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THE FIRST TOTAL SYNTHESIS OF TAXAMAIRIN B Taxamairin B, representive of rare naturally-occuring rearrang-ed 9(10→20)-abeo-8, 11, 13-triene diterpenoids, has been firstsynthesized by a eleven-step route in an overall yield of 8.19%,starting from commercially available catechol and 1,3-cyclohexan-dione. The improved Friedel-Crafts annulation, thermodynamicallycontrolled-geminal pairing methylation, the selective oxidation ofallyl group and the selective reduction of the less-hindrancecarbon-carbon double bond are the key steps.

二。美丽红豆杉素B的全合成研究 1,美丽红豆杉素B的首次全合成以价廉,易得的邻苯二酚和1,3-环己二酮为原料,经过改良的Friedel-Crafts烷基化反应,热力学控制的α,β-不饱和酮结构的α一位双烷基化,烯丙位的选择性氧化,以及选择性还原位阻较小的碳碳双键等十一步反应,以8.19%的总收率首次完成了美丽红豆杉素B的全合成。

These results indicate that the potent antianaphylaxis effect of myricetin may be associated with the inhibition of typeⅠand type Ⅳ allergic reaction .

杨梅素具有抗过敏作用,机制可能与抑制Ⅰ、Ⅳ型变态反应有关。关键词杨梅素;抗过敏;被动皮肤过敏反应;瘙痒反应;迟发型超敏反应

1H NMR spectroscopic analysis of aromatic protons combined with theoretical analysis of molecular structures proved the existence of two rotational isomers at 300 K, as well as a rapid interconversion equilibrium at 330 K for both compounds Ⅰ and Ⅱ. However, only one conformer exists for compound Ⅲ and puerarin containing 7-phenolic hydroxyl instead of propyl in A-ring as the case of compounds Ⅰ and Ⅱ. Based on UV-Visible absorption data of neutral and basic solutions, and on the density function calculations, the 7-phenolic hydroxyl group in A-ring was found to be more acidic than the 4'-phenolic hydroxyl group in B-ring. The mechanism of derivation reaction and the structure-reactivity relationship of puerarin as an antioxidant were further discussed.

其中7-丙基葛根素Ⅱ属于新型取代衍生物;变温1H NMR和理论计算结果表明,在300 K时,葛根素和4'-丙基葛根素以单一构型存在;而7,4'-二丙基葛根素和7-丙基葛根素则存在两种核磁可分辨的旋转异构体,当温度升至330 K时,两种异构体可以相互转化;通过对比分析葛根素及其衍生物脱质子产物的紫外可见吸收光谱并结合理论计算,确定了A环上7位酚羟基比B环上4'位酚羟基先脱去质子,并由此进一步阐明了葛根素衍生化反应机理以及在抗氧化作用中可能的活性位点和结构活性关系。

Based on the previous literatures, the following major innovation works were carried out in this dissertation:(1) The derivatization reaction conditions of ephedrine and pseudoephedrine with sensitive derivation reagent in aqueous system were studied and two new methods were developed for the assay of them by microemulsion electrokinetic chromatography and micellar electrokinetic chromatography with LIF detection. The sensitivity and analysis times were greatly improved compared with the previous reports;(2) A new method of CZE with indirect LIF detection was developed for the simultaneous determination of six coumarin compounds (esculin, esculetin, isofraxidin, genistein, naringin and sophoricoside) with fluorescein as the probe. The proposed method enlarges the application range of LIF detector, and provides new approach for the analysis of certain compounds difficult to derivatize;(3) Based on the above research, an MEKC with indirect LIF detection method for the simultaneous determination of adenine and guanine in DNA extracts from fungus, maize and soybean was established;(4) A new method for the investigation of the complexes formed between human serum albumin and ampicillin sodium under the simulated physiology conditions using laser light scattering technique was developed.

该论文在综述前人工作的基础上,开展了如下未见文献报道的创新性的研究工作:(1)使用灵敏的衍生试剂对麻黄碱和伪麻黄碱在水体系中的衍生反应条件进行了系统研究,建立了微乳电动色谱-激光诱导荧光检测法和胶束电动色谱—激光诱导荧光检测法测定麻黄碱和伪麻黄碱的灵敏分析新方法,与以前的报道相比,灵敏度和分析时间均有很大改善;(2)使用荧光素钠作为背景荧光试剂,建立了同时分析测定六种黄酮类化合物(秦皮甲素、秦皮乙素、异秦皮定、染料木素、柚皮苷和槐角苷)的毛细管区带电泳—间接激光诱导荧光检测新方法,扩大了激光诱导荧光检测的应用范围,对难衍生化合物的分离分析提供了一种新思路和新途径;(3)以荧光素钠作为背景荧光试剂,建立了一种用于同时测定食品提取DNA中的腺嘌呤和鸟嘌呤含量的胶束电动色谱—间接激光诱导荧光检测新方法;(4)用动态和静态激光散射法研究了模拟生理条件下人血清白蛋白与氨比西林钠盐相互作用所形成的复合物,为药物分子与蛋白质的相互作用、药代动力学等的研究提供了一种新思路。

The research showed that:(1) Dendroctonus micans and Ips nitidus responded to pheromone of low concentration,which demonstrated that the olfactory response threshold of these two species to pheromone was very low,and the response value increased with the concentration.

