气滞胃痛颗粒挥发性成分表征及药材归属研究

目的利用气相色谱-质谱联用技术研究气滞胃痛颗粒中挥发性成分并对其挥发性成分进行药材归属。方法采用水蒸汽蒸馏法提取挥发油,利用气质联用技术将所得质谱图经计算机数据处理和NIST298、WIL EY275标准质谱图库检索鉴定各种化学成分、确定其所属药材并采用面积归一化法计算各成分的相对百分含量。结果共检测出34种化合物,主要来自于枳壳和香附2味药材,其主要成分分别是α-蒎烯(1.051%)、1-甲基-4-(1-甲基乙基)-1,4-环己二烯(9.701%)、β-月桂烯(2.417%)、间异丙基甲苯(2.148%),柠檬烯(54.789%)、3,7-二甲基-1,6-辛二烯-3-醇(17.507%)、α-萜品醇(2.325%)等。结论此方法稳定可靠,重现性好,适用于气滞胃痛颗粒中挥发性成分分析,为气滞胃痛颗粒物质基础的阐明提供依据。     

药对陈皮—干姜与其单味药挥发性成分的比较分析

目的:比较分析药对陈皮-干姜与其单味药的挥发性成分.方法:采用水蒸气蒸馏法分别提取陈皮,干姜药材及药对挥发性成分,应用气相色谱-质谱联用(GC-MS)技术对各样品中的挥发性成分进行比较分析,并采用峰面积归一化法计算百分含量.结果:从陈皮挥发性成分中检出的4-异丙基甲苯、D-柠檬烯、壬醛、大根香叶烯等成分和干姜挥发性成分中检出的甲基庚烯酮、α-法尼烯、5-甲基-2-(1-甲基乙烯基)-4-己烯-1-醇乙醇酯、α-长叶蒎烯等成分在药对挥发油中均未检出;而药对陈皮-干姜中新增成分冰片、2-甲基丙酸-3,7-二甲基-2,6-辛二醇酯、β-桉叶醇、肉桂苯氨基甲酸酯等.结论:药对陈皮-干姜配伍后挥发性化学成分与单味药相比有明显差异.     

HS-SPME-GC-MS分析不同产地丁香挥发性成分

目的:分析丁香挥发性成分的化学组成,并比较不同产地丁香中挥发性成分组成的差异。方法:采用顶空固相微萃取 (HS-SPME)技术萃取丁香中挥发性成分,结合气相色谱/质谱(GC/MS)联用技术对丁香的挥发性成分进行定性、定量分析。结果:5个不同产地的丁香药材挥发性成分中含量最高的成分为丁香酚,其次为石竹烯、α-葎草烯;不同产地丁香挥发性成分中共有成分为α-蒎烯、丁香酚、石竹烯、α-葎草烯和δ-杜松烯。结论:运用HS-SPME-GC-MS能够快速获取丁香的挥发性成分的化学组成信息,不同产地丁香中挥发性成分中丁香酚和石竹烯两者的含量之和存在较大差异,研究结果可为丁香的质量评价提供参考依据。     

碰碰香不同部位挥发性成分的分析

目的:对碰碰香中的挥发性成分进行SPME-GC-MS定性定量分析。方法:采用固相微萃取-气相色谱-质谱(SPME-GC-MS)联用技术对碰碰香不同部位挥发性成分进行分析,利用峰面积归一化法测定各个成分的相对百分含量。结果:从碰碰香的3个不同部位中总共分离出40个成分,主要含有酮、烷烃、烯烃、芳香烃、醇和酯等类化合物。3个部位中共有成分5个。其中根中含量最高的为莰烯(17.42%),茎和叶中含量最高的均为柠檬烯,含量分别为27.56%和27.07%。结论:碰碰香不同部位中的挥发性成分差异性很大。     

顶空固相微萃取-气质联用分析海桐中挥发性成分

目的:分析海桐果实中挥发性化学成分的组成。方法:采用顶空固相微萃取(HS-SPME)技术对海桐果实进行萃取,用气相色谱-质谱(GC-MS)法进行分离分析。结果:共分离并鉴定出22种化学成分。萃取物中含量最高的成分是α-蒎烯(72.38%),其次为γ-杜松烯(5.66%)、1-异丙烯基-3-异丙酯苯(5.21%)。结论:首次采用HS-SPME-GC-MS联用技术分析海桐果实中的挥发性成分,为海桐挥发性成分的研究及开发利用提供了科学依据。     

