KNO_3/Al_2O_3的制备及其对催化合成假紫罗兰酮的影响

采用了浸渍法制备了KNO3/Al2O3固体碱催化剂,考察了催化剂制备条件对假紫罗兰酮合成的影响,并对其进行了Hammett指示剂法、FTIR、XRD表征分析。结果表明:所制备的催化剂在催化合成假紫罗兰酮的缩合反应中表现出良好的活性,当活性组分KNO3的负载质量分数为25%、浸渍时间为6 h、焙烧温度为600℃时,所制备的催化剂催化合成假紫罗兰酮产率可达87.5%。对催化剂的表征结果表明,催化剂的活性与高温焙烧KNO3和Al2O3发生相互作用形成的Al-O-K结构及KNO3分解产物K2O有关。     

路易斯酸催化莰烯异构酯化合成乙酸异龙脑酯的研究

以路易斯酸为催化剂催化莰烯与冰乙酸酯化制备乙酸异龙脑酯,通过催化剂筛选和反应条件的优化,获得了莰烯与冰乙酸酯化反应合成乙酸异龙脑酯的最佳反应条件,即:FeCl_3为催化剂,添加量为莰烯质量的10%,反应温度在25℃,反应时间2h,n(莰烯)∶n(冰乙酸)1∶3。在此条件下,采用含莰量94.9%的莰烯(莰烯84.8%,三环烯10.1%)为原料进行反应时,莰烯转化率接近99%,乙酸异龙脑酯选择性94%,乙酸异龙脑酯的平均产率88%。     

磁性固体酸S_2O_8~(2-)/ZrO_2-Al_2O_3-Fe_3O_4的制备及催化液化生物质的研究

利用沉淀-浸渍法制备了磁性固体酸催化剂S_2O_8~(2-)/Zr O_2-Al_2O_3-Fe_3O_4,将其应用于乙醇介质中能源植物柳枝稷的催化液化,并采用X射线衍射(XRD)、BET比表面积测定、NH_3程序升温脱附(NH_3-TPD)、傅里叶红外光谱(FT-IR)和振动样品磁强计(VSM)等测试方法对催化剂的物化性质和结构进行了表征,考察了Al/Zr物质的量比、煅烧温度等制备条件对其催化性能的影响,并研究了反应温度、反应时间、催化剂用量等对柳枝稷液化反应的影响。结果表明:当n(Al)∶n(Zr)为1∶1,煅烧温度为650℃时,制备的催化剂催化活性最高,在260℃、催化剂用量4%(以原料质量计)、反应时间2.5 h时,可以获得较好的液化效果,生物油产率达到56%。GC-MS分析表明产物生物油的主要成分为酯类、醇类及烃类物质。催化剂重复使用3次后,回收率达到87.5%,生物油产率仅下降12%。     

Pd/C催化剂的表面性质对1,8-二硝基萘加氢反应的影响

1,8-二氨基萘(1,8-DAN)是一种重要的精细化工中间体,其在染料、医药中间体和感光材料等行业有着广泛的应用。目前,主要采用化学还原剂还原的方法来合成,此工艺具有产生废渣、原子经济性低等缺点。因此,发展一种绿色环保的催化加氢方法具有重要意义。笔者以具有不同Pd纳米平均粒径的Pd/C为催化剂,通过1,8-二硝基萘催化加氢制备,考察了Pd纳米粒子尺寸对1,8-二硝基萘(1,8-DNN)加氢性能的影响,探索了催化剂表面结构与催化性能的关系。首先,以椰壳炭化料为原料,经水蒸气活化法制备出孔隙发达的载体活性炭,通过不同的还原方法制备出具有不同粒径的Pd/C催化剂,以1,8-DNN的加氢反应来评价其催化性能。应用X-射线衍射(XRD)、透射电镜(TEM)、X-射线光电子能谱(XPS)、N_2吸附等手段对催化剂表面性质进行表征。结果表明:在一定粒径范围内,钯纳米颗粒的尺寸越小,催化剂的活性越高,1,8-DAN的产率和选择性越高。氢气还原使得钯纳米颗粒严重团聚,而使用甲酸和NaBH_4还原的Pd/C催化剂,Pd纳米颗粒分散性较好,并且具有良好的均一性。使用NaBH_4还原的Pd/C催化剂催化1,8-DNN加氢制备1,8-DAN的转化率和产率可分别达到100%和99%,其催化性能高于商业化的Pd/C催化剂。循环回收实验结果表明,Pd/C催化剂在回收反应过程中十分稳定,连续循环5次,活性并没有明显降低。     

