基于GC-MS技术比较分析盐源与汉源花椒籽挥发油化学成分

doi:10.3864/j.issn.0578-1752.2025.23.019

中国农业科学 ›› 2025, Vol. 58 ›› Issue (23): 5057-5070.doi: 10.3864/j.issn.0578-1752.2025.23.019

基于GC-MS技术比较分析盐源与汉源花椒籽挥发油化学成分

张志淳¹^,²(), 何筱毅², 何成军², 辜冬琳², 钟恋², 苟琰², 高必兴², 耿昭²^,^*(), 李小红¹^,^*(), 陈斯恺³

¹ 成都大学食品与生物工程学院，成都 610106
² 四川省药品检验研究院（四川省医疗器械检测中心、四川养麝研究所）/国家药品监督管理局中成药质量评价重点实验室/工业和信息化部产业技术基础公共服务平台，成都 611731
³ 西南交通大学环境科学与工程学院，成都 611756

收稿日期:2025-07-18 接受日期:2025-10-29 出版日期:2025-12-01 发布日期:2025-12-09
通信作者:
耿昭，Tel：028-87877195；E-mail：gengzhao713@hotmail.com。
李小红，E-mail：lixiaohong136@126.com
联系方式: 张志淳，E-mail：lucky1022zy@163.com。
基金资助:
四川省自然科学基金(24NSFSC1280); 成都大学校级实验教学研究与改革项目(CDSYJG2022024)

Comparative Analysis of Volatile Oil Chemical Constituents from Zanthoxylum bungeanum Seeds in Yanyuan and Hanyuan Based on GC-MS Technology

ZHANG ZhiChun¹^,²(), HE XiaoYi², HE ChengJun², GU DongLin², ZHONG Lian², GOU Yan², GAO BiXing², GENG Zhao²^,^*(), LI XiaoHong¹^,^*(), CHEN SiKai³

¹ College of Food and Biological Engineering, Chengdu University, Chengdu 610106
² Sichuan Institute for Drug Control (Sichuan Testing Center of Medical Devices, Sichuan Institute of Musk Deer Breeding)/ Key Laboratory for Quality Evaluation of Traditional Chinese Medicine, Traditional Chinese Patent Medicine, The National Medical Products Administration/ Public Service Platforms for Industrial Technological Base, Ministry of Industry and Information Technology, Chengdu 611731
³ School of Environmental Science and Engineering, Southwest Jiaotong University, Chengdu 611756

Received:2025-07-18 Accepted:2025-10-29 Published:2025-12-01 Online:2025-12-09

摘要/Abstract

摘要：

【背景】花椒籽作为花椒加工副产物，含油量丰富，具有较高开发潜力，但常用作肥料或以废料形式丢弃，造成资源浪费。【目的】 为提升其利用价值，实现资源高效利用，本研究聚焦于不同产地花椒籽挥发油的关键特征，探究盐源与汉源两大代表性产地花椒籽挥发油中化学成分组成，分析其挥发油化学成分异同性及变化规律。【方法】采集四川省盐源县与汉源县花椒籽样品，采用水蒸气蒸馏法提取挥发油，运用气相色谱-质谱联用技术（GC-MS）进行成分鉴定。通过比对对照品、NIST数据库及文献数据综合分析鉴定挥发油成分，采用峰面积归一化法计算各成分相对含量。运用正交偏最小二乘判别分析（OPLS-DA），筛选具有产地判别能力的差异标志物。【结果】从13批样品中共鉴定出124种挥发性成分，其中醇类化合物28种，萜烯类化合物23种，醛类化合物20种，酮类化合物19种，酯类化合物13种，脂肪酸类5种，烯烃类3种，烷烃类2种，以及其他类别化合物（包括酚类、环醚类、噻唑类等）共计10种，未知化合物1种。以VIP>1、P<0.05为标准对盐源与汉源花椒籽挥发油成分进行筛选，共筛选出22个差异挥发性成分，盐源产地花椒籽挥发油中，萜烯类（如D-柠檬烯）和酯类（如乙酸芳樟酯）化合物的相对含量普遍较高；而汉源产地花椒籽挥发油中，醛类（如壬醛、癸醛）和酮类（如香芹酮）化合物的相对含量则较高。此外，正庚醇为汉源特有成分。【结论】盐源与汉源花椒籽挥发油化学成分存在一定相似性，但在具体成分及其相对含量上存在一定的差异，这种差异可能由地理位置、生长环境及种植培育方式等多方面因素共同作用导致。这些特征性差异可为花椒籽的产地鉴别、品质评价及地理标志产品开发提供关键科学依据。

