滇桂艾纳香石油醚部位化学成分及挥发性成分的分析-analysis of chemical constituents an(5)

实验用为阴干并粉碎的滇桂艾纳香地上部分。1.2实验仪器挥发油提取器；超临界CO2提取器；GC-MSAgilent6890N/5973NGC-MS联用仪，美国Agilent公司。1.3实验试剂蒸馏水，乙醚(重蒸)，石油醚(分析纯)2实验方法与结果2.1挥发性成分的提取2.1.1水蒸气蒸馏提取取滇桂艾纳香的新鲜药材100g，臵于2000ml的圆底烧瓶中，加水1000ml浸泡6个小时后，用水蒸气蒸馏提取7个小时。放掉挥发油提取器中的水，用乙醚将挥发油提取器中的挥发油萃取出来，出油率约为0.04%，萃取的挥发油加入少量无水硫酸钠脱水，备用。2.1.2超临界CO2提取取滇桂艾纳香的新鲜药材10g，臵于超临界提取器中提取即得。2.1.3石油醚浸泡提取取滇桂艾纳香鲜药材20g，臵于250ml的锥形瓶中，加入200ml石油醚，浸泡48小时，过滤后挥干溶剂，得到黄色状物，得率约为0.04%，物质用乙醚溶解，加入少量无水硫酸钠脱水，备用。2.2挥发性成分的分离分析2.2.1GC-MS分离分析条件GC条件：色谱柱HP-5MS(5%PhenylMethylSiloxane,30m×0.25mm×0.25μm)弹性石英毛细管柱。

进样口温度：250℃，载气：He；流速：1ml/min。MS条件：电离方式：EI；离子源温度；230℃；电子能量：70Ev;发射电流：0.25mA;质量分析器：四级杆，温度250℃；质量扫描范围：30～500amu；美国NIST02谱库检索。2.2.2挥发性成分分离的升温程序2.2.2.1滇桂艾纳香水蒸气蒸馏提取物的升温程序取1μl水蒸气蒸馏提取物注入仪器，分流比split为20:1，升温过程为：起始温度为70oC（保持3min），以10oC/min升温至140oC（保持8min），以2oC/min升温至155oC（保持2min），以5oC/min升温至170oC（保持5min），以3oC/min升温至210oC（保持3min），以10oC/min升温至270oC（保持2min）。2.2.2.2滇桂艾纳香超临界CO2提取物的升温程序取1μl超临界CO2提取物注入仪器，分流比split为20:1，升温过程为：起始温度为70oC（保持3min），以10oC/min升温至140oC（保持8min），以2oC/min升温至155oC（保持2min），以5oC/min升温至170oC（保持5min），以3oC/min升温至210oC（保持3min），以10oC/min升温至270oC（保持2min）。

2.2.2.3滇桂艾纳香石油醚浸泡提取物的升温程序取1μl石油醚浸泡提取物样品注入仪器，分流比split为6:1，升温过程为：起始温度为130oC，以8oC/min升温至150oC（保持2min），以5oC/min升温至200oC（保持2min），以5oC/min升温至230oC（保持1min），以6oC/min升温至250oC（保持1min）。2.2.3样品分析经气相色谱分离分析得到的组分，用面积归一化法测定各组分的百分含量，并检测成分的GC-MS总离子流色谱，所得的色谱图用美国NIST02谱库检索，并按各峰的质谱裂片图与文献资料核对。2.3结果从滇桂艾纳香水蒸汽蒸馏物分离分析出34个组分，鉴定了26个化合物（占挥发油总质量的85.88％），分析和鉴定结果见图4-1和表4-1。从滇桂艾纳香超临界CO2提取物分离分析出56个组分，鉴定了40个化合物（占挥发油总质量的80.44％），分析和鉴定结果见图4-2和表4-2。从滇桂艾纳香石油醚浸提物分离分析鉴定了14个化合物（占挥发油总质量的85.2％），分析和鉴定结果见图4-3和表4-3。AbundanceTIC:DGANX02-1水提.D320000030000002800000260000024000002200000200000018000001600000140000012000001000000800000600000400000200000Time-->5.0010.0015.0020.0025.0030.0035.0040.00图4-1滇桂艾纳香水蒸汽蒸馏提取物的总离子色谱AbundanceTIC:DGANX02-超临界提取.D500000045000004000000350000030000002500000200000015000001000000500000Time-->5.0010.0015.0020.0025.0030.0035.0040.0045.0050.0055.00图4-2滇桂艾纳香超临界CO2提取物的总离子色谱AbundanceTIC:LIUXH11.D750000700000650000600000550000500000450000400000350000300000250000200000150000100000500004.006.008.0010.0012.0014.0016.0018.0020.0022.0024.0026.00Time-->图4-3滇桂艾纳香石油醚浸泡提取物的总离子色谱表4-1滇桂艾纳香水蒸汽蒸馏提取物鉴定表峰号分子式分子量名称保留时间百分含(min)(%)1，2C15H24204α-荜澄茄油烯alpha.