First charge collection and position-precision data on the medium-resistivity silicon strip detectors before and after neutron irradiation up to 2x10(14) n/cm(2)

Test strip detectors of 125 mu m, 500 mu m, and 1 mm pitches with about 1 cm(2) areas have been made on medium-resistivity silicon wafers (1.3 and 2.7 k Ohm cm). Detectors of 500 mu m pitch have been tested for charge collection and position precision before and after neutron irradiation (up to 2 x 10(14) n/cm(2)) using 820 and 1030 nm laser lights with different beam-spot sizes. It has been found that for a bias of 250 V a strip detector made of 1.3 k Ohm cm (300 mu m thick) can be fully depleted before and after an irradiation of 2 x 10(14) n/cm(2). For a 500 mu m pitch strip detector made of 2.7 k Ohm cm tested with an 1030 nm laser light with 200 mu m spot size, the position reconstruction error is about 14 mu m before irradiation, and 17 mu m after about 1.7 x 10(13) n/cm(2) irradiation. We demonstrated in this work that medium resistivity silicon strip detectors can work just as well as the traditional high-resistivity ones, but with higher radiation tolerance. We also tested charge sharing and position reconstruction using a 1030 nm wavelength (300 mu m absorption length in Si at RT) laser, which provides a simulation of MIP particles in high-physics experiments in terms of charge collection and position reconstruction, (C) 1999 Elsevier Science B.V. All rights reserved.

Heterojunction solar cells with n-type nanocrystalline silicon emitters on p-type c-Si wafers

Hydrogenated nanocrystalline silicon (nc-Si:H) n-layers have been used to prepare heterojunction solar cells on flat p-type crystalline silicon (c-Si) wafers. The nc-Si:H n-layers were deposited by radio-frequency (RF) plasma enhanced chemical vapor deposition (PECVD), and characterized using Raman spectroscopy, optical transmittance and activation energy of dark-conductivity. The nc-Si:H n-layers obtained comprise fine grained nanocrystallites embedded in amorphous matrix, which have a wider bandgap and a smaller activation energy. Heterojunction solar cells incorporated with the nc-Si n-layer were fabricated using configuration of Ag (100 nm)/1T0 (80 nm)/n-nc-Si:H (15 nm)/buffer a-Si:H/p-c-Si (300 mu m)/Al (200 nm), where a very thin intrinsic a-Si:H buffer layer was used to passivate the p-c-Si surface, followed by a hydrogen plasma treatment prior to the deposition of the thin nanocrystalline layer. The results show that heterojunction solar cells subjected to these surface treatments exhibit a remarkable increase in the efficiency, up to 14.1% on an area of 2.43 cm(2). (c) 2006 Elsevier B.V. All rights reserved.

Fatty-acids and their C-13 signatures in seep carbonates from hydrocarbon seeps on the upper (GC 185) and lower (AC 645) continental slope of the Gulf of Mexico

Here we reported the fatty-acids and their δ 13C values in seep carbonates collected from Green Canyon lease block 185 (GC 185; Sample GC-F) at upper continental slope (water depth: ∼540 m), and Alaminos Canyon lease block 645 (GC 645; Sample AC-E) at lower continental slope (water depth: ∼2200 m) of the Gulf of Mexico. More than thirty kinds of fatty acids were detected in both samples. These fatty acids are maximized at C16. There is a clear even-over-odd carbon number predominance in carbon number range. The fatty acids are mainly composed of n-fatty acids, iso-/anteiso-fatty acids and terminally branched odd-numbered fatty acids (iso/anteiso). The low δ 13C values (−39.99‰ to.32.36‰) of n-C12:0, n-C13:0, i-C14:0and n-C14:0 suggest that they may relate to the chemosynthetic communities at seep sites. The unsaturated fatty acids n-C18:2 and C18:1Δ9 have the same δ 13C values, they may originate from theBeggiatoa/Thioploca. Unlike other fatty acids, the terminally branched fatty acids (iso/anteiso) show lowerδ 13C values (as low as −63.95‰) suggesting a possible relationship to sulfate reducing bacteria, which is common during anaerobic oxidation of methane at seep sites.

黄土丘陵区草地土壤微生物C、N及呼吸熵对植被恢复的响应

以野外样地调查和室内分析法研究了黄土丘陵区不同植被恢复年限下草地土壤微生物C、N及土壤呼吸熵的变化。结果表明,土壤微生物量碳明显地随着植被恢复年限的增加而增加。在恢复前23a,土壤微生物量碳在0～20cm土层年增加率为24.1%;20～40cm为104.4%。植被恢复23a后,0～20cm土层增长率为0.83%,20～40cm为0.19%。土壤微生物量N表现为在植被恢复的初期略有下降,3a后,开始出现明显增加。0～20cm土层年增长率为20.14%,20～40cm为15.11%。在植被恢复23a后,0～20cm土层的年增长率为0.14%,20～40cm变化不大。土壤微生物呼吸强度随着恢复年限的增加逐渐加强;土壤呼吸熵随植被封育时间的增加而呈对数降低趋势。土壤呼吸熵(qCO2)在反映土壤的生物质量变化时,显得更加稳定,受植物生长状况影响较小。相关分析表明,土壤微生物量和土壤微生物活性与土壤有机质、碱解氮和粘粒含量显著正相关;与土壤粉粒含量明显负相关;表层土壤pH值对其也有明显影响。草地植被自然恢复过程可增加土壤微生物活性,有利于土壤质量的提高。

