近无毛灰岩香茶菜的研究

从云南省会泽县产近无毛灰岩香茶莱〔Rabdosia calcicola (Hand. -Mazz.) Hara var. subculva (Hand. -Mazz.) C. Y. Wu et H. W. Li〕叶中分得两个二萜化合物,一个为新化合物,命名为灰岩香茶菜甲素(calcieolin A),另一个为已知化合物维西香茶菜甲素(weisiensin A),经各项光谱数据和化学反应确定,灰岩香茶菜甲素为3β-羟基-1α,6α,7β,11β-四乙酰氧基-对映-贝壳杉-16-烯-15-酮(1);维西香茶菜甲素结构应为3β,6α-二羟基-1α,7β,11β-三乙酰氧基-对映—贝壳杉-16-烯-15酮(2)。     

细叶香茶菜中两个新的对映-贝壳杉烷二萜化合物

从云南中甸产细叶香茶菜(Isodon tenuifolia (W. W. Smith) Kudo)的地上部分分离得到6个化合物, 它们的结构通过波谱方法得到鉴定。其中化合物1和2为新的对映-贝壳杉烷二萜化合物, 即细叶香茶菜甲素(3β,6α,15β-trihydroxy-1α,7β-diacetoxy-11β,16β-epoxy-ent-kaurane) (1) 和细叶香茶菜乙素(1α,6α,11β-trihydroxy-3β,7β-diacetoxy-ent-kaur-16-en-15-one) (2)。     

细叶香茶菜中两个新的对映—贝壳杉烷二萜化合物

从云南中甸产细叶香茶菜 (Isodontenuifolia (W .W .Smith)Kudo)的地上部分分离得到 6个化合物 ,它们的结构通过波谱方法得到鉴定。其中化合物 1和 2为新的对映_贝壳杉烷二萜化合物 ,即细叶香茶菜甲素 (3β ,6α ,15 β_trihydroxy_1α ,7β_diacetoxy_11β ,16 β_epoxy_ent_kaurane) (1)和细叶香茶菜乙素 (1α,6α ,11β_trihydroxy_3β,7β_diacetoxy_ent_kaur_16_en_15_one) (2 )。     

叶穗香茶菜的二萜成分

从云南省中甸县产叶穗香茶菜[Rabdosia phyllostachys(Diels)Hara]叶中分得1个新二萜化合物,命名为叶穗香茶菜乙素(phyllostachysin B),经各项波谱数据确定,叶穗香茶菜乙素为6β,11β,14β—三羟基-15α-乙酰氧基-对映-贝壳杉-16-烯-20 醛-7-酮。另一个为已知化合物叶穗香茶菜甲素(phyllostachysin A)。     

细锥香茶菜二萜的研究

从四川省峨眉山产细锥香茶菜[Rabdosia coetsa(Buch-Ham,ex,D.Don)Hara]乙醚抽提物中分得了一个新二萜化合物,命名为细锥香茶菜丁素(rabdocoetsin D),其结构经各项波谱数据和化学证据确定为1α,7β-二羟基-11β-乙酰氧基-对映-7β,20-环氧-贝壳杉-16-烯-15-酮(1)。另外还分离到3个已知二萜,细锥香茶菜乙素(rabdocoetsin B)、细锥香茶菜丙素(rabdocoetsin C)、瘿花香茶菜甲素(rosthorin A)。     

丽江产紫萼香茶中一新二萜甙

从丽江紫萼香茶菜（Ｉsodon forestii(Diels)Kudo)中分离得到７个化合物,经波谱方法鉴定了它们的结构,其中化合物１为新的萜甙,命名为Ａbieforrestin,已知化合物分别为：腺花素（Adenanthin),显脉香茶菜素（Nervosanin),乌苏酸（Ursolic acid),2α－羟基鸟苏酸（2－Hydroxy-ursolic acid),β－谷甾醇（β－Sitoserol)及胡萝卜甙（Daucosterol).     