-Cubebene10.63，11.101.033C15H24204(+)-双环倍半菲兰烯(+)-Epi-bicyclosesquiphellandrene11.360.824C15H24204异丁香烯Isocaryophillene11.710.295C15H24204丁香烯Caryophyllene11.992.176C15H24204(E)-7,11-二甲基-3-亚甲基-1,6,10-十二碳三烯12.726.561,6,10-Dodecatriene,7,11-dimethyl-3-methylene-,(E)-7,C15H24204(1S-顺式)-1,2,3,5,6,8a-六氢-4,7-二甲基-1-(1-甲乙基)-苯13.23,6.7516Naphthalene,1,2,3,5,6,8a-hexahydro-4,7-dimethyl-1-(1-methylethyl)-,(1S-cis)-14.638C15H242042,6,6,9-四甲基-三环[5.4.0.02,8]十一-9-烯13.370.94Tricyclo[5.4.0.02,8]undec-9-ene,2,6,6,9-tetramethyl-9C15H222021-(1,5-二甲基-4-己烯)-4-甲基苯Benzene,1-(1,5-dimethyl-4-hexenyl)-4-methyl-13.488.0110C15H242044-二烯-10s,11s-雪松烯-3(12)10s,11s-Himachala-3(12),4-diene13.6129.7111C15H24204[s-(R*,S*)]-5-(1,5-二甲基-4-己烯)-2-甲基-环己二烯13.799.9112C15H242041,3-Cyclohexadiene,5-(1,5-dimethyl-4-hexenyl)-2-methyl-,[s-(R*,S*)]-1-乙烯基-1-甲基-2-(1-甲乙基)-4-(1-甲基亚乙基)-环己烯13.881.41Cyclohexane,1-ethenyl-1-methyl-2-(1-methylethenyl)-4-(1-methylethylidene)-13C15H24204?-2,4a,5,6,7,8-六氢-3,5,5,9-四甲基-1H-苯并环庚烯13.990.861H-Benzocycloheptene,2,4a,5,6,7,8-hexahydro-3,5,5,9-tetramethyl-,?-14C15H24204α-法尼烯alpha.-Farnesene14.081.8115，C15H242042-异丙基酯-5-甲基-9-亚甲基-双环[4.4.0]癸-1-烯14.41，1.8421Bicyclo[4.4.0]dec-1-ene,2-isopropyl-5-methyl-9-methylene-19.4617C15H24204(1S-顺式)-1,2,3,7,8,8a-六氢-1,6-二甲基-4-(1-甲乙基)-苯Naphthalene,14.720.741,2,3,7,8,8a-hexahydro-1,6-dimethyl-4-(1-methylethyl)-,(1R-cis)-18C15H242041,2,3,4,4a,7-六氢-1,6-二甲基-4-(1-甲乙基)-苯14.920.55Naphthalene,1,2,3,4,4a,7-hexahydro-1,6-dimethyl-4-(1-methylethyl)-19C15H24O220(-)-斯己醇(-)-Spathulenol16.591.1920C15H24204(1.α.,3a.α.,7.α.,8a.β.)-八氢-1,9,9-三甲基-4-甲基烯-1H-3a,7-亚甲基奥16.811.271H-3a,7-Methanoazulene,octahydro-1,9,9-trimethyl-4-methylene-,(1.alpha.,3a.alpha.,7.alpha.,8a.beta.)