Ni-P/rGO复合催化剂的制备、表征及其松香加氢性能研究

以鳞片石墨为原料,采用改良后的Hummer s法制备了氧化石墨烯(GO)分散液,然后以化学还原法制备非晶态Ni-P/rGO复合催化剂,并以松香加氢为探针反应考察了催化剂制备条件对催化性能的影响,进一步通过正交试验优化了松香加氢反应的工艺条件。结果表明:在Ni元素与GO质量比为6∶1、溶液pH值为11、n(P)/n(Ni)为5∶1、温度为70℃的优化制备条件下,以及反应时间4.5 h、催化剂用量5%、反应温度200℃和反应压力4.5 MPa的适宜加氢反应条件下,该催化剂对松香加氢具有较高的活性,枞酸型树脂酸转化率达99.37%,且重现性良好,该催化剂重复使用7次仍能保持较高的催化活性。X射线衍射(XRD)、透射电镜(TEM)、X射线光电子能谱(XPS)表征结果表明:非晶态Ni-P/rGO复合催化剂已经成功制备,未与rGO复合的Ni-P粒子颗粒较大且分散性较差,使用7次后复合催化剂中Ni 0含量相对下降,活性组分流失导致催化活性稍有降低。     

MCM-41分子筛膜的制备、改性及其在酯交换反应中的应用

采用原位水热合成法在氧化铝陶瓷膜(CM)表面原位合成出了孔道规则有序的MCM-41/CM分子筛膜。再采用浸渍法将SO2-4/Zr O2负载在MCM-41/CM分子筛膜上对MCM-41进行酸改性,制得负载型固体酸催化剂SO2-4/Zr O2/MCM-41/CM,并用于催化棕榈油与甲醇的酯交换反应制备生物柴油。结果表明,当Zr(NO3)4的浓度为0.4 mol/L、硫酸浓度为2 mol/L、焙烧温度为550℃时,制备出的负载型固体酸催化剂SO2-4/Zr O2/MCM-41/CM活性最高。通过考察反应条件对酯交换反应的影响,得出最佳的反应条件,即当催化剂用量5%(以活性组分负载率计)、反应时间为60 min、反应温度为100℃、醇油物质的量之比为10∶1时,脂肪酸甲酯的收率可达92%以上,重复使用5次后,脂肪酸甲酯收率仍达80%以上。     

SnO2-Pt/γ-Al2O3催化葡萄糖制备乳酸甲酯的研究

以γ-Al2O3为载体,采用浸渍法制备了SnO2-Pt/γ-Al2O3催化剂,探讨工艺参数(反应温度、反应时间、催化剂用量)对葡萄糖催化转化制备乳酸甲酯的影响,并对催化剂的重复使用性能以及放大实验进行探索。同时采用扫描电子显微镜(SEM)、X光射线电子能谱(XPS)、X射线衍射(XRD)、氮气吸附-脱附、NH3程序升温脱附(NH3-TPD)等对SnO2-Pt/γ-Al2O3催化剂进行了表征。结果表明:金属Pt和SnO2均匀地分散到γ-Al2O3载体上,催化剂体系同时具有B酸和L酸的分布,比表面积为117.08m^2/g,孔容为0.23cm^3/g,平均孔径为6.54nm,催化活性明显。当葡萄糖为1g、催化剂用量(以葡萄糖质量计)为10%、葡萄糖与甲醇料液比为1∶10(g∶mL)、反应温度220℃、反应10h的条件下,SnO2-Pt/γ-Al2O3表现出较高催化活性,葡萄糖转化率为92.63%,乳酸甲酯选择性高达20.08%,且催化剂表现出良好的重复使用性能和放大稳定性,重复使用3次时,葡萄糖转化率仍达88.43%,乳酸甲酯选择性达19.27%;物料投加量放大10倍时,葡萄糖转化率仍达86.27%,乳酸甲酯选择性达18.71%。     

