青蒿素及其衍生物的抗寄生虫活性研究进展

青蒿素是一种从菊科蒿属植物黄花蒿(Artemisia annua L.)中分离出来的倍半萜类天然产物,具有广泛的生物活性,如抗肿瘤、抗炎、抗菌、抗恶性疟原虫等.青蒿素也是重要的抗疟先导化合物,目前临床上使用的青蒿素类抗疟药物有双氢青蒿素、蒿甲醚、青蒿琥酯.近年来的研究发现,青蒿素及其衍生物对弓形虫、血吸虫、犬新孢子虫、...     

青蒿素及其衍生物对菜青虫的生物活性

以二氢青蒿素为原料合成了10种双二氧青蒿素醚和5种单二氢青蒿素醚,用常规的非选择性叶碟法测定了质量浓度为1.0 g/L的合成化合物、青蒿素和二氢青蒿素对菜青虫的生物活性.结果表明:双醚对菜青虫的拒食活性最为显著,处理后24、48 h的拒食率分别为85.4%～96.9%和90.9%～98.6%,单醚分别为45.5%～60.6%和50.9%～68.2%,二氢青蒿素为36.6%和42.4%,青蒿素为40.1%和47.0%;双醚同样具有较高的杀虫活性,其处理后96 h的校正死亡率为72.7%～95.5%,单醚为45.4%～54.6%,二氢青蒿素为49.9%,青蒿素的杀虫活性不显著.结合活性数据,初步讨论了青蒿素衍生物的构效关系.     

周期密度泛函理论研究1,3-二醚类内给电子体在β-MgCl_2(110)面吸附过程

本文利用基于周期性密度泛函理论的的量子力学从头计算方法对1,3-二醚类内给电子体在β-MgCl_2(110)面上的吸附作用进行了研究。通过模拟计算其吸附能,键长和键角,发现1,3-二醚在β-MgCl_2(110)面上吸附有三种稳定状态,分别是:螯合配位,双层双点配位和错位双层双点配位三种构象,其中螯合配位构象为最稳定构象,我们研究发现螯合构象中1,3-二醚分子平面与β-MgCl_2(110)面Cl-Mg-Cl较长对角线平行时,具有最稳定构象,本文研究结果将对探索Ziegler-Natta催化剂的微观结构具有指导意义。     

(S)-(-)-4-[反式-4’-(反式-4”-丙基环己基)-环己基]-1-(1-甲基庚氧基)-2,6-二氟苯的合成

报道了手性添加剂(S)-(-)-4-[反式-4’-(反式-4"-丙基环己基)-环己基]-1-(1-甲基庚氧基)-2,6-二氟苯的合成方法,通过格氏偶联、硫酸氢钾催化脱水、催化氢化、顺反异构化、超低温反应、双氧水氧化、M itsunobu成醚反应共7步反应合成了目标产物,总收率21%。经IR、MS、1H NMR鉴定,结构正确,并测定了其扭曲力。     

3,6-二氯水杨酸合成工艺条件的探讨

以2,5-二氯苯酚为原料,经与碱试剂反应脱水成盐,Kolbe-Schmitt羧基化,酸化,合成高效除草剂麦草畏的关键中间产物3,6-二氯水杨酸。探索了工业化生产的较佳的工艺条件。     

蒿甲醚的合成工艺改进

本研究以青蒿素为原料,采用一锅法合成β-蒿甲醚。简化了操作,避免了中间体的后处理过程,改进后的工艺反应周期短、成本低,同时避免使用腐蚀性的强酸,β-异构体总收率达85%,产物结构经IR和1H NMR确认。适合工业化生产。     

10-(异丙基-2-醇)-9,10-二氢-9-氧杂-10-膦杂菲-10-氧化物的合成

以9,10-二氢-9-氧杂-10-膦杂菲-10-氧化物(DOPO)和丙酮为原料,合成10-(异丙基-2-醇)-9,10-二氢-9-氧杂-10-膦杂菲-10-氧化物。考察了原料摩尔比、反应温度和反应时间对产物收率的影响。结果表明,较优工艺条件为:n(丙酮)∶n(DOPO)=12∶1,反应温度为50℃,反应时间为30 min时,DOPO的转化率为99%,目标产物收率为90%。     

