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HS-SPME-GC-MS结合化学计量法分析刺五加不同部位的挥发性成分

何嘉伟 江汉美 黄振阳 曾格格 戴全武 刘天琪 韩蔓

何嘉伟, 江汉美, 黄振阳, 曾格格, 戴全武, 刘天琪, 韩蔓. HS-SPME-GC-MS结合化学计量法分析刺五加不同部位的挥发性成分[J]. 南京中医药大学学报, 2023, 39(2): 146-156. doi: 10.14148/j.issn.1672-0482.2023.0146
引用本文: 何嘉伟, 江汉美, 黄振阳, 曾格格, 戴全武, 刘天琪, 韩蔓. HS-SPME-GC-MS结合化学计量法分析刺五加不同部位的挥发性成分[J]. 南京中医药大学学报, 2023, 39(2): 146-156. doi: 10.14148/j.issn.1672-0482.2023.0146
HE Jia-wei, JIANG Han-mei, HUANG Zhen-yang, ZENG Ge-ge, DAI Quan-wu, LIU Tian-qi, HAN Man. Analysis of the Volatile Components of Different Parts of Acanthopanax Senticosus by HS-SPME-GC-MS Combined with Chemometric Methods[J]. Journal of Nanjing University of traditional Chinese Medicine, 2023, 39(2): 146-156. doi: 10.14148/j.issn.1672-0482.2023.0146
Citation: HE Jia-wei, JIANG Han-mei, HUANG Zhen-yang, ZENG Ge-ge, DAI Quan-wu, LIU Tian-qi, HAN Man. Analysis of the Volatile Components of Different Parts of Acanthopanax Senticosus by HS-SPME-GC-MS Combined with Chemometric Methods[J]. Journal of Nanjing University of traditional Chinese Medicine, 2023, 39(2): 146-156. doi: 10.14148/j.issn.1672-0482.2023.0146

HS-SPME-GC-MS结合化学计量法分析刺五加不同部位的挥发性成分

doi: 10.14148/j.issn.1672-0482.2023.0146
基金项目: 

湖北省技术创新专项重大项目 2016ACA146

详细信息
    作者简介:

    何嘉伟, 男, 硕士研究生, E-mail: jw03061713@163.com

    通讯作者:

    江汉美, 女, 教授, 主要从事中药物质基础及其作用机制研究, E-mail: 13807186811@163.com

  • 中图分类号: R284

Analysis of the Volatile Components of Different Parts of Acanthopanax Senticosus by HS-SPME-GC-MS Combined with Chemometric Methods

  • 摘要:   目的  对刺五加不同部位的挥发性成分进行比较分析, 为其后续的临床应用及开发提供科学参考。  方法  采用顶空固相微萃取-气相色谱-质谱联用法(HS-SPME-GC-MS), 提取分析刺五加各部位样品的挥发性成分, 用峰面积归一化法测定和比对各成分的相对含量, 并结合主成分分析(PCA)和聚类分析(HCA)方法分析其成分的差异。  结果  从刺五加各部位样品中共鉴定出167种挥发性成分, 根、皮、茎、叶、果分别鉴定出71、61、59、48、54种挥发性成分, 主要以烯类和醇类化合物为主。5个部位有10个共有成分, 包括萜品油烯、β-石竹烯、α-律草烯等。HCA分析结果将刺五加根、果聚为一类, 皮、叶聚为一类, 茎单独一类; PCA综合得分依次为根、茎、果、叶、皮。  结论  刺五加各部位挥发性成分的种类和含量均有差异, 为刺五加非常规药用部位的药食两用深入开发利用提供科学依据。

     

  • 图  1  各因素对刺五加挥发性成分萃取效果的影响

    Figure  1.  Effect of various factors on the extraction effect of volatile components of Acanthopanax senticosus

    图  2  刺五加不同部位挥发性成分总离子流图

    注: A.根; B.皮; C.茎; D.叶; E.果

    Figure  2.  Total ion flow diagram of volatile components in different parts of Acanthopanax senticosu

