基于HS-SPME-GC-MS与化学计量学的不同品种宣木瓜挥发性成分解析
Integrating HS-SPME-GC-MS and Chemometrics to Decode the Volatile Profiles in Different Cultivars of Chaenomeles speciosa Fruits
DOI: 10.12677/aac.2026.164029, PDF,    科研立项经费支持
作者: 朱茹燕*, 王小粤*, 宋慧欣, 柴新义, 于士军#：滁州学院现代农业与食品工程学院，安徽 滁州；王 伟：宣城市农业农村局农产品质量安全中心，安徽 宣城；Abdullah Gera, 徐延平#：潍坊理工学院现代农业与环境学院，山东 潍坊
关键词: 木瓜；顶空固相微萃取–气相色谱–质谱联用；挥发性化合物；化学计量学；品种判别；Chaenomeles speciosa； HS-SPME-GC-MS； Volatile Compounds； Chemometrics； Cultivar Discrimination
摘要: 本研究采用顶空固相微萃取–气相色谱–质谱联用(HS-SPME-GC-MS)技术，结合主成分分析(PCA)、偏最小二乘判别分析(PLS-DA)和正交偏最小二乘判别分析(OPLS-DA)等化学计量学方法，系统地分析了安徽宣城产的罗汉脐(LHQ)、苹果红(PGH)和芝麻点(ZMD)三个不同品种宣木瓜的挥发性成分。研究共鉴定出123种挥发性化合物，其中83种为三品种共有。结果显示，LHQ品种检出的挥发性化合物种类最多；三个品种均以烯烃类物质占比最高，与PGH和ZMD相比，LHQ中醇类和环氧化合物的相对峰面积占比较高。多变量统计分析清晰地将三个品种区分开，并成功筛选出29种品种潜在差异标志物。通过两两比较，进一步确定了β-Selinene、(R)-Camphor、Longifolene等七种化合物是区分这三个品种的共同核心判别物质。研究为宣木瓜的品种鉴别、品质评价和定向开发利用提供了化学依据。
Abstract: The volatile profiles of three Chaenomeles speciosa cultivars grown in Xuancheng, Anhui Province, China, Luohanqi (LHQ), Pingguohong (PGH), and Zhimadian (ZMD), were characterized by headspace solid-phase microextraction coupled with gas chromatography-mass spectrometry (HS-SPME-GC-MS) and analyzed using principal component analysis (PCA), partial least squares discriminant analysis (PLS-DA), and orthogonal PLS-DA (OPLS-DA). In total, 123 volatile compounds were identified, of which 83 were shared by all three cultivars. The results showed that the LHQ variety had the highest number of volatile compounds. Alkene compounds accounted for the highest proportion in all three varieties. Compared with PGH and ZMD, LHQ exhibited higher relative peak area percentages of alcohols and epoxy compounds. Multivariate analyses clearly differentiated the three cultivars and identified 29 candidate discriminatory markers. Pairwise comparisons further highlighted seven compounds, including β-Selinene, (R)-Camphor and Longifolene, as key discriminants among the cultivars. These findings provide a chemical basis for cultivar authentication, quality evaluation, and targeted utilization of C. speciosa fruit.
文章引用：朱茹燕, 王小粤, 宋慧欣, 王伟, 柴新义, Abdullah Gera, 徐延平, 于士军. 基于HS-SPME-GC-MS与化学计量学的不同品种宣木瓜挥发性成分解析[J]. 分析化学进展, 2026, 16(4): 272-286. https://doi.org/10.12677/aac.2026.164029

参考文献

[1] Hou, M., Lin, C., Zhu, L. and Bian, Z. (2025) Phenolics from Chaenomeles speciosa Leaves: Ionic Liquid-Based Ultrasound-Assisted Extraction, Adsorptive Purification, UPLC-QqQ-MS/MS Quantification, and Bioactivity Assessment. Ultrasonics Sonochemistry, 114, Article ID: 107282.
https://doi.org/10.1016/j.ultsonch.2025.107282
[2] Duan, Z., Jin, C., Deng, Y., Liu, J., Gu, C., Wang, J., et al. (2023) Exploring the Chondroprotective Effect of Chaenomeles speciosa on Glucose-6-Phosphate Isomerase Model Mice Using an Integrated Approach of Network Pharmacology and Experimental Validation. Journal of Ethnopharmacology, 314, Article ID: 116553.
https://doi.org/10.1016/j.jep.2023.116553
[3] Miao, J., Zhao, C., Li, X., Chen, X., Mao, X., Huang, H., et al. (2016) Chemical Composition and Bioactivities of Two Common Chaenomeles Fruits in China: Chaenomeles speciosa and Chaenomeles sinensis. Journal of Food Science, 81, 2049-2058.
https://doi.org/10.1111/1750-3841.13377
[4] Zheng, X., Wang, H., Zhang, P., Gao, L., Yan, N., Li, P., et al. (2018) Chemical Composition, Antioxidant Activity and Α-Glucosidase Inhibitory Activity of Chaenomeles speciosa from Four Production Areas in China. Molecules, 23, Article No. 2518.
