应用高效液相色谱和电喷雾质谱联用技术分析鉴定车前草中的苯乙醇苷化合物

本文采用高效液相色谱与电喷雾质谱联用技术在线分析鉴定了车前草提取物中的三种苯乙醇苷化合物。实验采用反相C18色谱柱,0.2%的醋酸水溶液和乙腈梯度洗脱,车前草中的苯乙醇苷化合物得到很好的分离。在电喷雾质谱负离子条件下,获得了三种苯乙醇苷化合物的分子离子峰,分子量信息,进一步通过质谱的源内CID技术得到相应化合物的结构信息。通过得到的这些信息与文献中的已知化合物或标准品对照从而推断出化合物的结构。     

1,3-二羟基呫吨酮类化合物的简洁合成及清除亚硝酸根作用研究

以间苯三酚为起始原料,在伊顿试剂的催化作用下,与不同取代水杨酸反应合成1,3-二羟基呫吨酮类化合物3a~3l 12个,收率63%~87%,并探讨了反应机理及结构-反应活性关系.利用紫外分光光度法测定了所合成化合物对亚硝酸盐的清除作用,结果表明,在37℃、pH 3及反应时间为30 min条件下,1,3-呫吨酮类化合物对亚硝酸根均有较好的清除作用,其中化合物3f和3b的清除作用最强,清除率达34%.同时对1,3-二羟基呫吨酮类化合物清除亚硝酸盐的作用机制及构效关系进行了探讨.     

化合物结构特征与其基因表达信息的互补性研究

化合物分子指纹在化合物相似性比较、生物芯片技术在分子标记识别中都有着重要的应用, 因而受到广泛的重视. 但是由于这两个研究对象依传统的观点, 分属于化学信息学和生物信息学两个不同的研究领域, 因此一直未能在同一研究对象中同时得到应用. 近年来, 小分子刺激的生物芯片数据的大量出现, 使得联合化合物的结构特征及其基因表达谱信息共同的用于药物筛选成为可能. 为此, 根据本质和外延互补的哲学思想, 提出了综合运用这两种数据来共同描述化合物的新方法. 通过(1)只利用化合物分子指纹, (2)只利用化合物基因表达谱信息和(3)前面两种方法互补等三种方法在化合物相似性比较的研究中, 发现本文提出的互补方法比前两种方法的查询结果更准确: (1)使结构和功能两方面均相似的化合物之间的相似性更高, (2)并且能有效使那些仅在某一方面表现非常特殊的化合物能够暴露出来, 而得到有效地排除. 本研究给化学信息者和生物信息者重新审视以往的数据, 联合致力于药物的筛选提供了线索. 化合物分子指纹(本质)和基因表达谱(外延)的互补原理则为药物的筛选提供更有效的依据, 并最终加快药物的研发进程.     

甾族化合物差向异构体的~(13)C光谱分析

七十年代对於甾族化合物的CNMR谱研究主要采用质子噪音去偶、偏共振去偶、相关化合物比较,辅以同位素标记、镧系化学位移试剂和弛豫时间等技术。质子噪音去偶~(13)C谱具有谱线简单和灵敏度高等特点,但失去了偶合信息。偏共振去偶谱保留了偶合信息,得到的J~r值虽较真正的~1J_(CH)值要小,一般说来能较有效地区分碳原子类型,但对甾族化合物因偶合的多重谱线彼此重叠,降低了用偏共振谱指配的有效性。目前,对於复杂化合物的~(13)C谱     

朝鲜淫羊藿中黄酮类化合物的高效液相色谱与电喷雾质谱联用研究

利用高效液相色谱与电喷雾质谱联用技术研究了朝鲜淫羊藿中的黄酮类化合物。实验采用反相C18色谱柱，二元线性梯度洗脱，分离并检测了朝鲜淫羊藿中的6种黄酮类化合物；通过与电喷雾质谱联用获得了这几种化合物的分子量信息，利用质谱的源内碰撞诱导解离技术对这几种化合物进行了结构鉴定。     

基于药效团模型设计合成新型ALS抑制剂

以ALS抑制剂药效团模型为基础建立了提问结构,将药效团模型中的生物结构信息输入到多种小分子三维结构数据库(NCI-3D和ACD-3D数据库)中,分别搜寻出100多个符合特征结构信息的全新结构候选化合物.以这些命中结构的分子特征信息为基础设计合成了一系列新型的ALS抑制剂,初步生物活性测试结果表明,预期有生物活性的化合物显示出一定的ALS酶抑制剂活性.     

