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The investigation of the catalytic activity and stereoselectivity of ligand 10 was also carried out under another standard set of K〓Fe 〓 conditions (〓/ligand/substrate=0.002: 0.01: 1). The AD reaction of seven olefins gave corresponding diols in 72~99% yield (except for ethyl cinnamate, 48%) and 91~99% ees, which was comparable to those obtained from the reactions using the commercial ligand 〓PHAL.

将单季铵盐手性配体10用于AD反应的另一个催化体系〓BuOH-H〓O/K〓Fe〓中考察其催化活性和立体选择性,在七种烯烃的AD反应中,〓、配体与底物的摩尔比为0.002:0.01:1时,化学产率为72~99%(肉桂酸乙酯除外,为48%),ee值为91~99.9%,与商品配体〓PHAL的催化结果相当。

These dendritic NOBIN derived Schiff base ligands have been applied to titanium catalyzed hetero-Diels-Alder reaction of Danishefshy's diene and aldehydes, affording the corresponding 2-substituted 2, 3-dihydro-4H-pyran-4-one in quantitative yields and excellent enantioselectivities (up to 97. 2%ee). Comparing the reactivities and enantioselectivities of reaction catalyzed by the titanium complexes of these Schiff base ligands, it was found that a series of ligands L〓 were superior to the other three series of ligands L〓, L〓 and L〓, a significant positive NLE and a dendrimer effect existed in the L〓 dendritic catalyst system. The disposition of the dendritic wedges and the dendron size in the ligands were observed to have a significant impact on the enantioselectivity of the reaction.

NOBIN衍生的树枝状大分子希夫碱手性配体与钛形成的配合物在催化不对称杂Diels-Alder反应中的应用将得到的四个系列NOBIN衍生的树枝状希夫碱三齿手性配体与四异丙氧基钛形成的配合物用于催化Danishefsky's diene与醛的不对称杂Diels-Alder反应,通过反应条件的优化,获得了定量的收率和最高达97.2%ee值的对映选择性;考察了这四个系列NOBIN衍生的树枝状希夫碱钛配合物的催化活性和对映选择性,结果发现它们的活性次序依次为L〓≈L〓>L〓>L〓,对映选择性次序依次为L〓>L〓>L〓>L〓。

Experimental process: jing and 3- methyl -2- methyl ethyl ketonesynthesizes by the benzene zong; Again the glacial acetic acidcatalysis produces 2, 3, 3 - trimethyl - 3H - yinduo; Again has thealkylate response production yinduo iodide after the methyl iodide;The iodide takes off molecular HI under NaOH to become freejier thealkali; Adds 5 - nitryls salicylic aldehydes in the ethyl alcohol forthe solvent under if to respond finally produces 6 '- the nitryl yinduolin spiral benzene and pinan; Through the infrared spectrum andthe ultimate analysis irrevocably proved its structure, and studiedthe annulus with to open the annulus the light to send changes colorthe performance, explained in different solvent medium ultravioletabsorption spectrometry solvent effect, and the comparisondiscoloration the response speed number difference, finally mixed itadds to the methyl methacrylate, the peroxidation benzoin formyl in the plexiglass, tested 6 '- the nitryl yinduolin spiralbenzene and pinan in the glass fatigue resistance, thethermostability.

实验过程:由苯肼和3-甲基-2-丁酮合成腙;再冰醋酸催化生成2 ,3 ,3—三甲基—3H—吲哚;再经过碘甲烷发生烷基化反应生成吲哚碘化物;碘化物在NaOH下脱去一分子HI成为费歇尔碱;在乙醇为溶剂下加5-硝基水杨醛与其反应最后生成6'—硝基吲哚啉螺苯并吡喃;通过红外光谱和元素分析确证其结构,并研究了环体与开环体的光致变色性能,解释了在不同溶剂介质中紫外吸收光谱的溶剂效应,并比较褪色反应速率数的差异,最后将其掺加到甲基丙烯酸甲酯,过氧化二苯甲酰有机玻璃中,测试6'—硝基吲哚啉螺苯并吡喃在玻璃中的抗疲劳性、热稳定性。

It is shown that the methanol dimer and methanol cluster are the predominant species of methanol in gaseousness. So we believe that rather the methanol dimer is the original reactant of the methanol dehydration reaction to dimethyl ether than the mono-methanol.