蓝萼香茶菜化学成分的研究

从长白山产蓝萼香茶菜[Ralxlosia Japonica(Burm.f.)Hara var.glaucocalyx(Maxim.)Hara]地上全草中分得13个化合物,根据理化常数和波谱学数据分别鉴定为：木栓酮(1)、β-谷淄醇(2)、乙酰熊果酸(3)、齐墩果酸(4)、熊果酸(5)、蓝萼香茶菜素A(6)、2α-羟基熊果酸(7)、2α,3α-二羟基熊果酸(8)、ent-7β,14α,15三羟基-16-贝壳杉烯-3-酮(9)、山香三萜二烯酸(10)、槲皮素(11)、β-谷甾醇3-O-β-D-吡喃葡萄糖苷(12)和果糖(13)。化合物8为第一次从该植物中分得,化合物10为第一次从该属植物中分得。     

腺花香茶菜地下根茎化学成分研究

采用硅胶、RP-18等柱色谱,从腺花香茶菜地下根茎70%丙酮提取物的乙酸乙酯部位分离得到16个化合物,通过理化性质和波谱数据分别鉴定为维西香茶菜甲素(1)、2α-羟基齐墩果酸(2)、2α,23-二羟基齐墩果酸(3)、2β,3β-二-O-异丙叉基-齐墩果-12-烯-28-酸(4)、乙酰熊果酸(5)、1-棕榈酸单甘油酯(6)、1-油酸单甘油酯(7)、1-亚油酸单甘油酯(8)、1,2-亚油酸甘油二酯(9)、α-亚麻酸甲酯(10)、棕榈酸(11)、硬脂酸(12)、油酸(13)、7α-羟基豆甾醇(14)、7β-羟基谷甾醇(15)、β-谷甾醇(16)。化合物4、6～10和13～15为首次从该属植物中分离得到,化合物2、3、5、11和12为首次从该植物中分离得到。     

兰萼丙素的结构

从北京地区产兰萼香茶菜[Rabdosia japonica (Burm. f.)Hara var.glaucocalyx(Maxim.)Hara]叶中分得三个对映-贝壳杉烯二萜化合物,其中二个为已知物兰萼甲素(2)和乙素(3),另一个为新化合物,命名为兰萼丙素,经光谱和化学方法证明,其结构为对映-7β,14α,15α-三羟基-16-贝壳杉烯-3-酮(1)。     

胶粘香茶菜素的化学结构

从胶粘香茶菜叶的乙醚提取物中分得两个二萜化合物‘经各项光谱数据和化学反应确定,其中一个为四环二萜化合物,对映-贝壳杉烷-16β,17-二醇(ent-kauran-16β,17-diol)(1);另一个为三环二萜对映-异海松烷型(ent-isopimarane type)新化合物,命名为胶粘香茶菜素(glutinosin)(2)。对映-异海松烷型二萜化合物的分离和鉴定,对于从化学上阐明香茶菜属植物中大量存在的对映-贝壳杉烯型四环二萜化合物的生源关系有一定的学术意义。     

Synthesis and nuclear magnetic resonance study of 3-dehydroecdysteroids

Several 3-dehydro- (or 3-oxo-) ecdysteroids have been prepared by enzymatic and/or chemical means. Methods for their purification using various high-performance liquid chromatography systems are described. Proton and carbon nuclear magnetic resonance analyses show that 3-dehydroecdysteroids when dissolved in water or methanol (but not in chloroform) present a temperature-dependent equilibrium between two forms. The possible structure of these two forms is discussed.     

Systematic crosstalk in plasmalogen and diacyl lipid biosynthesis for their differential yet concerted molecular functions in the cell

Plasmalogen is a major phospholipid of mammalian cell membranes. Recently it is becoming evident that the sn-1 vinyl-ether linkage in plasmalogen, contrasting to the ester linkage in the counterpart diacyl glycerophospholipid, yields differential molecular characteristics for these lipids especially related to hydrocarbon-chain order, so as to concertedly regulate biological membrane processes. A role played by NMR in gaining information in this respect, ranging from molecular to tissue levels, draws particular attention. We note here that a broad range of enzymes in de novo synthesis pathway of plasmalogen commonly constitute that of diacyl glycerophospholipid. This fact forms the basis for systematic crosstalk that not only controls a quantitative balance between these lipids, but also senses a defect causing loss of lipid in either pathway for compensation by increase of the counterpart lipid. However, this inherent counterbalancing mechanism paradoxically amplifies imbalance in differential effects of these lipids in a diseased state on membrane processes. While sharing of enzymes has been recognized, it is now possible to overview the crosstalk with growing information for specific enzymes involved. The overview provides a fundamental clue to consider cell and tissue type-dependent schemes in regulating membrane processes by plasmalogen and diacyl glycerophospholipid in health and disease.     