    图  3  刺五加不同部位挥发性成分种类差异图

    注:AS-R. 根;AS-V. 皮;AS-S. 茎;AS-L. 叶;AS-F. 果

    Figure  3.  Differences in the types of volatile components in different parts of Acanthopanax senticosus

    图  4  刺五加不同部位挥发性成分Venn图

    注:AS-R. 根;AS-V. 皮;AS-S. 茎;AS-L. 叶;AS-F. 果

    Figure  4.  Venn map of volatile components in different parts of Acanthopanax senticosus

    图  5  刺五加不同部位挥发性成分聚类热图

    注:AS-R. 根;AS-V. 皮;AS-S. 茎;AS-L. 叶;AS-F. 果

    Figure  5.  Cluster heat map of volatile components in different parts of Acanthopanax senticosus

    图  6  刺五加不同部位挥发性成分PCA散点图

    注: AS-R. 根;AS-V. 皮;AS-S. 茎;AS-L. 叶;AS-F. 果

    Figure  6.  PCA scatter plot of volatile components in different parts of Acanthopanax senticosus

    表  1  刺五加不同部位的挥发性成分及相对含量

    Table  1.   Volatile components and relative contents in different parts of Acanthopanax senticosus

    序号 中文名 英文名 分子式 相对含量/%
    1 正十一烷 Undecane C11H24 0.94 - - - -
    2 正十二烷 Dodecane C12H26 6.01 - - - -
    3 6, 7-二羟基香豆素 Esculetin C9H6O4 - 0.18 - - -
    4 萜品油烯 Terpinolene C10H16 1.62 1.10 0.62 2.50 8.13
    5 2, 6, 10-三甲基十二烷 Farnesane C15H32 0.72 - - - -
    6 3-甲基十一烷 3-Methylundecane C12H26 0.62 - - - -
    7 反, 反-2, 4-庚二烯醛 2, 4-Heptadienal C7H10O - - - 0.24 -
    8 环五聚二甲基硅氧烷 Decamethylcyclopentasiloxane C10H30O5Si5 - - - - 0.11
    9 1-乙基环己醇 1-Ethylcyclohexan-1-ol C8H16O 0.55 - - - -
    10 (-)-顺式-桃金娘烷醇 (-)-cis-Myrtanol C10H18O - 0.96 - - -
    11 5-乙基癸烷 5-Ethyldecane C12H26 0.64 - - - -
    12 3-辛烯-2-酮 3-Octen-2-one C8H14O - - 0.11 - -
    13 4-异丙烯基甲苯 4, α-Dimethylstyrene C10H12 - - 0.33 - 0.57
    14 4-乙基癸烷 4-Ethyldecane C12H26 0.37 - - - -
    15 5-甲基-十一烷 5-Methylundecane C12H26 0.47 - - - -
    16 2-甲基-1-苯基丙烯 2-Methyl-1-phenylpropene C10H12 - 0.23 - - -
    17 2-己基-1-辛醇 2-Hexyloctan-1-ol C14H30O 0.13 - - - -
    18 4-侧柏醇 Sabinene hydrate C10H18O - - 0.42 0.26 1.5
    19 乙酸 Hexanoic acid C6H12O2 3.34 - 3.42 0.23 1.47
    20 油酸 Oleic acid C18H34O2 0.38 - - - -
    21 异蒲勒醇 Isopulegol C10H18O - 0.17 - - -
    22 2-壬酮 2-Nonanon C9H18O - - - - 0.1
    23 壬醛 Nonanal C9H18O 2.26 - 0.42 - -
    24 芳樟醇 Linalool C10H18O - 1.43 - 1.19 1.22
    25 3-亚甲基十一烷 3-Methylideneundecane C12H24 0.22 - - - -
    27 硬脂酸苯酯 Phenyl stearate C24H40O2 - 0.16 - - -
    28 苯甲醇 Benzyl alcohol C7H8O - - - 0.15 0.17
    29 1-癸烯 1-Decene C10H20 - 0.28 - - -
    30 (-)-α-侧柏酮 (-)-α-Thujone C10H16O - - 0.28 - -
    32 植物醇 Phytol C20H40O 0.11 - - - -
    33 3, 5-辛二烯-2-酮 3, 5-Octadien-2-one C8H12O - - - 0.16 -
