广西地不容生物碱的研究

本文就防己科植物的一个新种广西地不容(Stephania kwangsiensis H.S.Lo,Sp.NOV.)的块根中的生物碱进行了分离和研究,除了分离得已知的生物碱l-四氢巴马亭,l-卡巴任碱、d-异紫堇定、l-罗默碱和去氢罗默碱外,尚分离得一种属于去氢阿朴啡(dehydroaporphine)类的新生物碱,即1,2-次甲二氧基-8-甲氧基去氢阿朴啡(1,2-methylenedioxy-8-methoxydehydro-aporphine),命名为去氢千金藤碱(dehydrostephanine)。     

蛇足石杉中一个新的Phlegmariurine型生物碱

目的研究石杉科植物蛇足石杉Huperzia serrata (Thunb.) Trev.的生物碱成分。方法应用各种色谱技术进行分离纯化，经衍生物制备和光谱数据分析鉴定其结构。结果从蛇足石杉中分离得到1个新生物碱。结论该化合物为一新的phlegmariurine型生物碱，命名为8β-羟基马尾杉碱乙（8β-hydroxy phlegmariurine B）。     

花椒根的生物碱研究

自芸番科(Rutaceae)花椒属植物花椒(zanthoxylum bungeanum Maxim)根中分得六种生物碱。其中主要生物碱Zanthobungeanine为新的吡喃-2-喹诺酮型生物碱,经光谱分析推定其结构为(Ⅲ)。五种已知生物碱为11-甲氧基白屈菜红碱(11-methoxychelerythrine)(Ⅰ),去甲基白屈莱红碱(des-N-methylchelerythrine)(Ⅱ),arnottianamide(Ⅶ),茵芋碱(skimmianine)(Ⅵ)和L-N-acetylanonanine(Ⅳ)。后者在本属植物中尚属首次发现。此外,还分离鉴定了β-谷甾醇(Ⅴ)。Zanthobungeanine具广谱抗真菌作用,但活性不强。     

四川轮环藤根中两种新双苄基异喹啉生物碱的分离鉴定

从中国特有植物四川轮环藤(Cyclea sutchuenensis Gagnep.)根中除分得已知的轮环藤碱(Ⅰ)和异粒枝碱(Ⅱ)外,还分离得到两种新双苄基异喹啉生物碱,分别命名为异轮环藤碱(Ⅲ)和四川轮环藤辛碱(Ⅳ)。经物理常数和波谱数据分析鉴定,证明Ⅲ为轮环藤碱的差向异构体,Ⅳ系一种新型的8-12′,12-7′首尾双氧桥双苄基异喹啉生物碱。     

猪毛菜中一新生物碱

研究猪毛菜中的生物碱。采用各种色谱技术进行分离，通过理化性质及波谱分析进行结构鉴定。从猪毛菜地上部分的95%乙醇提取物中分离得到4个酰胺类生物碱，其化学结构分别确定为N-反式阿魏酰基-3-甲基多巴胺(1)、3-［4-(β-D-吡喃葡糖氧基)-3-甲氧基苯基］-N-［2-(4-羟基-3-甲氧基苯基)乙基］-2-丙胺(2)，猪毛菜碱A(3)，猪毛菜碱B(4)。化合物4为一新化合物，命名为猪毛菜碱B，化合物2为首次从该属植物中分离得到。     

东阳元胡块茎中的生物碱的化学研究

从浙江省东阳元胡(Corydalis turtschaninovii Bess.f.yanhusuo Y.H.Chou et C.C.Hsü)的块茎中分离了15个生物碱。通过理化常数测定,光谱分析及衍生物制备等方法鉴定了结构,其中9个生物碱文献已报道。(+)-紫堇碱(Ⅰ),(±)-四氢巴马亭(Ⅱ),(—)-四氢黄连碱(Ⅲ),(—)-四氢非洲防己胺(Ⅳ),(+)-紫堇球碱(Ⅴ),去氢紫茧碱(Ⅵ),(+)-海罂粟碱(Ⅶ)普鲁托品(Ⅷ),α-别隐品碱(Ⅸ),5个为首次从该植物中得到的已知化合物(—)-四氢小檗碱(Ⅹ)巴马亭(Ⅺ),非洲防己胺(Ⅻ),(+)-N-甲基樟苍碱(ⅩⅢ)去氢海罂粟碱(ⅩⅣ),1个为新生物碱,暂命名为元胡宁(XV yuanhunine).     