环戊二烯基轻稀土氯化物的合成及其稳定性的研究

I LnCl_3-LiCl-THF配合物的研究深入地研究了氯化稀土和氯化锂于四氢呋喃溶液中，以不同的摩尔比，在不同条件下的反应。实验结果表明，反应速度随着稀土元素原子半径的减小，LiCl/LnCl_3摩尔比的增大，以及四氢呋喃用量的增加而加快。通过紫外质谱元素分析和X-射线单晶结构分析等证明，随着不同的LiCl/LnCl_3摩尔比和结晶条件的不同，可以得到不同组成的LnCl_3-LiCl-TNF配合物。对(LaCl)(THF)_2(μ_2-Cl)_4[Li(THF)_2]_2和(LaCl)DME(μ_3-Cl)(μ_2-Cl)_5(La·DME)Li(THF)_2晶体的结构分析表明，前者为单斜晶系，P21/C空间群。a=10.542(4), b=32.236(4), c=11.182(6)A °; β=113.50(3) °, V=3484.97 A °~3. Z=4, R=0.0471；后者为三斜晶系，PT空间群，晶胞参数是：a=11.123(3), b=16.564(5), c=8.653(3)A °;α=95.16(3), β=95.63(3), γ=74.71(3) °;V=1527.0A °~3。Z=2，R=0.0303。实验结果还表明，μ_2-和μ_3-氯桥键是LnCl_3-LiCl-THF类配合物中最基本、最重要的配位键，这种键是通过多重键的方式起着稳定分子结构的作用。当进行与有机配体的交换反应时，由于它们的特殊稳定性，能起到阻止轻稀土有机配合物歧化反应的作用。II环戊二烯基轻镧系氯化物的合成及其稳定性的研究对(G_5H_5)_3Ln·THF和LnCl_3·3LiCl-THF (Ln=La, Nd)溶液反应的研究表明，由于μ_2-氯桥键的作用，轻稀土环戊二烯基化合物中环戊二烯基的再分配反应，在0℃或室温下都能迅速进行。通过两者不同的摩尔比反应，经元素分析、红外光谱、~1H NMR和质谱鉴定，方便地合成了C_5H_5 LnCl_2·2LiCl·5THF和(C_5H_5)_2LnCl.LiCl·nTHF (Ln=La, Nd)等配合物。这一结果表明(C_5H_5)_2LnCl.LiCl·nTHF配合物不仅能稳定地存在于THF溶液中，而且能在一定条件下析出结晶。对(C_5H_5)_2LaCl.LiCl·4THF的晶体结构测定表明，该晶体属于正交晶系，Pc2m空间群。a=12.306(4), b=23.056(6), c=26.701(11)A°; V=7575.81A°~3;而(C_5H_5)_2LaCl·LiCl(DME)_2THF晶体则属于六方晶系，a=12.967(4), b=12.967(4), c=24.108(10)A°;V=3510 A°~3。通过(G_5H_5)_3Ln·THF与LnCl_3·3THF (Ln=La, Nd)的反应进一步研究了轻稀土环戊二烯基氯化物的稳定性。经元素分析，红外光谱和晶体结构分析表明合成了[(η~5-C_5H_5)_4La_3Cl_5·3THF]_2·9THF和(C_5H_5)_2 NdCl·THF配合物，前者属于三斜晶系，P1空间群。a=11.690(3), b=11.750(5), c=18.433(6)A°; α=98.75(3), β=95.62(3), γ=118.92(2)°; V=2147.06 A°~3. Z=1, R=0.099。对环戊二烯基轻稀土氯化物的稳定性进行了较详细地讨论。结果表明，THF的用量和化合物的溶解度是影响产物组成的决定因素。当THF的量不足以溶解所生成的产物时，就会歧化成溶解度最大((C_5H_5)_3Ln·THF)和最小(LnCl_3·nTHF)的两种组分。反之，环戊二烯基轻稀土化合物(Ln=La, Nd)中环戊二烯基的再分配反应就能顺利进行。经元素分析和结构测定，在((C_5H_5)_3Nd·THF)和NdCl_3·LiCl-THF溶液的反应体系中，偶然分离得到了[(η~5-C_5H_5)_4Nd_4(μ_4-o)(μ_2-Cl)_8] [Li(DMP)_2THF]_2这一不合常规的化合物，其晶体属于正交晶系，Pna2,空间群a=19.010(7), b=23.231(6), c=14.180(4); V=6261.91 A°~3。Z=4, R=0.054。说明在一定条件下,μ-氧桥键也起到了稳定分子结构的作用。推测了各类环戊二烯基轻稀土氯化物在THF中的合成反应机理,在LiCl存在的反应体系中Ln cl cl Li桥键能与环戊二烯基发生交换反应;在(C_5H_5)_3Ln·THF和LnCl_3·3THF的反应体系中,首先存在着LnCl_3分子之间的互相作用，因而易于形成双核或多核配合物。这类配合物以晶体形式析出时，易于发生结构上的变化，即化合物的结晶形态与溶液中的形态不一定相同。探索了环戊二烯基烯丙基稀土化合物新的合成方法。找到了真空加热脱水制备氯化稀土的最佳条件，其产物纯度在97%以上。通过加入Co_3O_4/Wo_3催化助燃剂的方法，提高了测定稀土有机化合物中碳含量的准确性。

固斑蝰蛇毒C-型凝集素样蛋白Dabocetin及L-氨基酸氧化酶DRS-LAO的研究

本论文研究了从圆斑蛙蛇泰国亚种（Daboia russellii siamensis）蛇毒中纯化的C一型凝集素样蛋白Dabocetin和L一氨基酸氧化酶DRS一AO的理化性质、生物学活性和分子克隆。Dabocetin是分子量约为28扔。的异二聚体蛋白，它由分子量约为15.0kDa和14．5kDa的两个同源亚基以和p共价结合形成。N－末端氨基酸序列比较显示，Dabocetin与目前已知的蛇毒c一型凝集素样蛋白有很高的同源性。即使在终浓度达50．0。叫而时，Dabocetin也不能直接诱导血小板聚集。此外，在终浓度为40.00μg/ml时，Dabocetin几乎不能抑制由AdP，TMVA和stejnulxin诱导的血小板聚集。但是，Dabocetin呈剂量依赖地抑制瑞斯托霉素诱导的血小板凝集，其半数抑制率ICS。值为10.80ug/ml。流式细胞仪分析表明，Dabocetin显著抑制单克隆抗体522与GPIba的结合，提示Dabocetin很可能是一个GPIb结合蛋白。从圆斑蛙蛇的毒腺中克隆到了7个编码不同蛇毒C一型凝集素样蛋白亚基的七DNA（命名为DRs一1至DRs一7）。其中，DRsLS编码Dabocetin的a亚基，DRS一6编码Dabocetin的p亚基。DRs一1和DRS一2很可能是圆斑蛙蛇毒腺中表达的X因子激活剂的两条轻链LCZ和LCI的山NA。DRS一3，DRS毛4和DRSL7可能是圆斑蛙蛇毒腺中表达的C一型凝集素样蛋白p亚基的。NA。DRsLAO是一个新的L一氨基酸氧化酶，比活力为1．98U加噶。十二烷基磺酸钠一聚丙烯酞氨凝胶电泳（SDs-PAGE）分析显示，该酶在还原和非还原条件下均呈现一条蛋白带，表观分子量约为58kDa。N-末端氨基酸序列比较显示，DRS一AO与目前已知的蛇毒L一氨基酸氧化酶有很高的同源性。该酶的最适底物为L一亮氨酸，最适pH为8．8。DRs一Ao呈剂量依赖地抑制扔P和仆IvA诱导的血小板聚集，其半数抑制率ICS。值分别为32.8μg/ml和32.3μg/ml。DRS-LAO对金黄色葡萄球菌（灯Cc25923）和耐甲氧西林金黄色葡萄球菌有较强的抗菌作用。DRs一AO对金黄色葡萄球菌必Tcc25923）的最低抑菌浓度卿C）和最低杀菌浓度耐甲氧西林金黄色葡萄球菌的孤CS。和呱Cg。值分别为18．。林留时和36.0μg/ml；DRSLAo对耐甲氧西林金黄色葡萄球菌的MBC50和MBCg。值分别为36.0μg/ml和72.0μg/ml。通过对DRS一AO的分子克隆，得到了编码DRS-AO的部分cDNA序列。

First charge collection and position-precision data on the medium-resistivity silicon strip detectors before and after neutron irradiation up to 2x10(14) n/cm(2)

Test strip detectors of 125 mu m, 500 mu m, and 1 mm pitches with about 1 cm(2) areas have been made on medium-resistivity silicon wafers (1.3 and 2.7 k Ohm cm). Detectors of 500 mu m pitch have been tested for charge collection and position precision before and after neutron irradiation (up to 2 x 10(14) n/cm(2)) using 820 and 1030 nm laser lights with different beam-spot sizes. It has been found that for a bias of 250 V a strip detector made of 1.3 k Ohm cm (300 mu m thick) can be fully depleted before and after an irradiation of 2 x 10(14) n/cm(2). For a 500 mu m pitch strip detector made of 2.7 k Ohm cm tested with an 1030 nm laser light with 200 mu m spot size, the position reconstruction error is about 14 mu m before irradiation, and 17 mu m after about 1.7 x 10(13) n/cm(2) irradiation. We demonstrated in this work that medium resistivity silicon strip detectors can work just as well as the traditional high-resistivity ones, but with higher radiation tolerance. We also tested charge sharing and position reconstruction using a 1030 nm wavelength (300 mu m absorption length in Si at RT) laser, which provides a simulation of MIP particles in high-physics experiments in terms of charge collection and position reconstruction, (C) 1999 Elsevier Science B.V. All rights reserved.