氯化铝催化假性紫罗兰酮环化反应的研究

首次将Lewis酸催化剂氯化铝应用于假性紫罗兰酮环化反应.该催化剂能有效促进假性紫罗兰酮闭环,具有工艺条件温和、后处理简单、易于操作等特点.通过工艺优化获得了较佳的反应条件:反应温度0℃,催化剂与原料质量比3∶4,反应时间3h.用GC-MS方法进行分析表明,氯化铝催化环化假性紫罗兰酮生成了β-紫罗兰酮与二氢-α-紫罗兰酮,产率分别为45.54%和43.55%,假性紫罗兰酮总转化率96.00%.氯化铝催化剂可重复使用,无污染产生,具有绿色合成的特点.     

诺蒎酮的合成工艺研究

对β-蒎烯氧化制备诺蒎酮的合成工艺进行优化,探讨了反应时间、反应温度、催化剂类型及用量、氧化剂类型及用量和溶剂种类等因素对反应转化率和选择性的影响。研究结果显示:5.00 g β-蒎烯,3 mL 2 mol/L H₂SO₄,反应时间为3 h,反应温度为21～24℃,催化剂为十六烷基三甲基溴化铵(CTAB),用量0.20 g,氧化剂为高锰酸钾,n(高锰酸钾)∶n(β-蒎烯)为3.2∶1,溶剂为丙酮,在机械搅拌条件下,诺蒎酮合成反应的转化率达99.5%,选择性高达92.2%。     

NaY分子筛负载金属Salen催化剂催化α-蒎烯环氧化

采用普通热溶剂法和微波加热法将SalenMnCl成功负载于NaY分子筛的超笼中,通过FT-IR、XRD、TG和比表面分析方法对催化剂进行了表征。以此负载型催化剂催化低浓度过氧乙酸氧化α-蒎烯制备α-环氧蒎烷,比较了2种方法制备的催化剂性能,然后用响应曲面法探索最佳反应条件,并在该条件下研究负载型催化剂循环使用情况。结果表明,2种方法制备的分子筛负载型SalenMnCl催化剂均可催化α-蒎烯环氧化反应,且催化效果微波法优于普通热溶剂法。微波法制备的SalenMnCl/Y-MW催化剂催化反应的最优条件为:过氧乙酸与α-蒎烯物质的量之比值为1.43,反应温度为10℃,反应时间为3.75 h,在此条件下产物产率达91.60%。同时,该负载型催化剂重复使用5次,产物产率仍达76%以上,其具有较好的稳定性,可循环利用。     

Tangential and radial shrinkage variation within trees in sugi (<Emphasis Type="Italic">Cryptomeria japonica</Emphasis>) cultivars

The transverse shrinkage variation within trees was examined for five sugi cultivars. The within-tree trends of tangential shrinkage (α _T) were different by cultivar, whereas radial shrinkage (α _R) increased from pith to bark in most cultivars. The tangential/radial shrinkage ratio (α _T/α _R) decreased from pith to bark in most cultivars, because the radial variation of α _R was larger than that of α _T. The cultivars showed significant differences among cultivars in α _T, α _R, and α _T/α _R, but the difference among cultivars for α _T/α _R was smaller. The relationships between transverse shrinkage and microfi bril angle (MFA), basic density (BD), tree ring parameters, and modulus of elasticity were examined. The α _T and α _R showed positive relationships with BD, latewood percentage, latewood density, and modulus of elasticity, and negative relationships with MFA and ring width. The relationships with earlywood density were weak. Sugi exhibited variation in transverse shrinkage within stem and among cultivars, with the variation affected by MFA, density, and tree ring parameters. Part of this article was presented at the 56th Annual Meeting of the Japan Wood Research Society, Akita, Japan, August 2006, and the 57th Annual Meeting of the Japan Wood Research Society, Hiroshima, Japan, August 2007     

The pharmacokinetical study of plant alkaloid tetrandrine with a simple HPLC method in rabbits

