化合物

Both three-dimensional chiral compounds have intriguing chiral channels, which are built up of homochiral intertwined double helices. The circular dichroism spectra of 1 and 2 in water have shown they are stable in solution, which document they will be significantly useful in asymmetric catalysis and chiral medicine.

以Keggin结构多金属氧酸盐为建筑单元，通过手性的铜-脯氨酸配合物作为模板剂构筑了2个基于Keggin结构多金属氧酸盐的3D纯手性化合物，化合物1和2是一对对映体，代表了世界上第一例3D手性多酸化合物，具有由同手性螺旋缠绕形成的手性孔道，水溶液中的圆二色谱表征这个3D手性化合物可稳定存在，显示这个物种可以在不对称催化及手性药物方面有潜在的巨大的应用价值。

Quercetin, quercetin rhamnoside, hyperin, syringoside and eleutheroside E wereisolated from the flower of Acanthopanax senticosus. Searching bioactive natural compound and establishing quality evaluation standard arefocused on this experiment. Using cold immersing of 70% methanol to extract from flower ofAcanthopanax senticosus and integrating macroporous resin, silica gel column chromatography,sephadex gel to abstract. We obtained five monomer compounds (compoundⅠ-compoundⅤ),quercetin, quercetin rhamnoside, hyperin, syringoside and eleutheroside E. That five compoundswere determined by HPLC in eight parts of Acanthopanax senticosus (flower, root, leaf fruit,shoot, new shoot, phloem of shoot, skin of shoot), which provide science bases for establishingquality evaluation system and settle infarctate foundation.

本文以从刺五加花蕾中寻找具有重要生物活性的天然化合物和建立质量评价标准为主要目的，对其化学成分进行研究，采用70％甲醇冷浸的方法对刺五加花蕾中的成分进行提取，运用大孔树脂吸附色谱法、硅胶柱层析法以及葡聚糖凝胶柱层析相结合的方法进行分离，得到5种单体化合物，分别为槲皮素、槲皮素鼠李糖苷、金丝桃苷、紫丁香苷和刺五加苷E；利用高效液相色谱法对这5种化合物在刺五加花蕾中的含量进行了测定；考察了8个部位(花蕾、根、叶、果、茎干、新枝、茎韧皮部、茎皮)中这5种化合物的含量分布情况，并作一比较，为今后建立刺五加质量评价体系提供了科学依据，奠定了坚实的基础。

Several anti-tumor cell lines and carbonic anhydrase Ⅱ model were established. More than 10000 compounds and extracts from plants were screened using these models and about 10 compounds showed strong inhibitory activities. Two species of plants Inula helianthus-aquatica and Saussurea deltoidea were chosen to investigate chemical and bioactivity constituents based on the results of screening of extracts and fractions. 58 compounds were isolated and identified from these two plants, 6 compounds were found to be new and 14 compounds showed anti-tumor activities. We also studied the anti-tumor mechanism of the compound bigelovin isolated from Inula helianthus-aquatica. Bigelovin was found with apoptotic activity against cell line U266 by lowering the amount of important transcription factor E2F-1 which inhibits the cell cycle at G0/G1 stage. Docking study on 7 natural new phenolic inhibitors of CA Ⅱ and 3D-QSAR study on 61 sulfonamide inhibitors of CA Ⅱwere also investigated. The calculated results were in good correlation with experimental results.

基于以上两种重要疾病和研究组方向，本论文工作开展了多个肿瘤细胞株和碳酸酐酶Ⅱ靶标模型的建立和筛选工作，累计筛选1万多个/次样品，发现10余个活性较强化合物；从粗提取物筛选结果中选取两种抗肿瘤活性强的菊科植物水朝阳旋覆花(Inula helianthus-aquatica)和三角叶凤毛菊进行了系统化学和活性成分研究，分离鉴定了58个化合物，发现6个新化合物和14个抗肿瘤活性化合物；通过合作对水朝阳旋覆花中活性较强的bigelovin进行了抗肿瘤作用机制研究，发现它可能是通过降低G2期重要的转录因子E2F-1，致使细胞周期阻滞在G0/G1期，引起多发性骨髓瘤U266细胞凋亡；开展了7个新的天然酚类CAⅡ抑制剂的对接研究和61个合成的系列磺酰胺类CAⅡ抑制剂的3D-QSAR分析，结果表明计算与实验一致。

The dissertation mainly consists of two parts:1. The Reaction Chemistry of Alkynes under Palladium Catalysis Part 1 studies the reaction α,β-unsaturated carbonyl compounds with alkenylpalladium intermediate generated by nucleopalladation, and discovered 1 the Pd-catalyzed tandem addition reaction of halides, alkynes and α,β-unsaturated carbonyls,2 the four-component tandem addition reaction of halides, alkynes and α,β-unsaturated carbonyls, 3 the tandem intramolecular oxypalladation-conjugate additionreaction of alkynoic acids with α,β-enals. These new reactions provide notonly efficient highly stereoselective methods for the synthesis of γ,δ-unsaturated,polyunsaturated carbonyl compounds and γ-lactonic aldehydes, but also thebasic transformations for a number of C-C bond formation reactions which can be usedto design synthesis of many acyclic, cyclic or polycyclic compounds.