UASB反应器处理维生素C生产废水研究

维生素C生产废水有机物浓度高、成分复杂、排放量大，是一种亟待处理的典型工业废水。本研究分别采用实验室规模和中试规模的升流式厌氧颗粒污泥床反应器（UASB）对该制药工业废水的厌氧生物处理工艺进行了较为深入的研究。同时采用两种不依赖于纯培养的分子生物学手段—变性梯度凝胶电泳（DGGE）和扩增核糖体DNA限制性分析（ARDRA）技术揭示了UASB反应器不同运行阶段污泥中微生物群落多样性组成及变化。此外，首次研究了零价铁（Fe0）在厌氧消化过程中对反应器运行及微生物群落结构的影响。 采用城市污水处理厂厌氧消化池絮状污泥和处理啤酒废水的颗粒污泥混合接种，小试中温（35±1℃）UASB反应器在其运行的第65天启动成功。反应器稳定运行阶段，在进水COD浓度为9000mg/L、水力停留时间为12h、容积负荷为13.6 kgCOD/m3.d条件下，其COD去除率稳定在85~90%之间，沼气产率达到4.5 m3/m3.d，沼气甲烷含量平均为72%。中试UASB反应器的接种污泥为厌氧消化污泥，其启动时间相对较长，为90天。在稳定运行期，反应器的进水COD浓度为8000~10000mg/L，水力停留时间和容积负荷分别保持在12~16h和10.6~14.2 kgCOD/m3.d范围，该阶段反应器的平均COD去除率稳定在85%左右，沼气产率平均为5.2m3/m3.d，沼气中甲烷含量为69%。上述结果表明中温UASB工艺用于维生素C生产废水处理是高效、可行的。 与对照反应器相比，添加Fe0的小试UASB反应器的COD去除率和沼气产量分别提高了6.5%和10.2%。同时，磷酸盐平均去除率为79%，比对照提高了64%，目前尚未见类似研究报道。在中试规模的UASB反应器中补充一定量的Fe0可缩短反应器启动时间，促进颗粒污泥的形成，该结果可能具有重要的应用价值。培养试验进一步表明，Fe0可以作为产甲烷菌还原CO2生成甲烷的电子供体。培养实验还表明，当系统中存在硝酸盐（0.40 mM）和硫酸盐（0.26 mM）时，Fe0促产甲烷过程受到一定程度的抑制。 采用细菌通用引物968F/1401R和341F/907R获得的PCR-DGGE指纹图谱均表明UASB反应器不同运行阶段细菌种群结构变化明显。小试和中试稳定期污泥的微生物多样性均高于各自初始接种污泥。产甲烷菌通用引物340F/519R的PCR-DGGE结果显示，虽然接种污泥中产甲烷菌的丰富度系数略低于稳定期，但总体而言，反应器运行期间产甲烷菌的种群组成相对稳定。 通过构建不同处理和不同运行阶段污泥样品的16S rRNA基因文库并对克隆基因进行限制性内切酶消化、测序分析。结果表明，稳定期两个反应器微生物群落结构相似，但与各自接种污泥差异明显。小试UASB反应器接种污泥中细菌的优势菌群分别为变形菌纲的δ亚纲（28.7%）和β亚纲（17.4%），至稳定运行期则演替为革兰氏阳性低GC菌群（21.9%）和变形菌纲的δ亚纲（14.0%）。中试反应器接种污泥Green non-sulfer bacteria（25.9%）和变形菌纲的δ亚纲（16.4%）类群占优势，而稳定期Green non-sulfer bacteria类群（17.9%）、革兰氏阳性低GC菌群（16.2%）和变形菌纲的δ亚纲（15.4%）为优势菌群。 产甲烷菌的优势克隆为SRJ 230、SRJ 26和SRJ 583，前两者分别与Methanosaeta concilii和未培养的Methanobacteria-like克隆Gran7M4的同源性达到97%和98%，后者与Methanomethylovorans. sp同源性为99%。接种污泥中上述类群占总克隆数量的比例较低。小试、中试接种污泥中产甲烷菌分别占7.8%和3.0%，但稳定运行期，该比例明显增加，分别达到21.9%和18.8%。上述结果表明启动期与稳定期污泥产甲烷菌种群组成相对稳定，但各类群数量明显增加。 添加Fe0的UASB反应器稳定运行期污泥中产甲烷菌比例（31.2%）高于对照反应器（24.2%）, 革兰氏阳性低GC类群、变形菌纲的δ亚纲比例差异不明显，而变形菌纲β亚纲（6.0%）和Green non-sulfer bacteria（9.2%）的比例均分别低于对照反应器（13.1%和17.1%）。该结果表明，添加Fe0使反应器内微生物群落多样性发生了显著变化。 此外，在添加Fe0的UASB反应器中检测到特异性的克隆SRJ 341和SRJ 320，两者分别同磷酸盐去除和铁氧化有关的克隆子Orbal D41和Clone195的序列相似性达95%和96%。这两个类群可能分别与磷酸盐去除及铁促产甲烷作用密切相关。这一结果尚未见报道。

维生素C二步发酵新组合菌G.529及其应用

本文筛选一株苏芸金杆菌与氧化葡萄糖酸杆菌组成的新组合菌G. B529，并对其生物学性质进行研究，结果表明：新组合菌的摇瓶发酵转化率较原菌系提高4.83个百分点，发酵速度快，且具有耐受高浓度（10%）山梨糖的特性。为使G. B529的潜能得到最大程度的发挥，对其影响因素进行研究。首先应用均匀设计方法确立了G. B529的发酵培养基优化配比，在所实验的范围内，发酵转化率与玉米浆浓度成正相关性，尿素浓度 1．45%佩W/V)时，转化率达最大。其次种液各参数对发酵影响实验确立了判断种子质量高低的方法。结果显示种液中的大菌OD值一1.6 X小菌OD值可以作为种液的质量指数。最后对种子质量的影响实验显示适当提高玉米浆、葡萄糖等成分的浓度与降低尿素的浓度及调高pH值均有利于种液质量的改善。同时低接种量、大通气量和选择种龄为14小时均有助于种液质量指数的提高。 新组合菌系在选定的条件下枷3罐中4批发酵显示出很强的发酵能力，平均醇酸转化率较对照提高8.16个百分点，周期缩短10.6小时。其在300M3罐中生产试用行，连续26批次的平均醇酸转化率达87.40%,较生产用菌提高3.32个百分点。平均周期也缩短1．3小时。

不同施肥制度下土壤微生物体C、N量季节变化及其在土壤N素供给中的作用

本文利用改进的“氯仿薰蒸天菌法”比较了两种不同施肥制度下土壤微生物体C.N量及其季节变化，估算土壤生物量的周转速度和在土壤N素供给中的作用。循环处理土壤的基础呼吸较非循环处理高出14%。N矿化强度高出20%。土壤生物量平均增长11%。表明循环处理分解有机物料和供给养分的能力较非循环处理强。并且随着土壤有机肥料的循环回田。土壤生物量的周转速度加快。年矿化量增加。成为土壤供N中不可忽视的N源之一。同时耕层土壤微生物体生物具有明显的季节变化。全年呈春秋低，夏季高的变化趋势。据1988年偏低的估算，土壤生物量年变化幅度为±15%（非循环）和±17%（循环）。周转速度为37%（非循环）和48%（循环），年矿化量占土壤供N总量的10%（非循环）和13%（循环）。

