甲基化作用

We prepared the pyrethric acid II through four reactions: esterification, oxidation, decomposition, diesterification. And the original synthesis route of the pyrethric acidII was improved: the yield of oxidation of allyl rise through increasing the activity of Selenium dioxide; in the document, tert-butyl-trans -2, 2-dimethy1-3-(2"-methoxycarbony1-1"-propenyl)cyclopropanecarboxy late was synthesized from tert-butyl-trans-2,2-dimethyl-3-(2 -formyl-r -propenyl) cyclopropanecarboxylate with two steps, with low yield.

我们经过酯化，氧化，成双酯，热分解四步反应，成功地得到了第二菊酸，并改进了原第二菊酸的合成路线：通过改变二氧化硒的活性提高了烯丙甲基的氧化产率；将原路线中醛氧化成羧酸、羧酸酯化的两步反应改为醛和甲醇、二氧化锰等作用一步直接酯化的方法，减少了反应步骤，提高了总收率。

To produce the scientific evidence for developing and manufacturing new antitumor drugs.Methods: 1 The inhibitory effect on cell growth of Hela was measured by MTT assay in treated or untreated groups (3.125, 6.25, 12.5, 25, 50μg/ml TAM and control) for three different treatment times (24h, 48h and 72h).2 Apoptosis and cell cycle were measured by FCM in four experimental groups (0, 4, 16, 40μg/ml TAM) for 48h.3 Adopting Wright and Giemse's staining to observe the morphology of Hela cells which treated with 40μg/ml TAM.4 Using invasion experiment to detect the Hela cells'invasive abilities which treated with 40μg/ml TAM.5 The protein expressional levels of P-ERK, ERK, C-myc and Cyclin D1 in Hela cells untreated or treated with 4, 16, 40μg/ml TAM for 24h were measured by Western blot.6 Expression of anti-apoptotic gene bcl-2, apoptotic gene bax and MMP-9 in Hela cells of four experimental groups (0, 4, 16, 40μg/ml TAM for 24h), were observed by revers transcription PCR.7 The protein expression of P-ERK, ERK, Bcl-2 and Bax in Hela cells treated with 40μg/ml TAM for 24h observed by laser scanning microscopes.

1采用四甲基偶氮唑蓝法检测不同浓度北豆根总碱(3.125、6.25、12.5、25、50μg/ml)处理不同时间(24、48和72小时)对Hela细胞增殖反应的抑制作用。2采用流式细胞技术(flow cytometry，FCM)检测不同浓度北豆根总碱(0、4、16、40μg/ml)作用48小时，对Hela细胞凋亡及周期变化的影响。3瑞氏-姬姆萨染色后显微镜观察北豆根总碱(0、40μg/ml)作用24小时后Hela细胞形态学变化。4采用Transwell小室法检测北豆根总碱(0、40μg/ml)作用24小时后对Hela细胞侵袭性的影响。5采用免疫印迹方法检测不同浓度北豆根总碱(0、4、16、40μg/ml)作用24小时后，Hela细胞中磷酸化ERK、ERK、C-myc、CyclinD1的表达变化。6采用逆转录-聚合酶链反应(revers transcription PCR，RT-PCR)半定量检测北豆根总碱(0、4、16、40μg/ml)作用24小时，Hela细胞抗凋亡基因bcl-2、促凋亡基因bax、基质金属蛋白酶-9(MMP-9)的表达变化。7应用激光共聚焦显微镜(laser scanning microscope，LSM)观察北豆根总碱(0、40μg/ml)作用24小时后，Hela细胞内P-ERK、ERK、Bcl-2、Bax蛋白的表达变化。