氚核磁共振波谱在氚标记甾族化合物制备中的应用

本文介绍了十一种氚化甾族化合物的氚核磁共振谱。我们依照英国放化中心和英国萨里大学报道数据,(甾体骨架上的CH及CH_2各位置的谱线归属,应用了定位标记化合物作为对照)归属了其氚在化合物中标记的位置,根据其积分曲线定出了各位氚的相对百分含量。同时图谱中又提供了立体构型的信息,为氚化甾族化合物制备过程中,催化剂的选择,实验条件的控制及反应机理等研究提供了理论依据。     

N,N′-双-(2-羟基苯亚甲基)-烷基(芳基)甲二胺类化合物质谱研究

本文对双Schiff碱类化合物的质谱进行了研究,由于其结构的特殊性,质谱的裂解过程中出现一些特殊的碎片离子,它包括羟基氢的迁移、双键的转换以及分子结构重排等,为研究这类化合物的结构和性质提供了重要的信息。     

塑料制品中高关注物质测定方法的研究进展

综述了塑料制品中高关注物质测定方法的研究进展。介绍了邻苯二甲酸酯、有机锡、阻燃剂和全氟化合物等4类高关注物质的化合物信息,总结了气相色谱法、液相色谱法及质谱法测定塑料制品中上述高关注物质,并展望了高关注物质测定方法的发展趋势(引用文献40篇)。     

七叶一枝花中薯蓣皂苷的分离及结构鉴定研究

本文利用高效液相色谱-串联质谱联用方法研究了七叶一枝花中的薯蓣皂苷。实验采用高效液相色谱分离了七叶一枝花中的3种薯蓣皂苷;通过与电喷雾质谱联用获得了这几种化合物的分子量信息;再用MS/MS获得了这几种化合物进一步的结构信息。采用此方法可快速分析鉴定从七叶一枝花中分离得到的薯蓣皂苷。     

Insect pheromones and their analogs

A four-stage asymmetric synthesis of (+)-disparlure [(7R,8S)-(+)-cis-methyl-7,8-epoxyoctadecane (V)] has been effected from 8-methylnon-2Z-en-l-ol (I), obtained by the carboalumination of acetylene with tris(5-methylhexyl)aluminum using the Sharpless reaction. The asymmetric epoxidation of (I), (Ar, mol. sieve A, (+)-DET, (iOPr)₄Ti, t-BuOOH, ?15°C, 20 h; H₂O, 1 h, NaOH, ?7°C, 30 min) gave 8-methyl-2S,3R-epoxynonan-l-ol (II), which was oxidized (kieselguhr-CrO₃-Py, 0°C, 2 h; 25°C, 2 h) to 8-methyl-2S,3R-epoxynonan-l-al (III). The coupling of (III) with n-C₈H₁₇CH=PPh₃ (?78°C, 1 h; 25°C, 15 h) gave 2-methyl-7R,8S-epoxyoctadec-9Z-ene (IV), the hydrogenation (H₂/5% Pd-C, 25°C, 5 days) of which led to (V) in admixture with an isomerization product. Compound (V) was isolated by HPLC. Substance, yield, [α] _D ²⁵ : (II), 73, ?2.75°; (III), 80, [80.8°; (IV), 50, +37.25°; (V), 50, +0.8°. The IR and PMR spectra of (II–IV), the¹³C NMR spectra of (II) and (III), and the mass spectrum of (IV) are given.     

Insect pheromones and their analogues

A stereospecific synthesis has been achieved of tetradec-11E-enal and of tetradec-11E-en-l-ol and its acetate — components of the pheromones of many species of insects of the order Lepidoptera — from the readily available undecenoic acid, using the Knoevenagel reaction and catalytic hydroalumination.Institute of Chemistry, Bashkir Scientific Center, Urals Branch, Russian Academy of Sciences, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 272–276, March–April, 1992.     

Insect pheromones and their analogs

Two methods of synthesizing -geranyl propionate — a component of the sex pheromone of San Jose scale — have been developed: the hydride reduction of the corresponding 6-chloro derivative and the electrochemical reduction of the 6-dimethylsulfonium derivative.For the preceding communication, see [1].Institute of Chemistry, Bashkir Scientific Center, Urals Division, Academy of Sciences of the USSR, Ufa. N. D. Zelinskii Institute of Organic Chemistry, Academy of Sciences of the USSR, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 419–421, May–June, 1989.     

