针捕集法、静态顶空法和水蒸气蒸馏法结合GC-MS对紫花地丁挥发性成分的比较
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摘要
目的:系统研究紫花地丁的挥发性成分,并比较针捕集法、静态顶空法和水蒸气蒸馏法在紫花地丁挥发性成分分析上的异同。方法:采用针捕集法、静态顶空法和水蒸气蒸馏法并结合GC-MS分别对紫花地丁的挥发性成分进行了分离和鉴定研究,首次使用填充了Tenax,Carbopack X和Carboxen 1000共3种吸附剂的捕集针,采用峰面积归一化法确定各成分的相对质量分数。结果:采用针捕集法从紫花地丁中共鉴定出挥发性成分112个,主要为中等挥发性的成分,以脂肪醛、酮、醇、单萜、倍半萜和芳香族类化合物为主。采用静态顶空法共从中鉴定出挥发性成分37个,主要为高挥发性成分;采用水蒸气蒸馏法共从中鉴定出挥发性成分78个,主要为低挥发性成分。采用这3种方法检出的共有挥发性成分只有13种。结论:该研究将为全面分析中药挥发性成分提供了新的研究方法,相对于静态顶空法和传统的水蒸气蒸馏法,针捕集法具有分析速度快、操作简单、富集效果好和灵敏度高等特点。这3种方法在分析挥发性成分类型上是互补的,不能相互替代。
Objective:To systemically investigate the volatile organic compounds(VOCs) of Viola yedoensis,and to compare the VOCs differences of V.yedoensis obtained by the needle trap,static headspace and hydrostillation methods.Method:The needle trap,static headspace and hydrostillation methods coupled with gas chromatography-mass spectrometer(GC-MS) were developed for isolation and identification of the VOCs in V.yedoensis.The relative content of each component was obtained by peak area normalization with a triple-bed needle packed with Tenax,Carbopack X and Carboxen 1000 sorbents.Result:The 112 compounds were trapped by using needle trap,mainly moderate volatile components,including aldehydes,ketones,alcohols,monoterpenes,sesquiterpenoids and aromatic compounds.The static headspace and hydrodistillation methods were allowed to obtain 37(mainly the high-volatile components) and 78 compounds(mainly low-volatile components),respectively.Only 13 common volatile components were detected in all these three methods.Conclusion:The results clearly demonstrated that the needle trap method is an alternative method for sampling VOCs of herbs,characterized by fast analysis,simple operation,good enrichment effect and high sensitivity.These three methods for VOCs analysis are complementary for each other.
Objective:To systemically investigate the volatile organic compounds(VOCs) of Viola yedoensis,and to compare the VOCs differences of V.yedoensis obtained by the needle trap,static headspace and hydrostillation methods.Method:The needle trap,static headspace and hydrostillation methods coupled with gas chromatography-mass spectrometer(GC-MS) were developed for isolation and identification of the VOCs in V.yedoensis.The relative content of each component was obtained by peak area normalization with a triple-bed needle packed with Tenax,Carbopack X and Carboxen 1000 sorbents.Result:The 112 compounds were trapped by using needle trap,mainly moderate volatile components,including aldehydes,ketones,alcohols,monoterpenes,sesquiterpenoids and aromatic compounds.The static headspace and hydrodistillation methods were allowed to obtain 37(mainly the high-volatile components) and 78 compounds(mainly low-volatile components),respectively.Only 13 common volatile components were detected in all these three methods.Conclusion:The results clearly demonstrated that the needle trap method is an alternative method for sampling VOCs of herbs,characterized by fast analysis,simple operation,good enrichment effect and high sensitivity.These three methods for VOCs analysis are complementary for each other.
引文
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[20]CAO G,LI Q,WU X,et al.Coupling needle-trap devices with comprehensive two-dimensional gas chromatography with high-resolution time-of-flight mass spectrometry to rapidly reveal the chemical transformation of volatile components from sulfur-fumigated ginseng[J].J Sep Sci,2015,38(7):1248-1253.
[21]QIN Y,PANG Y M,CHENG Z H.Needle trap device as a new sampling and preconcentration approach for volatile organic compounds of herbal medicines and its application to the analysis of volatile components in Viola tianschanica[J].Phytochem Anal,2016,27(6):364-374.
[22]Lord H L,ZHAN W,Pawliszyn J.Fundamentals and applications of needle trap devices,a critical review[J].Anal Chim Acta,2010,667:3-18.