四种药用植物的化学成分及芍药苷的微生物转化研究

本学位论文共有5章。第一章报道白芍的化学成分及芍药苷的微生物转化研究成果；第二章报道天山雪莲的化学成分研究；第三章报道两面针的化学成分研究；第四章报道通关藤的化学成分研究成果；第五章概述了花椒属植物中最近十年报道的新化合物及药理研究情况。 在第1章的第一部分报道了白芍（Paeonia lactiflora Pall.）的化学成分。我们采用正、反相硅胶柱层析等各种分离方法，从白芍的干燥根中共分离出14个化合物，其中1个为新化合物，其结构通过波谱分析证实为没食子酰白芍苷，另外还有2个为首次从该植物中分离得到。第二部分报道了芍药苷的微生物转化生产芍药苷代谢素-I的研究，从15株厌氧菌中筛选出10株有转化活性的菌株，其中短乳杆菌Lactobacillus brevis AS1.12的转化活性最好，对其转化条件进行了初步的筛选，确定了相对合理的转化工艺。 在第2章报道了天山雪莲（Saussurea involucrate Kar.et Kir.）全草乙醇提取物化学成分的分离纯化和结构鉴定。通过正、反相硅胶柱层析等分离纯化和MS、NMR等波谱解析，共分离鉴定了28个化合物，结构类型分属于黄酮、倍半萜和木脂素等，其中2个新倍半萜化合物的结构分别表征为6α-羟基云木香酸6-β-D-吡喃葡萄糖苷和11βH-11,13-二氢去氢云木香内酯8α-O-(6′-乙酰)-β-D-吡喃葡萄糖苷。 第3章报道了两面针（Zanthoxylum nitidum （Roxb.）DC.）干燥根的乙醇提取物化学成分的分离纯化和结构鉴定。通过正、反相硅胶柱层析等分离纯化和MS、NMR等波谱解析以及X-射线单晶衍射，共分离鉴定了16个生物碱，结构类型分属于苯并啡啶类、喹啉类和阿朴啡类等，其中2个新苯并啡啶类生物碱的结构分别表征为二聚双氢两面针碱和丙酮基双氢崖定椒碱。 第4章报道了通关藤（Marsdenia tenacissima (Roxb.) Wight et Arn.）水提取物化学成分的分离纯化和结构鉴定。通过正、反相硅胶柱层析等分离纯化和MS、NMR等波谱解析以及X-射线单晶衍射，共分离鉴定了14个化合物，结构类型均属于C21多羟基甾醇，其中4个新化合物tenacigenoside A, tenacigenoside B, tenacigenoside C和tenacigenoside D的结构分别表征为3-O-6-deoxy-3-O-methyl-β-D-allopyranosyl-(1→4)-β-D-oleandropyranosyl-17β-tenacigenin B (62), 3-O-2,6- dideoxy-4-O-methyl-D-lyxo-hexopyranosly-11α-O- methylbutyryl-12β-O-acetyl-tenacigenin B (63), 3-O-6-deoxy-3-O-methyl-β-D- allopyranosyl-(1→4)-β-D-oleandropyranosyl-11α-O-tigloyl-tenacigenin C (64)和3-O-6-deoxy-3-O-methyl-β-D-allopyranosyl-(1→4)-β-D-oleandropyranosyl-11α-O-2- methylbutyryl-tenacigenin C (65)。 第5章概述了花椒属植物的化学成分及药理活性研究进展。 This dissertation consists of 5 chapters. The first chapter elaborate the phytochemical investigation of Paeonia lactiflora Pall., and microbial transformation of paeoniforin. The second, third and four chapters elaborate the phytochemical investigation of Saussurea involucrate Kar.et Kir., Zanthoxylum nitidum (Roxb.) DC. and Marsdenia tenacissima (Roxb.) Wight et Arn., respectively. Chapter 5 is a review on chemical constituents and bioactivities of Zanthoxylum species. The part one of chapter 1 focus on the isolation and identification of chemical constituents from P. lactiflora. Fourteen compounds were isolated from the roots of P. lactiflora by repeat column chromatography over normal and reversed phase silica gel. Among them, one is a new compound and the structure was suggested as galloyl-albiflorin by spectral evidence. In addition, two compounds were firstly reported in this plant. The part 2 is about microbial transformation of paeoniforin. Chapters 2, 3 and 4 were isolations and identifications of chemical constituents from S. involucrate, Z. nitidum and M. tenacissima, respectively. From the aerial parts of S. involucrate, 28 compounds including 7 flavonoids and 13 sesquiterpenoids were isolated and identified. Among them, 2 new compounds were characterized as 6α-hydroxycostic acid 6-β-D-glucoside and 11βH-11,13-dihydrodehydro- costuslactone 8α-O-(6'-acetyl)-β-D-glucoside, respectively, by means of spectroscopic analysis. Otherwise, 11 ones were firstly reported from this plant. The third chapter is about the phytochemical investigation of Z. nitidum. Sixteen compounds were isolated and identified. Among them, 2 new benzophenanthridine alkaloids were characterized as 8-acetonyldihydrofagaridine and 1,3-bis(8-dihydronitidinyl)-acetone by spectroscopic analysis. The fourth chapter is about the phytochemical investigation of M. tenacissima. Fourteen compounds were isolated and identified. Among them, 4 new compounds, tenacigenosides A~D, were characterized as 3-O-6-deoxy-3-O-methyl-β-D-allopyranosyl-(1→4)-β-D-oleandropyranosyl-17β- tenacigenin B, 3-O-2,6-dideoxy-4-O-methyl-D-lyxo-hexopyranosly-11α-O-methyl butyryl-12β-O-acetyl-tenacigenin B, 3-O-6-deoxy-3-O-methyl-β-D-allopyranosyl- (1→4)-β-D-oleandropyranosyl-11α-O-tigloyl-tenacigenin C, and 3-O-6-deoxy-3-O- methyl-β-D-allopyranosyl-(1→4)-β-D-oleandropyranosyl-11α-O-2-methylbutyryl- tenacigenin C. Chapter 5 is a review on recent progress in bioactive constituents from plants of Zanthoxylum species.