草果挥发油成分的气相色谱-质谱联用分析

目的用气相色谱-质谱(GC-MS)法鉴定云南产草果果实中挥发油的化学成分。方法采用水蒸气蒸馏法对草果果实挥发性成分进行提取,运用GC-MS法对其进行分析鉴定,归一法确定各成分的相对百分含量。气相色谱用HP-5MS毛细管柱(0.25 mm×0.25μm,30 m),进样口温度为250℃;柱温为40℃(保持2 min)至150℃(保持2 min),升温速度为10℃/min,150℃至250℃(保持5 min),升温速度为15℃/min;分流比为10∶1;流速为1.0 mL/min。结果鉴定了33个化合物,主要的成分有桉油精(14.58%),3,7-二甲基-2,6-辛二烯醛(6.66%),α,α,4-三甲基-3-环己烯1-甲醇(8.49%),α-蒎烯(5.65%),β-蒎烯(4.54%)等。结论该方法分离效果良好,可用于草果药材的质量评价。     

不同产地及种属罗布麻叶挥发油的GC-MS成分分析

目的分析不同产地及种属罗布麻叶挥发油的化学成分。方法用水蒸气蒸馏法提取罗布麻叶挥发油,以气相色谱-质谱联用技术进行挥发油的化学成分分析。结果不同产地及种属罗布麻叶挥发油的化学成分有较大的不同。运城红麻中含有较多的烯、酮、酸,占挥发油含量的31.78%,并首次从中得到7-甲基-6,9-二烯-氧杂环十二烷-2-酮、3-叔丁基-4-羟基茴香醚、高胡椒乙胺、芴、菲及叶绿醇;东北红麻中含有较多的酸、酮,占挥发油含量的28.44%,首次从中得到2-甲基-6-对甲基苯基-2-庚烯、肉豆蔻醛;陕西红麻中含有较多的烯、酮,占挥发油含量的39.89%,首次从中得到长叶烯、柏木烯、香叶基丙酮、棕榈酸及其甲酯;运城白麻中含有较多的长链碳原子饱和烃类物质,占挥发油含量的19.88%,此外含有占挥发油18.03%的酮类物质。结论不同产地采集的生药材,其挥发性物质的含量和成分有一定的差别,罗布麻的挥发性成分应分别加以研究利用。     

胀果甘草叶挥发性化学成分的分析研究

目的分析胀果甘草叶的挥发性化学成分。方法采用水蒸气蒸馏法提取,运用毛细管气相色谱-质谱联用法分析测定,用计算机检索NIST02质谱数据库确定其挥发性化学成分,用面积归一化法进行定量分析。结果经毛细管色谱分离出56个峰,并且确认了其中的46种化合物,所鉴定化合物的含量占精油总量的82.1%。结论胀果甘草叶的挥发性化学成分主要为十九烷(9.75%)、二十九烷(7.98%)以及孑丁香烯(7.36%)、(1,α2,β5α)-2,6,6-三甲基-二环[3,1,1]庚烷(5.83%)、2,6,11-三甲基-十二烷(5.31%)、1-氯-十八烷(4.81%)、十八烷(4.70%)、(E)-乙酸-3,7-二甲基-2,6-辛二烯-1-酯(4.64%)、二十烷(3.44%)、1-二十二烯(3.43%)、(-)-E-蒎烷(3.07%)、甲壬酮(2.48%)等,上述十二种化合物的含量占总量的62.80%。     