黄牛木属植物的化学成分与生物活性研究进展

本文综述了从1963年以来黄牛木属植物的化学成分和生物活性研究,概括了该属植物中部分口山酮和蒽醌化合物的NMR数据。     

珙桐叶中喹啉类生物碱甙--pumiloside结构鉴定

首次从珙桐叶甲醇提取物的水溶性部分得到一配糖体化合物一喹啉类生物碱甙（pumiloside）,它是抗肿瘤物质喜树碱的生物合成前体。本文对其结构进行鉴定。     

Determining the optimal size of small molecule mixtures for high throughput NMR screening

High-throughput screening (HTS) using NMR spectroscopy has become a common component of the drug discovery effort and is widely used throughout the pharmaceutical industry. NMR provides additional information about the nature of small molecule-protein interactions compared to traditional HTS methods. In order to achieve comparable efficiency, small molecules are often screened as mixtures in NMR-based assays. Nevertheless, an analysis of the efficiency of mixtures and a corresponding determination of the optimum mixture size (OMS) that minimizes the amount of material and instrumentation time required for an NMR screen has been lacking. A model for calculating OMS based on the application of the hypergeometric distribution function to determine the probability of a hit for various mixture sizes and hit rates is presented. An alternative method for the deconvolution of large screening mixtures is also discussed. These methods have been applied in a high-throughput NMR screening assay using a small, directed library.     

Improved frequency resolution in multidimensional constant-time experiments by multidimensional Bayesian analysis

Summary The resolution of spectral frequencies in NMR data obtained from discrete Fourier transformation (DFT) along D constant-time dimensions can be improved significantly through extrapolation of the D-dimensional free induction decay (FID) by multidimensional Bayesian analysis. Starting from Bayesian probability theory for parameter estimation and model detection of one-dimensional time-domain data [Bretthorst, (1990) J. Magn. Reson., 88, 533–551; 552–570; 571–595], a theory for the D-dimensional case has been developed and implemented in an algorithm called BAMBAM (BAyesian Model Building Algorithm in Multidimensions). BAMBAM finds the most probable sinusoidal model to account for the systematic portion of any D-dimensional stationary FID. According to the parameters estimated by the algorithm, the FID is extrapolated in D dimensions prior to apodization and Fourier transformation. Multidimensional Bayesian analysis allows for the detection of signals not resolved by the DFT alone or even by sequential one-dimensional extrapolation from mirror-image linear prediction prior to the DFT. The procedure has been tested with a theoretical two-dimensional dataset and with four-dimensional HN(CO)CAHA (Kay et al. (1992) J. Magn. Reson., 98, 443–450) data from a small protein (8 kDa) where BAMBAM was applied to the ¹³C and H constant-time dimensions.To whom correspondence should be addressed.     

Computer-assisted assignment of multidimensional NMR spectra of proteins: Application to 3D NOESY-HMQC and TOCSY-HMQC spectra

Summary An algorithm based on the technique of combinatorial minimization is used for the semi-automated assignment of multidimensional heteronuclear spectra. The program (ALFA) produces the best assignment compatible with the available input data. Even partially misleading or missing data do not seriously corrupt the final assignment. Ambiguous sequences of the possible assignment and all alternatives are indicated. The program can also use additional non-spectroscopic data to assist in the assignment procedure. For example, information from the X-ray structure of the protein and/or information about the secondary structure can be used. The assignment procedure was tested on spectra of mucous trypsin inhibitor, a protein of 107 residues.