农吉利抗癌有效成分的分离及其衍生物的合成

从民间治疗皮肤癌的一种野百合属植物农吉利(Crotalaria sessilufkira L.)中分离出两个生物碱(Ⅰ,Ⅱ)。结构测定表明碱Ⅰ为一野百合碱(monocrotaline);碱Ⅱ为下向千里光次碱(Retronecine)和阔叶千里光次酸(platynecic acid)组成的一个新的双稠吡咯啶生物碱。碱Ⅰ对小鼠肉瘤180,白血病615,瓦克癌256均有抑制作用。为了降低其对肝脏的毒性,合成了碱Ⅰ的八个衍生物(1～8),其中1,7,8对瓦克癌256有抑制作用,但都因毒性较大而未推荐临床试用。     

广西九里香化学成分研究

目的　对广西九里香(Murraya kwangsiensis)的化学成分进行研究。方法　利用硅胶柱色谱和薄层色谱方法对广西九里香的95%乙醇提取物进行分离;采用UV,IR,MS,¹HNMR和¹³CNMR等技术对所得化合物进行结构研究。结果　分离鉴定了7个化合物,其中5个为咔巴唑生物碱:murrayafoline-A,murrayanine,koenine,isomahanine和广西九里香碱(kwangsine),两个非生物碱化合物：棕榈酸和β-谷甾醇。结论　广西九里香碱(kwangsine)为新化合物,其他化合物均为首次从该植物中分离得到。     

狭叶山胡椒根中的生物碱成分

目的研究狭叶山胡椒根中的生物碱成分。方法采用硅胶、MCI-DHP-20P反相填料柱色谱进行分离，通过MS，¹H NMR，¹³C NMR，HMQC，HMBC等波谱方法进行结构鉴定，同时采用半合成方法确证结构。结果共分离得到7个生物碱类化合物，分别为樟苍碱(I)、N-甲基樟苍碱(II)、波尔定(III)、异波尔定(IV)、降波尔定(V)、magnocurarine (VI)、N-乙氧甲酰基樟苍碱(VII)，通过合成方法验证了N-乙氧甲酰基樟苍碱的化学结构。结论所有化合物皆首次从该植物中分得，其中N-乙氧甲酰基樟苍碱为首次从自然界分离得到。     

露蕊乌头的二萜生物碱

从露蕊乌头(Aconitum gymnandrum Maxim)中分离到11个二萜生物碱,利用光谱方法确定结构,证明其中一个为新生物碱,命名为露乌定,其余10个分别鉴定为14-乙酰基-8-O-甲基-塔拉胺(tal-atisamine,Ⅱ)、acoforine(Ⅲ)、非洲防己碱(columbidine,Ⅳ)、乌头碱(aconitine,Ⅴ)、ranaeonitine(Ⅵ)、塔拉定(talatizidine,Ⅶ)、异塔拉定(isotalatizidine.Ⅷ)、露乌碱(gymanaconitine,Ⅸ)、塔拉胺(talatisamine,Ⅹ)和阿替辛盐酸盐(atisine.HCl)。其中碱Ⅱ为首次在自然界中发现,碱Ⅲ～Ⅶ为首次从该植物中分离得到。     

Investigation of the diterpene alkaloids of Aconitum species native to the Carpathian Basin

Aconitum species accumulate highly toxic diterpene alkaloids, which have attracted considerable interest because of their complex structure, interesting chemistry and noteworthy physiological effects. The authors carried out phytochemical analysis of two Aconitum species native to the Carpathian Basin, aiming the isolation of diterpene alkaloids. The multistep chromatographic purification of the extracts of A. vulparia whole plant and A. toxicum root resulted in the isolation of 16 alkaloids. Structure elucidation by means of spectroscopic investigations revealed the presence of 3 (acovulparine, vulparine, acotoxinine) new and 13 already known compounds (anthranoyllycoctonine, delectinine, delcosine, finetiadine, lycoctonine, N-methyl-N-deethyllycocotine, septentriodine, aconitine, aconosine, dolaconine, neoline, songorine, songo-ramine). Alkaloids isolated from A. vulparia are C19 diterpene alkaloids possessing aconitane skeleton, whilst from A. toxicum two C20 diterpene alkaloids with napelline and five diterpene alkaloids with aconitane skeleton were identified. The pharmacological testing of the majority of the isolated compounds has not been reported in the literature yet. Since some of the diterpene alkaloids are structurally very similar to compounds which were active in different in vitro or in vivo experiments, the pharmacological testing of the alkaloids reported in this article seems to be reasonable. The investigation of the compounds may help to reveal structure-activity relationships as well.     