2-C-支链-1,6-脱水吡喃葡萄糖的开环反应及吡喃烯糖的合成研究

在糖化学合成中，1,6-脱水吡喃糖不仅是合成具有生物活性低聚糖、糖共体、抗原、抗体以及天然产物等化合物重要原料，而且还是许多具有生物活性的天然产物的结构单元。同时，它还具有[3,2,1]的双环缩醛结构，使其在糖化学合成中具有高的立体选择性和区域选择性，同时减少了C-1 和C-6 位的保护和去保护的优点。此外，环内的缩醛开环后，又可以相应地在C-1 和C-6 位进行官能团转化以及糖苷化反应。 本文报道了一种新的1,6-脱水吡喃糖的合成方法，并设计合成了2-C-支链-1,6-脱水吡喃葡萄糖1-195、1-197、1-198 以及2-C-支链-6-硫代1,6-脱水吡喃葡萄糖1-225。到目前为止，1,6-脱水糖开环并进行糖苷化反应，存在选择性较差、产率低的缺点。我们发现，在乙腈做溶剂的条件下，NiCl5 能高立体选择性高产率地催化化合物1-195、1-197、1-198 开环并与ROH、RSH 发生糖苷化反应。在NiCl5-乙腈条件下，合成了一系列2-C-支链-α-糖苷和2-C-支链-β-硫代糖苷，并对2-C-支链1,6-脱水吡喃葡萄糖的生成机理以及开环机理进行了探讨。 烯糖在糖化学合成中是重要的起始原料，从Fischer 首次合成烯糖至今，一直不断地有新的合成方法出现。但目前文献报道的方法存在所用试剂有毒、价格贵和操作繁琐等缺点。我们对Fischer-Zach 方法进行了改进， 发现Zn-NaH2PO4-H2O 和Zn-PEG600-H2O 体系都能很好地合成烯糖。该方法具有条件温和、绿色环保、操作简单的优点。在Zn-NaH2PO4 溶液或Zn-PEG600 条件下，以溴代糖为原料，高产率地合成一系列的烯糖。 The 1,6-anhydrohexopyranoses are crucial subunits of myriad bioactive nature products, as well as important syntons of carbohydrate chemistry which have been extensively used to prepare the biologically potential oligosaccharides, glycoconjugates, antibiotics, and structurally varied nature products. Their particular [3.2.1] bicyclic skeleton makes them have high regio- and stereo-control in a variety of reactions, and such structure avoids protecting hydroxyl groups at C1 and C6.Additionally, the cleavage of the internal acetal under acidic conditions could be beneficial for further transformations of functional group and glycosylation of the corresponding pyranosyl sugar at the C6 or C1 site. Herein we developed a novel approach to prepare the 1,6-anhydrohexopyranose, and synthesized the 2-C-branched-1,6-anhydrohexopyranose 1-195, 1-197, 1-198 and 2-C-branched-6-thio-1,6-anhydrohexopyranose 1-225. Until now, glycosylation of 1,6-anhydrohexopyranoses has been limited because of the low yields and low stereoselectivity. In this paper, we found that NiCl5-MeCN system could selectively cleave the ring of 1,6-anhydrohexopyranoses with alcohols and thiols at room temperature in high yields. A series of 2-C-branched-α-glycosides and 2-C-branched-β-thioglycosides have been synthesized via NiCl5-catalyzed. Furthermore, we investigated the formation and ring-opening mechanism of 2-C-acetylmethyl-1,6-anhydrohexopyranose. Glycals are significant starting material in carbohydrate chemistry. After the Fischer-Zach method for forming glucal was reported for the first time, the numerous synthetic methods for glycals have been explored. However, there are several drawbacks in the existing methods, such as the usage of very expensive and toxic reagents, intricate operation, and the influence of acid-sensitive and base-sensitive functional group. We improved the Fischer-Zach method and developed a facile, mild and environmentally benign methodology towards the synthesis of the glycals in Zn-NaH2PO4-H2O or Zn-PEG600-H2O system. Our method involves the treatment of glycosyl bromides with Zn in NaH2PO4 aqueous solution or PEG600-H2O at room temperature, affording various glycals in excellent yields.

吲哚生物碱Desbromoarborescidine A 的全合成及烯胺C-亚磺酰化反应研究

从新几内亚核桃木的树皮中分离得到的吲哚类喹诺里西定生物碱10-Desbromoarborescidine A，因发现其具有阻滞钙离子通道的活性而倍受关注。10-Desbromoarborescidine A由A、B、C、D四个环组成，只有一个手性中心，是吲哚生物碱中结构较简单的一种，常作为此类生物碱全合成方法的模型化合物。但迄今为止，能高效而简便的实现手性10-Desbromoarborescidine A不对称全合成方法线路不多，大多数以不对称诱导的方式建立其手性中心，手性催化的方式仅有一例金属催化。从逆合成分析可知，Desbromoarborescidine A的全合成可以通过亚胺不对称催化还原进行关键的手性中心构建，而本课题组在之前的研究中通过手性有机小分子催化剂的发展，已将三氯硅烷氢转移还原亚胺发展成了一类简便实用、高效、高对映选择性并具有优良底物适应范围的不对称催化反应，我们希望以这一反应作为关键手段，发展一条Desbromoarborescidine A及其类似物不对称合成新路线。 根据我们设计的新路线，首先成功合成了其关键中间体，然后我们进行了关键的不对称催化尝试。用本实验室已有的高性能有机小分子催化剂虽得到了较好的对应选择性，但是产率很低。同时，为了验证整条线路的可行性，我们也用消旋的中间体进行拉通线路的尝试。但不幸的是，在脱除保护基时遇到了很大困难。尝试换不同的保护基，或改变脱保护基的顺序，都未能成功合成目标产物。究其原因可能是由于吲哚的特殊性造成的，吲哚类亚胺与常规的芳香亚胺有较大的差异，其NH基团无论保护还是不保护，对与其2位相联接的C=N双键均有很大的影响，导致其不对称催化还原难以进行。另外，由于所设计的还原产物含有处在吲哚苄位的胺基，稳定性较差，造成保护基脱除困难。 烯胺C-亚磺酰化反应是本课题组最近发现的一个新反应，之前未见文献报道。本研究对该反应进行了反应条件优化和底物扩展，发现带Cbz，Ac，COt-Bu，CO2Et，Bz等保护基的一系列环状和非环状烯胺在亚磺酸钠、DMAc和MeSiCl3的共同作用下能高效高产率生成β-胺基烯基亚砜类新化合物，为合成多官能团化的烯基亚砜新化合物提供了一条简便实用的途径。 The main constituent of Dracontomelum mangiferum B1, indoloquinolizidine alkaloid 10-Desbromoarborescidine A, has drawn great attention due to its calcium channel blocking activity. Its molecular structure is relatively simple compared with the other alkaloids of the same type, which has only one chiral center, albeit with four cycles A, B, C, and D. This compound is often used as a model target for exploring different strategies for the total synthesis of indole alkaloids. Nevertheless, so far there still lack practical and highly efficient methods for the asymmetric total synthesis of 10-Desbromoarborescidine A. Most of the current available methods rely on stoichiometric asymmetric synthesis for the construction of the chiral center. There is only one example reporting utilization of asymmetric catalysis, but with transition metal complex as the catalyst. Our retrosynthetic analysis shows that catalytic asymmetric reduction of imine could be used as the key step for the construction of the chiral center of Desbromoarborescidine A. Since in the previous studies our group has developed the asymmetric reduction of imines by trichlorosilane into a practical and highly efficient and enantioselective method using newly designed chiral organocatalysts, we hope to apply this method to develop a novel synthetic route for the total synthesis of Desbromoarborescidine A and its analogues in this study. According to the newly designed synthetic route, we first accomplished the synthesis of the key intermediates which was then examined for the critical asymmetric catalysis. The asymmetric reduction using the highly efficient organocatalysts, developed in our lab afforded high ee but poor yield. We tried different reaction conditions to improve the yield, but failed to get any good results. Simultaneously, to vertify the feasibility of the synthetic route we designed, we also tired to go through the route toward the racemic synthesis of Desbromoarborescidine A. But unfortunately, protection and deprotection proved to be big hurdles. All the different protection groups and different sequences of protection and deprotection we tried failed to get us through the designed synthetic sequence and furnish the final product. Most likely, the indole part is the culprit behind the failures.The NH group of the indole, no matter protected or not, may impact the catalytic asymmetric reduction of C-N double bond connected with 2-C. Additionally, the reduction product we designed contains an amino group in the β-position of the indole, which may cause problems due to its instability. C-sulfenylation of enamines is a novel reaction discovered recently by our group, which has not been seen before in the literature. In this study, optimization of the reaction conditions and exploration of the substrate scope were further undertaken for this reaction, which reveal that a series of enamines with N-Cbz, Ac, COt-Bu, CO2Et protection groups could all undergo smooth C-sulfinylations with the comined use of sodium benzene sulphinate, DAMc and MeSiCl3, efficiently furnishing the β-amino vinylsulfoxide products in high yield, affording a practical and highly efficient methods for synthesis of functional vinylsulfoxides.