[23]Prikryl P,Kubinec R,Jurdakova H,et al.Comparison of needle concentrator with SPME for GC determination of benzene,toluene,ethylbenzene,and xylenes in aqueous samples[J].Chromatographia,2006,64(1/2):65-70.
[2]DU D,CHENG Z,CHEN D.Anti-complement sesquiterpenes form Viola yedoensis[J].Fitoterapia,2015,101:73-79.
[3]曹捷,秦艳,尹成乐,等.紫花地丁化学成分及抗氧化活性研究[J].中国实验方剂学杂志,2013,19(21):77-81.
[4]孙艺方,杜利利,周乐,等.紫花地丁抗菌活性成分研究[J].中国中药杂志,2011,36(19):2666-2671.
[5]吴欢,占远,陈海芳,等.UHPLC-ESI-Q-TOF-MS/MS对紫花地丁中化学成分的快速表征[J].中国实验方剂学杂志,2016,22(24):70-75.
[6]杜冬生,程志红,陈道峰.紫花地丁中的抗补体生物碱类成分研究[J].中国中药杂志,2017,42(24):4794-4800.
[7]祁伟,董岩.紫花地丁挥发油化学成分分析及其抑菌作用研究[J].德州学院学报,2011,27(2):41-45.
[8]CHEN X,Kokubun T,Houghton P J,et al.Antibacterial activity of the Chinese traditional medicine,Zi Hua Di Ding[J].Phytother Res,2010,18(6):497-500.
[9]刘嘉,徐润生,程存归.两产地紫花地丁挥发油的化学成分研究[J].中成药,2009,31(10):1575-1577.
[10]何春兰,张刚平,王如意,等.HS-SPME-GC-MS和主成分分析红车轴草不同部位挥发油成分[J].中国实验方剂学杂志,2018,24(5):71-81.
[11]Raut J S,Karuppayil S M.A status review on the medicinal properties of essential oils[J].Ind Crop Prod,2014,62:250-264.
[12]魏长玲,郭宝林.紫苏叶挥发油的不同化学型及研究进展[J].中国中药杂志,2015,40(15):2937-2944.
[13]邓爱平,李颖,吴志涛,等.苍术化学成分和药理的研究进展[J].中国中药杂志,2016,41(21):3904-3913.
[14]杜旌畅,谢晓芳,熊亮,等.川芎挥发油的化学成分与药理活性研究进展[J].中国中药杂志,2016,41(23):4328-4333.
[15]Ormeno E,Goldstein A,Niinemets U.Extracting and trapping biogenic volatile organic compounds stored in plant species[J].Trends Anal Chem,2011,30(7):978-989.
[16]LI C,XU F,CHEN C,et al.Comparative analysis of two species of Asari Radix et Rhizoma by electronic nose,headspace GC-MS and chemometrics[J].J Pharm Biomed Anal,2013,85(11):231-238.
[17]Fernandez-Garcia E.Use of headspace sampling in the quantitative analysis of Artisanal spanish cheese aroma[J].J Agric Food Chem,1996,44(7):1833-1839.
[18]Kedziora K,Wasiak W.Extraction media used in needle trap devices-progress in development and application[J].J Chromatogr A,2017,1505:1-17.
[19]吴恒,吴雨松,朱玲超,等.Needle trap-GC-MS法分析云南不同产地薄荷的挥发性成分[J].云南大学学报:自然科学版,2015,37(2):265-271.
[20]CAO G,LI Q,WU X,et al.Coupling needle-trap devices with comprehensive two-dimensional gas chromatography with high-resolution time-of-flight mass spectrometry to rapidly reveal the chemical transformation of volatile components from sulfur-fumigated ginseng[J].J Sep Sci,2015,38(7):1248-1253.
[21]QIN Y,PANG Y M,CHENG Z H.Needle trap device as a new sampling and preconcentration approach for volatile organic compounds of herbal medicines and its application to the analysis of volatile components in Viola tianschanica[J].Phytochem Anal,2016,27(6):364-374.
[22]Lord H L,ZHAN W,Pawliszyn J.Fundamentals and applications of needle trap devices,a critical review[J].Anal Chim Acta,2010,667:3-18.
[23]Prikryl P,Kubinec R,Jurdakova H,et al.Comparison of needle concentrator with SPME for GC determination of benzene,toluene,ethylbenzene,and xylenes in aqueous samples[J].Chromatographia,2006,64(1/2):65-70.