利用FTIR对苯基异氰酸酯与不同含水率纤维素反应的研究

通过FTIR红外光谱对苯基异氰酸酯与醇、水、不同含水率纤维素反应产物的研究 ,确定了产物的红外光谱吸收峰的归属。研究发现 :异氰酸酯与绝干纤维素羟基反应产物是氨基甲酸酯 ,随着纤维素含水率的增加 ,异氰酸酯与纤维素的反应越来越低 ,与水反应的比例越来越高 ;当纤维素含水率为 9 78%时 ,异氰酸酯绝大部分与水反应生成取代脲     

DSC法研究苯基异氰酸酯与木素、纤维素、木粉的反应特性

用差式扫描量热法(DSC)对苯基异氰酸酯与木素、纤维素、木粉的反应进行探究.在不同升温速率下,试验对比苯基异氰酸酯分别与木素、木粉在绝干含水率和平衡含水率(木素为3%,木粉为5%)条件下的反应特征;同时研究木素存在下苯基异氰酸酯与纤维素的反应特性.基于对DSC图的讨论分析和Ozawa方程,求解苯基异氰酸酯分别与木素、木粉反应的活化能,初步揭示异氰酸酯分别与木素、纤维素、木材的胶接反应特性.研究表明:苯基异氰酸酯与木素反应温度和活化能相对于苯基异氰酸酯与木粉反应的温度和活化能要低;木素与纤维素混合时,异氰酸酯主要与木素反应,当纤维素的含量较大时,纤维素与异氰酸酯反应程度加大;当木材含水率为5%时,水分导致含水木材与异氰酸酯反应活化能降低了34%.     

高含水率状态下桦木与异氰酸酯的胶接化学反应历程

对湿固化异氰酸酯胶黏剂粘接高含水率桦木的胶接机理进行系统研究。利用计算化学方法这一崭新的手段,采用Material Studio软件中DMol3模块,采用基于密度泛函理论的量子化学程序,通过模拟胶接体系中异氰酸酯基团(NCO)与自由水(H2O)及桦木中不同化学环境羟基(—OH)的反应历程,搜索反应的过渡态,计算反应活化能以及反应总能量,判定反应进行的难易以及先后次序。研究结果表明胶接体系中—NCO基团与自由水反应的活化能与—NCO基团与纤维素中—OH的反应活化能相接近,反应存在竞争关系。胶接体系中—NCO与纤维素上—OH相对来说较容易反应,且反应进行的顺序是C6C3C1C2,均为放热反应;与木质素上—OH不容易反应,反应进行的顺序是紫丁香基丙烷(Lig-S)愈创木基丙烷(Lig-G)对羟苯基丙烷(Lig-H),其中羟基与Lig-S和Lig-G的反应是放热反应,与Lig-H的反应是吸热反应。     

利用DSC研究异氰酸酯与纤维素的反应机理

应用DSC分析中的等温扫描和等速升温扫描,研究异氰酸酯与不同含水率纤维素反应机理。等温DSC研究揭示含水纤维素与异氰酸酯反应时,存在无规成核机理、扩散机理和相界面机理等多种情形,水分迁移作用和异氰酸酯与水反应速率较快是致使异氰酸酯与含水纤维素的反应机理复杂的关键。通过等速升温DSC研究,找到一种能够描述异氰酸酯与不同含水纤维素等速升温反应的机理函数。     

硅烷偶联剂处理竹粉化学结构变化及其反应路径

利用X射线光电子能谱(XPS)、X射线粉末衍射(XRD)和红外光谱(IR)研究硅烷偶联剂(KH-560)改性前后竹粉结构的变化,并推测硅烷偶联剂对竹粉表面改性的机理.实验结果表明,KH-560水解后,通过形成氢键和脱水缩合两个阶段结合到竹粉的表面.硅烷偶联剂改性后的竹粉结晶结构没有明显的变化,IR谱图出现了醚键的吸收,XPS在101.18 eV处出现了Si的发射峰,C1s分峰所对应的结合能由288.16 eV变为288.52 eV,氧原子在530.98 eV处C=O双键的分峰消失,说明在没有外力或化学试剂作用的情况下,竹纤维素分子间较强的相互作用力使反应无法发生在竹纤维素上,而主要是在木质素的醛基C=O上进行.     