-22C15H24204Di-epi-α-雪松烯-(I)Di-epi-.alpha.-cedrene-(I)19.732.5523C15H26206(E)-长叶蒎烷Longipinane,(E)-20.087.6224C15H28O226E-2-十四烯-1-醇E-2-Tetradecen-1-ol23.010.6525C15H24O2205-(1,5-二甲基-4-已烯)-2-甲基-苯酚24.990.63Phenol,5-(1,5-dimethyl-4-hexenyl)-2-methyl-,26C20H40O296植物醇Phytol42.50.56表4-2滇桂艾纳香超临界CO2提取物鉴定表峰号分子式分子量名称保留时间百分含量(min)(%)1C10H16136α-蒎烯1S-.alpha.-Pinene3.750.752C10H16136α-水芹烯.alpha.-Phellandrene5.051.953C10H180154桉油精Eucalyptol5.523.494C10H160152(1S)-1,7,7-三甲基-二环[2.2.1]庚烷-2-酮7.521.525C10H180154Bicyclo[2.2.1]heptan-2-one,1,7,7-trimethyl-,(1S)-(1S-内)-1,7,7-三甲基-二环[2.2.1]庚烷-2-醇7.891.43Bicyclo[2.2.1]heptan-2-ol,1,7,7-trimethyl-,(1S-endo)-6C10H180154(R)-4-甲基-1-(1-甲乙基)-3-环己烯-1-醇4-methyl-1-(1-methylethyl)-,(R)-8.050.337C10H180154(S)-4-甲基-3-环己烯-1-甲醇8.270.753-Cyclohexene-1-methanol,.alpha.,.alpha.,4-trimethyl-,(S)-8C10H140150(1S)-4,6,6-三甲基-二环[3.1.1]庚-3-烯-2-酮8.591.28Bicyclo[3.1.1]hept-3-en-2-one,4,6,6-trimethyl-,(1S)-9C10H120148茴香脑Benzene,1-methoxy-4-(1-propenyl)-9.712.1010C15H24204石竹烯Caryophyllene12.021.5811C9H6021462H-1-苯并吡喃-2-酮2H-1-Benzopyran-2-one12.460.9212C15H242041,1,4,8-四甲基-4,7,10-环十一碳三烯12.791.494,7,10-Cycloundecatriene,1,1,4,8-tetramethyl-,cis,cis,cis-13C11H2202186桂皮酸乙酯2-Propenoicacid,3-phenyl-,ethylester13.020.5014C15H32212十五烷Pentadecane13.811.0215C14H2202062,4-二叔丁基-苯酚Phenol,2,4-bis(1,1-dimethylethyl)-14.341.5616C13H16032206,7-甲氧基-2,2-甲基-2H-1-苯并吡喃20.460.692H-1-Benzopyran,2H-1-6,7-dimethoxy-2,2-dimethyl-17C12H14032063-(4-甲氧苯基)-2-丙烯乙酯-2-Propenoicacid,3-(4-methoxyphenyl)-,ethylester25.457.4918C16H12052841,6-二羟基-8-甲氧基-3-甲基-9,10-蒽二酮39.501.3319C6H11N979,10-Anthracenedione,1,6-dihydroxy-8-methoxy-3-methyl-(CAS)(E)-1-(1,4-二甲氧基-2-甲基萘-2-基)-3-甲基戊-2-烯42.8014.32(E)-1-(1,4-dimethoxy-2-methylnaphthalen-2-yl)-3-methylpent-2-ene20C18H3202280亚油酸9,12-Octadecadienoicacid(Z,Z)-44.621.4321C17H320252(R)-(-)-14-甲基-8-己二烯-1-醇(R)-(-)-14-Methyl-8-hexadecyn-1-ol44.850.4222C20H300286弥罗松酚Ferruginol50.00.9523C20H42282二十烷Eicosane55.101.6224C20H3804342二(2-乙基己酯)-邻苯二甲酸Bis(2-ethylhexyl)phthalate55.983.7725C21H320300(5.