含双萘的脱氢枞酸三芳胺化合物的合成及光谱性能

以歧化松香为原料先制得脱氢枞酸,然后通过对脱氢枞酸进行酯化、溴代、硝化、加氢还原、C—N偶联等方法合成了一种含双萘的脱氢枞酸三芳胺化合物——13-[N,N-双(α-萘)]胺基-脱异丙基脱氢枞酸甲酯,并用IR、~1H NMR、¹³C NMR和MS等手段对其结构进行表征。研究了化合物在甲醇、二氧六环、四氢呋喃、二氯甲烷和环己烷5种不同极性溶剂中的紫外吸收和荧光发射特征,以及化合物的荧光寿命和量子产率,结果显示:化合物有3个紫外吸收峰,在甲醇、二氧六环和环己烷中,第一个吸收峰在218 nm处,而在四氢呋喃和二氯甲烷中吸收峰有较大红移,且吸光度有较大不同;在265、342 nm处的两个吸收峰,不同溶剂中的吸收波长一致,且吸光度相差不大;在这5种溶剂中,化合物在甲醇中发射波长最大(448 nm),荧光强度最小,在环己烷中发射波长最小(405 nm),而荧光强度最大,在二氧六环、四氢呋喃和二氯甲烷溶液中,随着溶剂极性减小,发射波长依次增大;化合物有明显的溶致变色效应。化合物在甲醇溶液中的荧光寿命为3.72 ns,量子产率为8.32%。     

3'-(3,3-二甲基双环[2.2.1]庚-2-亚基)-5'-苯基-异噁唑啉的合成与表征

以2-(3,3-二甲基双环[2.2.1]庚-2-亚基)乙醛肟(莰烯醛肟)和苯乙烯为原料,通过环加成反应合成了未见报道的3'-(3,3-二甲基双环[2.2.1]庚-2-亚基)-5'-苯基-异噁唑啉,并采用FT-IR、GC-MS、~1H NMR以及~(13)C NMR等手段对产物进行表征,确定了产物结构。探讨了溶剂种类、催化剂种类及用量、氧化剂过硫酸氢钾复合盐(Oxone)用量、苯乙烯用量以及反应时间对反应转化率和得率的影响,得到适宜的工艺条件为:50%甲醇为溶剂,氯化钾为催化剂,n(莰烯醛肟)∶n(氯化钾)∶n(Oxone)∶n(苯乙烯)=1.0∶0.5∶1.5∶2.0,反应时间10 h,在此条件下,产物得率为88.07%。     

脱氢松香酸甲酯喹啉衍生物的合成与表征

以脱氢松香酸甲酯(Ⅱ)为起始原料,通过在12位溴代得到12-溴-脱氢松香酸甲酯(Ⅲ),再经过在13位选择性硝化后还原制得中间体13-氨基脱异丙基脱氢松香酸甲酯(Ⅴ),Ⅴ继续与甘油在浓硫酸作用下缩合得(4R,12bS)-4,12b-二甲基-1,2,3,4,4a,5,6,12b-八氢化萘并[1,2-g]喹啉-4-羧酸甲酯(Ⅵ)和(7R,10aS)-7,10a-二甲基-5,6,6a,7,8,9,10,10a-八氢化萘并[2,1-f]喹啉-7-羧酸甲酯(Ⅶ)两种松香基喹啉衍生物,这两种产物的产率分别为51.2%和20.3%,质量分数分别为71.6%和28.4%,产物的结构通过IR,1HNMR和元素分析进行了表征。     

松节油基吡嗪系化合物的合成及其对聚氨酯预聚反应的催化作用

以松节油为原料,分别经选择性氧化、环化、脱氢等反应,合成了新型吡嗪系化合物,并通过FT-IR、GCMS、1H NMR、13C NMR等分析手段对松节油基吡嗪系化合物的结构进行表征。将合成得到的松节油基吡嗪系化合物作为催化剂,采用化学滴定法研究其对六亚甲基二异氰酸酯(HDI)与异丁醇的预聚反应的催化性能,通过数学模型法对预聚反应的表观动力学进行分析,并计算不同松节油基胺类催化剂作用下的反应速率常数。研究结果表明,2-甲基-2,3-二氢樟脑并[2,3-e]吡嗪对聚氨酯的催化作用明显大于N,N-二甲基环己胺;樟脑并[2,3-b]吡嗪的催化作用与N,N-二甲基环己胺接近;2,3-二氢樟脑并[2,3-e]吡嗪、樟脑并[2,3-b]-5,6-二氢吡嗪并[e]环己烷、2-甲基樟脑并[2,3-b]吡嗪、樟脑并[2,3-b]吡嗪并[e]环己烷基本无催化效果。本研究结果表明结构中连接甲基等推电子基团时,可增强催化剂的碱性,从而使其达到较好的催化效果。     