瑞香狼毒（Stellera chamaejasme L.）对高寒草甸系统生长和非生长季节碳氮循环的影响及其花粉化感效应

瑞香狼毒（Stellera chamaejasme L.）是瑞香科（Thymelaeaceae）狼毒属的一种多年生野草，有毒。据调查，从20 世纪60 年代开始至今，狼毒在青藏高原东缘的高寒草甸上不断蔓延、密度不断变大，在一些地段甚至成为优势物种。有关狼毒在高寒草甸蔓延的生态系统效应的研究尚未见报道。本文从系统碳、氮循环的角度，分别研究狼毒在生长和非生长季节对高寒草甸生态系统的影响。同时，从花粉化感的角度，深入研究狼毒对当地同花期物种有性繁殖的影响。系统地研究高寒草甸生态系统物质循环过程，特别是非生长季节微生物和土壤碳氮库的动态变化，有助于揭示狼毒在系统物质循环方面的“物种效应”以及这种效应的季节变化，为丰富有关高海拔生态系统，特别是其非生长季的物质循环的科学理论做出贡献。同时，碳氮循环和花粉化感的研究还有助于深刻地理解狼毒作为一种入侵性很强的杂草的特殊的蔓延机制，从而为狼毒的有效防治、高寒草甸的科学管理提供依据。 针对狼毒在青藏高原高寒草甸上蔓延的生态系统碳氮循环方面的影响，开展以下2 方面的研究：（1）在生长季，研究松潘县尕米寺附近（北纬32°53'，东经103°40'，海拔3190 m）的两种地形（平地和阳坡）条件下狼毒对土壤碳氮循环影响及可能的原因。狼毒和其它几个主要物种（圆穗蓼（Polygonummacrophyllum D. Don var. Macrophyllum），草地早熟禾（Poa pretensis L.），四川嵩草（Kobresia setchwanensis Hand.-Maizz.），鹅绒委陵菜（Potentilla anserina L.var. anserine）和鳞叶龙胆（Gentiana squarrosa Ledeb.）的地上凋落物产量以及地上凋落物和根的化学组成被测量。在有-无狼毒斑块下，各种土壤的库（比如，铵态氮、硝态氮、无机磷和微生物生物量）和周转率（包括净矿化、净硝化、总硝化、反硝化和微生物呼吸速率）被测量和比较。（2）在非生长季节，尤其是春季冻融交替期，选取了两个研究地点——尕米寺和卡卡沟（北纬32°59'，东经103°41'，海拔3400 m），分别测定有狼毒和无狼毒斑块下土壤微生物生物量碳和氮、可溶性有机碳和氮以及铵态氮和硝态氮的动态变化。同时，分别在上述两个地点有-无狼毒的样地上，研究6 个主要物种（狼毒、圆穗蓼、草地早熟禾、四川嵩草、鹅绒委陵菜和鳞叶龙胆）从秋季开始、为期1 年的凋落物分解过程。 针对狼毒花粉化感对同花期其它物种可能的花粉化感作用开展以下工作：在实验室中，用一系列浓度的狼毒花粉水浸提液对与它同花期的其它物种以及自身花粉进行测试，测定花粉萌发率；在野外自然条件下的其它物种的柱头上施用上述浓度的狼毒花粉水浸提液，观测种子结实率，同时，观察狼毒花粉的种间花粉散布数量。 生长季节的研究结果表明，狼毒地上凋落物氮含量比其它几个主要物种更高，而木质素-总氮比更低。狼毒显著地增加其斑块下表层土壤中有机质的含量，而有-无狼毒的亚表层土壤在有机碳和总磷方面没有显著差异。狼毒表土中硝态氮含量在平地和阳坡比无狼毒土壤分别高113%和90%。狼毒表土中微生物生物量碳和氮量显著高于无狼毒表土。无论是平地还是阳坡，狼毒土壤的总硝化和微生物呼吸速率显著高于无狼毒土壤；而它们的反硝化速率只在平地有显著的差异。狼毒与其它物种间地上凋落物的产量和质量的差异可能是导致有-无狼毒土壤碳氮循环差异的原因。我们假设，狼毒可能通过增加贫氮生态系统土壤中的有效氮含量提高其入侵能力。 非生长季的研究结果表明，在青藏高原东缘的高寒草甸上，土壤微生物生3物量在11 月的秋-冬过渡期达到第一个峰值；在春季的冻融交替期，微生物生物量达到第二个峰值后又迅速降低。无机氮以及可溶性有机碳氮与微生物生物量有相似的变化过程。微生物碳氮比呈现显著的季节性变化。隆冬季节的微生物生物量碳氮比显著高于生长旺季的微生物碳氮比。这种变化可能暗示冬、夏季微生物的群落组成和对资源的利用有所不同。有-无狼毒斑块下土壤微生物和土壤碳、氮库一般只在秋-冬过渡期有显著差异，有狼毒土壤微生物生物量和土壤碳、氮库显著高于无狼毒土壤；而在之后的冬季和春季没有显著差异。所有6 个物种凋落物在非生长季分解率为24%-50%，均高于生长季的10%到30%。其中在秋-冬过渡期，凋落物开始埋藏的两周时间内，分解最快，达10%-20%。不同物种凋落物全年的分解率和分解过程有显著差异。圆穗蓼在全年的分解都较缓慢（非生长季26%，生长季15%），草地早熟禾和四川嵩草等全年的分解速率比较均匀（非生长季和生长季均为30%，非生长季略高），而狼毒在非生长季分解较快（约50%），而在接下来的生长季分解变得缓慢（约12%）。所有物种的凋落物氮含量在非生长季下降，而在随后的生长季上升。 实验室的花粉萌发试验证明，狼毒花粉对自身花粉萌发没有自毒作用，而其它受试的所有物种（圆穗蓼，秦艽（Gentiana macrophylla Pall. var. fetissowii），湿生扁蕾（Gentianopsis paludosa (Hook. f.) Ma var. paludosa），鳞叶龙胆，椭圆叶花锚（Halenia elliptica D. Don var. elliptica），蓝钟花（Cyananthus hookeri C. B.Cl. var. grandiflorus Marq.），小米草（Euphrasia pectinata Ten.），川西翠雀花（Delphinium tongolense Franch.），高原毛茛（Ranunculus tanguticus (Maxim.)Ovcz. var. tanguticus）和鹅绒委陵菜）的花粉萌发率随着狼毒花粉浸提液浓度的增加呈显著的非线性降低。大约3 个狼毒花粉的浸提液就可以抑制受试的多数物种的50%的花粉萌发。在鳞叶龙胆和小米草柱头上狼毒花粉的数量分别为5.76 个和3.35 个。狼毒花粉散布数量的差异最可能的原因在于是否有共同的传粉昆虫。花的形状（辐射对称VS 左右对称）、植株或花的密度以及花期重叠性可以部分解释这种差异。在野外试验中，我们发现6 个物种（秦艽、湿生扁蕾、鳞叶龙胆、椭圆叶花锚、蓝钟花和小米草）的种子结实率随狼毒花粉浸提液浓度的增加呈显著的非线性降低。鳞叶龙胆和小米草柱头上狼毒花粉的数量（分别是5.76 个和3.35 个）分别达到了抑制它们63%和55%种子结实率的水平。因此，狼毒对鳞叶龙胆和小米草可能存在明显的花粉化感抑制作用。狼毒周围的物种可能通过花期在季节或昼夜上的分异避免受到狼毒花粉化感的影响或者通过无性繁殖来维持种群繁衍，因此狼毒通过花粉化感作用对其周围物种繁殖的影响程度还需要进一步地研究。如果狼毒的花粉化感抑制作用确实存在，那么它可能成为一种自然选择压力，进而影响物种的进化。 Stellera chamaejasme L., a perennial toxic weed, has emerged and quicklydominated and spread in the high-frigid meadow on the eastern Tibetan Plateau ofChina since the 1960s. In the present study, effects of S. chamaejasme on carbon andnitrogen cycles on the high-frigid meadow on the eastern Qinghai-Tibetan Plateau ingrowing and non-growing season, and its pollen allelopathic effects on the sympatricspecies were determined. The present study that focused on carbon and nitrogencycles, especially on microbial biomass and pools of carbon and nitrogen innon-growing season, could profoundly illuminate plant-species effects on carbon andnutrient cycles and its seasonal pattern and help to understand spread mechanism ofS. chamaejasme as an aggressive weed. The present study also contributed to furtherunderstand carbon and nutrient cycles on alpine regions in non-growing season andprovide a basis on weed control of S. chamaejasme and scientific management in thehigh-frigid ecosystem. Effects of S. chamaejasme on carbon and nitrogen cycles on the high-frigidmeadow on the eastern Qinghai-Tibetan Plateau were determined. The study couldbe divided into two parts. (1) In the growing season, we quantified the effects of S.chamaejasme on carbon and nitrogen cycles in two types of topographic habitats, theflat valley and the south-facing slope, where S. chamaejasme was favored to spreadlitter and root were measured to explain the likely effects of S. chamaejasme on soilcarbon and nutrient cycles. The sizes of various soil pools, e.g. nitrite, ammonium,inorganic phosphorus and microbial biomass, and turnover rates including netmineralization, gross nitrification, denitrification and microbial respiration weredetermined. (2) In the non-growing season study, microbial biomass carbon andnitrogen, soluble organic carbon and nitrogen, ammonium and nitrate weredetermined through the non-growing season, especially in the processes offreeze-thaw of spring in two high-frigid sites, i.e. Kaka valley and Gami temple, onthe eastern Qinghai-Tibetan Plateau. Meanwhile, litter decomposition of six commonspecies, including Stellera chamaejasme L., Polygonum macrophyllum D. Don var.Macrophyllum, Poa pretensis L., Kobresia setchwanensis L., Potentilla anserina L.var. anserine and Gentiana squarrosa Ledeb., were also examined under theabove-mentioned experimental design through one whole-year, which began in theautumn in 2006. In the study of pollen allelopathy, several work, including in vitro study oneffects of extract of pollen from S. chamaejasme on sympatric species and pollenfrom itself, field experiments on effects of pollen extract with the same regime ofconcentrations on seed set and field observation on heterospecific pollen transfer ofS. chamaejasme to six of those sympatric species has been done. The results in the growing