研究表明,在气相中,甲醇分子主要以二聚体和多聚体的形式存在,据此提出甲醇脱水反应的原始反应物是甲醇二聚体,而不是单个甲醇分子。

Cephalotaxine ester of 2-oxo-6-methylheptanoic acid was treated with lithium diisopropylamide and Me O-(1-methoxyisopropyl)glycolate to give a mixture of homoisoharringtonine and its stereoisomers with 56% yield. The four stereoisomers separated by TLC showed identical mass spectra and almost superimposed IR but with different 1H NMR spectra. The configuration of the 2'-C and 3'-C of the four isomers were postulated based upon their 1H NMR spectra as compared with the 1H NMR spectra of isoharringtonine and its stereoisomers.

2-氧代-6-甲基庚酰基三尖杉碱(3)与0-(1-甲氧基异丙基)羟基乙酸甲酯(4)在强碱性试剂二异丙胺锂存在下,起亲核加成反应,反应中间体5在室温用酸性丙酮水解,得到一种新的三尖杉酯类生物碱一一高异三尖杉酯碱(6c)及其立体异构体(6a、6b、6d)的混合物,产率56%、通过制备薄层层析分得这四个立体异构体,它们的1H NMR和异三尖杉酯碱及其立体异构体的1H NMR类似,推定了它们的绝对构型。

METHODS:Guinea-pigs were sensitized by ovalbumin and the effects of LMWH on the constriction of ileum smooth muscle induced by OA were observed in vitro;The effects of LMWH on the degranulation of pericranium mast cell induced by OA were observed throu gh the passive anaphylaxis ratmodel which was made by vaccinating antiserum at pericranium;Licking response was induced by 4-aminopyridine(4-AP) scat scruff in mice,then the effect of LMWH on licking response was studied the capillary p emeabilty increasing induced by glactal acetic acid and the effect of LMWH on ca pillary pemeability were studied.

用卵白蛋白(ovalbumin,OA)免疫豚鼠造成过敏模型,观察LMWH对OA所致的豚鼠离体回肠平滑肌收缩的影响;在大鼠颅骨骨膜接种抗血清使肥大细胞被动致敏,观察LMWH对OA引起肥大细胞脱颗粒的影响;以4-氨基吡啶诱发小鼠舔体反应,观察LMWH对舔体反应的影响;以冰醋酸使小鼠毛细血管通透性增加,观察LMWH对通透性的影响。

Protease treatment of the plasma membranes could abolish the binding but NaIO_4 and glycosidase could not, indicating that nsLTP144 bound to plasma membranes protein without carbohydrate moiety. Using the homobifunctional cross-linking regent bissuberate (BS~3) and rice plasma membranes incubated with ~(125)I-Trx-nsLTP144, we identified, after SDS-polyacrylamide gel electrophoresis and autoradiography, a putative protein receptor on the rice plasma membranes with the molecular mass around 60 kDa. NsLTP144 can not trigger extracelluar alkalization in arabidopsis, but can abolish the extracellular alkalization effect of phytopathogen elicitor cryptogein, suggesting that cryptogein and nsLTP144 may bind to the same membrane protein. In vitro pull-down assay showed that nsLTP144 interacted with OsCaM1, a possible extracellular calmodulin, implying that nsLTP144 and OsCaM1 could function in the same signal transduction pathway. These results shed light on revealing the roles of nsLTP in vivo and make it promising to finally characterize the plasma membranes receptor of nsLTP.

