药对金银花—金银藤、陈皮—枳壳和四种桂花的挥发油成分研究
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摘要
挥发油是中药和植物中一类具有重要药理作用的成分,其化学成分十分复杂,常含有几十甚至上百种化合物。挥发油的分析一般采用GC-MS进行分离和鉴定,但在GC-MS图谱中常含有重叠峰和隐藏峰,给化合物的定性和定量带来了困难。近年来迅速发展的化学计量学多元分辨技术如直观推导式演进特征投影(Heuristic evolving latent projections, HELP)法等,将色谱的分离能力与光谱的定性鉴别能力相结合,使全面定性、定量分析挥发油复杂体系成为可能。本论文以挥发油为研究目标,分别提取了药对金银花-金银藤、陈皮-枳壳及其单味药以及四个桂花品种(金桂、银桂、丹桂和四季桂)的挥发油,首先利用GC-MS进行分离检测,然后利用化学计量学方法和保留指数实现对挥发油化学成分的定性、定量分析。
金银花挥发油共鉴定出44种化合物,占挥发油总量的87.22%。金银藤挥发油共鉴定出39种化合物,占挥发油总量的94.54%。药对金银花-金银藤挥发油共鉴定出50种化合物,占挥发油总量的90.08%。药对金银花-金银藤挥发油中化学成分有32种来自金银花,33种来自金银藤,新产生了10种化学成分,三者的共有成分为25种。三者的主要成分均为十六烷酸和9,12-十八碳二烯酸乙酯,两者合计分别占药对金银花-金银藤、金银花、金银藤挥发油含量的71.32%、57.33%和84.88%。
陈皮挥发油共鉴定出45种化合物,占挥发油总量的99.02%。枳壳挥发油共鉴定出52种化合物,占挥发油总量的98.27%。药对陈皮-枳壳挥发油共鉴定出63种化合物,占挥发油总量的97.98%。药对陈皮-枳壳挥发油中化学成分有34种来自陈皮,42种来自枳壳,新产生了16种化学成分,三者的共有成分为29种。三者的主要成分均为D-柠檬烯和γ-松油烯,两者合计分别占药对陈皮-枳壳、陈皮、枳壳挥发油含量的80.96%、90.74%和76.93%。
丹桂挥发油共鉴定出53种化合物,占挥发油总量的90.87%。金桂挥发油共鉴定出58种化合物,占挥发油总量的89.04%。银桂挥发油共鉴定出53种化合物,占挥发油总量的84.38%。四季桂挥发油共鉴定出57种化合物,占挥发油总量的89.73%。四者的共有成分为33种,主要成分均为γ-癸内酯,(E)-β-紫罗兰酮,β-二氢紫罗兰酮,β-紫罗兰醇,这四个化合物合计分别占丹桂、金桂、银桂和四季桂挥发油含量的35.84%、61.24%、29.5%和50.53%。
Volatile oil is one of important constituents in traditional Chinese medicine (TCM) and plants, and it has great important pharmacological effects. Volatile oil is a very complex system and contains tens and even hundreds of chemical constituents. The analysis of volatile oil is usually conducted by GC-MS, and the GC-MS data from volatile oil, however, often involves many overlapped and embedded peaks. These overlapped and embedded peaks bring many difficulties when carrying out quantitative and qualitative analysis. With the rapid development of some chemometric multi-resolution techniques such as heuristic evolving latent projections(HELP), it is possible to completely conduct the qualitative and quantitative analysis of volatile oil by the combined information on separation and identification from chromatography and spectrometry. In this study, volatile oil was the research object, and the volatile oils from herbal pair (HP) flos lonicerae-caulis lonicerae(FL-CL) and its single herbs, pericarpium citri reticulatae-fructus aurantii(PCR-FA) and its single herbs, and four osmanthus fragrans species, osmanthus fragrans var. aurantiacus (OFVA), osmanthus fragrans var. thunbergii (OFVT), osmanthus fragrans var. latifolius (OFVL) and osmanthus fragrans var. semperflorens(OFVS) were firstly separated and detected with gas chromatography-mass spectrometry(GC-MS), and then chemometric resolution methods and temperature-programmed retention indices(PTRIs) were employed to carry out the qualitative and quantitative analysis for volatile oils.
