藏红花花瓣和雄蕊挥发油化学成分GC-MS分析及比较

采用水蒸气蒸馏法从藏红花花瓣和雄蕊中提取挥发油,用GC-MS技术结合计算机检索对其二者化学成分进行分离和鉴定,用色谱峰面积归一化法计算各组分的相对含量.花瓣中共鉴定出16种化合物,主要成分为正二十六烷(11.60％)、正十五烷(11.31％)、棕榈酸甲酯(10.82％)、油酸甲酯(10.35％)、2,4-二叔丁基苯酚(9.63％)、亚油酸甲酯(7.18％)、藏红花醛(5.66％);雄蕊中共鉴定出20种化合物,主要成分为油酸甲酯(30.83％)、亚油酸甲酯(24.12％)、环已醇(16.80％)、硬脂酸甲酯(12.88％)、棕榈酸甲酯(8.97％)、花生酸甲酯(1.18％)、苯并噻唑(1.01％).     

Main chemical compositions with volatility in peel essential oil and seed oil of Pittosporum pentandrum var.f ormosanum capsule

采用GC-MS技术,对台琼海桐蒴果皮的水蒸气蒸馏油样,以及蒴果籽的索氏提取油样的甲酯化样品进行分析.样品中各化学成分的相对含量用面积归一化法确定.在实验条件下,果皮油样共分离出24个峰,鉴定了17个,占总峰面积的94.70％.其主要成分为柠檬烯(24.27％)、y-榄香烯(8.30％)、β-榄香烯(17.13％)、α-榄香烯(16.02％)、长叶龙脑(15.52％)和α-松油醇(2.17％),α-石竹烯(1.88％).果籽油的甲酯化样品共分离出16个峰,鉴定了12个,占总峰面积的96.69％,其主要成分为棕榈油酸(34.83％)、反油酸(26.63％)、14-甲基-十五烷酸(17.08％),十八烷酸(1.88％),十四烷酸(1.61％).分析结果说明台琼海桐蒴果皮富含挥发性芳香油,而蒴果籽油含有多种脂肪酸.     

小果微花藤种仁油主要脂肪酸和甘油三酯组成的研究

小果微花藤(茶茱萸科)[Iodes vitiginea(Hance)Hemsl.](Icacinaccae)种仁含油39-50％,经气相色谱分析,油的主要脂肪酸为十六碳烯酸和棕捅酸。利用臭氧化反应、色谱-质谱和红外光谱方法,鉴定十六碳烯酸为顺-Δ′-十六碳烯酸。用高效液相色谱从油中分离出13个甘油三酯(峰),其中8种甘油三酯进行了色谱鉴定。总甘油三酯中,主要甘油三酯为 HHH(18.4％),HHP(32.3％),PHP(16.8％)。     

云南金钱槭叶子中的酚性成分

利用各种色谱技术从云南金钱槭(Dipteronia dyeriana)叶片中分离得到13个化合物。通过波谱学方法鉴定为11,12-诃子裂酸二甲酯(1),12,13-诃子裂酸二甲酯(2),11-诃子裂酸甲酯(3),12-诃子裂酸甲酯(4),13-诃子裂酸甲酯(5),鞣料云实素(6),类叶升麻苷(7),短叶苏木酚酸甲酯(8),3-O-没食子酰基莽草酸(9),樱桃苷(10),山萘酚-3-O-β-D-木糖基-(1→2)-β-D-葡萄糖苷(11),没食子酸(12),莽草酸(13)。所有化合物均首次从金钱槭属植物中分离得到。     

茉莉花[Jasminum sambac (L.)Aiton]净油的成分研究

用层析法、气-质联用和红外光谱等方法对茉莉花净油的主要成分作了分离和鉴定,用气相色谱法作了定量测定。主要成分有苯甲酸顺-3-己烯酯(16.5％),芳樟醇(14.33％),石竹烯(13.24％),乙酸苯甲酯(11.04％),苯甲醇(10.12％)等16个成分。还鉴定微量成分3个。     

四川米易逸生植物毛叶丁香罗勒精油化学成分研究

用气相色谱保留指数定性法,气相色谱-质谱-计算机联用技术和标准品叠加法研究了米易县的逸生植物——毛叶丁香罗勒(Ocimum gratissimum L.var.suvae Willd)的精油化学成分。从分离出的53个色谱峰鉴定出21个化合物.主要成分是丁香酚(84.500％)、顺-罗勒烯(4.567％)、顺-石竹烯(1.516％),α-依兰油烯(2.457％)。已鉴定成分相对含量占全油的96.641％.此精油的丁香酚含量明显高于其它地区栽培的同种植物.     