A simple HPLC method was developed to quantify rabbit plasma tetrandrine (Tet) with propranolol (Pro) as internal standard. Based on the established method Tet and Pro were eluted at 7.1 and 12.0 min, respectively. It was shown that the concentration-time data of Tet fit the classical two-compartment model, no matter the drug was administered intravenously or orally to rabbits. The values of AUC_0 → ∞, clearance (Cl_0 → ∞), volume of distribution (Vd), and elimination half-life (t_1/2β) of Tet were 59861.149 ± 26962.196 μg/L ? min, 0.503 ± 0.173 L/min/kg, 179 ± 76.185 L/kg, and 283.808 ± 162.937 min for intravenous injection of 5 mg/kg, or 18986.217 ± 7462.308 μg/L ? min, 0.805 ± 0.267 L/min/kg, 110.284 ± 94.176 L/kg, and 732.919 ± 847.32 min for gavage administration of 10 mg/kg , respectively. The results indicate that Tet displays a limited absorption in intestinal tract, even though it has a favorable pharmacokinetic profile after oral or intravenous administration.     

Aboveground biomass and nitrogen in four short-rotation woody crop species growing with different water and nutrient availabilities

We quantified the effect of water and nutrient availability on aboveground biomass and nitrogen accumulation and partitioning in four species from the southeastern United States, loblolly pine (Pinus taeda), slash pine (Pinus elliottii), sweetgum (Liquidambar styraciflua), and sycamore (Platanus occidentalis). The 6-year-old stands received five levels of resource input (control, irrigation with 3.05 cm water week⁻¹, irrigation + 57 kg N ha⁻¹ year⁻¹, irrigation + 85 kg N ha⁻¹ year⁻¹, and irrigation + 114 kg N ha⁻¹ year⁻¹). Irrigation significantly increased foliage, stem, and branch biomass for sweetgum and sycamore, culminating in 103% and 238% increases in total aboveground biomass. Fertilization significantly increased aboveground components for all species resulting in 49, 58, 281, and 132% increases in total aboveground biomass for loblolly pine, slash pine, sweetgum, and sycamore, respectively. Standing total aboveground biomass of the fertilized treatments reached 79, 59, 48, and 54 Mg ha⁻¹ for loblolly pine, slash pine, sweetgum, and sycamore, respectively. Fertilization increased foliar nitrogen concentration for loblolly pine, sweetgum, and sycamore foliage. Irrigation increased total stand nitrogen content by 6, 14, 93, and 161% for loblolly pine, slash pine, sweetgum, and sycamore, respectively. Fertilization increased total nitrogen content by 62, 53, 172, and 69% with maximum nitrogen contents of 267, 212, 237, and 203 kg ha⁻¹ for loblolly pine, slash pine, sweetgum, and sycamore, respectively. Growth efficiency (stem growth per unit of leaf biomass) and nitrogen use efficiency (stem growth per unit of foliar nitrogen content) increased for the sycamore and sweetgum, but not the loblolly or slash pine.     

Tephrosia species and provenances for improved fallows in southern Africa

Seeking an alternative to Sesbania spp. tree fallows, a Tephrosia species and provenance trial was conducted at Msekera Research Station, Chipata (Zambia) to evaluate eleven Tephrosia vogelii and three Tephrosia candida provenances. They were tested for biomass production, quality of biomass, resistance to root-knot nematodes, nitrogen release, and for their effects on soil nitrogen dynamics. At the end of 1.5 years, the T. candida provenances 02970, 02971 and 02972 from Madagascar produced two times greater amount of aboveground biomass than the T. vogelii provenances. There was little variability among the T. vogelii provenances in terms of litter and biomass production. Weed growth was significantly greater under T. vogelii than T. candida provenances. While Tephrosia vogelii provenance 98/02 from Zambia and T. candida 02972 were highly tolerant to the Meloidogyne incognita nematodes, T. vogelii provenances 02977, 98/03, 02973 from Kenya, Zambia and Malawi, respectively, were highly susceptible to the nematodes. The Tephrosia species and provenances showed a wide variability in terms of N, lignin and polyphenol concentration in their foliage. Mineralization of N in the foliage of T. candida provenances 02970 and 02971 and T. vogelii provenances 98/04 and 02974 from Malawi occurred rapidly within 14 weeks of incubation. At the end of the 2-year growth period, there was significantly greater total inorganic N under T. candida provenance 02972 (12.5 mg kg⁻¹) than T. vogelii (5 mg kg⁻¹) provenance Mungwi 98/02. Maize (Zea mays L.) yields after T. candida provenances were greater than those after T. vogelii provenances. Further testing of the most promising provenances is needed for their effects on subsequent maize yields under a range of farm conditions. This revised version was published online in June 2006 with corrections to the Cover Date.     