    34 白菖醇 6-epi-Shyobunol C15H26O 0.21 - - - -
    35 6-甲基-5-庚烯-2-醇 Sulcatol C8H16O - - - 0.5 -
    36 龙脑烯醛 (R)-α-Campholenaldehyde C10H16O - 0.29 0.59 - 0.19
    37 (-)-补身醇 Drimenol C15H26O 0.12 - - - -
    39 (-)-反式一松香芹醇 (-)-trans-Pinocarveol C10H16O - 0.38 0.61 - 0.23
    40 (1R)-(+)-诺蒎酮 (1R)-(+)-Nopinone C9H14O - - - 0.26 -
    41 4-(1-甲基乙基)环己醇 4-Isopropylcyclohexanol C9H18O - - - - 0.32
    42 樟脑 Camphor C10H16O 1.36 - - - 0.25
    43 异薄荷酮 Isomenthone C10H18O - - - 0.82 -
    44 异橙花醛 Isoneral C10H16O - 0.28 - - -
    45 反式马鞭草酚 trans-Verbenol C10H16O - - 0.41 - -
    46 α-环氧蒎烷 α-Pinene oxide C10H16O - 0.62 - - -
    47 萜品烯 4-Terpineol C10H18O 2.38 1.28 0.72 1.24 5.4
    48 反式-2-壬烯醛 trans-2-Nonenal C9H16O 0.75 - - - -
    49 匹诺酮 Pinocarvone C10H14O - - 0.27 - -
    50 螺内酯 Spironolactone C24H32O4S - 0.17 - - -
    51 苯乙醇 2-Phenylethanol C8H10O - - - - 0.69
    52 薄荷脑 2-Isopropyl-5-methylcyclohexanol C10H20O 1.36 - - 12.75 -
    53 L-薄荷醇 L-Menthol C10H20O - 0.61 0.38 - -
    54 冰片 Borneol C10H18O 0.93 0.28 0.1 - 0.24
    55 4-烯丙基苯甲醚 Estragole C10H12O 6.86 0.62 1.88 0.47 4.04
    57 十三烷 Tridecane C13H28 2.97 - - - -
    58 α-松油醇 α-Terpineol C10H18O - 0.85 - 0.15 0.99
    59 5-异丙基双环[3.1.0]己烷-2-酮 1-Propan-2-ylbicyclo[3.1.0]hexan-4-one C9H14O - - 0.77 - -
    60 2-异丙基-5-甲基茴香醚 Thymyl methyl ether C11H16O 0.53 - - - -
    61 桃金娘烯醛 Myrtenal C10H14O - 0.19 0.42 - -
    62 1, 3, 3-三甲基-2-乙烯基环己烯 1, 3, 3-Trimethyl-2-vinyl-1-cyclohexene C11H18 - - - - 0.67
    63 1-溴十八烷 1-Bromooctadecane C18H37Br 0.32 - - - -
    64 三甲基苯甲醇 2-(4-Methylphenyl)propan-2-ol C10H14O - 0.2 0.57 - 0.48
    65 乙酸芳樟酯 Linalyl acetate C12H20O2 - - - 0.46 -
    66 β-环柠檬醛 β-Cyclocitral C10H16O - - - 0.19 -
    67 4-异丙基环己-2-烯-1-酮 4-(1-Methylethyl)-2-cyclohexen-1-one C9H14O - - - - 0.12
    68 7-甲基十七烷 7-Methylheptadecane C18H38 0.15 - - - -
    69 邻硝基苯十二烷醚 1-Dodecoxy-2-nitrobenzene C18H29NO3 0.24 - - - -
    70 (1R, 5R)-rel-香芹醇 cis-Carveol C10H16O - 0.25 0.38 - -
    71 优葛缕酮 Eucarvone C10H14O - - - - 0.42
    72 薄荷醛 3-p-Menthen-7-al C10H16O 0.73 - - - -
    73 α-菖蒲醇 α-acorenol C15H26O 0.25 0.16 - - 0.12
    74 马鞭草烯醇 (S)-(-)-Verbenone C10H14O - - 0.29 - -
    75 乙酸龙脑酯 Bornyl acetate C12H20O2 1.78 - - - -
    76 δ-榄香烯 δ-Elemene C15H24 - 3.58 0.32 1.99 2.58
    77 4-异丙基苯甲醛 Cuminaldehyde C10H12O 1.24 - - - -
    78 (-)-α-荜澄茄油烯 (-)-α-Cubebene C15H24 - - 3.16 0.45 -
    79 正戊基2-呋喃酮 2-Hexanoylfuran C10H14O2 - 0.57 - - -