氨基甲酸酯类化合物的合成及其AChE抑制活性研究

以松节油主要组分3-蒈烯为原料首先合成了3-异丙基-5-甲酚(1)和香芹酚(2),从这2个化合物出发通过异氰酸酯法(方法A)和氨基甲酰氯法(方法B)进一步制备了14个含异丙基甲酚结构的氨基甲酸酯类化合物,并测定了所合成16个化合物对乙酰胆碱脂酶(AChE)的抑制活性。研究结果表明：酚类化合物与异氰酸酯反应是制备氨基甲酸酯的高效合成工艺,其中异氰酸酯中N-取代基结构越大反应越容易发生,芳基取代产物的摩尔得率可达90%以上。在AChE抑制活性方面,3-异丙基-5-甲酚衍生物的抑制活性普遍高于香芹酚衍生物,N-脂基取代产物的抑制活性显著高于N-芳基取代产物,且短链脂基取代产物的抑制活性高于长链脂基和环脂基。3-异丙基-5-甲酚的N-甲基取代产物表现出优良的AChE抑制活性,抑制效率达到石杉碱甲的90.5%,超过同为氨基甲酸酯阳性对照利凡斯的明(89.6%),而其N,N-二甲基取代产物的抑制活性又明显高于N-甲基取代产物,抑制效率达到石杉碱甲的97.9%。浓度与抑制率关系表明：3-异丙基-5-甲基苯基-N,N-二甲基氨基甲酸酯(Ⅰ-2)在浓度大于1.25 mmol/L后表现出与石杉碱甲基本等同...     

微晶纤维素的定向硫酸酯化修饰及其结构表征

为了构建具有不同取代模式的纤维素硫酸酯化学库,用以研究其构效关系,提出用定向硫酸酯化修饰微晶纤维素(MCC)的方法控制硫酸酯基在纤维素硫酸酯上的位置与分布.通过对MCC选择性酰氯酯化,向C-6引入大体积保护基团(CH3)3COC-,C-6被保护的中间产物经过硫酸酯化和脱保护基团反应,得到两种纤维素硫酸酯Na-MCS1和Na-MCS2,通过红外光谱、紫外 -可见光谱和13C NMR鉴定了中间产物和目标产物的结构,定量13C NMR揭示了Na-MCS1和Na-MCS2的硫酸酯基取代模式分别为C-6、C-2位同时取代和C-2位取代.     

季铵盐/酰胺类低共熔溶剂的制备及其对纤维素的溶解性能

以季铵盐类和酰胺类化合物为原料,合成了包括四甲基氯化铵/己内酰胺(TMACl/CPL)、四乙基氯化铵/己内酰胺(TEACl/CPL)、四丁基氯化铵/己内酰胺(TBACl/CPL)、四丁基醋酸铵/己内酰胺(TBAAc/CPL)、四丁基硫酸氢铵/己内酰胺(TBAHSO4/CPL)、四丁基溴化铵/己内酰胺(TBABr/CPL)等系列季铵盐/酰胺类低共熔溶剂(DES)。通过红外和核磁表征了季铵盐和酰胺之间C=O—H—C和C—N—H—C多重氢键的形成过程。应用DES溶解纤维素时,探讨了季铵盐/酰胺类DES中烷基链长、阴离子结构、溶解时间、温度和黏度等对纤维素溶解性能的影响,结果表明:丁基比乙基和甲基具有更高的溶解能力;不同的阴离子Br~-、Cl~-、Ac~-和HSO_4~-中,Ac~-与己内酰胺的作用可为纤维素溶解过程中提供更多的活性位点; TBAAc/CPL为较优的DES,在100℃、70 min,纤维素的溶解度为7.8%。季铵盐/酰胺类组分间的氢键结构对纤维素的溶解作用机制研究发现:纤维素原有的致密有序结构转化为毛糙无序状态,纤维素典型—OH、—CH伸缩振动吸收峰、以及C—O—C不对称伸缩振动峰均未发生改变,纤维素在TBAAc/CPL中溶解时未发生衍生反应,XRD分析发现纤维素再生后的2θ由15.36°、16.68°和22.10°转变为21.99°,晶型由纤维素Ⅰ型变为Ⅱ型。     

