两种硫酸酯化纤维素钠的结构和抗凝血活性研究

硫酸微晶纤维素钠(Na-MCS)和硫酸三醋酸纤维素钠盐(Na-CAS)分别是以微晶纤维素和三醋酸纤维素为原料、CISO3-DMF硫酸化方法制备的两种硫酸酯化纤维素钠，对其分别进行了结构和抗凝血活性的研究。红外光谱分析发现，两种硫酸酯化纤维素钠均存在硫酸酯键，元素分析测得其硫酸取代度分别为1．70和0.83，13C NMR进一步揭示了Na-MCS中硫酸酯基的分布为C-6位完全取代和C-2位部分取代，Na-CAS中硫酸酯基的取代仅发生在C-6位。抗凝血活性研究表明，添加Na-MCS和Na-CAS均能延长全血复钙时问、活化部分凝血活酶时问和凝血酶时间，但Na-CAS的抗凝血活性远低于Na-MCS。将抗凝血活性突出的Na-MCS与肝素钠相比，其抗凝血活性更强。     

β-1,4-葡聚糖硫酸酯的制备及其抗凝血活性

对微晶纤维素(MCC)进行硫酸酯化修饰,得到多种β-1,4-葡聚糖硫酸酯(GS),其硫酸取代度(Ds)在1.10～1.70范围内.选择Ds为1.70的GS用于结构分析和抗凝血活性研究.IR分析表明,MCC通过硫酸化反应引入了硫酸酯基,13C NMR揭示,硫酸酯化主要发生在C6,部分在C2,而C3位不发生硫酸酯化反应.凝血分析表明,0.2 mg/L的GS即可显著延长血浆的活化凝血活酶时间(tAPTT)和凝血酶时间(tTT),使血浆tAPTT延长两倍,所需GS的剂量为0.7 mg/L,低于活性为150 IU/mg的肝素,在一定质量浓度范围内,GS的体外抗凝血活性与肝素相当.显色分析揭示,GS的抗凝血机制主要在于通过抗凝血酶AT-Ⅲ的调节作用抑制凝血因子Ⅱa和Xa的活性.     

C化学位移特点研究

由诺卜醇和丙酸酐合成了丙酸诺卜酯，用MS，IR，^1HNMR及^13CNMR分析进行了结构表征，利用^13C化学位移分析出其构象是：C-1-C-2-C-3-C-4-C-5部分处于同一平面，整个6，6-二甲基双环[3.1.1]庚-2-烯部分呈“Y”形。丙酸诺卜酯可以看成是阿朴蒎烯在C-2发生取代的衍生物，取代基对^13C化学位移的影响主要集中在C-2，C-1和C-3，对其它碳原子的影响比较小。     

蓖麻油基活性聚合用引发剂的合成及其聚合特性研究

将2-溴代异丁酰溴和蓖麻油的羟基按物质的量比1∶1进行酯化反应,一步法合成蓖麻油基的活性聚合用原子转移自由基聚合(ATRP)引发剂,采用FT-IR、1H NMR和13C NMR对其结构进行表征。红外谱图中3500 cm-1处的羟基的伸缩振动峰减弱,1740 cm-1处的酯基峰增强,表明蓖麻油中的羟基官能团基转变为酯基,溴代异丁酰基官能团成功接枝到蓖麻油分子上,1H NMR和13C NMR谱图的分析结果进一步证明蓖麻油基ATRP引发剂的合成和结构的正确性。采用单体/引发剂/溴化亚铜/配体物质的量之比100∶1∶0.5∶1,反应温度60℃(苯乙烯80℃)的聚合反应体系,GPC、1H NMR和13C NMR谱图结果显示,蓖麻油基ATRP引发剂可以高效的引发甲基丙烯酸甲酯,以及苯乙烯的ATRP聚合反应,整个过程高效和可控制。     

草酸二异龙脑酯的合成及其结构表征

通过莰烯和草酸在硼酐催化作用下的重排加成(酯化)反应合成了草酸二异龙脑酯,探讨了原料配比、催化剂用量、反应温度以及反应时间对酯化反应的影响。研究结果表明,莰烯(13.6 g)、草酸和催化剂的质量比为1.7∶2∶1,反应温度为55℃、反应时间为96 h的条件下,莰烯的转化率为89.5%,草酸二异龙脑酯的选择性为95.6%。产物通过IR、LCMS-IT-TOF、1H NMR、13C NMR等手段进行了结构鉴定与表征。     