胀果甘草叶挥发性化学成分的分析研究

目的分析胀果甘草叶的挥发性化学成分。方法采用水蒸气蒸馏法提取,运用毛细管气相色谱-质谱联用法分析测定,用计算机检索NIST02质谱数据库确定其挥发性化学成分,用面积归一化法进行定量分析。结果经毛细管色谱分离出56个峰,并且确认了其中的46种化合物,所鉴定化合物的含量占精油总量的82.1%。结论胀果甘草叶的挥发性化学成分主要为十九烷(9.75%)、二十九烷(7.98%)以及孑丁香烯(7.36%)、(1,α2,β5α)-2,6,6-三甲基-二环[3,1,1]庚烷(5.83%)、2,6,11-三甲基-十二烷(5.31%)、1-氯-十八烷(4.81%)、十八烷(4.70%)、(E)-乙酸-3,7-二甲基-2,6-辛二烯-1-酯(4.64%)、二十烷(3.44%)、1-二十二烯(3.43%)、(-)-E-蒎烷(3.07%)、甲壬酮(2.48%)等,上述十二种化合物的含量占总量的62.80%。     

顶空固相微萃取-气质联用技术分析川芎酒炙前后的挥发性成分

目的:比较川芎生品和酒炙品挥发性成分的差异,为川芎的药理活性研究及临床应用提供参考。方法:采用顶空固相微萃取-气质联用技术分析川芎酒炙前后的挥发性成分,并运用面积归一化法计算各成分的相对百分含量。结果:从川芎生品中分离出28个成分,鉴定出24个成分,占总挥发性成分的99.70%,含量较高的分别为2-甲基-2,3-二氢-1H-茚-2-醇(20.06%)、α-芹子烯(17.97%)及4-乙基-壬烯-5-炔(9.24%)。从川芎酒炙品中分离出21个成分,鉴定出18个成分,占总挥发性成分的89.74%,含量最高的为4-乙基-壬烯-5-炔(12.97%),其次为4-蒈烯(11.74%)和α-芹子烯(10.79%);与生品相比,有效镇痛成分α-蒎烯、β-榄香烯含量有所增加。结论:川芎酒炙前后挥发性成分及相对百分含量存在一定差异,酒炙后挥发性成分相对减少,但有镇痛作用的成分含量增加,镇痛效果优于生品。     

2-甲基-4-(2,6,6-三甲基-1-环己烯-1-基)-2-丁烯醛的合成

2,6,6-三甲基-1-环己烯-1-甲醛与(3-甲氧基-2-甲基烯丙基)膦酸二乙酯经Wittig-Homer缩合制得1-甲氧基-2-甲基-4-(2,6,6-三甲基-1-环己烯-1-基)-1,3-丁二烯,然后经酸催化水解得到维生素A的关键中间体2-甲基-4-(2,6,6-三甲基-1-环己烯-1-基)-2-丁烯醛,总收率约47%.     

六氢假紫罗酮的新合成法

氯异戊烯与亚异丙基丙酮在相转移催化条件下缩合得2和3,以氢氧化钠代替 DBU 在分馏塔内使副产物3异构化为2,并对缩合的条件进行了研究,2经格氏、重排及氢化等反应得六氢假紫罗酮(1),纯度98%,总收率43.4%。     

High-performance liquid chromatographic method for the simultaneous determination of 24 fragrance allergens to study scented products

The European legislation on cosmetic products has recently required the declaration of 26 compounds (24 volatile chemicals and 2 natural extracts) on the label of final products when exceeding a stipulated cut-off level. In this work a rapid reliable and specific RP-HPLC method coupled with diode array detector (DAD) has been developed for the simultaneous determination and quantification of the 24 volatile chemicals: amyl cinnamal, benzyl alcohol, cinnamyl alcohol, citral, eugenol, hydroxy-citronellal, isoeugenol, amylcinnamyl alcohol, benzyl salicylate, cinnamal, coumarin, geraniol, Lyral (hydroxy-methylpentylcyclohexene carboxaldehyde), anisyl alcohol, benzyl cinnamate, farnesol, Lilial (2-(4-tert-butylbenzyl)propionaldehyde) linalool, benzyl benzoate, citronellol, hexyl cinnamal, limonene, methylheptin carbonate, alpha-isomethyl ionone (3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one). The 24 analytes were appropriately separated over a running time of 40 min, on a C18 column using a simple gradient elution (acetonitrile/water) with flow rate from 0.7 to 1.0 ml/min and UV acquisition at 210, 254 and 280 nm. All calibration curves showed good linearity (r2>0.99) within test ranges. The method was successfully applied to the qualitative and quantitative determination of the potential allergens in four commercial scented products, with satisfactory accuracy and precision. The results indicated that this simple and efficient method can be used for quality assessment of complex matrices such us cosmetic scented products.     