Influences of forest tending works on carbon distribution and cycling in a Pinus densiflora S. et Z. stand in Korea

This study was conducted to determine carbon (C) dynamics following forest tending works (FTW) which are one of the most important forest management activities conducted by Korean forest police and managers. We measured organic C storage (above- and below-ground biomass C, forest floor C, and soil C at 50 cm depth), soil environmental factors (soil CO₂ efflux, soil temperature, soil water content, soil pH, and soil organic C concentration), and organic C input and output (litterfall and litter decomposition rates) for one year in FTW and non-FTW (control) stands of approximately 40-year-old red pine (Pinus densiflora S. et Z.) forests in the Hwangmaesan Soopkakkugi model forest in Sancheonggun, Gyeongsangnam-do, Korea. This forest was thinned in 2005 as a representative FTW practice. The total C stored in tree biomass was significantly lower (P < 0.05) in the FTW stand (40.17 Mg C ha⁻¹) than in the control stand (64.52 Mg C ha⁻¹). However, C storage of forest floor and soil layers measured at four different depths was not changed by FTW, except for that at the surface soil depth (0–10 cm). The organic C input due to litterfall and output due to needle litter decomposition were both significantly lower in the FTW stand than in the control stand (2.02 Mg C ha⁻¹ year⁻¹ vs. 2.80 Mg C ha⁻¹ year⁻¹ and 308 g C kg⁻¹ year⁻¹ vs. 364 g C kg⁻¹ year⁻¹, respectively, both P < 0.05). Soil environmental factors were significantly affected (P < 0.05) by FTW, except for soil CO₂ efflux rates and organic C concentration at soil depth of 0–20 cm. The mean annual soil CO₂ efflux rates were the same in the FTW (0.24 g CO₂ m⁻² h⁻¹) and control (0.24 g CO₂ m⁻² h⁻¹) stands despite monthly variations of soil CO₂ efflux over the one-year study period. The mean soil organic C concentration at a soil depth of 0–20 cm was lower in the FTW stand (81.3 g kg⁻¹) than in the control stand (86.4 g kg⁻¹) but the difference was not significant (P > 0.05). In contrast, the mean soil temperature was significantly higher, the mean soil water content was significantly lower, and the soil pH was significantly higher in the FTW stand than in the control stand (10.34 °C vs. 8.98 °C, 48.2% vs. 56.4%, and pH 4.83 vs. pH 4.60, respectively, all P < 0.05). These results indicated that FTW can influence tree biomass C dynamics, organic C input and output, and soil environmental factors such as soil temperature, soil water content and soil pH, while soil C dynamics such as soil CO₂ efflux rates and soil organic C concentration were little affected by FTW in a red pine stand.     

Carbon dioxide exchange of a larch forest after a typhoon disturbance

A typhoon event catastrophically destroyed a 45-year-old Japanese larch plantation in southern Hokkaido, northern Japan in September 2004, and about 90% of trees were blown down. Vegetation was measured to investigate its regeneration process and CO₂ flux, or net ecosystem production (NEP), was measured in 2006–2008 using an automated chamber system to investigate the effects of typhoon disturbance on the ecosystem carbon balance. Annual maximum aboveground biomass (AGB) increased from 2.7 Mg ha⁻¹ in 2006 to 4.0 Mg ha⁻¹ in 2007, whereas no change occurred in annual maximum leaf area index (LAI), which was 3.7 m² m⁻² in 2006 and 3.9 m² m⁻² in 2007. Red raspberry (Rubus idaeus) had become dominant within 2 years after the typhoon disturbance, and came to account for about 60% and 50% of AGB and LAI, respectively. In comparison with CO₂ fluxes measured by the eddy covariance technique in 2001–2003, for 4.5 months during the growing season, the sum of gross primary production (GPP) decreased on average by 739 gC m⁻² (64%) after the disturbance, whereas ecosystem respiration (RE) decreased by 501 gC m⁻² (51%). As a result, NEP decreased from 159 ± 57 gC m⁻² to −80 ± 30 gC m⁻², which shows that the ecosystem shifted from a carbon sink to a source. Seasonal variation in RE was strongly correlated to soil temperature. The interannual variation in the seasonal trend of RE was small. Light-saturated GPP (P_max) decreased from 30–45 μmol m⁻² s⁻¹ to 8–12 μmol m⁻² s⁻¹ during the summer season through the disturbance because of large reduction in LAI.     