SRNA-4非晶态合金催化双环戊二烯液相加氢反应研究

采用SRNA-4非晶态合金催化剂对双环戊二烯(DCPD)进行了加氢反应考察,研究了搅拌速度、温度、压力和催化剂浓度各条件对双环戊二烯加氢反应的影响.结果表明DCPD加氢反应为连串反应,中间产物主要为9,10-二氢双环戊二烯(9,10-DHDCPD)和少量1,2-二氢双环戊二烯(1,2-DHDCPD);DCPD易于加氢生成中间产物9,10-DHDCPD,其继续加氢为四氢双环戊二烯(endo-THDCPD)需要较为剧烈的条件.DCPD加氢过程选用两段法,第一段为温度110℃,第二段为130℃,压力均为1.5MPa,催化剂浓度1.18%.非晶态合金(催化剂)对DCPD的加氢反应活性明显高于Raney Ni,可进行1、2位加氢反应生成1,2-DHDCPD,并且催化剂用量少,反应温度和反应压力低,反应时间短,生成副产物少.     

超声强化溴化1-乙基-3-甲基咪唑从黄花蒿中提取青蒿素

利用超声强化[emim]Br(溴化1-乙基-3-甲基咪唑)-水体系从黄花蒿粉末中提取青蒿素. 正交实验和单因素实验结果表明,影响黄花蒿中青蒿素提取因素的显著性次序为液固比>提取时间>提取温度>超声波功率>占空比. 综合考虑单因素实验结果及成本,得出优化工艺条件为黄花蒿原料粒度0.38 mm,液固比50 mL/g,提取时间30 min,提取温度20℃,超声波功率600 W,占空比1.6 s/0.4 s. 在上述条件下青蒿素提取量为4.37 mg/g,提取率为97%.     

10-（异丙基．2-醇）-9，10-二氢-9-氧杂-10-膦杂菲-10-氧化物的合成

以9,10-二氢-9．氧杂-10-膦杂菲-10-氧化物（DOPO）和丙酮为原料,合成10-（异丙基-2-醇）-9,10-二氢．9-氧杂．10．膦杂菲．10-氧化物。考察了原料摩尔比、反应温度和反应时间对产物收率的影响。结果表明,较优工艺条件为：n（丙酮）：n（DOPO）=12：1,反应温度为50℃,反应时间为30min时,DOPO的转化率为99％,目标产物收率为90％。     

Ring position in cyclopropene fatty acids and stearic acid desaturation in hen liver

Four cyclopropene fatty acids, having the double bond of the cyclopropene ring at the 8,9, 9,10, 10,11 and 11,12 positions, respectively, were tested as inhibitors of stearic acid desaturation by the desaturase enzyme system of hen liver. The first three were powerful inhibitors, but the last was not. The cyclopropene acids with the 9,10 and 10,11 double bonds were equally strong inhibitors, while the acid with the 8,9 double bond was less effective. To account for the specificity of those cyclopropene fatty acids in which the C9 or C10 carbon atom is included in the cyclopropene ring, it is suggested that the conformation and structure of the CoA derivatives of these acids is such that they can irreversibly occupy the site on the enzyme responsible for 9,10-desaturation.     

The synthesis,two-photon absorption and blue upconversion fluorescence of novel,nitrogen-containing heterocyclic chromophores

Novel, nitrogen-containing heterocyclic chromophores based on either 1,2,4-triazine or an imidazole core were synthesized using a three-component, one-pot reaction under microwave irradiation. Structures were verified by ¹H NMR, IR, MS and elemental analyses while crystal structure was determined using X-ray diffraction. The two-photon absorption and two-photon upconverted blue fluorescent emission characteristics were investigated experimentally; preliminary structure–photophysical property relationships were established. Chromophores that contained the imidazole moiety displayed more potent two-photon absorption than compounds based upon 1,2,4-triazine and also exhibited a strong two-photon upconverted blue fluorescent emission peak at around 443–476 nm. Significant enhancement of the two-photon absorption cross-section was achieved by fusing a benzoxazole moiety onto the phenanthro[9,10-d]imidazole ring.     

反式-9,10-二氢-9,10-二对甲苯基-9,10-菲二醇包结性能的研究

合成了主体分子反式-9,10-二氢-9,10-二对甲苯基-9,10-菲二醇(1),它可以和苯、喹啉形成晶体包结物,通过m.p.、IR、粉末XRD对它们进行了表征,通过^1HNMR积分计算包结物主客体物质的量比分别为：n1：n苯=3：2;n1：n喹啉=1：1。     

Chlorinated alcohols: III. 9,10-Dichlorostearylamine

9,10-Dichlorostearylamine was prepared by the hydrogenation of 9,10-dichlorostearonitrile, catalyzed by Rh/C, and by the chlorination of oleylamine hydrochloride. The dichloro amine was surprisingly heat-stable and could be purified by molecular distillation at 170 C (0.1 mm). Also described are the preparations of 9,10-dichlorostearoyl chloride, 9,10-dichlorostearamide and 9,10-dichlorostearonitrile. The chlorination of oleonitrile is not a simple reaction and the 9,10-dichlorostearonitrile was best prepared by dehydration of the amide.     