    80 α-长叶蒎烯 α-Longipinene C15H24 - 5.12 0.7 - -
    81 3, 5-二甲氧基甲苯 3, 5-Dimethoxytoluene C9H12O2 - - - - 1.88
    82 黄樟素 Safrole C10H10O2 - - - - 1.84
    83 异黄樟素 Isosafrole C10H10O2 - 0.24 - - -
    84 胡椒酮 Piperitone C10H16O - - - 1.63 -
    85 茴香脑 Anethole C10H12O 21.08 - - - -
    86 雪松烯 Cedrene C15H24 0.4 1.01 - - 0.44
    87 正十四烷 Tetradecane C14H30 - - 1.08 - -
    88 (-)-α-蒎烯 α-Copaene C15H24 1.66 0.67 2.23 0.85 1.15
    89 (+)-1, 7-二表-α-雪松烯 Di-epi-α-cedrene C15H24 - 0.2 - - -
    90 α-愈创木烯 α-Guaiene C15H24 - - 0.5 - -
    91 (+)-香橙烯 Aromandendrene C15H24 - - - - 2.01
    92 表蓝桉醇 Epiglobulol C15H26O - - 0.27 - -
    93 2, 5-十八碳二炔酸甲酯 Methyl octadeca-2, 5-diynoate C19H30O2 - 0.2 - - -
    94 巴伦西亚橘烯 (+)-Valencene C15H24 2.72 - - - -
    95 β-榄香烯 β-Elemene C15H24 - 3.28 2.7 3.6 1.18
    96 肉桂醛 Cinnamaldehyde C9H8O - 1.96 - - 2.2
    97 (-)-α-雪松烯 (-)-α-Cedrene C15H24 2.3 - - - -
    98 3-吡啶丙烯酸乙酯 Ethyl 3-pyridineacrylate C10H11NO2 - - 0.54 - -
    99 毕澄茄烯 β-Cubebene C15H24 - - 0.22 0.59 -
    100 β-石竹烯 Caryophyllene C15H24 4.23 5.78 5.22 7.52 7
    101 马兜铃-9-烯 (-)-Aristolene C15H24 - - - 0.62 0.4
    102 香树烯 Aromandendrene C15H24 0.85 1.77 0.61 0.13 -
    103 E-β-金合欢烯 cis-β-Farnesene C15H24 0.79 2.8 5.14 4.78 13.74
    104 正十五烷 Pentadecane C15H32 0.52 - 1.5 - -
    105 去氢香树烯 Dehydro-Aromadendrene C15H22 - 0.34 - - -
    106 α-律草烯 Humulene C15H24 1.15 3.39 2.76 5.52 3.25
    107 γ-依兰油烯 γ-Muurolene C15H24 - 2.1 2.91 2.92 2.28
    108 甲基丁香酚 O-methyleugenol C11H14O2 0.19 0.41 - - -
    109 反式-α-香柑油烯 trans-α-Bergamotene C15H24 - - - - 0.83
    110 α-姜黄烯 α-Curcumene C15H22 - 3.6 14.75 0.7 0.65
    111 β-芹子烯 β-Selinene C15H24 6.12 2.61 - 2.85 4.95
    112 α-芹子烯 α-Selinene C15H24 1.88 - - - -
    113 β-红没药烯 β-Bisabolene C15H24 - 12.74 4.38 9.51 10.71
    114 香叶基丙酮 Geranylacetone C13H22O 0.17 - - 0.13 -
    115 β-杜松烯 β-Cadinene C15H24 2.13 2.56 9.57 2.25 1.64
    116 倍半萜桧烯 Sesquisabinene C15H24 - 1.22 2.26 1.97 -
    117 荜澄茄油烯 Cubenene C15H24 0.29 - 1.64 - -
    118 α-依兰油烯 α-Muurolene C15H24 0.42 - - 0.15 0.19
    119 佛术烯 (+)-Valencene C15H24 - 1.02 - - -
    120 荜澄茄醇 Cubebol C15H26O 0.13 - 1.96 - -
    121 正十六烷 Hexadecane C16H34 0.13 - - - -
    122 氯代十八烷 1-Chlorooctadecane C18H37Cl - - 0.43 - -
    123 异戊酸香叶酯 Geranyl isovalerate C15H26O2 - 0.39 - - -
    124 香草醛乳糖苷 Vanillin lactoside C20H28O13 0.18 - - - -
    125 β-紫罗兰酮 β-Ionone C13H20O - - - 1.05 -
    126 β-愈创木烯 β-Guaiene C15H24 - - - - 0.14