发现~(125)I-Trx-nsLTP144、~(125)I-Trx-nsLTP110与水稻细胞质膜均具有特异性结合,而且结合是饱和性的、可被竞争的,符合配体-受体结合的典型特征,同时用于对照实验的蛋白质~(125)I-Thioredoxin没有此特性,表明水稻细胞质膜上存在nsLTP的受体;利用可氧化糖基的NaIO_4和水解糖基的N\'-糖苷酶F处理水稻细胞质膜,再进行结合实验,结合活性几乎不受影响;而利用胰蛋白酶处理细胞膜则使得结合能力几乎完全丧失,表明其受体为没有经过糖基化修饰的蛋白质;利用交联剂BS~3交联配体一受体后,再进行SDS-PAGE分离和放射自显影,结果显示水稻细胞质膜上的nsLTP受体中有一个60kDa的蛋白质可以与nsLTP144发生特异性的结合,可能是其受体;细胞外碱化实验表明,nsLTP144不能促使拟南芥原生质体细胞培养液的细胞外碱化反应,却能猝灭来自植物病原菌的激发子Cryptogein刺激拟南芥原生质体产生的细胞外碱化反应,表明nsLTP和Cryptogein结合细胞膜上相同的位点,保护了植物细胞免受Cryptogein导致的细胞程序性死亡,并诱导系统获得性抗性的产生;体外Pull-down实验表明,nsLTP144和水稻的OsCaM1具有相互作用,暗示了nsLTP144和OsCaM1可能同在一个信号通路上起作用。

Specifically, itcontains 8 chapters.In chapter 1, the formation, structures, properties and the futureprospect of liposome were thoroughly reviewed;In chapter 2, the stibility and permeability of phopholipid -eleostericacid liposome were studied together with the effect of polymerizationof eleostearic acid. This membrane system was very sensitive to 〓,the effect of 〓 was clarified to increase the aggregation/fusion ofliposomes and made the permeability of mixed liposomes much higher;In chapter 3, two polymerizable conjugated diyne bolaamphiphiles were synthesized. They could form very stable mixed liposome, andthe diyne could be polymerized by UV light in bilayer liposomes, as aresult, the stability of mixed liposome against solvent or surfactantafter polymerization were enhanced. In chapter 4, two kinds of amphiphilic amino acids were synthesized andstable liposomes were formed therefrom After the condensationpolymerization of amino acid in bilayer liposomes, stable polypeptide liposomes were obtained, which had lower phase transition temperatureand higher permeability.In chapter 5, four kinds of glycolipids were synthesized and theiraggregation behavior in water was comparied. When incorporated intophospholipid bilayer membranes, they could increase the phase transitiontemperatures and inhibit the aggregation and fusion of mixedliposomesat lower temperature.In chapter 6 and 7, three kinds of steroidal bolaamphiphiles withdifferent chain lengths were synthesized. Incorporation of steroidalmoiety to the center of lipid bilayer membrane obviously increased themobility of lipid membrane and shifted Tc to lower temperature side incomparasion with cholesterol. The bolaamphiphile which was shorter thanthe hosted lipid bilayer membrane thickness influenced the lipid packingmore obviously.