内型异莰烷基甲醇及其衍生物的NMR研究

利用1H NMR、13C NMR、DEPT等一维和1H-1H COSY、HSQC、HMBC及1H-1H NOESY等二维核磁共振波谱技术确定了6种内型异莰烷基甲醇及其衍生物的结构,并对其1H NMR和13C NMR信号进行了全归属,初步探讨了取代基对化学位移的影响.此6种化合物的核磁数据可作为该类化合物的参考.     

脱氢枞酸基柔性单体的合成和聚合活性分析

以脱氢枞酸为原料,经酰氯化反应后与己二醇反应合成脱氢枞酸羟己酯,然后再用甲基丙烯酰氯进行酯化反应,合成基于脱氢枞酸的柔性单体——脱氢枞酸(2-甲基丙烯酰氧基己基)酯,得率41%。并分别采用了FT-IR、1H NMR、13C NMR、DSC和GPC对其结构和性能进行表征。研究结果表明,脱氢枞酸(2-甲基丙烯酰氧基己基)酯在引发剂的存在下可以发生聚合反应,均聚物相对分子质量为20 000~30 000,玻璃化转变温度约为-21.82℃。     

纤维素前驱物6-~(13)C标记示踪研究纤维素与木质素连接方式

从细胞壁多糖的角度分析糖单元与木质素苯丙烷结构单元之间的共价键连接方式,合成了带6-13C标记的纤维素前驱物尿苷二磷酸葡萄糖,并将其与苯丙氨酸解氨酶(PAL)的抑制剂L-2-氨氧基-3-苯基丙酸(AOPP)及外源性木质素前驱物松柏醇-β-D-葡萄糖苷一起投入生长中的银杏植物体内,分析结果证明了(6-13C)尿苷二磷酸葡萄糖是对植物中纤维素进行选择性13C标记的合适的前驱物。从正常生长的银杏新生木质部组织提取木质素-碳水化合物复合体(LCC),并用纤维素酶和半纤维素酶酶解LCC得LCC酶解产物(EDLCC)。红外光谱及13C NMR检测LCC和EDLCC,分析证实了纤维素6位碳与木质素以苯甲醚键方式连接。     

利用ESCA对苯基异氰酸酯与不同含水率纤维素反应的研究

通过ESCA分析研究 ,确定纤维素的C1S电子结合能在 2 85 95eV左右只有一个对称单峰 ;苯基异氰酸酯与水反应产物N ,N -二苯基取代脲的C1S电子结合能有 2个峰值 ,分别是 :羰基 (2 88 6± 0 1)eV ,苯环峰 (2 84 7±0 1)eV ;随着纤维素含水率的增加 ,苯基异氰酸酯与水反应的比例越来越多 ,当含水率为 9 78%的纤维素与苯基异氰酸酯反应时 ,与水反应的异氰酸酯基占总消耗异氰酸酯基的 92 98%。通过刻蚀技术研究发现 ,苯基异氰酸酯反应产物主要分布于纤维素的表面。     

松树皮多聚原花青素片段化产物的分离鉴定及活性

采用多种柱层析手段,分别从基于茶多酚的思茅松和马尾松树皮多聚原花青素片段化反应产物中分离得到1个主要产物。通过MS、1H NMR和13C NMR波谱解析,其化学结构鉴定为(-)-表儿茶素-(4β-8)-(-)-表没食子儿茶素3-O-没食子酸酯(1)。结果表明,茶多酚中的(-)-表没食子儿茶素3-O-没食子酸酯(EGCG)在片段化反应中扮演着重要角色,化合物1是EGCG通过4β-8与(-)-表儿茶素C-4位上的正离子键合形成而来。采用DPPH、ABTS自由基清除活性测定方法评价了化合物1的抗氧化活性,其清除DPPH、ABTS自由基的能力均高于茶多酚、多聚原花青素及其片段化总产物,SC50值分别为6.12±0.03 g/m L和41.41±0.66 g/m L。     

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.