关键词: 花椒籽挥发油, 气相色谱－质谱技术, 多元统计分析方法, 成分鉴定, 差异分析

Abstract:

【Background】 As a by-product of Zanthoxylum bungeanum processing, Zanthoxylum bungeanum seeds are rich in oil and have high development potential. However, most of them are used as fertilizers or discarded in the form of waste, resulting in waste of resources. 【Objective】 In order to improve its utilization value and realize the efficient utilization of resources, this study focused on the key characteristics of volatile oil of Zanthoxylum bungeanum seeds from different producing areas, explored the chemical composition of volatile oil of Zanthoxylum bungeanum seeds from two representative producing areas of Yanyuan and Hanyuan, and analyzed the similarities and differences of chemical components of volatile oil and their changing rules.【Method】Zanthoxylum bungeanum seeds samples were collected from Yanyuan County and Hanyuan County, Sichuan Province. The volatile oil in these seeds was extracted by steam distillation, and the components were identified by gas chromatography-mass spectrometry (GC-MS). The volatile oil components were identified by comparing the reference substance, NIST database and literature data, and the relative content of each component was calculated by peak area normalization method. Orthogonal partial least squares discriminant analysis (OPLS-DA) was used to screen differential markers with origin discrimination ability. 【Result】 A total of 124 volatile components were identified from 13 batches of samples, including 28 alcohols, 23 terpenes, 20 aldehydes, 19 ketones, 13 esters, 5 fatty acids, 3 alkenes, 2 alkanes, 10 other types of compounds (including phenols, cyclic ethers, thiazoles, etc.) and 1 unknown compound. With VIP> 1 and P< 0.05 as the standard, the volatile oil components of Zanthoxylum bungeanum seeds from Yanyuan and Hanyuan were screened, and 22 different volatile components were screened out. The relative content of terpenes (such as D-limonene) and esters (such as linalyl acetate) in the volatile oil of Zanthoxylum bungeanum seeds from Yanyuan were generally higher. The relative content of aldehydes (such as nonanal, decanal) and ketones (such as carvone) in the volatile oil of Zanthoxylum bungeanum seeds from Hanyuan were higher. In addition, 1-heptanol was a unique component of Hanyuan. 【Conclusion】 There were some similarities in the chemical composition of volatile oil between Yanyuan and Hanyuan Zanthoxylum bungeanum seeds, but there were some differences in the specific components and their relative content. This difference might be caused by many factors, such as geographical location, growth environment and cultivation methods, which changed the chemical composition of volatile oil. These characteristic differences could provide the key scientific basis for the origin identification, quality evaluation and geographical indication product development of Zanthoxylum bungeanum seeds.

Key words: Zanthoxylum bungeanum seed volatile oil, GC-MS, multivariate statistical analysis methods, identification of constituents, difference analysis

张志淳, 何筱毅, 何成军, 辜冬琳, 钟恋, 苟琰, 高必兴, 耿昭, 李小红, 陈斯恺. 基于GC-MS技术比较分析盐源与汉源花椒籽挥发油化学成分[J]. 中国农业科学, 2025, 58(23): 5057-5070.

ZHANG ZhiChun, HE XiaoYi, HE ChengJun, GU DongLin, ZHONG Lian, GOU Yan, GAO BiXing, GENG Zhao, LI XiaoHong, CHEN SiKai. Comparative Analysis of Volatile Oil Chemical Constituents from Zanthoxylum bungeanum Seeds in Yanyuan and Hanyuan Based on GC-MS Technology[J]. Scientia Agricultura Sinica, 2025, 58(23): 5057-5070.