发酵无花果香料的挥发性成分分析

利用微生物发酵无花果开发特色香料,并采用同时蒸馏萃取装置收集挥发性成分并用气相色谱一质谱仪对生物技术制备的无花果香料挥发性成分进行分离和鉴定,经毛细管色谱分离出47种组分,确认了其中的45种成分,并用面积归一化法测定了各种成分的百分含量,其主要成分为：9,12-十八碳二烯酸乙酯(27．34％)、十六酸乙酯(23．99％)、邻苯二甲酸二丁酯(6．18％)、邻苯二甲酸二异丁酯(5．52％)、9,12-十八碳二烯酸甲酯(4．72％)、十六酸甲酯(4．67％)、9,12,15-十八碳三烯酸乙酯(4．48％)、9-十八碳烯酸乙酯(3．80％)、糠醛(2．53％)、9,12,15-十八碳三烯酸甲酯(1．85％)、十八酸乙酯(1．42％)、9-十八碳烯酸甲酯(1．26％)等。     

金丝带缩酚酸类化学成分研究

对采自青海省的金丝带[Lethariella zahlbruckneri(Dr.)Krog.]的乙酸乙酯部分进行研究,采用硅胶柱色谱、半制备高效液相和重结晶技术进行分离纯化,通过1 H-NMR、13 C-NMR技术对化合物结构进行鉴定,结果共分离鉴定了5个化合物,包括:1个缩酚酸类:雪茶素(5);4个缩酚酸和缩酚酸环醚裂解产物:赤星衣酸甲酯(1),β-苔黑酚酸甲酯(2),苔色酸甲酯(3)和苔色酸乙酯(4)。其中化合物1、3、4、5均为首次从该植物中分得。     

台琼海桐蒴果皮油及籽油的主要挥发性化学成分

采用GC-MS技术,对台琼海桐蒴果皮的水蒸气蒸馏油样,以及蒴果籽的索氏提取油样的甲酯化样品进行分析。样品中各化学成分的相对含量用面积归一化法确定。在实验条件下,果皮油样共分离出24个峰,鉴定了17个,占总峰面积的94.70%。其主要成分为柠檬烯(24.27%)、γ-榄香烯(8.30%)、β-榄香烯(17.13%)、α-榄香烯(16.02%)、长叶龙脑(15.52%)和α-松油醇(2.17%),α-石竹烯(1.88%)。果籽油的甲酯化样品共分离出16个峰,鉴定了12个,占总峰面积的96.69%,其主要成分为棕榈油酸(34.83%)、反油酸(26.63%)、14-甲基-十五烷酸(17.08%),十八烷酸(1.88%),十四烷酸(1.61%)。分析结果说明台琼海桐蒴果皮富含挥发性芳香油,而蒴果籽油含有多种脂肪酸。     

羊角拗根脂溶性成分的GC-MS分析

采用气相色谱-质谱联用(GC-MS)技术对羊角拗根脂溶性成分进行分析,应用色谱峰面积归一化法定量分析各成分的相对百分含量,共分离鉴定出27种成分,占其总量的60.86％.根的脂溶性成分主要为何帕-22(29)-烯-3β-醇(32.70％)、棕榈酸乙酯(6.35％)、2-十五烷酮(4.76％)、蒲公英赛酮(2.84％)、豆甾醇(2.50％)、棕榈酸(2.08％).     

Chemical constituents of Lavatera trimestris L.--antioxidant and antimicrobial activities

Nine phenolic compounds, such as cis-/trans-p-coumaric acid, cis-/trans-p-coumaric acid methyl ester, glucose ester of cis-/trans-p-coumaric acid, caffeic acid methyl ester, kaempferol 7-O-beta-D-glucoside and kaempferol 3-O-beta-D-glucoside, were isolated from Lavatera trimestris flowers by chromatographic techniques and their structures were elucidated by spectral means (NMR). All compounds were tested for their antioxidant activity, while the methanolic extract was tested also for its antimicrobial activity. Also several non-polar constituents have been identified using GC and GC/MS methods. This is the first time that phenolic esters and non-polar constituents were identified in the flowers of L. trimestris L.     