    127 9-甲氧基菖蒲烯 9-Methoxycalamenene C16H24O - 0.21 0.33 - 0.16
    128 13, 14-二氢-15(R)-前列腺素E1 13, 14-Dihydro-15(R)-Prostaglandin E1 C20H36O5 0.23 - - - -
    129 瑞香[草]氫醌 p-Cymene-2, 5-diol C10H14O2 0.12 - - - -
    130 正三十七醇 1-Heptatriacotanol C37H76O - - 0.16 - 0.22
    131 异丁香酚甲醚 Isomethyleugenol C11H14O2 - 0.33 - - -
    132 橙花叔醇 Nerolidol C15H26O - - 1.59 0.14 -
    133 肉豆蔻醚 Myristicin C11H12O3 - 0.83 - - 0.12
    134 二苯并呋喃 Dibenzofuran C12H8O 0.15 - - - -
    135 4(15), 5, 10(14)-大根香叶三烯-1-醇 4(15), 5, 10(14)-Germacratrien-1-ol C15H24O - 0.8 1.55 1.3 0.37
    136 2-反式十八碳烯-1-醇 E-2-Octadecadecen-1-ol C18H36O 0.14 - - - -
    137 正十七烷 Heptadecane C17H36 0.39 - 1.94 0.41 -
    138 美他帕明 Metapramine C16H18N2 - 0.89 - - -
    139 桉油烯醇 10'-Apocarotenal C15H24O 0.13 6.03 3.49 5.81 0.62
    140 异匙叶桉油烯醇 Isospathulenol C15H24O - - 0.35 5.97 3.66
    141 环氧马兜铃烯 Aristolene epoxide C15H24O - 0.4 1.33 0.82 0.46
    142 环氧化蛇麻烯Ⅱ (1R, 3Z, 7Z, 11S)-1, 5, 5, 8-Tetramethyl-12-oxabicyclo[9.1.0]dodeca-3, 7-diene C15H24O - 0.29 0.39 0.47 0.12
    143 (-)-蓝桉醇 (-)-Globulol C15H26O - - - - 0.17
    144 异水菖蒲酮 Isoshyobunone C15H24O - 0.33 0.35 - -
    145 异香树烯环氧化物 Isoaromadendrene epoxide C15H24O - - 0.75 0.24 -
    146 T-杜松醇 T-cadino C15H26O - - 0.69 - -
    147 红没药醇氧化物 Bisabolol oxide B C15H26O2 - 7.62 - - -
    148 邻苯二甲酸二乙酯 Diethyl phthalate C12H14O4 0.3 - - - -
    149 (-)-愈创醇 Guaiol C15H26O - 1.56 - - -
    150 百秋李醇 Patchouli alcohol C15H26O 0.1 - - - -
    151 氧化喇叭烯 Ledene oxide-(Ⅰ) C15H24O - - 0.35 - -
    152 2, 6, 10-三甲基十四烷 2, 6, 10-Trimethyltetradecane C17H36 0.1 - - - -
    153 红没药醇 α-Bisabolol C15H26O - 8.24 0.3 8.15 2.82
    154 石竹素 (-)-Caryophyllene oxide C15H24O 0.25 0.16 1.88 1.33 0.53
    155 韦得醇 Methyl 4-heptylbenzoate C15H22O2 - - - - 0.27
    156 金合欢醇 Farnesol C15H26O - 0.13 - - -
    157 2, 6-二氨基庚二酸 2, 6-Diaminopimelic acid C7H14N2O4 0.29 - - - -
    158 Z-亚丁基苯酞 Z-Butylidenephthalide C12H14O2 0.83 - - - -
    159 3-丁基-1(3H)-异苯并呋喃酮 3-Butylisobenzofuran-1(3H)-one C12H14O2 1.23 - - - -
    160 西松烯 Cembrene C20H32 - 0.24 0.38 0.4 -
    161 α-香附酮 α-Cyperone C15H22O2 0.17 - - - -
    162 植酮 Phytone C18H36O - - - 0.17 -
    163 E-藁本内酯 E-ligustilide C12H14O2 2.39 - - - -
    164 新蛇床内酯 Neocnidilide C12H18O2 0.66 - - - -
    165 川芎内酯 Senkyunolide C12H16O2 1 - - - -
    166 海松-8(14), 15-二烯 Pimara-8(14), 15-diene C20H32 0.69 - - - -
    167 棕榈酸 Palmitic acid C16H32O2 0.27 - - - -
    注: -表示目前分析方法下无法检出。
    下载: 导出CSV