α.)-4,4-二甲基-雄甾-2-烯-17-酮Androst-2-en-17-one,4,4-dimethyl-,(5.alpha.)-56.510.56(CAS)26C16H2603266十二烯基丁二酸酐2-Dodecen-1-yl(-)succinicanhydride56.590.3127C16H34226二十六烷Hexacosane56.661.0428C20H2803316(4α,6α,7β)-4内酯-6,7-二羟基-γ-内酯-16-内-18-羧酸Kaur-16-en-18-oicacid,6,7-dihydroxy-,.gamma.-lactone、,(4.alpha.,6.alpha.,7.beta.)-56.831.1229C18H1804298α-氧-3-(2-氧-1--苯基乙烯基)-二环[2.2.1]庚烷-2-乙酸甲酯57.001.91Bicyclo[2.2.1]heptane-2-aceticacid,.alpha.-oxo-exo-3-(2-oxo-1-phenylethenyl-)-,methylester30,C22H1606376(-)-1',4-二甲氧基-2,3'-二甲基-[1,2'-联苯]-5,5',8,8'-四酮57.07,1.6931,[1,2'-Binaphthalene]-5,5',8,8'-tetrone,1',4-dihydroxy-2,3'-dimethyl-,(-)-57.29,3558.2832C25H32332二十五烷Pentacosane57.340.4133,C27H36360二十七烷Heptacosane57.89,10.553458.2236C14H2002042-甲基-1-苯-3-四甲基-9H-咔唑2-Methyl-1-phenyl-3-trimehtylsilyl-9H-carbazole59.023.4337C6H902N31551-甲酰基-5,6-二羟基-8,9-甲氧吡咯[2.1-a]异喹啉-2-羧酸乙酯59.161.64ethyl1-formyl-5,6-dihydro-8,9-dimethoxypyrrolo[2.1-a]isoquinoline-2-carboxylate38C25H423422,6,10,14,18-五甲基-2,6,10,14,18-二十烯59.393.862,6,10,14,18-Pentamethyl-2,6,10,14,18-eicosapentaene39C8H8021362,6-二甲基-p-醌4-(4-苄基-2,6-二甲基苯胺)59.450.182,6-Dimethyl-p-benzoquinone4-(4-benzyl-2,6-dimethylanil)40C10H903N191正齐墩果-12-烯NOROLEAN-12-ENE59.680.88表4-3滇桂艾纳香石油醚浸泡提取物鉴定表峰号分子式分子量名称保留时间(min)百分含(%)1C18H38254十八烷Octadecane10.507.262C19H40268十九烷Nonadecane12.464.213C18H36O2284棕榈酸乙酯Hexadecanoicacid,ethylester14.294.134C20H42282二十烷Eicosane14.374.135C21H44296二十一烷Heneicosane16.498.516C22H46310二十二烷Docosane18.784.537C19H38O2298(6R,7S,9R,10S)-6,7,10-双环氧十九烷(6R,7S,9R,10S)-6,7,10-Bisepoxynonadecane21.564.148C24H50338二十四烷Tetracosane22.754.939C25H52352二十五烷Pentacosane24.7310.5710C23H48324二十三烷Tricosane25.344.6411C18H382542,6,10-三甲基-十五烷Pentadecane,2,6,10-trimethyl-25.679.3012C26H54366二十六烷Hexacosane26.474.3813C27H56380二十七烷Heptacosane27.019.9714C20H422822,6,10,14-四甲基-十六烷Hexadecane,2,6,10,14-tetramethyl-27.399.053小结与讨论3.1滇桂艾纳香水蒸汽蒸馏提取物中已鉴定的23个化合物，占挥发油成分总量的85.88%。