核磁共振光谱和X射线光电子能谱对纤维低聚糖的分析

1H-1HCOSY和13C-1HHSQC谱对通过Bio-GelP-2柱(2.5cm×125cm)分离制备的纤维三糖、纤维四糖和纤维五糖进行分析。结果表明,在水溶液中纤维低聚糖还原末端C1位α构型与β构型之比(α/β)随聚合度增大而减小,纤维三糖主要是α构型(α/β,0.52),而纤维四糖和纤维五糖主要是β构型(α/β,分别是0.34和0.25)。X射线光电子能谱(XPS)分析表明纤维低聚糖的C1s主要有2种电子结合能,分别为284.8(C1s1,C—O)和286.1eV(C1s2,O—C—O),C1s1与C1s2之比(C1s1/C1s2)随聚合度增大而增大。     

亚热带5种树种倒木分解对土壤碳氮的影响

为了探讨亚热带地区倒木分解对土壤C、N的影响,以江西九连山国家自然保护区为研究区域,运用空间代时间的方法,测定不同分解等级下5种倒木(丝栗栲Castanopsis fargesii、米槠Castanopsis carlesii、木荷Schima superba、杉木Cunninghamia lanceolata、马尾松Pinus massoniana)的木质素、纤维素、C、N、密度、含水率以及倒木下土壤的C、N、容重、含水率。结果表明:1)同一分解等级下5种倒木的纤维素、C、N含量差异显著。5种倒木的平均纤维素和C含量在轻度分解等级下分别比在重度分解等级降低了206.3%和28.3%,而平均N含量升高了31.9%。同一分解等级下,常绿阔叶倒木的C、N含量与针叶倒木之间差异显著。在3种(轻、中、重度)分解等级下,常绿阔叶倒木的平均C含量比针叶倒木高16.2%、23.7%和25.3%;平均N含量分别比针叶倒木高12.7%、6.2%和43.5%。2)同一树种倒木下土壤的C、N含量在不同分解等级之间差异显著。5种树种倒木下土壤的平均C、N含量在轻度分解等级下分别比在重度分解等级下高25.8%、35.6%。在3种分解等级下,常绿阔叶倒木下土壤的平均C含量比针叶倒木下土壤显著高了27.0%、21.6%和20.7%;而平均N含量分别比针叶倒木下土壤显著高了21.4%、23.6%和20.8%。3)倒木下土壤C含量与倒木C含量呈显著正相关,系数为0.59,与倒木C/N呈显著负相关,系数为-0.64。倒木下土壤N含量与倒木N含量呈显著正相关,系数为0.52。倒木下土壤含水量与土壤容重呈显著负相关,系数为-0.61。     

Browsing Damage on Pine (Pinus sylvestris and P. contorta) by a migrating moose (Alces alces) Population in Winter: Relation to Habitat Composition and Road Barriers

In Scandinavia, moose (Alces alces L.) sometimes cause severe browsing damage to economically-important pine. Moose-vehicle accidents have spurred construction of fences along roads, and these may interfere with moose migration between summer and winter ranges, or the road alone may be a barrier. If this happens and moose build up along roads, landowners may suffer economically. Therefore, this study investigated whether roads, fences or other factors influence the use of young pine stands by moose. Eighty stands along roads in northern Sweden were evaluated in which individually-browsed branches were counted on 9972 pines. Moose browsing was not significantly related to birch (Betula pendula Roth, B. pubescens Ehrh.) density, nor did it differ between pines (Pinus contorta Douglas or P. sylvestris L.). However, increased pine density, site productivity and proximity to a highway were associated with increased browsing. Further large-scale studies are needed to understand moose habitat selection and the effects of roads.     