    表  2  刺五加不同部位挥发性成分的种类及相对含量(%)

    Table  2.   Types and relative contents of volatile components in different parts of Acanthopanax senticosus(%)

    类别
    数量 相对含量 数量 相对含量 数量 相对含量 数量 相对含量 数量 相对含量
    烷类 15 14.57 1 0.62 4 4.95 1 0.41 1 0.11
    烯类 19 29.63 26 57.82 24 63.19 22 51.83 23 68.08
    醛类 4 4.98 4 2.72 3 1.43 2 0.43 2 2.39
    醇类 10 1.87 14 21.77 15 13.01 10 23.62 16 13.85
    酮类 3 1.57 2 0.90 5 1.78 7 4.22 3 0.64
    酯类 5 6.13 7 0.92 1 0.54 1 0.46 0 0
    酚类 1 0.19 1 0.41 1 0.41 0 0 0 0
    醚类 3 7.63 3 1.78 1 1.88 1 0.47 2 4.16
    芳香族类 4 24.73 3 0.70 2 0.43 1 12.75 5 4.78
    氧化物类 1 0.25 2 7.78 2 2.63 2 1.57 1 0.53
    有机酸类 4 4.28 0 0 1 3.42 1 0.23 1 1.47
    其他类 5 1.51 1 0.89 0 0 0 0 0 0
    下载: 导出CSV

    表  3  主成分的特征值及其贡献率

    Table  3.   The eigenvalues of principal components and their contribution rates

    主成分 初始特征值
    合计 方差/% 累积/%
    1 2.50 50.04 50.04
    2 1.00 20.06 70.10
    3 0.71 14.25 84.35
    4 0.43 8.63 92.98
    5 0.35 7.02 100.00
    下载: 导出CSV

    表  4  刺五加不同部位挥发性成分因子得分、主成分得分和综合得分

    Table  4.   Factor scores, principal component scores and composite scores of volatile components in different parts of Acanthopanax senticosus

    部位 因子得分 主成分得分 综合得分(Y)
    F1 F2 Y1 Y2
    1.04 0.16 1.64 0.26 1.25
    -0.60 -0.91 -0.95 -1.44 -1.09
    -0.61 1.02 -0.96 1.62 -0.22
    -0.60 -0.43 -0.95 -0.68 -0.87
    -0.35 -0.61 -0.56 -0.97 -0.67
    下载: 导出CSV
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  • 收稿日期:  2022-05-18
  • 网络出版日期:  2023-02-17
  • 发布日期:  2023-02-10

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