Post-fire soil respiration in relation to burnt wood management in a Mediterranean mountain ecosystem

After a wildfire, the management of burnt wood may determine microclimatic conditions and microbiological activity with the potential to affect soil respiration. To experimentally analyze the effect on soil respiration, we manipulated a recently burned pine forest in a Mediterranean mountain (Sierra Nevada National and Natural Park, SE Spain). Three representative treatments of post-fire burnt wood management were established at two elevations: (1) “salvage logging” (SL), where all trees were cut, trunks removed, and branches chipped; (2) “non-intervention” (NI), leaving all burnt trees standing; and (3) “cut plus lopping” (CL), a treatment where burnt trees were felled, with the main branches lopped off, but left in situ partially covering the ground surface. Seasonal measurements were carried out over the course of two years. In addition, we performed continuous diurnal campaigns and an irrigation experiment to ascertain the roles of soil temperature and moisture in determining CO₂ fluxes across treatments. Soil CO₂ fluxes were highest in CL (average of 3.34 ± 0.19 μmol m⁻² s⁻¹) and the lowest in SL (2.21 ± 0.11 μmol m⁻² s⁻¹). Across seasons, basal values were registered during summer (average of 1.46 ± 0.04 μmol m⁻² s⁻¹), but increased during the humid seasons (up to 10.07 ± 1.08 μmol m⁻² s⁻¹ in spring in CL). Seasonal and treatment patterns were consistent at the two elevations (1477 and 2317 m a.s.l.), although respiration was half as high at the higher altitude.Respiration was mainly controlled by soil moisture. Watering during the summer drought boosted CO₂ effluxes (up to 37 ± 6 μmol m⁻² s⁻¹ just after water addition), which then decreased to basal values as the soil dried. About 64% of CO₂ emissions during the first 24 h could be attributed to the degasification of soil pores, with the rest likely related to biological processes. The patterns of CO₂ effluxes under experimental watering were similar to the seasonal tendencies, with the highest pulse in CL. Temperature, however, had a weak effect on soil respiration, with Q₁₀ values of ca. 1 across seasons and soil moisture conditions. These results represent a first step towards illustrating the effects of post-fire burnt wood management on soil respiration, and eventually carbon sequestration.     

Dry matter partitions and specific leaf weight of soybean change with tree competition in an intercropping system

In 2004 and 2005, the yield, leaf area, dry weight and dry weight partitions of soybeans were determined at the Agroforestry Research Site (ARS) (est. 1987, Ontario, Canada). Soybean was intercropped with poplar (Populus deltoides x nigra DN-177 L., 556 m³crown tree⁻¹), silver maple (Acer saccharinum L., 308 m³), black walnut (Juglans nigra L., 148 m³) and pecan (Carya illinoensis Wangenh., 114 m³), or grown alone (monoculture). Yield of soybean was not different in either year between the monoculture and the black walnut or pecan intercrops. In the poplar and silver maple treatments, yield was 66 and 85% (2004 and 2005) lower than in the monoculture. Despite the fact that different tree species were used, there was a significant negative linear regression between yield and tree crown volume (R ² = 0.76, P = 0.0049 and R ² = 0.93, P < 0.0001 in 2004 and 2005, respectively). With increasing tree crown volume, soybean tended to partition more dry matter to the photosynthetic and reproductive parts and less to structural tissue and petiole. This demonstrates the phenotypic flexibility of the crop component in agroforestry systems. Contrary to theoretical predictions, soybean leaves were thicker as shade increased (increase by 6.2 × 10⁻⁴–1.2 × 10⁻³ mg cm⁻², per unit of crown volume), pointing to competitive interactions specific to tree-based intercrops.     