Insect pheromones and their analogs

A highly selective synthesis of 2-methyl-cis-7, 8-epoxyoctadecane — the racemic analog of the sex pheromone of the gypsy moth Porthetria dispar L. — (Z)-disparlure — has been developed that is based on the functionally differentiated partial ozonization of cycloocta-IZ.5Z-diene.Institute of Petroleum and Catalysis, Academy of Sciences of the Republic of Bashkortostan, 450075, Ufa, Prospekt Oktyabrya, 141. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 901–904, November-December, 1995. Original article submitted February 21, 1995.     

Insect pheromones and their analogs

(Z)-hexadec-11-enal and (Z)-hexadec-11-1-yl acetate — components of the sex pheromone of insects of the generaHeliothis andManestra, respectively — have been synthesized by the condensation of undec-10-enal with hex-1-yne, deoxygenation of the heptadec-1-en-12-yn-11-ol formed via the corresponding tosylate to heptadec-1-en-12-yne, and the selective oxonolysis of the latter.Institute of Chemistry, Bashkir Branch, Academy of Sciences of the USSR, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 440–444, May–June, 1987.     

Insect pheromones and their analogs

A four-stage asymmetric synthesis of (+)-disparlure [(7R,8S)-(+)-cis-methyl-7,8-epoxyoctadecane (V)] has been effected from 8-methylnon-2Z-en-l-ol (I), obtained by the carboalumination of acetylene with tris(5-methylhexyl)aluminum using the Sharpless reaction. The asymmetric epoxidation of (I), (Ar, mol. sieve A, (+)-DET, (iOPr)₄Ti, t-BuOOH, –15°C, 20 h; H₂O, 1 h, NaOH, –7°C, 30 min) gave 8-methyl-2S,3R-epoxynonan-l-ol (II), which was oxidized (kieselguhr-CrO₃-Py, 0°C, 2 h; 25°C, 2 h) to 8-methyl-2S,3R-epoxynonan-l-al (III). The coupling of (III) with n-C₈H₁₇CH=PPh₃ (–78°C, 1 h; 25°C, 15 h) gave 2-methyl-7R,8S-epoxyoctadec-9Z-ene (IV), the hydrogenation (H₂/5% Pd-C, 25°C, 5 days) of which led to (V) in admixture with an isomerization product. Compound (V) was isolated by HPLC. Substance, yield, [] _D ²⁵ : (II), 73, –2.75°; (III), 80, [80.8°; (IV), 50, +37.25°; (V), 50, +0.8°. The IR and PMR spectra of (II–IV), the¹³C NMR spectra of (II) and (III), and the mass spectrum of (IV) are given.Institute of Chemistry, Bashkir Scientific Center, Urals Branch, Academy of Sciences of the USSR, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 715–718, September–October, 1989.     

Insect pheromones and their analogues

The synthesis has been effected of octa-2E,6E-diene-1,8-diol diisovalerate — the sex pheromone of the Crimean click beetleAgriotes tauricus — by the carboxymethylenation of the readily available 6-methylhept-5-en-2-one, the allyl oxidation of a terminal methyl group, reduction of the ester fraction, and interaction of the diol so obtained with isovaleryl chloride. The required pheromone can also be obtained from available cyclic oligomers of isoprene.     

Insect pheromones and their analogues

Pheromone components of insects of the generaHeliothis andMamestra have been synthesized with the use of functionally differentiated ozonolysis of cyclododecene.Institute of Chemistry, Bashkir Scientific Center, Urals Branch, Academy of Sciences of the USSR, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 132–135, January–February, 1991.     

Insect pheromones and their analogues

A scheme has been developed for the synthesis of (R)-(–)-10-methyltridecan-2-one, the sex pheromone of the southern corn rootworm (Diabrotica undecimpunctata) using as the chiral synthon (R)-(+)-methylheptenal obtained by the hydroperoxide oxidation of the readily available (S)-(+)-dihydromyrcene.Institute of Chemistry, Bashkir Scientific Center, Urals Branch, Russian Academy of Sciences, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 125–129, January–February, 1992.