全反式维甲酸-正丁酸（丙戊酸）前体药物的设计、合成及抗肿瘤活性研究

目的合成全反式维甲酸（ATRA）的前体药物，增强ATRA对急性早幼粒白血病（APL）细胞的分化诱导作用。方法以乙二醇、对苯二酚、乙醇胺及乙二胺等为连接物，通过酯键和酰胺键将分化诱导剂ATRA与组蛋白去乙酰酶（mAC）抑制剂正丁酸、丙戊酸连接起来，形成前体药物。结果合成了13个ATRA与正丁酸或丙戊酸相连接的前体药物，化合物的结构经^1H-NMR、MS和IR确证。结论考察部分化合物对急性早幼粒细胞白血病细胞株NB4的生长抑制作用和对急性早幼粒白血病（APL）细胞分化诱导作用，初步的药理实验结果表明，ATRA与丙戊酸通过酰胺键连接时，对NB4细胞分化诱导能力显著增加。     

Mechanism of action of retinyl compounds on wound healing IV: effect of desmethylretinoic acid and its vinylogs on granuloma formation.

The effect of side-chain length of desmethylretinoic acid on granuloma formation induced by implantation of cotton pellets was studied. As in the homologous series of retinoic acid studies, compounds with side chains shorter than retinoic acid were not active while compounds with side chains as long or longer than retinoic acid were active. The compound with a chain two carbons longer than retinoic acid was the most active. The hydroxyproline and hexosamine contents of the granuloma were analyzed. The mechanisms of action of these active compounds on wound healing are discussed.     

Comparative analysis of phenolic acids in mistletoe plants from various hosts

Phenolic acids present in mistletoe plants collected from various hosts were analysed with the use of HPLC. The following numbers of compounds were found in the mistletoe plant material gathered from respective hosts: Sorbus aucuparia- 12 compounds; Acer plantanoides--14 compounds: Malus domestica, Pyrus communis and Populus nigra--13 compounds each; Quercus robur--15 compounds. Altogether 21 phenolic acids were chromatographically identified in the tested material. The compounds were either free or combined as esters or glycosides. Comparative chromatography revealed qualitative differences in the investigated compounds between the various plant materials. For example o-coumaric acid was only found in mistletoe hosted by Quercus robur. Digallic acid was only found in the plant material hosted by Acer plantanoides. Qualitative and quantitative composition of mistletoes hosted by Malus domestica and Pyrus communis showed considerable similarities as far as phenolic acids were concerned. Moreover. vanillic acid. absent in all other batches of plant material, seemed to be characteristic of the above mistletoes. Quantitative HPLC analysis demonstrated a considerable content of salicylic acid (39.55 mg%) in mistletoe hosted by Sorbus aucuparia. Apart from the above material, this compound was only present in small quantities in plants hosted by Populus nigra (15.63 mg%) and Quercus robur (2.63 mg%).     

Extraction and cleanup methods for analysis of phenolic and neutral organohalogens in plasma

A method for the analysis of potential endocrine-disrupting compounds, such as phenolic halogenated compounds (e.g., chlorinated and brominated phenols) and hydroxylated PCBs, in blood plasma is presented. Neutral halogenated compounds, specifically brominated diphenyl ethers and PCBs, are also included in the evaluation. An efficient denaturation and extraction step is described, and three methods for lipid removal are evaluated. The latter includes a nondestructive method based on high-resolution gel permeation chromatography (HR-GPC), a newly developed silica gel/sulfuric acid column, and lipid removal by sulfuric acid treatment. Recoveries, based on gas chromatography with an electron capture detector (GC-ECD), were between 70 and 90% for most of the studied compounds. The recoveries of phenolic compounds were generally slightly lower than those of the neutral compounds. The sulfuric acid treatment and silica gel/sulfuric acid column gave the highest yields for acid stable compounds, although a few target compounds were lost during that treatment and all compounds were recovered with the HR-GPC method.     