https://doi.org/10.3390/molecules23102518
[5] Huang, G., Xi, Z., Li, J., Chen, C., Yang, G., Sun, L., et al. (2013) Isolation of Two New Phenolic Compounds from the Fruit of Chaenomeles speciosa (Sweet) Nakai. Phytochemistry Letters, 6, 526-530.
https://doi.org/10.1016/j.phytol.2013.06.011
[6] Zhang, R., Li, S., Zhu, Z. and He, J. (2019) Recent Advances in Valorization of Chaenomeles Fruit: A Review of Botanical Profile, Phytochemistry, Advanced Extraction Technologies and Bioactivities. Trends in Food Science & Technology, 91, 467-482.
https://doi.org/10.1016/j.tifs.2019.07.012
[7] Hou, M., Shi, J., Lin, C., Zhu, L. and Bian, Z. (2024) Ultrasound-Assisted Extraction of Triterpenoids from Chaenomeles speciosa Leaves: Process Optimization, Adsorptive Enrichment, Chemical Profiling, and Protection against Ulcerative Colitis. Ultrasonics Sonochemistry, 111, Article ID: 107136.
https://doi.org/10.1016/j.ultsonch.2024.107136
[8] Turkiewicz, I.P., Wojdyło, A., Tkacz, K. and Nowicka, P. (2020) Carotenoids, Chlorophylls, Vitamin E and Amino Acid Profile in Fruits of Nineteen Chaenomeles Cultivars. Journal of Food Composition and Analysis, 93, Article ID: 103608.
https://doi.org/10.1016/j.jfca.2020.103608
[9] Yu, A., Hu, W., Bi, H., Fu, L., Wang, Z., Wang, M., et al. (2024) Recent Advances in Polysaccharides from Chaenomeles speciosa (Sweet) Nakai.: Extraction, Purification, Structural Characteristics, Health Benefits, and Applications. Molecules, 29, Article No. 2984.
https://doi.org/10.3390/molecules29132984
[10] Huang, D.D., Jiang, S.G., Du, Z.N., Chen, Y., Xue, D., Wang, X., et al. (2022) Analgesic and Anti-Arthritic Activities of Polysaccharides in Chaenomeles speciosa. Frontiers in Pharmacology, 13, Article ID: 744915.
https://doi.org/10.3389/fphar.2022.744915
[11] Xu, R., Deng, P., Ma, Y., Li, K., Ren, F. and Li, N. (2024) Anti-Hyperuricemic Effects of Extracts from Chaenomeles speciosa (Sweet) Nakai Fruits on Hyperuricemic Rats. Metabolites, 14, Article No. 117.
https://doi.org/10.3390/metabo14020117
[12] Zhang, L., Cheng, Y., Liu, A., Wang, H., Wang, Y. and Du, G. (2010) Antioxidant, Anti-Inflammatory and Anti-Influenza Properties of Components from Chaenomeles speciosa. Molecules, 15, 8507-8517.
https://doi.org/10.3390/molecules15118507
[13] Cheng, X., Shi, S., Su, J., Xu, Y., Ordaz-Ortiz, J.J., Li, N., et al. (2020) Structural Characterization of a Heteropolysaccharide from Fruit of Chaenomelese speciosa (Sweet) Nakai and Its Antitumor Activity. Carbohydrate Polymers, 236, Article ID: 116065.
https://doi.org/10.1016/j.carbpol.2020.116065
[14] Wang, W., An, M., Zhao, G., Wang, Y., Yang, D., Zhang, D., et al. (2023) Ultrasonic-Assisted Customized Natural Deep Eutectic Solvents Extraction of Polyphenols from Chaenomeles speciosa. Microchemical Journal, 193, Article ID: 108952.
https://doi.org/10.1016/j.microc.2023.108952
[15] Deng, Y., Huang, L., Zhang, C., Xie, P., Cheng, J., Wang, X., et al. (2020) Novel Polysaccharide from Chaenomeles speciosa Seeds: Structural Characterization, α-Amylase and α-Glucosidase Inhibitory Activity Evaluation. International Journal of Biological Macromolecules, 153, 755-766.
https://doi.org/10.1016/j.ijbiomac.2020.03.057
[16] Hu, F.X., Liu, C., Wang, F., Zhou, C., Zhu, M., Sun-Waterhouse, D., et al. (2023) Phenolic Compounds from Chaenomeles speciosa Alleviate Inflammation in Lipopolysaccharide-Treated RAW264.7 Macrophages via the NF-κB and MAPK Pathways. Food Science and Human Wellness, 12, 1071-1080.
https://doi.org/10.1016/j.fshw.2022.10.025
[17] Zhang, S., Ren, Y., Zhao, Q., Wu, Y., Zhuo, Y. and Li, H. (2023) Drought‐Induced CsMYB6 Interacts with CsbHLH111 to Regulate Anthocyanin Biosynthesis in Chaenomeles speciosa. Physiologia Plantarum, 175, e13859.
https://doi.org/10.1111/ppl.13859
[18] Deng, Y., Huang, L., Zhang, C., et al. (2019) Physicochemical and Functional Properties of Water Soluble Gum from Wrinkle Floweringquince (Chaenomeles speciosa) Seeds. Journal of Bioresources and Bioproducts, 4, 222-230.
