林业科学 ›› 2021, Vol. 57 ›› Issue (2): 150-159.doi: 10.11707/j.1001-7488.20210215
王茜,尚丽丽,晏婷婷,陈媛,付跃进,李改云*
收稿日期:
2018-12-19
出版日期:
2021-02-25
发布日期:
2021-03-29
通讯作者:
李改云
基金资助:
Qian Wang,Lili Shang,Tingting Yan,Yuan Chen,Yuejin Fu,Gaiyun Li*
Received:
2018-12-19
Online:
2021-02-25
Published:
2021-03-29
Contact:
Gaiyun Li
摘要:
目的: 针对不同地区所产沉香品质差别较大以及传统沉香产地鉴别主要依赖经验判断等问题,研究不同产地沉香的高效液相色谱(HPLC)指纹特征,探讨色谱指纹分析技术对沉香产地溯源的可行性,为沉香资源品质评价和原产地保护提供科学依据。方法: 以36批次来自3个不同产地的沉香为研究对象,优化高效液相色谱分离条件,基于"中药色谱指纹图谱相似度评价系统"获得色谱峰保留时间、峰面积信息,筛选不同产地沉香的高效液相色谱指纹图谱,并利用指纹特征峰变量进行主成分分析(PCA)和正交偏最小二乘判别分析(OPLS-DA),建立沉香产地判别方法。结果: 不同产地沉香高效液相色谱指纹图谱的85个特征峰变量分析发现,莞香系沉香的色酮种类最多,相对含量最高;星洲系沉香的沉香四醇色谱峰极高,其余色酮相对含量较低;惠安系沉香的色酮种类较多,相对含量较莞香系稍低,较星洲系稍高,依其产地地理位置分布,在3个产地中体现出一定过渡性;主成分分析显示,样品基本上可依据产地不同聚合成3类;正交偏最小二乘判别分析对训练集和检验集样品产地的判别正确率均为100%。结论: 不同产地沉香2-(2-苯乙基)色酮类成分的组成和含量存在较大差异,显示出一定地域性,利用高效液相色谱指纹图谱结合正交偏最小二乘判别分析可判别沉香产地,为濒危珍贵沉香的产地溯源提供一种新的鉴别方法。
中图分类号:
王茜,尚丽丽,晏婷婷,陈媛,付跃进,李改云. 不同产地沉香的高效液相色谱指纹特征[J]. 林业科学, 2021, 57(2): 150-159.
Qian Wang,Lili Shang,Tingting Yan,Yuan Chen,Yuejin Fu,Gaiyun Li. HPLC Fingerprint Characteristics of Agarwood from Different Origins[J]. Scientia Silvae Sinicae, 2021, 57(2): 150-159.
表1
OPLS-DA模型筛选得到的34个不同产地间标志性差异化合物色谱峰"
序号 No. | 色谱峰编号 ID of chromatogram peaks | 保留时间 Retention time/min | 前体离子 [M+H]+/(m/z)Protonated precursorion/(m/z) | 二级质谱碎片离子 MS/MS framents ions | 推荐色酮化合物 Proposed compound | 重要性值 VIP value |
1 | 43 | 66.777 | 281.194 9 | 121 | 2-[2-(4-甲氧基)苯乙基]色酮2-[2-(4-Methoxy)phenylethyl]chromone | 1.896 1 |
2 | 1 | 6.913 | 365.114 1 | 347, 329 | 沉香色酮A Aquilarone A | 1.788 0 |
3 | 29 | 42.990 | 297.112 0 | 137 | 2-[2-(3-甲氧基-4-羟基苯基)乙基]色酮2-[2-(3-Methoxy-4-hydroxyphenyl)ethyl]chromone | 1.436 7 |
4 | 10 | 19.770 | 331.117 7 | 313, 285 | 四氢色酮L Tetrahydrochromone L | 1.379 4 |
5 | 20 | 26.740 | 283.096 6 | 255 | Oxidoagarochromone A | 1.286 0 |
6 | 46 | 71.887 | 281.116 3 | 190, 91 | 6-甲氧基-2-(2-苯乙基)色酮6-Methoxy-2-(2-phenylethyl)chromone | 1.276 4 |
7 | 16 | 23.488 | 329.100 3 | 301, 137 | (5α, 6α, 7α, 8β)-5, 6, 7, 8-二环氧-2-[2-(3-羟基-4-甲氧基苯基)乙基]-5, 6, 7, 8-四氢色酮(5α, 6α, 7α, 8β)-5, 6, 7, 8-Diepoxy-2-[2-(3-hydroxy-4-methoxyphenyl)ethyl]-5, 6, 7, 8-tetrahydrochromone | 1.246 5 |