Synthesis and reactions of some new substituted pyridine and pyrimidine derivatives as analgesic, anticonvulsant and antiparkinsonian agents

A series of substituted pyridine and pyrimidine derivatives were synthesized as analgesic, anti convulsant, and antiparkinsonian agents by using compounds 1, 2, and 9 as starting materials. Pyr idino-imide derivative 3 was prepared by condensation of 1 with tetrachlorophthalic anhydride and compounds 4 and 5 were also obtained by reaction of compound 1 with 1,2,4,5-benzene-tetra carboxylic dianhydride and 1,4,5,8-naphthalenetetracarboxylic dianhydride, respectively. Similarly, compound 2 was reacted with previous anhydrides to afford the corresponding imide 6 and bis-imide derivatives 7 and 8, respectively. Bis-arylmethylene derivatives 9 were treated with hydrogen peroxide to afford the corresponding bis-oxiranocycloalkanone derivatives 10, which condensed with thiourea to give the corresponding thioxopyrimidine derivatives 11. Treatment of compound 11 with chloroacetic acid in the presence of anhydrous sodium acetate afforded the corresponding thiazolopyrim idine derivative 12 which condensed with aromatic aldehydes in acetic acid/acetic anhydride to give arylmethylene derivative 13. Also, compounds 13 could be prepared by reaction of compounds 11 with chloroacetic acid, aromatic aldehydes, and sodium acetate in a mixture of acetic acid and acetic anhydride. The pharmacological screening showed that many of these obtained compounds have good analgesic, anticonvulsant, and antiparkinsonian activities comparable to Valdecoxib, Carbamazepine, and Benzatropine as reference drugs.     

Synthesis and properties of chiral N,N-maleoyl derivatives and Diels-Alder reactions with cyclopentadiene

Maleyl amino acid derivatives were prepared from maleic anhydride and cyclized by reaction with ZnCl2 and hexamethyldisilazane yielding maleoyl derivatives. These derivatives were used as dienophiles in cycloadditions with cyclopentadiene. The isolated norbornene derivatives resulted from an endo addition, and might be interpreted as analogues of thalidomide. For comparing the properties of compounds prepared by this route, some reference compounds were synthesized from endo-bicyclo[2.2.1]hept-2-ene-5,6-dicarboxylic anhydride and amino acid derivatives. All compounds were characterized by spectroscopic methods, their stereochemistry is discussed, and results were compared with results from calculations.     

beta-lactam derivatives as enzyme inhibitors: carboxy peptidyl derivatives of (S)-4-oxoazetidine-2-carboxylate as peptidomimetics.

4-Oxoazetidine-2-carboxylic acid, protected at the nitrogen by silyl groups, was coupled with amino acid and oligopeptide esters. Desilylation and deprotection of the amino acid residues yielded the free beta-lactam peptides. Structure and properties were elucidated by spectroscopic methods and discussed. Some selected compounds were tested as fibrinogen inhibitors and for thrombocyte aggregation. None of the compounds showed any activity up to a concentration of 10(-5) Mol/l. Some other compounds exhibited a weak inhibitory activity against elastase (PPE).     

Phenolic components and antioxidant activity of Fernblock, an aqueous extract of the aerial parts of the fern Polypodium leucotomos

Fernblock, an aqueous extract of the aerial parts of the fern Polypodium leucotomos, used as raw material for topical and oral photoprotective formulations, was fractioned by HPLC and the main components with antioxidant capability were identified by means of UV spectra, electrochemical detection, and MSn. Phenolic compounds were identified as 3,4-dihydroxybenzoic acid, 4-hydroxybenzoic acid, vanillic acid, caffeic acid, 4-hydroxycinnamic acid, 4-hydroxycinnamoyl-quinic acid, ferulic acid, and five chlorogenic acid isomers. Total ferric antioxidant capacity (FRAP) of HPLC eluted fractions was measured. The results suggest that the herein identified compounds support, at least partially, the antioxidant and radical scavenging capacities of Fernblock.     

胡蔓藤中非生物碱类成分的分离与鉴定(Ⅲ)

目的研究胡蔓藤(Gelsemium elegans Benth.)中的化学成分。方法采用硅胶柱色谱和ODS柱色谱进行分离,Sephadex LH-20及制备液相进行纯化,根据理化性质和光谱分析进行结构鉴定。结果分离鉴定了8个化合物,分别为(+)-8-hydroxypinoresinol(1)、cleomiscosin C(2)、cleomiscosinA(3)、3,4-二羟基苯甲醛(3,4-dihydroxyphenyl aldehyde,4)、咖啡酸(caffeic acid,5)、1-O-咖啡酰基奎宁酸(1-O-caffeoylquinic acid,6)、4-O-咖啡酰基奎宁酸(4-O-caffeoylquinic acid,7)、1-O-咖啡酰基奎宁酸甲酯(1-O-caffeoylquinic acid methyl ester,8)。结论化合物1-8为首次从该属植物中分离得到。