Design, synthesis, and evaluation of novel mutual prodrugs (hybrid drugs) of all-trans-retinoic acid and histone deacetylase inhibitors with enhanced anticancer activities in breast and prostate cancer cells in vitro

Novel mutual prodrugs (MPs) of ATRA (all- trans-retinoic acid) and HDIs (histone deacetylase inhibitors) ( 10, 13, 17- 19) connected via glycine acyloxyalkyl carbamate linker (AC linker) or through a benzyl ester linker (1,6-elimination linker) were rationally designed and synthesized. Most of our novel MPs were potent inhibitors of growth of several hormone-insensitive/drug resistant breast cancer cell lines and the hormone-insensitive PC-3 prostate cancer cell line. The novel MPs exhibited differential antiproliferative potencies in both MDA-MB-231 and PC-3 cell lines. Whereas 19 (VNLG/124) [4-(butanoyloxymethyl)phenyl(2 E,4 E,6 E,8 E)-3,7-dimethyl-9-(2,6,6-trimethylcyclohex-1-enyl)nona-2,4,6,8-tetraenoate] with a GI 50 of 10 nM was the most potent MP versus the MDA-MB-231 cells, 13 (VNLG/66) [{ N-[ N-{2-[4-{[3-pyridylmethoxy)carbonyamino]methyl}phenyl) carbonylamino]phenyl} carbamoylcarbamoyloxy}methyl(2 E,4 E,6 E,8 E)-3,7-dimethyl-9-(2,6,6-trimethyl cyclohex-1-enyl)nona-2,4,6,8-tetraenoate] with a GI 50 = 40 nM was the most potent versus the PC-3 cells. MP 19 exhibited the most benefit because its GI 50 of 10 nM versus MDA-MB-231 cells was remarkably 1085-fold lower than that of parent ATRA and over 100000-fold lower than butyric acid (BA).     

Two new metabolites with cytotoxicities from deep-sea fungus,aspergillus sydowi YH11-2

Two new compounds, 2, 3, 5-trimethyl-6-(3-oxobutan-2-yl)-4H-pyran-4-one (1) and (2R)-2, 3- dihydro-7-hydroxy-6, 8-dimethyl-2-[(E)-prop-1-enyl] chromen-4-one (2), together with six known compounds (3-8), were isolated from a deep-sea fungus, identified as Aspergillus sydowi, by a bioassay-guided method. Their structures were elucidated by spectroscopic methods and the cytotoxicities were evaluated by SRB method.     

Microbiological oxidation of isophorone to 4-hydroxyisophorone and chemical transformation of 4-hydroxyisophorone to 2,3,5-trimethyl-p-benzoquinone

Oxidation of isophorone by various fungi was examined.Aspergillus niger oxidized isophorone to 4-hydroxyisophorone, 3-hydroxymethyl-5,5-dimethyl-2-cyclohexen-1-one and 5-hydroxymethyl-3,5-dimethyl-2-cyclohexen-1-one. 4-Oxoisophorone obtained by chromic acid oxidation of 4-hydroxyisophorone was transformed to 2,3,5-trimethyl-p-benzoquinone by acid treatment.     

Free radical oxidation of (E)-retinoic acid by the Fenton reagent: competing epoxidation and oxidative breakdown pathways and novel products of 5,6-epoxyretinoic acid transformation