RESULT: 1.Ouabain act on lens sodium-pump,under the LM,lens anterior capsular membrane discontinuous,epithelium cells clustered,occluding zonule seperated,lens fiber layers fractured.Under the EM,cells totally hollowed,mitochondria swelling,myelin figure appeared.RT-PCR examine the expression condition of αsubunit of sodium pump on mRNA level,α1、α2 and α3-isoform are all decreased.2.Digoxin act on lens sodium-pump,under the LM,lens cell oedema,linkage distructed,extensive exfoliation.Under the EM,plasma appeared little half-transparant hollow region,mitochondria swelling and ridge disappeared. RT-PCR examine,α1、α2 and α3-isoform are all decreased.3.Amphotericin B act on lens sodium-pump,under the LM,lens epithelium cells linked tightly,arranged in-line,lens fiber layers arranged tightly and regularily.Under the EM,abbundant cellular organes,exuberant cells function indicated. RT-PCR examine the expression condition of αsubunit of sodium pump on mRNA level,α1 and α3-isoform are increased significantly,demonstrated isoform-specific action.4D-thyroxine act on lens sodium-pump,under the LM,lens plasmalemma integrated,cells arranged tightly and regularily.Under the EM,nucleus fission appeared,desmosome half-desmosome and tensile microfilaments linked the cells. RT-PCR examine,α2 and α3-isoform are increased, also demonstrated isoform-specific action.5.Vitamin E act on lens sodium-pump,under the LM,lens anterior capsular membrane continuous and smooth,epithelium cells tightly linked,lens fiber layers appearede hollow region occasionally.Under the EM,lateral membrane high density belt appeared,abundant nucleolus. RT-PCR examine,onlyα1-isoform are increased, demonstrated significantly isoform-specific action.6.DMSO act on lens sodium-pump,under the LM,lens anterior capsular membrane slightly thicker,cells linkage partly distructed.Under the EM,plasmalemma denaturation,mitochondria swelling.RT-PCR examine,α1、α2 and α3-isoform are all altered slightly and haven't significant meanning.

结果：1、哇巴因作用于晶状体钠泵后，光镜下晶状体前囊膜断裂、上皮细胞聚积、闭合连接分离、纤维板层裂隙，电镜下全层细胞空泡化、线粒体肿胀出现髓样结构，RT-PCR法检测晶状体钠泵α亚单位α1、α2及α3三种重整异构体在mRNA水平的表达均减弱。2、地高辛作用于晶状体钠泵后，光镜下晶状体细胞水肿、细胞连接破坏、广泛剥离，电镜下胞质见少许半透明空化区、线粒体肿胀嵴消失，RT-PCR法检测晶状体钠泵α亚单位α1、α2及α3三种重整异构体在mRNA水平的表达均减弱。3、两性霉素B作用于晶状体钠泵后，光镜下晶状体上皮细胞紧密连接、线状排列、纤维板层紧密规整，电镜下细胞器丰富、细胞功能旺盛，RT-PCR法检测α1及α3表达显著增强、具有一定的重整异构作用特异性。4、D甲状腺素作用于晶状体钠泵后，光镜下晶状体质膜完整、细胞排列紧密规整，电镜下胞核见分裂像、细胞间有桥粒、半桥粒及张力微丝，RT-PCR法检测α2及α3表达均增强、亦有一定的重整异构作用特异性。5、维生素E作用于晶状体钠泵后，光镜下晶状体前囊膜连续光滑、上皮细胞紧密连接、纤维板层偶见空化，电镜下囊侧膜内有高电子密度带、细胞核仁丰富，RT-PCR法检测仅有α1的表达显著增强、具有极强的重整异构作用特异性。6、二甲基亚砜作用于晶状体钠泵后，光镜下晶状体前囊膜轻度增厚、细胞连接部分破坏，电镜下质膜变性、线粒体肿胀，RT-PCR法检测晶状体钠泵α亚单位α1、α2及α3三种重整异构体在mRNA水平的表达无显著改变。