8 | M | 15.986 | 319.119 4 | 301, 283 | 沉香色酮B Aquilarone B | 1.246 5 |
9 | 4 | 13.468 | 349.217 9 | 331, 313 | (5S, 6R, 7S)-5, 6, 7-三羟基-2-(3-羟基-4-甲氧基苯乙基)-5, 6, 7, 8-四氢色酮(5S, 6R, 7S)-5, 6, 7-Trihydroxy-2-(3-hydroxy-4-methoxyphenylethyl)-5, 6, 7, 8-tetrahydrochromone | 1.211 6 |
10 | e | 30.159 | 313.106 5 | 137 | 6-羟基-2-[2-(3-羟基-4-甲氧基)苯乙基]-色酮6-Hydroxy-2-[2-(3-hydroxy-4-methoxyl)phenylethyl]-chromone | 1.198 1 |
11 | 42 | 64.586 | 281.116 9 | 91 | 6-羟基-2-(2-苯乙基)色酮6-Hydroxy-2-(2-phenylethyl)chromone | 1.194 9 |
12 | C | 9.348 | 319.105 2 | 301, 283 | 5β, 6β, 7α, 8β-四羟基-2-(2-苯乙基)-5, 6, 7, 8-四氢色酮5β, 6β, 7α, 8β-Tetrahydroxy-2-(2-phenylethyl)-5, 6, 7, 8-tetarahydrochromone | 1.186 4 |
13 | H | 13.072 | 319.118 3 | 301, 283 | (5S, 6S, 7R)-5, 6, 7-三羟基-2-[2-(羟基苯基)乙基]-5, 6, 7, 8-四氢色酮(5S, 6S, 7R)-5, 6, 7-Trihydroxy-2-[2-(hydroxyphenyl)ethyl]-5, 6, 7, 8-tetrahydrochromone | 1.169 8 |
14 | O | 22.794 | 383.089 5 | 365, 347 | (5α, 6β, 7β, 8α)-8-氯-5, 6, 7-三羟基-2-[2-(3-羟基-4-甲氧基苯基)乙基]-5, 6, 7, 8-四氢色酮(5α, 6β, 7β, 8α)-8-Chloro-5, 6, 7-trihydroxy-2-[2-(3-hydroxy-4-methoxyphenyl)ethyl]-5, 6, 7, 8-tetrahydro-chromone | 1.168 8 |
15 | d | 12.172 | 349.128 1 | 331, 313 | (5S, 6R, 7R)-5, 6, 7-三羟基-2-[2-(3-羟基-4-甲氧基苯基)乙基]-5, 6, 7, 8-四氢色酮(5S, 6R, 7R)-5, 6, 7-Trihydroxy-2-[2-(3-hydroxy-4-methoxyphenyl)ethyl]-5, 6, 7, 8-tetrahydrochromone | 1.157 6 |
16 | 13 | 22.033 | 329.102 1 | 301 | Oxidoagarochromone C | 1.118 7 |
17 | J | 14.376 | 349.128 4 | 331, 313 | (5S, 6R, 7R, 8S)-2-[2-(4-甲氧基)苯乙基]-5, 6, 7, 8-四氢色酮(5S, 6R, 7R, 8S)-2-[2-(4-methoxy)phenylethyl]-5, 6, 7, 8-tetrahydrochromone | 1.102 1 |
18 | p | 76.687 | 297.082 3 | 121 | 6-甲氧基-2-[2-(4-羟基苯基)乙基]色酮6-Methoxy-2-[2-(4-hydroxyphenyl)ethyl]chromone | 1.101 1 |
19 | 6 | 17.324 | 347.111 4 | 329, 301 | 5, 6-环氧-7, 8-二羟基-2-[2-(3-羟基-4-甲氧基)苯乙基]-5, 6, 7, 8-四氢色酮5, 6-Edroxy-7, 8-dihydroxy-2-[2-(3-hydroxy-4-methoxy)phenylethyl]-5, 6, 7, 8-tetrahydrochromone | 1.100 4 |