研究结果表明:(1)云杉大小蠹与光臀八齿小蠹均能对其较低浓度的虫体信息素成分产生嗅觉反应,说明其对虫体信息素的感受阈值较低;且随着虫体信息素浓度的增大,反应值增加。

Arabidopsis response regulators,ARR4 and ARR5, were induced by the increased cytokinin contents at different time after seed germination. ARR4 responded to cytokinins at early time of seed germination, especially on the 6 d when seedlings were around true leaf initiation, while cytokinins induced ARR5 activation after 6 d of seed cultivation in light conditions, an obvious increase was on the 20 d when seedlings were around inflorescent shoot initiation.

拟南芥植物细胞分裂素反应调节基因ARR4和ARR5在植物发育的不同时期应答植物体内增加的植物细胞分裂素,ARR4的应答反应比ARR5早,种子萌发后的第6天幼苗真叶形成初期,ARR4基因被明显诱导;而ARR5的应答反应在幼苗真叶形成后的几个时间段均能检测到,并且在种子萌发后的第20天,花枝形成开始时特别明显。

In order to utilize lignin effectively, base on the situation in China, the study was carried on systematically, centering around the topic of two step sulfomethylation of the soda lignin of wheat straw (the first step is methylolation, the second is sulfonation) and its application. The main purpose is to develop a heterogeneous catalytic system which not only catalyzes but also homogenizes the lignin molecule in the reaction.

为真正高效利用碱木素,木论文根据我国实情,紧紧围绕着麦草碱木素两步磺甲基化(第一步为羟甲基化,第二步为磺化)及其应用这一主题,以开发出在反应过程中既可催化反应又能使木素分子均一化的多相催化体系为主要目标,系统地展开了研究。

The results suggested that chitinhad a good solubility in the new solvent when its at -30℃and below, but the solubilityof chitin no longer increasesd notable as the temperature reduced; The joined of urea, incertain degree, strengthened the solvency of alkali solvent to chitin. When theconcentration of sodium hydroxide is 8%~12%, Chitin had a good solubility, and theapparent viscosity of chitin solution could up to 4000 mpa·s~5000mpa·s at roomtemperature; In addition,the solubility of chitin in new solvent was high when therefrigerated time was three days and above, but the refrigerated time could not too long,otherwise, the deacetylize degree of chitin got more bigger. The properties of chitin solution were tested by revolving viscosimeter, FT-IR,X-RD and so on.

结果表明,在-30℃及以下甲壳素能很好的溶解于新溶剂中,但甲壳素的溶解度不再随温度的下降而有所增大,而是基本保持不变;尿素的加入,在一定程度上强化了强碱溶剂对甲壳素的溶解,当新溶剂中NaOH浓度为8%~12%时,甲壳素在试验温度下可以获得较好的溶解度,所得溶液在室温下的表观黏度达4000 mpa·s~5000mp·s;冷冻时间为3 d及以上时,有利于甲壳素的溶解,超过3 d,甲壳素的溶解度变化不大,另外,冷冻条件下,甲壳素在强碱溶剂中仍会发生脱乙酰化反应,冷冻时间不宜太长。

The monoclonal antibody was produced by the method of inoculating BALB/c mice intraperitoneally with the hybridoma cells, and purified with protein A-Sepharose 4B affinity chromatography.3 Establishing of ELISA protocol to detect hBLySTwo kind of different ELISA protocols were tried to study the experiment condition of detecting hBLyS level. Streptavidin was used to indirect coating in protocal 1, but biotin-avidin system was used to enlarge the final reaction signal in protocal 2. The optimal reaction condition was chosen by the experiments. The sensitivity of protocal 1 was poor, but the linear relation of protocal 2 standard curve was excellent when the concentration of hBLyS was between 3.2~400 ng/mL. So a protocal was established which sensitivity can reach to nanogram.

建立检测hBLyS蛋白含量的ELISA方法选用2种ELISA方案对hBLyS蛋白含量的测定方法进行研究,方案一用链霉亲和素做间接包被,方案二用生物素-亲和素系统做终反应放大;优化选择2种检测方法的反应条件;方法一的敏感度较低:方法二在hBLyS蛋白浓度为3.2~400 ng/mL范围内,标准曲线的线性关系良好;从而建立了一种可检测hBLyS蛋白浓度为ng级水平的ELISA方法。

A flow-injection chemiluminescence method for the determination of melatonin based on the CL reaction of melatonin with hydrogen peroxide and sodium hypochlorite in a basic alkaline solution was developed. The possible CL mechanism has been discussed, and a proposal for the reaction pathway was given that singlet oxygen was clarified to be produced in this reaction system and was responsible for the CL emission.

研究了褪黑素在碱性介质中与过氧化氢和次氯酸钠反应产生化学发光的行为;初步探讨了其化学发光反应的机理;提出了可能的化学发光反应历程;建立起流动注射化学发光测定褪黑素的新方法。

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