This dissertation is mainly focused on the reactivity of methylenecyclopropanes and comprises six parts. 1 The reactions of methylenecyclopropanes with phenylsulfenyl chloride, phenylselenyl chloride and diphenyl diselenide; 2 The coupling reactions of the ring-opening products derivated from methylenecyclopropanes; 3 The palladium-catalyzed ring-enlargement of mono-aryl group substituted methylenecyclopropanes to cyclobutenes. 4 The gold-catalyzed domino ring-opening and ring-closing hydroamination of methylenecyclopropanes with sulfonamides; 5 The Lewis acid-catalyzed reactions of mono-aryl group substituted methylenecyclopropanes with diethyl ketomalonate in the presence of water; 6 The iodobenzene diacetate mediated novel 1,3-dipolar cycloaddition of methylenecyclopropanes, vinylidenecyclopropanes, and methylenecyclobutane with phthalhydrazine.

本论文主要研究了亚甲基环丙烷类化合物的一些化学反应性能，共由以下六部分组成：1、亚甲基环丙烷类化合物与苯硫氯、苯硒氯及二苯基二硒的反应；2、亚甲基环丙烷类化合物开环产物的偶联反应；3、单芳基取代的亚甲基环丙烷类化合物在钯催化剂作用下的扩环反应；4、金化合物催化磺酰胺对亚甲基环丙烷类化合物的串联开环关环氨氢化反应；5、路易斯酸催化亚甲基环丙烷类化合物与丙酮二羧酸二乙酯在有水存在下的反应；6、醋酸碘苯促进的亚甲基环丙烷类化合物、亚乙烯基环丙烷类化合物及亚甲基环丁烷类化合物与邻苯二甲酰肼的新型1，3-偶极环加成反应。

Dihydrojasmone was synthesized from2-hexyl-5-methyl-1,2-oxaborolane,prepared frommethyl vinyl ketone and hexene,via the homologationwith 〓 followed by PCC oxidation and intra-molecular condensation.In stead of the oxidation ofthe C-B bond of 1,2-oxaborolane,fluoride inducedhalogenation of 2-alkoxy-1,2-oxaborolane was found togive 3-halopropanol.

硼氢化甲基乙烯基酮和已烯得到的2-已基-5-甲基-1，2-氧硼杂环戊烷与〓反应，再经PCC氧化，分子内缩合得到二氢茉莉酮。1，2-氧硼杂环戊烷的C-B键除氧化断裂之外，也能够在〓或KF作用下卤化断裂成碳卤键。

The stable or unstable state of the montmorillonite-water dispersion is mainly effected by the properties of montmorillonite, water, and stabilizers as well as their interactions, while the type, the structure, the properties and the concentration of the stabilizer play dominate roles. Based on the molecular designing clues, this research selected three sulfonated copolymers as the stabilizers, i.e. the sodium 2-acrylamido-2-methyl-1propane sulfonate /acrylamide /disodium itaconate terpolymer, the AMPS/AM/N-vinyl pyrrolidone terpolymer and the sodium styrenesulfonate /IA copolymer. The preparation and characterization of the sulfonated copolymers were discussed, the high-temperature stability of the montmorillonitewater dispersion was characterized with the rheology, the filtration, the particle size distribution, the electrostatic properties, and the adorption of the sulfonated copolymers onto montmorillonite particles. At the same time, a systematic mechanism of the hightemperature stabilization of the dispersion was presented.

本文构筑了分子设计的思路，选取AMPS(2-丙烯酰胺基-2-甲基丙磺酸钠)/AM/IA三元共聚物、AMPS/AM/NVP三元共聚物和SSA/IA二元共聚物等三种磺化共聚物作为蒙脱土-水分散体系的高温稳定剂，进行了磺化共聚物稳定剂的制备与表征；从流变学、滤失性能、粒度分布、电性质以及磺化共聚物在蒙脱土上的吸附作用等方面，对蒙脱土-水分散体系的高温稳定性进行了研究，考察了蒙脱土-水分散体系的高温稳定性能，同时提出了高温稳定机理。

