments We acknowledge the member companies of the Institute of Paper Science and Technology whose interest drives most of our research efforts. Additionally, we gratefully acknowledge the Department of Energy (grant DE-FC07-02ID14261) whose support has made part of this work possible.     

Summer precipitation influences the stable oxygen and carbon isotopic composition of tree-ring cellulose in Pinus ponderosa

The carbon and oxygen isotopic composition of tree-ring cellulose was examined in ponderosa pine (Pinus ponderosa Dougl.) trees in the western USA to study seasonal patterns of precipitation inputs. Two sites (California and Oregon) had minimal summer rainfall inputs, whereas a third site (Arizona) received as much as 70% of its annual precipitation during the summer months (North American monsoon). For the Arizona site, both the delta(18)O and delta(13)C values of latewood cellulose increased as the fraction of annual precipitation occurring in the summer (July through September) increased. There were no trends in latewood cellulose delta(18)O with the absolute amount of summer rain at any site. The delta(13)C composition of latewood cellulose declined with increasing total water year precipitation for all sites. Years with below-average total precipitation tended to have a higher proportion of their annual water inputs during the summer months. Relative humidity was negatively correlated with latewood cellulose delta(13)C at all sites. Trees at the Arizona site produced latewood cellulose that was significantly more enriched in (18)O compared with trees at the Oregon or California site, implying a greater reliance on an (18)O-enriched water source. Thus, tree-ring records of cellulose delta(18)O and delta(13)C may provide useful proxy information about seasonal precipitation inputs and the variability and intensity of the North American monsoon.     

Characterization of the products resulting from ethylene glycol liquefaction of cellulose

The composition of liquefied cellulose in the presence of ethylene glycol (EG) was studied. The liquefied products were fractionated and analyzed with highperformance liquid chromatography and nuclear magnetic resonance. EG-glucosides were detected as the only saccharides and 2-hydroxyethyl levulinate as the highly decomposed compound derived from cellulose. Quantitative analysis of the EG-glucosides and levulinic acid that comes from the levulinate shows the presence of the following mechanism in the EG-liquefaction of cellulose. First, cellulose is degraded and produces considerable amounts of EG-glucosides during the early stage of liquefaction. Then, when liquefaction is prolonged, the glucosides are decomposed, leading to a large quantity of levulinates.     

Preparation and characterization of electroless nickel-coated cellulose fibres

The aim of this project was to fabricate electroless nickel-coated cellulose fibres. Ultimately, these nickel-coated cellulose fibres will be used to develop a cost-effective polymer composite for electromagnetic interference (EMI) shielding and/or electrostatic discharge (ESD) applications. An attempt has been made to impart electrical conductivity onto cellulose fibres via an electroless nickel plating process. The aim was to achieve a homogeneous, continuous layer of Ni on the cellulose fibres, and the plating conditions were optimized to achieve this. The relationship between the coating morphology and the performance of the coated fibre was also of interest. Testing was carried out using cellulose filter paper and then loose cellulose fibres. Scanning electron microscopic (SEM) images of nickel-coated filter paper showed that nickel particles are bonded to the cellulose fibres. The coating appeared more compacted and continuous as plating time increased, corresponding to lower surface resistivity. This observation suggested a correlation between morphology and electrical conductivity of the coating. For nickel-coated cellulose fibres, after optimization of plating conditions, a uniform deposition of nickel particles around the cellulose surfaces was confirmed by SEM images. EDS and XRD results confirmed similar coating could be produced on filter paper and cellulose fibres. SEM images of cross-sectioned nickel-coated cellulose fibres illustrated nickel particles had penetrated into the inner walls of the cellulose fibres. This impregnation of the fibres should act to increase the bonding between nickel coating and cellulose fibres. These nickel-impregnated cellulose fibres could now be incorporated into a polymer matrix to create an electrically conducting composite with the right processing parameters.     

Studies on the thermal properties and structures of deoxyhalocelluloses

The thermal properties and structures of deoxyhalocelluloses were studied using thermogravimetric and differential scanning calorimetric analyses and an X-ray diffraction method. The X-ray diffraction curves of the cellulose derivatives were obtained after subjecting them to a specific treatment that was supposed to render a specific cellulose allomorph from the amorphous state cellulose; all of the cellulose derivatives examined without such treatment exhibited no crystalline features. Only deoxyfluorocellulose was found to give a diffraction pattern similar to that of the corresponding cellulose allomorph, which was cellulose IV in this case. On the basis of the thermal analyses, it was confirmed that chlorodeoxycellulose has a flameretardant property, whereas deoxyfluorocellulose was found not to be flame-retardant. The difference is supposedly due to the difference in the bonding energy between C-Cl and C-F.     