The nature of the products formed by reaction of all-trans retinoic acid (1) and its major metabolite, 5,6-epoxyretinoic acid (2), with the Fenton reagent was investigated. Oxidation of 1 in a vigorously stirred biphasic medium (0.1 M phosphate buffer, pH 7.4/ethyl acetate 5:1 v/v) with Fe2+/EDTA complex (2 mol equiv) and a 10-fold excess of H2O2 proceeded smoothly to give a very complex mixture of products. Repeated TLC fractionation of the reaction mixture after methylation allowed isolation of the main products which were identified as 2 methyl ester, (7E)-7,8-epoxyretinoic acid methyl ester (6), all-(E)-2,6-dimethyl-8-(2,6,6-trimethyl-2-cyclohexen-1-ylidene)-2,4,6-octatrienal (11), the novel (9E)-5,6,9,10-diepoxyretinoic acid methyl ester (7), and (9Z)-5,6,9,10-diepoxyretinoic acid methyl ester (8) (1:1 mixture of syn/anti isomers each), 5,6-epoxy-beta-ionone (9), 5,6-epoxy-beta-ionylideneacetaldehyde (10), and trace amounts of beta-ionone (12), beta-ionylideneacetaldehyde (13), and 4-oxoretinoic acid (3) methyl ester. When the oxidation was carried out with the substrate and the Fenton reagent at concentrations as low as 10 microM, the main detectable products were 2 methyl ester, 11, and 7/8. Under similar conditions, the epoxide 2 gave mainly products 7-10. A less efficient conversion of 1 and 2 but similar product patterns were observed with other oxidizing systems such as peroxidase/H2O2 and 13-hydroperoxyoctadecadienoic acid in the presence of Fe(II). Besides providing the first detailed insight into the products formed by reaction of a retinoid with the Fenton reagent, the results of this study disclose a novel nonenzymatic route from 1 to the epoxide 2 and offer an improved chemical basis to inquire into the mechanism of the antiinflammatory, antimutagenic, and cancer chemopreventive action of these retinoids.     

Studies on new antibiotics SF2415. II. The structural elucidation

Structures of new antibiotics SF2415A1, A2, A3, B1, B2 and B3 were deduced from spectroscopic analyses and degradation studies. The structure of SF2415A3, which has the most antibacterial activity, was proposed to be 3,4a-dichloro-9-diazo-3,4, 4a,10a-tetrahydro-6-hydroxy-2,2,7-trimethyl-10a-[(E)-3,7-dimethyl- 2,6-octadienyl]-(2H,9H)naphtho-[2,3-b]pyran-5,8,10-trione. All of antibiotics SF2415 have a semi-naphthoquinone structure.     

Sesquiterpenoids from Ferula fukanensis and their inhibitory effects on nitric oxide production

Six sesquiterpene derivatives, 2,3-dihydro-7-methoxy-2S*, 3R*-dimethyl-2-[4,8-dimethyl-3(E),7-nonadienyl]furo[3,2-c]coumarin (1) and 2,3-dihydro-7-methoxy-2R*,3R*-dimethyl-2-[4,8-dimethyl-3(E),7-nonadienyl]furo[3,2-c]coumarin (2), nerolidol (3), 1-(2,4-dihydroxyphenyl)-3,7,11-trimethyl-3-ninyl-6(E),10-dodecadien-1-one (4), 1-(2,4-dihydroxyphenyl)-3,7-dimethyl-3-vinyl-8-(4-methyl-2-furyl)-6(E)-octen-1-one (5) and dshamirone (6) were isolated from an 80% aqueous methanol extract of the roots of Ferula fukanensis. The sesquiterpenoids inhibited nitric oxide (NO) production and inducible NO synthase gene expression by a murine macrophage-like cell line (RAW 264.7) [1], which was activated by lipopolysaccharide and recombinant mouse interferon-.     

Synthesis and pharmacological activity of 6-[(E)-2-(2,6,6-trimethyl-1-cyclohexen-1-yl)ethen-1-yl]- and 6-(1,2,3,4-tetrahydro-1,1,4,4-tetramethyl-6-naphthyl)-2-naphthalenecarboxylic acids

6-[(E)-2-(2,6,6-Trimethyl-1-cyclohexen-1-yl)ethen-1-yl]- and 6-(1,2,3,4-tetrahydro-1,1,4,4-tetramethyl-6-naphthyl)-2-naphthalenecarboxylic acids (4 and 8) have been synthesized and show significant activity in reversing the keratinization process in hamster tracheal organ culture and in inhibiting the induction of ornithine decarboxylase in mouse skin by 12-O-tetradecanoylphorbol-13-acetate, two assays used to measure retinoid activity. The 2-naphthalenecarboxylic acid 8 was more active than 4.