In solid phase process, the polyiodides, which include triiodide, pentaiodide, heptaiodide, nonaiodide and undecaiodide tetra-n-butyl ammonium iodide, tetrabutyl ammonium bromide and tetramethyl ammonium iodide poly-compounds, were synthesized by the low-heat solid phase reaction between iodine and tetra-n-butyl ammonium iodide, tetrabutyl ammonium bromide or tetramethyl ammonium iodide; In complexation process, solution polyiodides were synthesized by complexing action of different agents; In resinifying process, triiodide, pentaiodide, heptaiodide resinic polyiodides were synthesized by ion-exchange when the strong basicity styrene anion exchange resin, potassium iodide and iodine were used as raw materials.

固相法是用正四丁基碘化铵、四丁基溴化铵或四甲基碘化铵分别与碘作用，通过低热固相反应，合成出碘三、碘五、碘七、碘九和碘十一形式的正四丁基碘化铵、四丁基溴化铵或四甲基碘化铵的系列高聚碘化合物；在络合法合成溶液高聚碘的实验中，选用几种络合剂通过络合作用首次合成了溶液高聚碘；树脂法合成高聚碘的实验是采用强碱性苯乙烯系阴离子交换树脂、碘化钾和碘为原料，通过离子交换，合成了碘三、碘五和碘七形式的树脂高聚碘。

The famciclovir was synthesized from purine by a series of steps by Acylation, Decarboxylation, Reduction ,and so on; Derivatives of these intermediates is described from the 6-chloro- 9H- purin-2-amine as raw materials in different conditions when the iodine and bromide were synthesized with the addition of two intermediate 6-bromo-9H-purin-2-amine and 6-iodo-9H-purin-2-amine; There is elaborated from the main part of a acetophenone, urineaminohydrochloride, phenylhydrazine, ethyl acetoacetate as raw material through a series of reactions to synthetic 3-phenyl-4-formylphenyl pyrazole and 5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-aldehyde two pyrazole aldehyde, and then with 2-amino-6-chlorine-9-(2-methicillin-oxo-co-methyl-4-yl) purine reaction of the two new pyrazole purine Schiff bases.

本论文主是采用以鸟嘌呤为原料，经过一系列的酰基化，脱羧，还原等反应作用下最终得到了产物2-氨基-9-(4-乙酰氧基-3-乙酰氧基甲基丁基)嘌呤；其中的中间体衍生物主要是阐述从以2-氨基-6-氯鸟嘌呤为原料通过在不同的条件下进行溴代与碘代分别合成了另外两种中间体2-氨基-6-溴鸟嘌呤及2-氨基-6-碘鸟嘌呤；还有一部分主要是阐述从以苯乙酮，盐酸氨基脲，苯肼，乙酰乙酸乙酯为原料通过一系列的反应先合成3-苯基-4-醛基吡唑及5-氯-3-甲基-1-苯基-1H-吡唑-4-甲醛这两个吡唑醛，然后再与2-氨基-6-氯-9-(2-甲氧羰基丁酸甲酯-4-基)嘌呤反应得到了两个新型的吡唑嘌呤席夫碱