本论文的主要工作分为两个部分：一、钯催化下炔烃的反应化学在本小组前人工作的基础上，我们详细研究了炔烃亲核钯化产生的烯基钯中间体与α，β-不饱和羰基化合物的反应，发现两价钯催化下卤离子-炔烃-α，β-不饱和醛酮的串联加成反应、卤离子-炔烃-α，β-不饱和醛酮的西组分串联加成及炔酸分子内氧钯化-串联Michael型加成反应；由此发展了γ，δ-不饱和醛酮、多不饱和羰基化合物和带有醛酮基侧链的γ-丁内酯衍生物的高立体选择性合成方法，这一过量卤离子存在下的烯基钯对α，β-不饱和羰基化合物共轭加成反应的发现，为大量碳-碳键形成反应的实现提供了基础，使我们能够从这一基本反应出发，设计和开发多种分子内、分子间的碳碳成键反应，以好的立体、区域选择性组建开链、环状及多环类型的化合物。

Among the open-chain crown ethers and cryptands with a same structure, the compounds disubstituted at the amide nitrogen atoms show the larger extractability for Am and Eu than the monosubstituted ones. The compounds disubstituted at the amide nitrogen atoms by two phenyl groups show the larger extractability for Am and Eu than those by two alkyl groups.

3在结构相同的开链冠醚和开链穴醚中，酰胺氮原子上二取代化合物对Am和Eu的萃取能力大于一取代化合物；酰胺氮原子上两个取代基都是苯基的化合物对Am和Eu的萃取能力大于两个取代基都是烷基的化合物。

The results show that, Au-19.25Ag-12.80Ge brazing alloy is better, its melting temperature range is 446.76494.40 ℃, and the temperature interval between the solidus and the liquidus is 47.64 ℃. When the brazing temperature is in the range of 510550 ℃, the alloy has a good spreadability and wettability with Ni. Interface structure observation reveals that there is one continuous intermetallic layer between the brazing alloy and the base metal Ni when welding. X-ray energy spectrum analysis results show that the intermetallic layer is Ge3Ni5, and because of its brittleness, the overthick intermetallic layer will decrease the shear strength of the welding joint, therefore, the welding technology should be controlled so as to gain an ideal welding interface structure.

研究结果表明：Au-19.25Ag-12.80Ge合金的性能较好，其熔化温度范围为446.76~494.40 ℃，结晶温度区间为47.64 ℃；焊接温度在510~550 ℃范围内时，Au-19.25Ag-12.80Ge钎料合金与Ni基体具有良好的铺展性和润湿性，焊接时钎料合金与Ni基体之间形成了一条连续的金属间化合物层，能谱分析表明该金属间化合物层为Ge3Ni5，由于该化合物较脆，过厚的金属间化合物层使焊接接头的剪切强度下降，故应适当控制焊接工艺以获得理想的焊接界面组织。

The results of bioassay experiments with 10 commonly used fungi showed that, all the title compounds had satisfactory fungicidal activity against Botrytis cinerea, the growth inhibition rate of compounds 5ae, 5ag, 5bd against Botrytis cinerea were up to 70% and for 5ad, 5cd, 5ce were more than 60%; compound 5bd exhibited fungicidal activity against Pellicularia sasakii with growth inhibition up to 60%, the growth inhibition rate of compound 5cg against Colletotrichum lagenarium was 69%.

抑菌活性生物测定结果表明，合成的大部分化合物对黄瓜灰霉病菌均有较好的生长抑制作用，其中，化合物5ae、5ag和5bd的抑制率达到70%；化合物5ad、5cd、5ce的抑制率大于60%；5bd对水稻纹枯病菌抑制率大于60%，化合物5cg对西瓜炭疽病菌的抑制率为69%。

Among them, I was a new compound, II～IV and VI～IX compounds were isolated from pholidota for the first time, X and XIV compounds were isolated from P.chinensis for the first time.

其中化合物I是新化合物；化合物II～IV、VI～IX为首次从该属植物中分离到；化合物X和XIV为首次从该种植物中分离到。

The biological tests indicate that most of the compounds synthesized have herbicidal activity in a certain degree and several compounds show certain bactericidal activity. Further anti-ALS enzyme test shows that two kinds of novel phosphonic ureas have good anti-ALS enzyme activity.

对合成的部分化合物进行了初步的生物活性测定，所设计的大部分化合物都显示出一定的除草活性，有的具有一定的杀菌活性；对两类膦酰脲化合物进行了离体ALS酶抑制试验，结果表明它们是很好的ALS酶抑制剂，同磺酰脲相当，有希望作为另一类ALS酶抑制剂的先导化合物。

The results of the ability of anti-oxidation scavenging DPPH free radical shows that polyhydroxy substituted N-benzoylserotonin derivatives (compound 1-10) have the generally better ability of anti-oxidation than control group, in which the IC50 of compound 1-10 ranges 8.75 to 18.02 μg/ml and the IC50 of trolox is 13.04 μg/ml. The abilities of anti-oxidation of compound 1, 4, 5, 7, and 10 are all better than the control group, trolox. Among all, compound 10 has the best ability of anti-oxidation (IC50 is 8.75 μg/ml). This study also discovers that the ability of scavenging DPPH free radical is strongly related to the number and the position of hydroxyl.

在清除DPPH自由基的抗氧化能力结果显示，相较於对照组水溶性维生素E之IC50值13.04 μg/ml，多羟基取代之N-色洛冬宁苯甲醯胺衍生物（化合物 1 ~ 10），皆具有相当不错的抗氧化能力，十种醯胺化合物的 IC50值介於8.75 ~ 18.02 μg/ml之间，化合物1、4、5、7、10的抗氧化能力效果皆优於对照组水溶性维生素E的IC50值，其中又以化合物10的效果最佳(IC50值8.75 μg/ml)，而清除DPPH自由基的能力发现与羟基的数量及其位置有关。

This one mode pays close attention to network credence foundation of the businessman very much.

这一模式非常关注商人的网络信用基础。

Cell morphology of bacterial ghost of Pasteurella multocida was observed by scanning electron microscopy and inactivation ratio was estimated by CFU analysi.

扫描电镜观察多杀性巴氏杆菌细菌幽灵和菌落形成单位评价遗传灭活率。