44 volatile constituents of FL were identified, representing 87.22% of the total content.39 volatile constituents of CL were identified, representing 94.54% of the total content.50 volatile constituents of HP FL-CL were identified, representing 90.08% of the total content. The results showed that there were 32 common volatile constituents between HP FL-CL and single herb FL, and 33 common volatile constituents between HP FL-CL and single herb CL, and 25 common volatile constituents among FL, CL and HP FL-CL. The results also showed that 10 new constituents appeared in the volatile oil of HP FL-CL. The major volatile constituents in FL, CL and HP FL-CL were n-Hexadecanoic acid and 9,12-Octadecadienoic acid, ethyl ester, the two constituents represented 71.32%、57.33% and 84.88% of the total content of volatile oil in HP FL-CL, FL and CL, respectively.
45 volatile constituents of PCR were identified, representing 99.02 % of the total content.52 volatile constituents of FA were identified, representing 98.27% of the total content.63 volatile constituents of HP PCR-FA were identified, representing 97.98% of the total content. The results showed that there were 34 common volatile constituents between HP PCR-FA and single herb PCR, and 42 common volatile constituents between HP PCR-FA and single herb FA, and 29 common volatile constituents among PCR, FA and HP PCR-FA. The results also showed that 16 new constituents appeared in the volatile oil of HP PCR-FA. The major volatile constituents in PCR, FA and HP PCR-FA were D-Limonene and 1-Methyl-4-(1-methyl ethyl)-1,4-cyclohexadiene (γ-Terpinen), the two constituents represented 80.96%、90.74% and 76.93% of the total content of volatile oil in HP PCR-FA, PCR and FA, respectively.
53 volatile constituents of OFVA were identified, representing 90.87 % of the total content.58 volatile constituents of OFVT were identified, representing 89.04% of the total content.53 volatile constituents of OFVL were identified, representing 84.38% of the total content.57 volatile constituents of OFVS were identified, representing 89.73% of the total content. The results showed that there were 33 common volatile constituents among OFVA, OFVT, OFVL and OFVS. The major volatile constituents in OFVA, OFVT, OFVL and OFVS were 5-Hexyldihydro-2(3H)-furanone(γ-Decalactone), (E)-4-(2,6,6-Trimethyl-1-cyclohexen-1-yl)-3-buten-2-one((E)-β-Ionone),4-(2,6,6-Trimethyl-1-cyclohexen-1-yl)-2-butanone(Dihydro-β-ionone) and 4-(2,6,6-Trimethyl-1-cyclohexen-l-yl)-3-buten-2-ol(β-Ionol), the four constituents represented 35.84%、61.24%、29.5% and 50.53% of the total content of volatile oil in OFVA, OFVT, OFVL and OFVS, respectively.
金银花挥发油共鉴定出44种化合物,占挥发油总量的87.22%。金银藤挥发油共鉴定出39种化合物,占挥发油总量的94.54%。药对金银花-金银藤挥发油共鉴定出50种化合物,占挥发油总量的90.08%。药对金银花-金银藤挥发油中化学成分有32种来自金银花,33种来自金银藤,新产生了10种化学成分,三者的共有成分为25种。三者的主要成分均为十六烷酸和9,12-十八碳二烯酸乙酯,两者合计分别占药对金银花-金银藤、金银花、金银藤挥发油含量的71.32%、57.33%和84.88%。
陈皮挥发油共鉴定出45种化合物,占挥发油总量的99.02%。枳壳挥发油共鉴定出52种化合物,占挥发油总量的98.27%。药对陈皮-枳壳挥发油共鉴定出63种化合物,占挥发油总量的97.98%。药对陈皮-枳壳挥发油中化学成分有34种来自陈皮,42种来自枳壳,新产生了16种化学成分,三者的共有成分为29种。三者的主要成分均为D-柠檬烯和γ-松油烯,两者合计分别占药对陈皮-枳壳、陈皮、枳壳挥发油含量的80.96%、90.74%和76.93%。
丹桂挥发油共鉴定出53种化合物,占挥发油总量的90.87%。金桂挥发油共鉴定出58种化合物,占挥发油总量的89.04%。银桂挥发油共鉴定出53种化合物,占挥发油总量的84.38%。四季桂挥发油共鉴定出57种化合物,占挥发油总量的89.73%。四者的共有成分为33种,主要成分均为γ-癸内酯,(E)-β-紫罗兰酮,β-二氢紫罗兰酮,β-紫罗兰醇,这四个化合物合计分别占丹桂、金桂、银桂和四季桂挥发油含量的35.84%、61.24%、29.5%和50.53%。