全文共分8章:第一章对脂质体的形成、结构、性质及展望进行了较为详细的文献综述;第二章研究了磷脂-桐酸脂质体的稳定性,通透能力及桐酸的聚合对这些性质的影响;磷脂-桐酸混合脂质体为一类对〓灵敏的脂质体,〓的作用首先是使脂质体集聚然后使脂质体融合,并加速内包荧光物的释放;第三章通过合成两种可聚合共轭双炔双极性双亲分子DDCA,DDOL,研究了共双炔分子在双分子层脂质体膜上的聚合及对脂质体性质的影响,聚合可以提高脂质体相对于溶剂及表面活性剂的稳定性;第四章合成了两类氨基酸为极性基团的双亲分子,它们均可以在超声下形成稳定的脂质体结构;氨基酸基团可以在脂质体上进行缩聚反应,若聚合后脂质体表面仍有足够的亲水能力,则可得到稳定的多肽型脂质体;聚合后脂质体的相变温度降低,通透能力增加;第五章合成了四种亲水基团为单糖基的双亲分子GL-l,GL-2,GL-3, GL-4,研究了它们在水中的分散情况、集合体形态与分子结构的关系;在DMPC双分子层膜中加入糖脂分子可以使脂质体的相变温度提高,阻止脂质体在低温放置时的集聚与融合;第六章-第七章合成了三种不同碳链长度的双极性含胆甾环双亲分子 CL-1,CL-2,CL-3;它们可以象胆固醇一样与磷脂混合形成稳定脂质体,胆甾环基团位于脂质体双分子层膜的中间;与胆固醇的作用相反,它们可以增加磷脂双分子层膜的流动性,降低混合脂质体的相变温度;三种分子的作用与其碳链长度和磷脂双分子层膜的厚度有关,比膜厚度短的分子影响最大。

To test this concept in transplant recipients, we evaluated complement, complement regulator, and T cell/proinflammatory marker gene expression by quantitative real-time polymerase chain reaction in 71 archived heart transplant biopsies and correlated the results with the histologic grade of rejection. Significantly more transcripts encoding alternative pathway components factor B, C3 and properdin, and C3a receptor and C5a receptor were detected in grade 3 versus grade 0 or 1 biopsies. The grade 3 rejections also contained significantly higher amounts of CD3, interferon gamma, perforin, and granzyme B genes.

为了明确移植受者中该理论的正确性,我们采用RT-PCR的方法检测了71例心脏移植物活检标本中补体、补体调节物以及T细胞/促炎症反应标记物基因表达及其与排斥反应的组织学分级的相关程度。3级的排斥反应相比于0或者1级的排斥反应其活检标本中旁路途径成分因子B、C3以及备解素和C3a与C5a的受体表达均明显升高。3级排斥分那英同样存在更多的CD3、IFN-gamma、穿孔素和颗粒酶B基因的表达。

In this study, Cryptomeria japonica was liquefied in phenol with H2SO4 and HCl as a catalyst. The epoxy resin was synthesized from epichlorohydrin and bisphenol A with the molar ratio of 5/1. Blending resins were prepared by mixing the liquefied Japanese cedar and epoxy resin with weight ratios of 30/100, 50/100 and 70/100, and the triethylene tetramine was added as a cross-linking hardener. The effect of mixing ratios of liquefied Japanese cedar to epoxy resin and amount of hardener added on the reactivity of blending resins and the properties of cured resins were investigated. Furthermore, polysiloxane and rice husk were added as foaming agent and filler, respectively, to the epoxy resin and blending resins. The foaming process, the bubbles shape, the mechanical properties, and the thermal stability of the epoxy foams were investigated.

中文摘要本研究将柳杉(Cryptomeria japonica; Japanese cedar)木材以酚为溶剂,H2SO4及HCl为催化剂进行液化处理,另以莫耳比5/1之环氧氯丙烷与双酚A反应合成环氧树脂,并将液化柳杉与环氧树脂以重量比30/100、50/100及70/100混合制备掺合树脂,并以三乙基四胺(Triethylene tetramine; TETA)为架桥硬化剂,探讨液化柳杉与环氧树脂混合比及硬化剂添加量对其掺合树脂之反应性,及其硬化树脂性质之影响;进一步於环氧树脂与掺合树脂中添加聚矽氧烷为发泡剂,稻壳粉为填料制备发泡体,探讨其发泡体之发泡过程、泡体形态、发泡体机械性质与热稳定性。

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With Death guitarist Schuldiner adopting vocal duties, the band made a major impact on the scene.

随着死亡的吉他手Schuldiner接受主唱的职务,乐队在现实中树立了重要的影响。

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关闭眼睛,深呼吸,一切不再是梦想,犹如。。。。。。