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花椒籽编号 Zanthoxylum bungeanum seeds number	采集来源 Source of collection
盐源1 Yanyuan 1	盐源县树河镇大水田村 Dashuitian Village, Shuhe Town, Yanyuan County
盐源2 Yanyuan 2	盐源县树河镇石门坎村 Shimenkan Village, Shuhe Town, Yanyuan County
盐源3 Yanyuan 3	盐源县树河镇贡椒经销点 Gongjiao sales outlet, Shuhe Town,Yanyuan County
盐源4 Yanyuan 4	盐源县平川镇青天铺村花椒专业合作社 Qingtianpu Village, Zanthoxylum bungeanum Maxim. Cooperative Pingchuan Town, Yanyuan County
盐源5 Yanyuan 5	盐源县平川镇青天铺村一组 Group 1, Qingtiangpu Village, Pingchuan Town, Yanyuan County
盐源6 Yanyuan 6	盐源县平川镇兴隆村 Xinglong Village, Pingchuan Town, Yanyuan County
汉源1 Hanyuan 1	汉源县宜东镇关华村八组 Group 8, Guanhua Village, Yidong Town, Hanyuan County
汉源2 Hanyuan 2	汉源县宜东镇川椒汇种植专业合作社 Chuanjiaohui planting specialised cooperative, Yidong Town, Hanyuan County
汉源3 Hanyuan 3	汉源县宜东镇大志花椒种植合作社湖南食品商会花椒直供部 Hunan Food Chamber of Commerce Sichuan Zanthoxylum bungeanum Maxim. Direct Supply Department, Dazhi Sichuan Zanthoxylum bungeanum Maxim. Cultivation Cooperative, Yidong Town, Hanyuan County
汉源4 Hanyuan 4	汉源县宜东镇新市村宜椒种植合作社 Yijiao Zanthoxylum bungeanum Maxim. Cultivation Cooperative, Xinshi Village, Yidong Town, Hanyuan County
汉源5 Hanyuan 5	汉源县清溪镇贡椒经销点同心村贡椒园 Gongjiao Sales Outlet, Tongxin Village, Gongjiao Orchard, Qingxi Town, Hanyuan County
汉源6 Hanyuan 6	汉源县清溪镇永安村 Yong'an Village, Qingxi Town, Hanyuan County
汉源7 Hanyuan 7	汉源县刚花椒种植合作社 Ganghuajiao Zanthoxylum bungeanum Maxim. Planting Cooperative, Hanyuan County

序号NO.	类别 Classification	化合物 Compound	VIP值 VIP value	P值 P-value	趋势 Trend
1	酯类 Esters	乙酸芳樟酯 Linalyl acetate	2.70	3.68×10^-2*	↓
2	酯类 Esters	乙酸松油酯 Terpinyl acetate	1.75	2.12×10^-5***	↓
3	酯类 Esters	己酸戊酯 Hexanoic acid, pentyl ester	1.46	4.00×10^-4***	↑
4	未知 Unknown	未知化合物1 Unknown Compound 1	1.11	5.78×10^-8***	↓
5	酮类 Ketones	香芹酮 Carvone	2.19	4.19×10^-2*	↑
6	萜烯类 Terpenes	D-柠檬烯 D-Limonene	3.20	4.40×10^-2*	↓
7	萜烯类 Terpenes	反式-柠檬烯环氧化物 trans-Limonene oxide	1.83	5.00×10^-4***	↑
8	醛类 Aldehydes	反式-2-癸烯醛 trans-2-Decenal	2.42	5.05×10^-7***	↑
9	醛类 Aldehydes	反式-2-十一烯醛 trans-2-Undecenal	2.32	4.73×10^-5***	↑
10	醛类 Aldehydes	反式-2-壬醛 trans-2-Nonenal	2.26	5.47×10^-6***	↑
11	醛类 Aldehydes	壬醛 Nonanal	2.13	7.00×10^-4***	↑
12	醛类 Aldehydes	正辛醛 Octanal	2.09	1.80×10^-3**	↑
13	醛类 Aldehydes	庚醛 Heptanal	2.05	1.16×10^-2*	↑
14	醛类 Aldehydes	反式-2-辛烯醛 trans-2-Octenal	1.74	4.02×10^-5***	↑
15	醛类 Aldehydes	(2E,4Z)-2,4-癸二烯醛 (2E,4Z)-2,4-Decanedienal	1.42	8.74×10^-6***	↑
16	醛类 Aldehydes	癸醛 Decanal	1.41	1.25×10^-6***	↑
17	醇类 Alcohols	芳樟醇 Linalool	4.49	4.00×10^-4***	↓
18	醇类 Alcohols	辛醇 Octanol	1.82	2.00×10^-4***	↑
19	醇类 Alcohols	正庚醇 1-Heptanol	1.66	8.02×10^-5***	↑
20	醇类 Alcohols	石竹素 Caryophyllene oxide	1.47	1.27×10^-2*	↓
21	醇类 Alcohols	1-异丙烯基-4-甲基-1,2-环己二醇 (1S-(1Alpha,2alpha,4beta)-1-isopropenyl-4-methyl- 1,2-cyclohexanediol	1.40	1.84×10^-2*	↓
22	醇类 Alcohols	正己醇 1-Hexanol	1.06	3.00×10^-4***	↑

基于GC-MS技术比较分析盐源与汉源花椒籽挥发油化学成分

Comparative Analysis of Volatile Oil Chemical Constituents from Zanthoxylum bungeanum Seeds in Yanyuan and Hanyuan Based on GC-MS Technology

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