Effects of Root Freezing on the Physiology and Growth of Picea glauca,Picea mariana and Pinus banksiana Seedlings Under Different Soil Moisture Regimes

The root systems of 2-yr-old Picea glauca, Picea mariana and Pinus banksiana seedlings were submitted to various frost temperatures during an artificial frost to induce different levels of root damage. Frost-damaged and control seedlings were placed in a greenhouse under high and low soil moisture regimes. Seedling growth and physiology were evaluated periodically. Seedling survival was reduced when root damage reached levels of 60-80%. Root systems of all three species showed partial to total recovery by the end of the experiment. In general, root freezing damage caused reductions in seedling growth, with these reductions becoming less significant over time. Root damage had little to no effect on black spruce and jack pine seedling physiology, while white spruce CO 2 uptake decreased with increasing root damage. Shoot nitrogen content of all three species decreased slightly with increasing root damage.     

Stand Structure in Pine,Spruce and Deciduous Forests: A Comparison Between Finnish and Russian Karelia

This study investigated the stand structure in pine, spruce and deciduous forests in the border district of Finland and Russia. A total of 46 mature forest stands was selected as pairs, the members of each pair being as similar as possible with respect to their forest site type, age, moisture and topography. The stands were then compared between the two countries by means of basal areas and number of stems. The proportions of dominating tree species were 2-12% lower, and correspondingly the proportions of secondary tree species higher, in Russian forests. The density of the forest stock was also higher in each forest type in Russia. The forests in the two countries differed most radically in terms of the abundance of dead trees. The amount was two to four times higher in Russian deciduous and spruce forests, and in pine forests the difference was 10-fold. The stand structures indicated that Russian coniferous stands, in particular, were more heterogeneous than intensively managed pine and spruce stands in Finland.     

Growth and Terminal Bud Formation in Picea abies Seedlings Grown with Alternating Diurnal Temperature and Different Light Qualities

The root collar diameter and the height:diameter ratio are of particular importance in container-grown seedlings where a high density in the containers may produce spindly seedlings. Temperature regimes and light quality are known to affect plant growth. The aim of this study was to identify responses in Picea abies (L.) Karst. seedlings grown with light providing different red:far-red ratios and under temperature regimes with alternating day (DT) and night temperature (NT) from negative (DT < NT) to positive (DT > NT) difference (DIF) between DT and NT. Experiments were conducted in controlled environment chambers and in a daylight phytotron. Only limited thermoperiodic responses appeared in P . abies seedlings with respect to seedling height and dry weight accumulation. The formation of terminal buds, however, was clearly delayed in seedlings grown at negative DIF. The results indicate a requirement for day extension light that is high in far-red, to prevent terminal bud formation under natural short-day conditions. An extended study should be conducted to clarify the minimum level of light intensity and the optimal light quality needed to prevent terminal bud formation under natural short-day conditions.     

CAD与建筑设计的关系

本文分析了CAD在设计中引起的正面和负面影响,并进行了系统的阐述,从而使设计者在应用中能够保持客观的态度。     

Natural Regeneration in Clear-cuts: Effects of Scarification,Slash Removal and Clear-cut Age

The effects of soil scarification (mounding), slash removal and clear-cut age on the natural regeneration in clear-cuts was evaluated using data from four sites in southern Sweden. The treatments were carried out during a good seed and establishment year for birch ( Betula pubescens Ehrh. and B. pendula Roth). Scarification had the strongest positive effect on the density of naturally regenerated seedlings, especially in birch, but also in pine ( Pinus sylvestris L.) and spruce [ Picea abies (L.) Karst]. Slash removal had a positive effect on birch density. No statistically significant effect of clear-cut age was found. In addition, no statistically significant interactions between clear-cut age and scarification or slash removal were found. The ingrowth of field vegetation was the fastest in areas that were not scarified, less rapid in areas scarified on old clear-cuts, and the slowest after scarification in fresh clear-cuts. In conclusion, it may be possible to control the density of birch during a good establishment year for birch. If birch is desired, the best combination of treatments is to remove the slash and scarify; otherwise, these treatments should be avoided.     