season showed that aboveground litter of S.chamaejasme had higher tissue nitrogen and lower lignin: nitrogen ratio than thoseco-occurring species. S. chamaejasme significantly increased topsoil organic matter,whereas no significant differences were found for organic C and total P in subsoilbetween under-Stellera and away-Stellera locations. The nitrate in Stellera topsoilwas 113% and 90% higher on the flat valley and on the south-facing slope,respectively. Both microbial biomass C and N were significantly higher in Stelleratopsoil. Gross nitrification and microbial respiration were significantly higher inStellera topsoil both on the flat valley and on the south-facing slope, whereassignificant differences of denitrification were found only on the flat valley. Thedifferences in the quantity and quality of aboveground litter are a likely mechanismresponsible for the changes of soil variables. We assumed that S. chamaejasme couldenhance their spread by increasing nutrient availability in N-deficient ecosystems. The results in the non-growing season showed that microbial biomass achievedthe first summit in late autumn and early winter on the eastern Qinghai-TibetanPlateau. In the stages of freeze-thaw of spring, microbial biomass firstly achieved thesecond summit and subsequently sharply decreased. Inorganic nitrogen, solubleorganic carbon and nitrogen had a similar dynamics with that of microbial biomass.Ratio of microbial biomass carbon and nitrogen had an obviously seasonal pattern.The highest microbial C: N were in the non-growing season, which weresignificantly higher than those in the growing season. The seasonal pattern inmicrobial biomass C: N suggested that large changes in composition of microbialpopulation and in resources those used by microbes between summer and winter.Generally, microbial biomass and pools size of carbon and nitrogen in Stellera soilwere significantly higher than those under adjacent locations in late autumn andearly winter, but there were not significant differences in winter and in spring. Litterof all the focal species (Stellera chamaejasme L., Polygonum macrophyllum D. Donvar. Macrophyllum, Poa pretensis L., Kobresia setchwanensis Hand.-Maizz.,Potentilla anserina L. var. anserine and G. squarrosa Ledeb.) decomposed about24%-50% in the non-growing season, which were higher than those in the growingseason (ranged from 10% to 30%). Litter decomposed 10%-20% within the first twoweeks in late autumn and early winter. Significant differences in the whole-yeardecomposition rate and in the processes of decomposition were found among species.Polygonum macrophyllum decomposed slowly through the whole year (26% and15% in the non-growing season and in the growing season, respectively). Certainspecies, such as P. pretensis L. and K. setchwanensis, decomposed at a similar rate(30% both in the non-growing and in the growing season, slightly higher in the8growing season than those in the growing season), whereas S. chamaejasmedecomposed more rapidly (about 50%) in the non-growing season and subsequentlydecomposition became slow (about 12%) in the growing season. Litter nitrogencontents of all the focal species firstly decreased in the non-growing season and thenincreased in the growing season. In vitro experiments of pollen allelopathy, the results showed that pollen from S.chamaejasme was not autotoxic, whereas pollen germination in all the sympatricspecies (Polygonum macrophyllum D. Don var. Macrophyllum, Gentianamacrophylla Pall. var. fetissowii, Gentianopsis paludosa (Hook. f.) Ma var. paludosa,Gentiana squarrosa Ledeb., Halenia elliptica D. Don var. elliptica, Cyananthushookeri C. B. Cl. var. grandiflorus Marq., Euphrasia pectinata Ten., Delphiniumtongolense Franch., Ranunculus tanguticus (Maxim.) Ovcz. var. tanguticus andPotentilla anserina L. var. anserina) decreased nonlinearly as the increasingconcentrations of extract of pollen from S. chamaejasme. Pollen Extract of threepollens from S. chamaejasme generally inhibited 50% pollen germination of most ofthe focal species. 5.76 and 3.35 pollens from S. chamaejasme were observed in fieldon stigmas of G. squarrosa and E. pectinata, respectively. Differences inheterospecific pollen transfer of S. chamaejasme could be attributed to the primaryreason whether they shared common pollinators. Flower morphology (e.g.zygomorphic or actinomorphic), plant or floral density and concurrence in floweringphonologies could explain, in part, the differences in heterospecific pollen transfer.In field experiments, the results showed that seed set in six sympatric species(Gentiana macrophylla Pall. var. fetissowii, Gentianopsis paludosa (Hook. f.) Mavar. paludosa, Gentiana squarrosa Ledeb., Halenia elliptica D. Don var. elliptica,Cyananthus hookeri C. B. Cl. var. grandiflorus Marq. and Euphrasia pectinata Ten.)decreased nonlinearly as the increasing concentrations of extract of pollen from S.chamaejasme. According to the nonlinear curves, the amounts of pollens from S.chamaejasme on stigmas of G. squarrosa and of E. pectinata (i.e. 5.76 grains and3.35 grains, respectively) could reduce 63% and 55% seed set of G. squarrosa and ofE. pectinata, respectively. Thus, allelopathic effects of S. chamaejasme on G.squarrosa and E. pectinata could be realistic. The sympatric species of S.chamaejasme could avoid pollen allelopathy of S. chamaejasme to sustainthemselves. This highlights the need to study how much pollen allelopathy in S.chamaejasme influences the sympatric species through divergence in seasonal ordiurnal flowering phonologies or through asexual reproduction. If pollen allelopathyin S. chamaejasme was confirmed, it could be as a pressure of natural selection andthus play an important role in species evolution.