Volatile oil is one of important constituents in traditional Chinese medicine (TCM) and plants, and it has great important pharmacological effects. Volatile oil is a very complex system and contains tens and even hundreds of chemical constituents. The analysis of volatile oil is usually conducted by GC-MS, and the GC-MS data from volatile oil, however, often involves many overlapped and embedded peaks. These overlapped and embedded peaks bring many difficulties when carrying out quantitative and qualitative analysis. With the rapid development of some chemometric multi-resolution techniques such as heuristic evolving latent projections(HELP), it is possible to completely conduct the qualitative and quantitative analysis of volatile oil by the combined information on separation and identification from chromatography and spectrometry. In this study, volatile oil was the research object, and the volatile oils from herbal pair (HP) flos lonicerae-caulis lonicerae(FL-CL) and its single herbs, pericarpium citri reticulatae-fructus aurantii(PCR-FA) and its single herbs, and four osmanthus fragrans species, osmanthus fragrans var. aurantiacus (OFVA), osmanthus fragrans var. thunbergii (OFVT), osmanthus fragrans var. latifolius (OFVL) and osmanthus fragrans var. semperflorens(OFVS) were firstly separated and detected with gas chromatography-mass spectrometry(GC-MS), and then chemometric resolution methods and temperature-programmed retention indices(PTRIs) were employed to carry out the qualitative and quantitative analysis for volatile oils.
44 volatile constituents of FL were identified, representing 87.22% of the total content.39 volatile constituents of CL were identified, representing 94.54% of the total content.50 volatile constituents of HP FL-CL were identified, representing 90.08% of the total content. The results showed that there were 32 common volatile constituents between HP FL-CL and single herb FL, and 33 common volatile constituents between HP FL-CL and single herb CL, and 25 common volatile constituents among FL, CL and HP FL-CL. The results also showed that 10 new constituents appeared in the volatile oil of HP FL-CL. The major volatile constituents in FL, CL and HP FL-CL were n-Hexadecanoic acid and 9,12-Octadecadienoic acid, ethyl ester, the two constituents represented 71.32%、57.33% and 84.88% of the total content of volatile oil in HP FL-CL, FL and CL, respectively.
45 volatile constituents of PCR were identified, representing 99.02 % of the total content.52 volatile constituents of FA were identified, representing 98.27% of the total content.63 volatile constituents of HP PCR-FA were identified, representing 97.98% of the total content. The results showed that there were 34 common volatile constituents between HP PCR-FA and single herb PCR, and 42 common volatile constituents between HP PCR-FA and single herb FA, and 29 common volatile constituents among PCR, FA and HP PCR-FA. The results also showed that 16 new constituents appeared in the volatile oil of HP PCR-FA. The major volatile constituents in PCR, FA and HP PCR-FA were D-Limonene and 1-Methyl-4-(1-methyl ethyl)-1,4-cyclohexadiene (γ-Terpinen), the two constituents represented 80.96%、90.74% and 76.93% of the total content of volatile oil in HP PCR-FA, PCR and FA, respectively.
53 volatile constituents of OFVA were identified, representing 90.87 % of the total content.58 volatile constituents of OFVT were identified, representing 89.04% of the total content.53 volatile constituents of OFVL were identified, representing 84.38% of the total content.57 volatile constituents of OFVS were identified, representing 89.73% of the total content. The results showed that there were 33 common volatile constituents among OFVA, OFVT, OFVL and OFVS. The major volatile constituents in OFVA, OFVT, OFVL and OFVS were 5-Hexyldihydro-2(3H)-furanone(γ-Decalactone), (E)-4-(2,6,6-Trimethyl-1-cyclohexen-1-yl)-3-buten-2-one((E)-β-Ionone),4-(2,6,6-Trimethyl-1-cyclohexen-1-yl)-2-butanone(Dihydro-β-ionone) and 4-(2,6,6-Trimethyl-1-cyclohexen-l-yl)-3-buten-2-ol(β-Ionol), the four constituents represented 35.84%、61.24%、29.5% and 50.53% of the total content of volatile oil in OFVA, OFVT, OFVL and OFVS, respectively.
引文
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