20 | 37 | 53.731 | 313.105 8 | 121 | 5, 8-二环氧-2-[2-(4-甲氧基)苯乙基]色酮5, 8-Dihydroxy-2-[2-(4-methoxy)phenylethyl]chromone | 1.099 5 |
21 | N | 16.288 | 349.127 3 | 331, 313 | 沉香色酮C Aquilarone C | 1.086 1 |
22 | f | 30.615 | 313.106 2 | 285, 121 | Oxidoagarochromone B | 1.074 3 |
23 | D | 9.780 | 365.123 2 | 347, 330 | 5, 6, 7, 8-四羟基-2-(3-羟基-4-甲氧基苯乙基)-5, 6, 7, 8-四氢-4H-色烯-4-酮5, 6, 7, 8-Tetrahydroxy-2-(3-hydroxy-4-methoxyphenylethyl)-5, 6, 7, 8-tetarahydro-4H-chromen-4-one | 1.069 0 |
24 | F | 11.109 | 365.218 2 | 347, 329 | 5α, 6α, 7α, 8β-四羟基-2-[2-(3-羟基-4-甲氧基苯基)乙基]-5, 6, 7, 8-四氢色酮5α, 6α, 7α, 8β-Tetrahydroxy-2-[2-(3-hydroxy-4-methoxyphenyl)ethyl]-5, 6, 7, 8-tetarahydrochromone | 1.067 4 |
25 | i | 35.051 | 313.107 5 | 285 | 6, 8-二环氧-2-[2-(4-甲氧基)苯乙基]色酮6, 8-Dihydroxy-2-[2-(4-methoxy)phenylethyl]chromone | 1.061 9 |
26 | 3 | 11.704 | 349.128 9 | 331, 313 | 5α, 6β, 7β, 8α-四羟基-2-[2-(4-甲氧基苯基)乙基]-5, 6, 7, 8-四氢色酮5α, 6β, 7β, 8α-Tetrahydroxy-2-[2-(4-methoxyphenyl)ethyl]-5, 6, 7, 8-tetrahydrochromone | 1.050 0 |
27 | c | 11.338 | 365.296 8 | 347, 329 | 5α, 6β, 7β, 8α-四羟基-2-[2-(3-羟基-4-甲氧基苯基)乙基]-5, 6, 7, 8-四氢色酮5α, 6β, 7β, 8α-Tetrahydroxy-2-[2-(3-hydroxy-4-methoxyphenyl)ethyl]-5, 6, 7, 8-tetarahydrochromone | 1.049 8 |
28 | 7 | 17.728 | 347.113 0 | 329, 301 | 5α, 6α-环氧-7β, 8α, 3′-三羟基-4′-甲氧基- 2-(2-苯乙基)色酮5α, 6α-Epoxy-7β, 8α, 3′-trihydroxy-4′-methoxy- 2-(2-phenylethyl)chromone | 1.046 5 |
29 | 27 | 41.099 | 283.085 4 | 177, 107 | 6-羟基-2-[2-(2-羟基苯基)乙基]色酮6-Hydroxy-2-[2-(2-hydroxyphenyl)ethyl]chromone | 1.042 1 |
30 | 41 | 61.576 | 311.127 5 | 220, 91 | 6, 7-二甲氧基-2-(2-苯乙基)色酮6, 7-Dimethoxy-2-(2-phenylethyl)chromone | 1.040 2 |
31 | 24 | 33.069 | 329.102 5 | 137 | 6, 8-二环氧-2-[2-(3-羟基-4-甲氧基)苯乙基]-色酮6, 8-Dihydroxy-2-[2-(3-hydroxy-4-methoxyl)phenylethyl]-chromone | 1.019 0 |
32 | B | 8.249 | 365.795 7 | 347, 329 | 沉香色酮D Aquilarone D | 1.016 4 |
33 | a | 8.681 | 365.123 2 | 347, 329 | 沉香色酮E Aquilarone E | 1.014 3 |
34 | 34 | 48.754 | 327.121 8 | 137 | 6-甲氧基-2-[2-(3-羟基-4-甲氧基)苯乙基]色酮6-Methoxy-2-[2-(3-hydroxy-4-methoxy)phenylethyl]-chromone | 1.009 6 |
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