箭叶橐吾挥发油化学成分的研究

运用气相色谱-质谱-计算机联用技术,结合标准谱库,对青海产箭叶橐吾的挥发油成分进行了研究,分离鉴定了39个化合物,主要成分为2-甲基丁烯酸(5．001％)、顺-β松油醇(2．082％)、反-β-松油醇(4．069％)、4-甲基-1-异丙基-R-3-环己烯-1-醇(15．467％)、十二烷(2．181％)、十四烷(2．276％)、Tau．-Muurolol(3．108％)、α-杜松醇(5．682％)、十六醛(2．266％)、6,10,14-三甲基-2-十五烷酮(3．421％)、三十烷(2．370％)、二十五烷(3．766％)等。     

Determination of monoenoic fatty acid double bond position by permanganate-periodate oxidation followed by high-performance liquid chromatography of carboxylic acid phenacyl esters

This investigation was carried out to develop methods for a reverse-phase, high-performance liquid chromatography analysis of the monocarboxylic and dicarboxylic acids produced by permanganate-periodate oxidation of monoenoic fatty acids. Oxidation reactions were performed using [U-14C]oleic acid and [U-14C]oleic acid methyl ester in order to measure reaction yields and product distributions. The 14C-labeled oxidation products consisted of nearly equal amounts of monocarboxylic and dicarboxylic acid (or dicarboxylic acid monomethyl ester), with few side products (yield greater than 98%). Conversion of the carboxylic acids to phenacyl esters proceeded to completion. HPLC of carboxylic acid phenacyl esters was performed using a C18 column with a linear solvent gradient beginning with acetonitrile/water (1/1) and ending with 100% acetonitrile. Excellent resolution was achieved for all components of a mixture of C5 through C12 monocarboxylic acid phenacyl esters and C6 through C11 dicarboxylic acid phenacyl esters. Resolution was also achieved for all components of a mixture of C5 through C12 monocarboxylic acid phenacyl esters and C6 through C11 dicarboxylic acid monomethyl, monophenacyl esters. The resolution obtained by HPLC demonstrates that, for a wide range of monoenoic fatty acids, both products of a permanganate-periodate oxidation can be identified on a single chromatogram. Free fatty acids and fatty acid methyl esters were analyzed with equal success. Neither the oxidation nor the esterification reaction caused detectable hydrolysis of methyl ester. The method is illustrated for free acids and methyl esters of 14:1 (cis-9), 16:1 (cis-9), 18:1 (cis-6), 18:1 (cis-9), and 18:1 (cis-11).     

Major constituents and cytotoxic effects of Ajuga chamaecistus ssp. tomentella

The n-butanolic fraction of a methanolic extract (80%) from aerial parts of Ajuga chamaecistus ssp. tomentella was analysed using different chromatographic methods. Column (CC) and high-performance liquid chromatography (HPLC) were used for isolation and purification. 13C, H NMR, H-H COSY, HSQC, HMBC, and ESI-MS were employed for identification of the compounds isolated from this fraction. The structures of the compounds were determined to be cis-melilotoside (1), trans-melilotoside (2), lavandulifolioside (3), 20-hydroxyecdysone (4), leonoside B (5), martynoside (6), ajugalactone (7), makisterone A (8), and 24-dehydroprecyasterone (9). This is the first report on the presence of cis- and trans-melilotoside in Ajuga species. Cytotoxic evaluation of the n-butanolic fraction, cis- and trans-melilotoside against cancer (T47D, HT-29, and Caco-2) and normal (NIH 3T3) cell lines by the mitochondrial tetrazolium test (MTT) showed no cytotoxic effects up to 400 microg/mL. The results of this study suggest that melilotoside, phenylethyl glycosides, and phytoecdysteroids are the main constituents of the n-butanolic fraction of Ajuga chamaecistus ssp. tomentella.     

The Chemical Components of the Absolute Oil from Jasminun sarnbac (L.) Aiton

This plant is widely cultivated in southeastern and southern China. The concrete and absolute got from their flower are used in perfumery industry. It is also used popularly as ornamental plant and sometimes as medicine. The main chemical components of the absolute have been determined by the methods of chromatography, GC-MS, IR and NMR. The quantitative determination of these components was carried out by GLC also. The result is as follows: 3-hexenyl acetate 1.09%, cis-3-hcxen-l-ol 1.40%, dipentene oxide 1.09%, linalool 14.33%, methyl benzoate 2.96%, benzyl acetate 11.04%, benzyl alcohol 10.12%, cadinene 4.67%, hexenylbenzoat 16.51%, methyl anthranilate 0.62%, octadecene 6.54%, methyl oleate 2.02%, methyl' octadeca-9-ynoate 0.62%. Three minor components have been determined also.     