Risk Perception Among Non-industrial Private Forest Owners

Based on an enquiry, risk perception among non-industrial private forest owners is described in relation to climate change and forestry hazards. Of the respondents, 11% took action to remedy the effects of climate change. Out of a given set, hazards were ranked according to each respondent's experience of recent substantial financial loss to the estate and in relation to his or her willingness to make investments aimed at risk reduction. For each hazard, the respondent assessed the risk in four classes ranging from very high to negligible risk. Six hazards were considered most problematic in all three aspects: browsing damage, falling timber prices, damage by wind, spruce bark beetle, root rot and pine weevil. A majority of the respondents claimed to take action to reduce the risk associated with at least one hazard, while 35% did not know whether they did. Excluding climate change, the need for decision support was the largest in relation to damage by wind owing to a combination of perceived high risk and a high level of ignorance in relation to whether risk-reducing measures were taken.     

Interactions in decomposition and N mineralization between tropical legume residue components

In situ produced plant residues contain a mixture of different plant components of varying quality. To assess synergistic or antagonistic interactions occurring during the decomposition and mineralization of such mixtures, individual plant parts (stems, leaves, leaf litter and roots) or the mixture of stems, leaves and leaf litter of the agroforestry species pigeonpea (Cajanus cajan) or of crop residues of peanut (Arachis hypogaea) or of the weed hairy indigo (Indigofera hirsuta) were incubated in pots for 19 weeks. Periodically, remaining plant residues were sieved out (>2 mm), weighed and N content as well as soil mineral N determined. Above- and below-ground residues of peanut decomposed fastest and showed the largest N release in agreement with their high N concentration and low-acid detergent fibre (ADF) : N ratio. Hairy indigo was hypothesized to be of lower quality than pigeonpea because of its high-polyphenol content. However, it decomposed faster than pigeonpea, largely because of the higher N and lower lignin concentration of its components. Ranking of individual plant components for N mineralization resulted in the following pattern, leaves > leaf litter > roots > stems. In mixtures of the different plant components a similar species order in decomposition was obtained, e.g. peanut > hairy indigo > pigeonpea. The amount of N released from the mixture was dominated by stem material that comprised 46–61% of the mixture. The interactions in mixtures were relatively small for peanut (generally high-quality components) as well as for pigeonpea (low proportion of high-quality components, i.e. N rich leaf material). However, a positive interaction occurred during later stages of N mineralization in the mixture of hairy indigo as it had a significant proportion of N rich components and absence of highly reactive polyphenols. Thus, for plants with low to intermediate chemical quality attributes, manipulating plant composition (e.g. by varying harvest age, affecting stem and leaf proportions) will be important to obtain significant interactions during decomposition when its components are mixed.     

Pasture production and tree growth in a young pine plantation fertilized with inorganic fertilizers and milk sewage in northwestern Spain

The use of organic waste materials such as milk sewage as an organic fertilizer could have the dual advantages of organic-waste disposal and reduced dependence on inorganic fertilizers. The effects of fertilization with (1) conventional mineral fertilization, (2) milk sewage sludge at 40 kg N ha⁻¹ target rate and (3) no fertilization on pasture production and tree growth were examined in an experiment consisting of two pasture mixtures under a one-year-old Pinus radiata plantation with a density of 2500 trees ha⁻¹. The two pasture mixtures were: (1) Dactylis glomerata L. var. saborto (25 kg ha⁻¹) + Trifolium repens L. group Ladino (4 kg ha⁻¹) + Trifolium pratense L. var. Marino (1 kg ha⁻¹); (2) Lolium perenne L. var. Tove (25 kg ha⁻¹) + Trifolium repens L. group Ladino (4 kg ha⁻¹) + Trifolium pratense L. var. Marino (1 kg ha⁻¹). The experiment began in the spring of 1995 using a randomized block design with three replicates in Castro Riberas de Lea (Lugo, Galicia, north-western Spain). Plot size was 12 × 8 m², with a 1 m buffer strip between plots. Two-year data showed that fertilization with either material had a positive effect on pasture production, with no significant difference between the two fertilization treatments. Tree growth in the milk sewage sludge plot was significantly higher than in the control plots. Inorganic fertilization increased pasture production, but affected tree growth negatively. The results show that milk sewage sludge could be used as a fertilizer in silvo-pastoral systems. This revised version was published online in June 2006 with corrections to the Cover Date.