毛白杨纤维素合酶基因PtCesA_4的克隆、表达及单核苷酸多态性分析

组合利用生物信息学和RT-PCR方法,首次从毛白杨未成熟木质部cDNA中分离出PtCesA4cDNA全长,并进行测序和序列分析,结果表明克隆的毛白杨PtCesA4 cDNA片段总长为3 757 bp,基因内部含有完整的开放阅读框架,大小为3 129 bp,可编码长度为1 042个氨基酸残基的蛋白质,所推导的蛋白质氨基酸序列与拟南芥AtCesA4、水稻OsCesA,和火炬松PtCesA2的蛋白质氨基酸序列同源性分别为80.3%,78.9%和75.6%.组织特异性Realtime-PCR结果显示,PtCesA4基因在杨树根、茎、叶片和顶端分生组织中均有表达,但其表达模式却不同:PtCesA4在成熟叶片、未成熟木质部和成熟木质部中表达丰度最高,在根部和顶端分生组织表达丰度中等,在树皮和韧皮部有少量表达,在形成层中表达丰度最低.在此基础上,组合利用MEGA3.1和DnaSP4.50.4软件对毛白杨40株基因型个体的PtCesA4序列进行比对和分析,检测到153个单核苷酸多态性(sinsh nueleotide polymorphism,SNP)位点,SNP频率为1/35 bp,多样性指数π/0.005 02.其中51个是常见SNPs,102个为罕见SNPs.在这些SNPs中,有118个属于转换,35个属于颠换.在外显子区域,共检测到69个SNP位点,其中59个为同义突变,10个为错义突变.对PtCesA4基因内SNPs进行的连锁不平衡分析结果显示,随着核苷酸序列长度的增加,SNPs的连锁不平衡在基因内部迅速衰退,因此,在毛白杨中,基于PtCesA4基因的连锁不平衡作图是可行的,而基于整个杨树基因组的连锁不平衡作图是不可行的.也是不必要的.研究结果为毛白杨PtCesA4基因的连锁不平衡作图及其基因辅助毛白杨木材纤维性状的分子育种提供了理论依据.     

Tracheid differentiation in Pinus radiata

Summary Differentiating tracheids in Pinus radiata D. Don have been examined with the electron microscope. Despite the fact that one of the major differentiation processes is cellulose formation, little ultrastructural evidence has been found to indicate how this occurs. On the other hand, there is ample evidence of the incorporation of non-cellulosic material into both the expanding primary wall and the developing secondary wall. The only structure which could possibly be related to cellulose formation is a system of osmiophilic particles which have been found in the space between the plasmalemma and the developing wall, or attached to the most recently formed wall layer. The absence of microtubules during the main phase of secondary wall formation supports the view that these structures are not involved directly in the biosynthesis of cellulose.The author wishes to thank Mrs B. A. Hodgkiss for technical assistance.     

Mechanics and pyrolysis analyses of rotation welding with pretreated wood dowels

This study examined the mechanics and pyrolysis analyses of rotation welding with treated dowels. Test results indicated that welding specimens with dowels immersed in CuCl₂ solution exhibited higher pullout resistance than untreated specimens. Scanning electron microscopy was used to observe and analyze the welding interface. Wood dowels immersed in CuCl₂ solution provided more flowing molten polymer to obtain better connection than untreated wood dowels. Based on the chemical analyses of X-ray photoelectron spectroscopy, and thermogravimetric analyses, the hydrolysis of cellulose and hemicellulose was detected after immersion of the dowels in a CuCl₂ solution. Pyrolysis of cellulose, hemicellulose and lignin occurred during the welding process. The hydrolysis of cellulose and hemicellulose may promote the pyrolysis and efficient connection of wood components during the welding process.     

Laboratory testing of wood mouse and common vole sensitivity to bromadiolone,sodium selenite,and cellulose

Maintaining the numbers of wood mice and common voles at an acceptable economic level, especially during years of massive outbreaks, is a major challenge in plant protection. Efforts to reduce the negative effects of rodenticides on the environment, to improve the integrated pest control system, and to minimize risks for human and animal health require investigation of the potentials of cellulose, as a natural product, and sodium selenite as rodenticides. The present study was conducted to determine the sensitivity of these rodent species to bromadiolone (a.i. 0.005 %), sodium selenite (a.i. 0.1 and 0.05 %), and cellulose (a.i. 45 %) baits. All experiments were done using no-choice and choice feeding trials. A low acceptance of cellulose baits was found in the choice feeding trial, and the time of first deaths indicate that stress and hunger increase the death rate in both species. The taste had a negative impact on the acceptability of baits containing sodium selenite. Low bait acceptance of cellulose and sodium selenite resulted in lower mortality of both species. The acquired results indicate that bromadiolone remains a more effective solution than cellulose and sodium selenite for control of wood mice and common voles.