牦牛粪便对青藏高原东部高寒草甸土壤养分系统的影响

川西北高寒草甸位于青藏高原东部地区，是我国四大牧区之一，也是长江和黄河等江河源区的重要水源涵养功能区。近几十年来，大量牦牛粪便被牧民作为生物能源、肥料或者食用菌产业的原料而利用，为草原生态系统的养分平衡增加了生态风险。鉴于在青藏高原地区针对牦牛粪便的相关研究尚未见报道，本文从粪便和土壤养分相互变化趋势的角度出发，研究了粪便在夏秋两季的分解状况和粪便其下及其周围土壤的养分变化。通过此研究，将有助于了解牦牛粪便在自然状态下的分解速率以及粪便对土壤养分及土壤微生物生物量的影响，为粪便对草地土壤生态系统的贡献提供概念性认识，同时也为高寒草甸草地这种脆弱生态系统的可持续管理提供理论依据。 针对牦牛粪便自身养分释放及其对土壤在时间和空间尺度上的影响，本文通过模拟牛粪堆积，在不同时间和固定区域内对牛粪和土壤进行了夏秋两季的采样测定，分析了牛粪及土壤NO3--N、NH4+-N、速效K、无机P、有机C、全N 和全P 含量随时间的变化趋势。得到如下结果： 1. 在研究区域内，牛粪对草地生态系统具有较强的养分（N、P）贡献能力。据初步统计，其估值大致为氮素699~932 kg ha-1，P 素为110~147 kg ha-1。牛粪（湿重、干重）在夏秋季节的分解速率具有较大差异，夏季显著快于秋季。夏季牛粪湿重、干重在2 个月左右之后分别降为初期的14%和24%，而秋季同期分别降为35%和52%。牛粪养分（NO3--N、NH4+-N、速效K、无机P、有机C、全N 和全P）的分解速率在夏季也要显著快于秋季。秋季经过2 个月左右的分解之后，牛粪以上含量分别降至初始态的32%、60%、36%、64%、58%、63%和43%，远高于夏季的同期水平。 2. 在不同季节，牛粪周围的土壤养分（NO3--N、NH4+-N、速效K 和无机P）含量变化随时间改变呈现相同的趋势。但是，牛粪周围不同远近下土壤养分随时间的动态变化幅度略有不同。粪下土壤养分含量随时间变化波动较大，距粪便越远，随时间变化的变幅越为平缓。总体来说，在夏季由于粪便分解较快，对土壤养分的持续作用时间不及秋季，秋季粪便分解变慢，表现出养分的缓释特征。其次，牛粪对粪下土壤影响的持续时间也长于对周围土壤的作用时间。 3. 粪便对土壤养分（NO3--N、NH4+-N、速效K、无机P）影响的范围在不同季节具有差异。夏季要高于秋季，但对周围土壤养分影响的持续时间低于秋季。在夏季短期内，牛粪对土壤NO3--N 和速效K 含量的影响范围能够超过30cm，而对NH4+-N 和无机P 的影响范围则介于10cm 和30cm 之间。在2 个月左右之后，牛粪对周围土壤养分的影响能力基本消失。在秋季，牛粪对周围土壤养分影响范围难以达到30cm 处。粪便在夏季对其下土壤和周围土壤的有机C、全N 和全P 含量并无显著影响，但在秋季能显著增加其下土壤有机C、全N 和全P 含量。 4. 牛粪在秋季对土壤SMB-C、SMB-N 和SMB-P 含量的影响能够持续2 个月以上，由于秋冬季节牛粪分解缓慢，因此推断这种效应持续时间至少能够1 年左右。另一方面，牛粪在秋季对土壤SMB-C、SMB-N 和SMB-P 含量的影响范围主要集中在其下土壤，而周围的影响效应并不明显。 The grassland on the eastern fringe of Qinghai-Tibetan Plateau was one of the four greatest pasture zones in our country and the main water conservation function zones in the hesastream of Yangtse River and Huanghe river. Rencent years, lots of dung in this area was used as biological energy, fertilizer or material of fungoid growing, leading to high risk of nutrient banlance in grassland ecosystem. In view of the researches on the impact of yak dung in this area are relatively rare, the present study focused on the relationship of dung and soil nutrient transformation in sunmer and autumn, which could profoundly illuminate the mechanism of dung decomposition and the effect of dung on soil chemical properties and soil microbe biomass. The present study also contributed to a basic understand and provided scientific management in the high-frigid ecosystem. Decomposition of yak dung and its effect on soil chemical properties in eastern grassland of Qinghai-Tibetan Plateau were determined. The study simulated the real dung pats, took dung and soil samples at different time and fixed-point in summer and autumn. The samples were analysed for NO3--N, NH4+-N, available K, inorganic P, total organic C (TOC), total N (TN), total P (TP). It was concluded that: 1. In study area, the yak dung supplied to ecosystem substantial nutrient. It is estimated that the N contribution of dung was approximately 699~932 kg ha-1, P contribution was approximately 110~147 kg ha-1. The rate of yak decomposition was more rapid in summer than autumn, the wet and dry weight of yak decreased to 14% and 24% respectively after 2 months when dung excreted in summer, with 35% and 52% in autumn. The content of NO3--N、NH4+-N、available K、inorganic P、TOC、TN and TP in dung decomposed more rapid in summer too. After 2 months when dung excreted in autumn, the content of above nutrient decreased to 32%、60%、36%、64%、58%、63% and 43% respectively，which were significantly higher than summer. 2. The content of NO3--N、NH4+-N、available K and inorganic P in soil around dung had the same transformation trend in each season, whereas it was distinguishing at different gradient of distance from dung, the nutrient in soil below dung had the most significant change while the more far from dung, the less change in soil. It was concluded that the yak dung had prolong impacts on soil in autumn compared with summer, besides, it aslo showed that the yak dung had protract effect on soil below dung compared with soil around dung. 3. The yak dung had expansive impact on soil around dung in summer whereas had relatively short effect compared with autumn. In short-term at summer, there was a significant increase about the content of NO3--N and available K around 30cm radius from dung pat while the content of NH4+-N and inorganic P between 10cm to 30cm. After 2 months, the impact almost disappeared. In autumn, the effect was hard to reach 30cm. The yak dung had no significant effects on the content of TOC、TN and TP in soil below or around dung in summer whereas there was a obvious increase in soil below dung pat in autumn. 4. The duration of effect of yak dung on soil microbial biomass(SMB) C、N and P was at least 2 months, maybe even more than 1 year. On the other hand, the impact of dung on SMB-C、SMB-N and SMB-P mainly acted on soil below dung while no obious effect on soil around dung.