Effects of seed water content and storage temperature on the germination parameters of white spruce, black spruce and lodgepole pine seed

The effect of seed water content (WC) (2–3, 5–6 and 22–25%, on a fresh weight basis), storage temperature (+4, −20, −80 and −196°C) and storage duration (6, 12, 24, 48 and 60 months) on the germination of white spruce (Picea glauca (Moench) Voss), black spruce (Picea mariana (Mill.) B.S.P.) and lodgepole pine (Pinus contorta Dougl. ex Loud. var. latifolia Engelm.) seed was investigated. Germination of white spruce control (untreated) seeds and seeds adjusted to 2–3% and 5–6% WC declined after 48 months of storage at −80 and −196°C, with a further decline at 60 months at −20, −80, −196°C. Germination remained high when control white spruce seeds and seeds with 2–3, 5–6% WC were stored at +4°C, over all storage durations. Generally, black spruce and lodgepole pine exhibited high germination at all storage temperatures at 2–3% and 5–6% WC as well as the control (untreated) seed, for up to 60 months in storage. Germination declined for all three species when seed was conditioned to 22–25% WC. This loss in germination was partially recovered in white spruce seed stored at +4, −20 and −80°C after storage durations of 24, 12 and 48 months, respectively, and in black spruce seeds stored at −20 and −196°C after storage durations of 24 months. Mean germination time (MGT) was relatively constant for all species, under all conditions, except for seed conditioned to 22–25% WC, where MGT increased for white spruce seed stored 48 months at −80 and −196°C, and for black spruce seed stored 24 months at +4 and −80°C and 60 months at −196°C. These results show that the optimal storage temperatures are 4°C for white spruce, and 4, −20, −80, and −196°C for black spruce and lodgepole pine, and 2–6% water content is optimal for all 3 species at these temperatures.     

Reaction behavior of lignin in supercritical methanol as studied with lignin model compounds

 The reaction behavior and kinetics of lignin model compounds were studied in supercritical methanol with a batch-type supercritical biomass conversion system. Guaiacol, veratrole, 2,6-dimethoxyphenol, and 1,2,3-trimethoxybenzene were used as model compounds for aromatic rings in lignin. In addition, 5-5, β-1, β-O-4, and α-O-4 types of dimeric lignin model compounds were used as representatives of linkages in lignin. As a result, aromatic rings and 5-5 (biphenyl)-type structures were stable in supercritical methanol, and the β-1 linkage was not cleaved in the β-1-type structure but converted rapidly to stilbene. On the other hand, β-ether and α-ether linkages of β-O-4 and α-O-4 lignin model compounds were cleaved rapidly, and these compounds decomposed to some monomeric compounds. Phenolic compounds were found to be more reactive than nonphenolic compounds. These results indicate that cleavages of ether linkages mainly contribute to the depolymerization of lignin, whereas condensed linkages such as the 5-5 and β-1 types are not cleaved in supercritical methanol. Therefore, it is suggested that the supercritical methanol treatment effectively depolymerizes lignin into the lower-molecular-weight products as a methanol-soluble portion mainly by cleavage of the β-ether structure, which is the dominant linkage in lignin. Received: December 19, 2001 / Accepted: April 30, 2002 Acknowledgments This research has been done under the research program for the development of technologies for establishing an ecosystem based on recycling in rural villages for the twenty-first century from the Ministry of Agriculture, Forestry and Fisheries, Japan; by a Grant-in-Aid for Scientific Research (B)(2) (no.12460144, 2001.4–2003.3) from the Ministry of Education, Culture, Sports, Science and Technology, Japan; and under the research program from Kansai Research Foundation for Technology Promotion, Japan. The authors thank them for their financial support. This study was presented in part at the 45th Lignin Symposium, Ehime, Japan, October 2000 and the 52nd Annual Meeting of the Japan Wood Research Society, Gifu, Japan, April 2002 Correspondence to:S. Saka