Two series of polyurethane acrylate grafted acrylic resins (Acr-g-TPU-PETA and Acr-gPPU-PETA) self-emulsifying systems are obtained by grafting -NCO group modified polyurethane acrylates with acrylic copolymer prepared from n-butyl acrylate, styrene,βhydroxyethyl methacrylate and acrylic acid The self-emulsifying systems showed Newtonian fluidity with viscosity closed to that of water, the solid contents were around 30% The T〓 of 15～4℃ for dried film before photocuring favored film formation at room temperature DSC and DMA results showed that PU-PETA is compatible with acrylic resin in the grafted resin The TG and dTG curves for Acr-g-PU-PETA samples were substantially different from the corresponding blends, and the brodened dTG peaks for photocured grafted resin suggest that there might be multiple interactions among chain segments The photocued film of the grafted resins self-emulsifying system exhibited good overall properties with polyurethane acrylate grafts ranging from 30% to 50%, and Acr-g-TPU-PETA series showed better properties than Acr-gPPU-PETA series The adhesion of the photocured film was 1～2 grade, impact strength was 50kg-cm and flexibility was 1mm The Shore hardness and the adhesion of the film decreased markedly if PETA was replaced by HEMA as photoactive group due to the lower C=C double bond content in the grafted resin The polyhydroxy amine-linked thioxanthones photoinitiators can be evenly dispersed in self-emulsifying system without color spot appearing in the dried film The films photocured with IV〓～IV〓 generally exhibited higher Shore hardness, gloss and solventresistance than that cured with Irgacure 2959 and did not induce the rusting of the iron substrate Pigmenting with titanium oxide had no effect on the photocuring The polyhydroxy amine-linked thioxanthone IV〓 and IV〓 can be new candidates for the formulation of titanium oxide pigmented photocurable water-borne coatings for their pale-yellow appearance and slight interference with the color of the coatings WB 4759 with high water-solubility coalesced and separated from the dried resin film, and even induced the rusting of iron substrate.

以丙烯酸丁酯，甲基丙烯酸-β-羟乙酯，丙烯酸及苯乙烯合成厂丙烯酸共聚树脂，并与含-NCO端基的聚氨酯丙烯酸酯接枝反应，经水性化后，得到两个系列（Acr-g-TPU-PETA和Acr-g-PPU-PETA）各5个不同配比的丙烯酸树脂接枝聚氨酯丙烯酸酯自乳化体系，粘度与水相近，为牛顿流体，固含量30％左右。光固化前干燥涂膜的玻璃化转变温度在-15℃～4℃之间，有利于室温下成膜。DSC及DMA谱表明两种树脂基本相容。Acr-g-PU-PETA的热失重行为明显不同于共混材料，接枝样dTG峰明显宽化，表明接枝样中链段之间的相互作刚有多重性，丙烯酸树脂与聚氨酯之间有一定的相容性。接枝树脂自乳化体系光固化涂层的综合性能以聚氨酯丙烯酸酯成分为50％～30％者相对较好，且以Acr-g-TPU-PETA系列更理想。光固化膜的附着力为1～2级，冲击强度为50kg·cm，柔软性多为1mm。以HEMA代替PETA作为接枝树脂的活性基团，碳—碳双键密度太低，光固化膜交联点太少，硬度和附着力均较差。多羟基胺连硫杂蒽酮光引发剂能均匀分散于树脂自乳化体系和接枝树脂干膜中，不出现色斑，光固化膜肖氏硬度一般高于以Irgacure 2959为光引发剂的光固化膜，光泽度及耐丁酮溶剂性能均有所提高，不会诱导铁基生锈，钛白着色对光固化结果几乎没有影响。本论文所合成的多羟基胺连硫杂蒽酮光引发剂IV〓与IV〓为浅黄色，对光固化涂层的颜色干扰较小，为配制钛白着色光固化水性涂料提供了新的光引发剂。水溶性太强的WB 4759在干膜中易聚结析出，且对所附着的铁基有诱导锈蚀作用。

The algicidal performances of monomer dimethyldiallylammonium chloride and a commercial algicide dodecyldimethylbenzylammonium chloride（ 1227 ） were contrasted with that of PDM.

对两种营养化的模拟水体，通过灭藻实验，研究了聚二甲基二烯丙基氯化铵系列样品的静态灭藻性能，考察了加药量、作用时间、特征黏度等因素对灭藻性能的影响规律，并与聚合物单体二甲基二烯丙基氯化铵及市售灭藻剂十二烷基二甲基苄基氯化铵（1227）的灭藻性能进行了对比。

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。