离子液体中通过ATRP法制备大豆蛋白胶黏剂北大核心

为提高大豆蛋白胶黏剂的胶合强度,在离子液体(1-丁基-2,3-二甲基咪唑氯盐[BDMIM][Cl])中,采用原子转移自由基聚合(ATRP)法将甲基丙烯酸缩水甘油酯(GMA)接枝到大豆蛋白分子主链,制备大豆蛋白胶黏剂。对原料大豆蛋白进行预处理,采用红外光谱和核磁氢谱对大豆蛋白结构和大豆蛋白接枝共聚物进行表征,并通过正交试验确定优化工艺条件。结果表明:改性胶黏剂的优化工艺参数为GMA 140 mL,CuBr(溴化亚铜)147.2 mg,油浴时间3 h,在此条件下制备的胶黏剂胶合强度达到1.44 MPa,符合国家标准GB/T 9846—2015Ⅱ类胶合板要求。     

木质素模型化合物香草醛Mannich反应及其产物化学结构表征

以木质素模型化合物香草醛、二乙醇胺及多聚甲醛为原料,1,4-二氧杂环己烷为溶剂,通过Mannich反应合成了香草醛胺基多元醇,研究了物料配比、反应温度、时间及溶剂用量等因素对Mannich反应的影响。实验结果表明:反应物料按物质的量比n(香草醛)∶n(甲醛)∶n(二乙醇胺)1∶1∶1,甲醛与二乙醇胺60℃反应2 h生成1,3-氧氮杂环戊烷,再将其滴入香草醛中,80℃反应3 h,二氧六环溶剂用量为100 mL/mol(以香草醛的物质的量计),二乙醇胺的转化率最高可达到84.92%。采用HPLC、LC-MS、FT-IR及1H NMR表征了香草醛胺基多元醇的化学结构,相对分子质量269。     

Mannich Reaction of Lignin Model Compound Vanillin and Chemical Structure Characterization of Its Product

以木质素模型化合物香草醛、二乙醇胺及多聚甲醛为原料,1,4-二氧杂环己烷为溶剂,通过Mannich反应合成了香草醛胺基多元醇,研究了物料配比、反应温度、时间及溶剂用量等因素对Mannich反应的影响.实验结果表明:反应物料按物质的量比n(香草醛):n(甲醛):n(二乙醇胺)1:1:1,甲醛与二乙醇胺60℃反应2h生成1,3-氧氮杂环戊烷,再将其滴入香草醛中,80℃反应3h,二氧六环溶剂用量为100 mL/mol(以香草醛的物质的量计),二乙醇胺的转化率最高可达到84.92％.采用HPLC、LC- MS、FT-IR及H NMR表征了香草醛胺基多元醇的化学结构,相对分子质量269.     

三芳胺基D-A结构化合物的溶致变色行为研究

研究了3个系列D-A结构化合物在5种不同极性溶剂中的荧光发射光谱及紫外吸收光谱,探讨了化合物的溶致变色规律,结果表明:3个系列化合物在不同极性溶剂中的荧光发射波长发生明显位移,在甲醇中发射波长最大,在环己烷中最小,但在二氧六环、四氢呋喃、二氯甲烷中,随着溶剂极性逐渐减小,发射波长发生红移;在不同极性溶剂中的荧光强度也各不相同,其中,在环己烷中最大,在甲醇中最小。化合物的紫外吸收波长受溶剂极性的影响,均在甲醇中有最小吸收波长,在不同极性溶剂中化合物的吸光度也不相同,在甲醇及环己烷中的吸光度较大。3个系列化合物均具备作为荧光分子探针探测外部环境极性大小的潜能。     