INVESTIGATION OF 4-METHYL STEROLS FROM CULTURED DINOFLAGELLATE ALGAL STRAINS

The marine dinoflagellates Prorocentrum micans, Gonyaulax polyedra, Gymnodinium sp., and Alexandrium tamarense, collected from the Adriatic Sea during red-tide blooms, were cultured to investigate the 4-methyl sterol constituents. To ascertain a possible influence of cell age on the 4-methyl sterol content, for one strain (Gymnodinium sp.)we investigated the composition of these constituents at exponential and stationary growing phases. The lipid material extracted with acetone from the lyophilized algal samples was fractionated by thin-layer chromatography. The 4-methyl sterols recovered from the layer were converted into the corresponding OTMS derivatives. Nine of 11 constituents were identified by gas chromatography and gas chromatography-mass spectrometry; only two minor constituents were characterized by their gas chromatographic parameters. All free methyl sterols identified in the algal samples had been detected previously in various dinoflagellates. The 4-methyl sterol fractions generally contained very few constituents. Except for the Gymnodinium sp. sample, collected at the exponential growing phase (GyD2 exp), which contains 4,24-dimethylcholestan-3-ol as a unique constituent, dinosterol was the major component. Moreover, 4,24-ethylcholestan-3-ol was also an important constituent of both Prorocentrum and Gonyaulax strains, whereas considerable amounts of dinostanol characterized all the Gymnodinium sp. strains. In addition, the latter contained several minor constituents such as 4-methylcholestan-3-ol, 4,24-dimethylcholesta-22-en-3-ol, and 4-methyl-24-ethylcholestan-3-ol. 4-Methyl-24-methylene-cholestan-3-ol was a constituent of the Gymnodinium sp. sample, collected at the stationary growing phase (GyD2 stat)only, whereas 4-methylgorgostanol was identified only in the Alexandrium tamarense Gt4 strain. Except for 4-methyl-24-ethylcholesta-8(14)-en-3-ol, all the methyl sterol constituents from our algae show a saturated polynuclear system. The pathways by which side-chain modifications occur in dinoflagellate 4-methyl sterols are considered, and a map of the fragmentation pattern of the trimethylsilyl-4-methyl sterols under electronic impact is also reported.     

华北大黑鳃金龟引诱剂配方筛选及引诱效果评价

【目的】筛选可有效引诱华北大黑鳃金龟Holotrichia oblita成虫的引诱剂配方用于生态防控。【方法】选取5种植物挥发物、2种华北大黑鳃金龟聚集信息素和1种性信息素,根据各化合物单体最佳引诱浓度进行两两混配,得到植物挥发物+聚集信息素、植物挥发物+性信息素和聚集信息素+性信息素共17种二元引诱剂配方。通过触角电位(EAG)反应和趋性行为反应逐步筛选出引诱效果较好的配方。将所筛选配方与其单一组分通过趋性行为反应进行引诱效果比较,并通过室内笼罩诱捕检验配方对华北大黑鳃金龟成虫的引诱效果。【结果】通过EAG反应及趋性行为反应从17种二元引诱剂配方中逐步筛选出了对华北大黑鳃金龟成虫具有较强引诱作用的3种配方,即顺-3-己烯基乙酸酯+顺-9-十八烯乙酸酯,1-己醇+顺-9-十八烯乙酸酯和邻苯二甲酸二丁酯+甘氨酸甲酯,它们引起的华北大黑鳃金龟雌虫EAG反应相对值分别为5 981%, 5 796%和5 722%,引起的雄虫EAG反应相对值分别为3 983%, 4 712%和3 809%。趋性行为反应试验中,引起华北大黑鳃金龟成虫选择反应率最高的为配方邻苯二甲酸二丁酯+甘氨酸甲酯,成虫选择反应率达71.21%,其次为配方1-己醇+顺-9-十八烯乙酸酯和顺-3-己烯基乙酸酯+顺-9-十八烯乙酸酯,成虫选择反应率分别达到70.84%和70.72%,均显著高于其他配方引起的选择反应率。3种二元组分引诱剂配方与其单一组分引诱效果的比较表明,配方顺-3-己烯基乙酸酯+顺-9-十八烯乙酸酯对单一组分顺-3-己烯基乙酸酯具有显著的增效作用,而对顺-9-十八烯乙酸酯增效作用不明显;配方1-己醇+顺-9-十八烯乙酸酯和邻苯二甲酸二丁酯+甘氨酸甲酯均对其单一组分增效作用显著。室内笼罩诱捕结果表明,配方顺-3-己烯基乙酸酯+顺-9-十八烯乙酸酯,1-己醇+顺-9-十八烯乙酸酯和邻苯二甲酸二丁酯+甘氨酸甲酯引诱成虫数均极显著高于石蜡油对照,配方顺-3-己烯基乙酸酯+顺-9-十八烯乙酸酯引起的选择反应率最高,达74.06%;其次为配方1-己醇+顺-9-十八烯乙酸酯和邻苯二甲酸二丁酯+甘氨酸甲酯,引起的选择反应率分别达到65.89%和64.25%;但3种配方引起的华北大黑鳃金龟成虫的选择反应率之间无显著性差异。【结论】顺-3-己烯基乙酸酯+顺-9-十八烯乙酸酯,1-己醇+顺-9-十八烯乙酸酯和邻苯二甲酸二丁酯+甘氨酸甲酯这3种二元引诱剂配方对华北大黑鳃金龟成虫均具有较强的引诱作用,均可作为用于生态治理华北大黑鳃金龟的有效引诱剂。     