The Relation between Packing Effects and Solid State Fluorescence of Dyes

The solid state fluorescence of diketopyrrolopyrrole dyes and perylene-3,4:9,10- tetracarboxylic bisimides with alkyl substituents are investigated and compared with noncovalent interactions. The latter are estimated by crystal structure analysis, heats and entropies of fusion and solubilities in organic solvents. Applications of the dyes are discussed.     

Incorporation of oxygen-18 into the oxirane ring ofcis-9,10-epoxyoctadecanoic acid

The synthesis ofcis-9,10-epoxyoctadecanoic acid by tissue slices of wheat plants infected withPuccinia graminis tritici (Wheat stem rust) has been investigated further. Synthetic methylcis-9,10-epoxyoctadecanoate and the same ester isolated from incubation in an atmosphere containing¹⁸O₂, or a medium containing H₂ ¹⁸O, were analyzed by mass spectrometry. These analyses revealed that molecular oxygen was incorporated into the oxirane ring ofcis-9,10-epoxyoctadecanoic acid. Presented in part at the AOCS Meeting, Minneapolis, October 1969.     

Reaction of lithium naphthalene with carboxylic acids containing the dichlorocyclopropane ring system

Carboxylic acids containing the dichlorocyclopropane ring system react with lithium naphthalene to give dechlorinated products. For example, from the reaction of 9,10-dichloromethylene octadecanoic acid and lithium naphthalene, a mixture of 9,10-nonadecadienoic acid as a main product and unidentified minor products were obtained.     

有效的[4+1]/[3+2+1]双环化反应构建茚并氧杂蒽杂环骨架及其晶体结构

茚并氧杂蒽类化合物C24H28O5是由邻苯二甲醛和5,5-二甲基-1,3-环己二酮在醋酸溶剂中,于室温下搅拌一步法反应制得,通过单晶X-射线衍射法测定其结构。该晶体属单斜晶系,空间群P2(1),晶胞参数a=1.006 92(11)nm,b=1.021 73(12)nm,c=2.430 6(2)nm,V=2.500 6(5)nm~3,Z=4,晶胞密度Dc=1.247 mg/m~3,吸收系数μ=0.087 mm~(-1),单胞中电子的数目F(000)=1 008,分子量Mr=469.56(单晶中包含一分子溶剂DMF)。晶体结构经全矩阵最小二乘法对各原子参数进行修正,最终得到的偏离因子为R=0.061 9,ωR=0.090 4。在晶体结构中新形成的茚环呈现信封式构象,同时形成的吡喃环显示为扭船式构象。     

Synthesis and Antialgal Activity of Dihydrophenanthrenes and Phenanthrenes II: Mimics of Naturally Occurring Compounds in Juncus effusus

9,10-Dihydrophenanthrenes and phenanthrenes, mimics of natural compounds with strong antialgal activity, have been synthesized through cross-coupling by zerovalent Ni of 1-(2-iodo-5-methoxy)-phenylethanol or 2-iodo-5-methoxyacetophenone with iodoxylenes. The synthetic compounds had a hydroxyl or a methoxyl group at C-2 and two methyls in the C ring. Assays on the green alga Selenastrum capricornutum showed that all the compounds, except 2-methoxy-5,7-dimethylphenanthrene, caused strong inhibition of algal growth at 10^–4 M. 2-Hydroxy-7,8-dimethyl-9,10-dihydrophenanthrene and 2-methoxy-5,6-dimethylphenanthrene fully inhibited growth at 10^–5 M.     

Effect of triglycerides containing 9,10-dihydroxystearic acid on polymorphism of sal (Shorea robusta) fat

The effect of the triglycerides containing 9,10-dihydroxystearic acid (DHS-TG) on the phase transition of polymorphic forms of normal triglycerides (TG) of sal fat was investigated by differential scanning calorimetry (DSC) under different cooling and heating modes. Four levels of DHS-TG, 2, 5, 8 and 10%, were used. DHS-TG accelerated the phase transition of lower melting crystal forms I → II → III of TG obtained under rapid (20°C/min) or slow (2°C/min) rates of cooling. They delayed the phase transition of crystal form III to IV of TG at 0°C. Also, DHS-TG reduced the heat of fusion (ΔH) of the stable form (V) of TG obtained after tempering at 0°C and at 26°C.