莰烯醛O-取代肟的合成及其抗肿瘤活性

以莰烯醛肟与卤代物为原料经亲核取代反应合成了9个未见报道的莰烯醛O-取代肟类化合物,分别为2-(3,3-二甲基双环[2.2.1]庚-2-亚基)乙醛O-苄基肟(2a)、2-(3,3-二甲基双环[2.2.1]庚-2-亚基)乙醛O-丁基肟(2b)、2-(3,3-二甲基双环[2.2.1]庚-2-亚基)乙醛O-(4-氯丁基)肟(2c)、2-(3,3-二甲基双环[2.2.1]庚-2-亚基)乙醛O-(3-溴苄基)肟(2d)、2-(3,3-二甲基双环[2.2.1]庚-2-亚基)乙醛O-(4-叔丁基苄基)肟(2e)、2-(3,3-二甲基双环[2.2.1]庚-2-亚基)乙醛O-(4-氯苄基)肟(2f)、2-(3,3-二甲基双环[2.2.1]庚-2-亚基)乙醛O-(4-氰基苄基)肟(2g)、2-(3,3-二甲基双环[2.2.1]庚-2-亚基)乙醛O-(2,6-二氯苄基)肟(2h)、2-(3,3-二甲基双环[2.2.1]庚-2-亚基)乙醛O-(邻氟苄基)肟(2i)。利用FT-IR、GC-MS、1H NMR以及13C NMR对产物结构进行了表征。以化合物2a为例,探索了不同工艺条件对产物得率的影响,在甲苯为溶剂,n(莰烯醛肟)∶n(氯化苄)∶n(四丁基溴化铵)为1.0∶1.8∶0.08,反应温度为60℃,反应时间为20 h的最佳工艺条件下,产物的得率为84.1%。通过体外抗肿瘤活性测试,探讨了化合物2a^2i对肝癌细胞HepG2和人乳腺癌细胞MCF7的抑制作用,结果表明:化合物2b对HepG2细胞的抑制作用较好,其半数抑制浓度(IC 50)值为36.3μmol/L;化合物2d、2h、2i对MCF7有一定的抑制作用,其中化合物2h对MCF7的抑制作用较好,其IC50值为19.2μmol/L。     

Synthesis of the Bomadiene from 2,6-Dibromocamphane

以α-蒎烯为原料与Br2进行加成、异构化反应合成2,6-二溴莰烷,以2,6-二溴莰烷为中间体制备冰片二烯.α-蒎烯合成2,6-二溴莰烷的条件:Br2和α-蒎烯为2.5∶1(物质的量之比),反应温度为0℃,反应时间24h,反应溶剂为二氯甲烷,此条件下α-蒎烯转化率为97.6％,定向转化为2,6-二溴莰烷的选择性最高(48.8％).提纯后的2,6-二溴莰烷纯度为99.0％,得率为45.6％.以提纯后的2,6-二溴莰烷为原料制备冰片二烯的适宜反应条件:反应温度100℃,反应时间5h,叔丁醇钾为消除试剂,叔丁醇钾与2,6-二溴莰烷投料比4∶1(物质的量比),DMF为溶剂.2,6-二溴莰烷转化率为99.12％,冰片二烯的选择性为99.0％,提纯后的冰片二烯纯度可达98.5％.采用FT-IR、GC-MS和1H NMR等方法对2,6-二溴莰烷和冰片二烯进行了结构鉴定.     

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。     

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.     

Key Habitats in the Norwegian Production Forest: A Case Study

This study investigated the forest history, structural characteristics, the presence of fungal species suggested to indicate ecological continuity in old-growth forest, and the species composition of saproxylic beetles in 30 old forest ''woodland key habitats'' (WKHs), and compared them with production forest in the same age-class in south-eastern Norway. No statistically significant differences in forest characteristics, community of saproxylic beetles or number of red-listed beetles were found between the WKHs and the production forest, probably owing to a combination of profound long-term logging and a lack of will to delineate sufficiently large WKHs in the one area with significantly less forestry impact. The study indicates the advantage of including forest history information in WKH selection where such data exist, and the importance of restoring habitats in heavily exploited forest landscapes.