Regio- and stereoselective metabolism of 7,12-dimethylbenz[a]anthracene by Mycobacterium vanbaalenii PYR-1

The degradation of 7,12-dimethylbenz[a]anthracene (DMBA), a carcinogenic polycyclic aromatic hydrocarbon, by cultures of Mycobacterium vanbaalenii PYR-1 was studied. When M. vanbaalenii PYR-1 was grown in the presence of DMBA for 136 h, high-pressure liquid chromatography (HPLC) analysis showed the presence of four ethyl acetate-extractable compounds and unutilized substrate. Characterization of the metabolites by mass and nuclear magnetic resonance spectrometry indicated initial attack at the C-5 and C-6 positions and on the methyl group attached to C-7 of DMBA. The metabolites were identified as cis-5,6-dihydro-5,6-dihydroxy-7,12-dimethylbenz[a]anthracene (DMBA cis-5,6-dihydrodiol), trans-5,6-dihydro-5,6-dihydroxy-7,12-dimethylbenz[a]anthracene (DMBA trans-5,6-dihydrodiol), and 7-hydroxymethyl-12-methylbenz[a]anthracene, suggesting dioxygenation and monooxygenation reactions. Chiral stationary-phase HPLC analysis of the dihydrodiols showed that DMBA cis-5,6-dihydrodiol had 95% 5S,6R and 5% 5R,6S absolute stereochemistry. On the other hand, the DMBA trans-5,6-dihydrodiol was a 100% 5S,6S enantiomer. A minor photooxidation product, 7,12-epidioxy-7,12-dimethylbenz[a]anthracene, was also formed. The results demonstrate that M. vanbaalenii PYR-1 is highly regio- and stereoselective in the degradation of DMBA.     

山鸡椒根部精油化学成分的研究

采用水蒸气蒸馏、气相层析、标准品加入和归一法等综合技术鉴定出山鸡椒根部精油含α-蒎烯、柠檬烯、1.8-桉叶素、对聚伞花素、香草醛、甲基庚烯酮、异胡薄荷醇、香叶醇甲酸酯、α-松油醇、香草醇,柠檬醛a,b、香叶醇、丁香酚十三个成分。     

Urinary metabolites of cis-9,10-methylene octadecanoic acid. cis-3,4-Methylene hexanedioic acid and related compounds.

cis-3,4-Methylene hexanedioic acid has been discovered in human urine. It has been isolated and identified by mass spectrometry and synthesis. The daily excretion in nine subjects on a free diet was 88 mumol/day (range, 32 to 144 mumol/day). cis-3,4-Methylene hexanedioic acid was given orally to a rat. About 90% of the dose was recovered unchanged in the urine within 24 h. Intragastric administration of cis-9,10-methylene [9,10-3H2]octadecanoic acid to rats gave four labeled urinary metabolites. The major one was cis-3,4-methylene hexanedioic acid, the others were 2,3-methylene pentanedioic acid and isomers of methylene heptanedioic acid and methylene octanedioic acid. Within 72 h, about 40% of the administered radioactivity could be recovered from the urine and another 40% from the carcass. About 20% of the recovered radioactivity was found to be water. Of the radioactivity administered to rats orally as cis-9,10-methylene [9,10-3H2]octadecanoic acid methyl ester, about 50% could be recovered from the lymph of the thoracic duct within 9 h. Intraperitoneal administration of cis-9,10-methylene octodecanoic acid methyl ester to rats gave the same metabolites. Of the given amount, 50 mol % could be recovered from the urine as cis-3,4-methylene hexanedioic acid and 19 mol % as homologues within 38 days.