[19] Hu, F., Li, F., Zheng, Z., Sun-Waterhouse, D. and Wang, Z. (2022) Surfactant-Mediated Ultrasonic-Assisted Extraction and Purification of Antioxidants from Chaenomeles speciosa (Sweet) Nakai for Chemical-and Cell-Based Antioxidant Capacity Evaluation. Molecules, 27, Article No. 7970.
https://doi.org/10.3390/molecules27227970
[20] Tan, W. and Li, Z. (2026) Network Pharmacology-Based Exploration: Non-Targeted Metabolites of Lactobacillus-Fermented Chaenomeles speciosa (Sweet) Nakai, Smilax glabra Roxb. and Pueraria montana var. Lobata in Uric Acid Metabolism Intervention. Biologics: Targets and Therapy, 20, Article ID: 578004.
https://doi.org/10.2147/btt.s578004
[21] Zhu, Q., Liao, C., Liu, Y., Wang, P., Guo, W., He, M., et al. (2012) Ethanolic Extract and Water-Soluble Polysaccharide from Chaenomeles speciosa Fruit Modulate Lipopolysaccharide-Induced Nitric Oxide Production in RAW264.7 Macrophage Cells. Journal of Ethnopharmacology, 144, 441-447.
https://doi.org/10.1016/j.jep.2012.09.042
[22] Zhou, L., Li, Y., Gong, X., Li, Z., Wang, H., Ma, L., et al. (2022) Preparation, Characterization, and Antitumor Activity of Chaenomeles speciosa Polysaccharide-Based Selenium Nanoparticles. Arabian Journal of Chemistry, 15, Article ID: 103943.
https://doi.org/10.1016/j.arabjc.2022.103943
[23] Ma, Y., Li, J., Li, J., Yang, L., Wu, G. and Liu, S. (2022) Comparative Metabolomics Study of Chaenomeles speciosa (Sweet) Nakai from Different Geographical Regions. Foods, 11, Article No. 1019.
https://doi.org/10.3390/foods11071019
[24] Zhang, X., Yu, X., Hu, R., Zhang, J. and Dong, W. (2026) Effects of Different Roasting Temperatures on the Flavor Characteristics of Shelled Macadamia Kernels: Analysis Based on HS-GC-IMS and HS-SPME-GC-MS. Food Research International, 232, Article ID: 118878.
https://doi.org/10.1016/j.foodres.2026.118878
[25] Song, X., Dai, F., Yao, J., Li, Z., Huang, Z., Liu, H., et al. (2023) Characterization of the Volatile Profile of Feijoa (Acca sellowiana) Fruit at Different Ripening Stages by HS-SPME-GC/MS. LWT, 184, Article ID: 115011.
https://doi.org/10.1016/j.lwt.2023.115011
[26] Song, Y., Li, J., Ding, Q., Yang, X., Yu, J., Zhang, Y., et al. (2025) Exploring Key Aroma Differences of Three Fenghuang Dancong Oolong Teas and Their Perception Interactions with Caffeine via Sensomics Approach. Food Research International, 202, Article ID: 115665.
https://doi.org/10.1016/j.foodres.2025.115665
[27] Gao, Y., Wang, J., Li, M., Wang, J., Qiao, L., Zhang, N., et al. (2025) Aroma Profiling of Chinese Chrysanthemum (Chrysanthemum morifolium Ramat.) Using Flavoromics Analysis. Journal of Food Composition and Analysis, 138, Article ID: 107014.
https://doi.org/10.1016/j.jfca.2024.107014
[28] Dudareva, N., Andersson, S., Orlova, I., Gatto, N., Reichelt, M., Rhodes, D., et al. (2005) The Nonmevalonate Pathway Supports Both Monoterpene and Sesquiterpene Formation in Snapdragon Flowers. Proceedings of the National Academy of Sciences, 102, 933-938.
https://doi.org/10.1073/pnas.0407360102
[29] Martin, D.M., Fäldt, J. and Bohlmann, J. (2004) Functional Characterization of Nine Norway Spruce TPS Genes and Evolution of Gymnosperm Terpene Synthases of the TPS-D Subfamily. Plant Physiology, 135, 1908-1927.
https://doi.org/10.1104/pp.104.042028
[30] Koo, H.J. and Gang, D.R. (2012) Suites of Terpene Synthases Explain Differential Terpenoid Production in Ginger and Turmeric Tissues. PLOS ONE, 7, e51481.
https://doi.org/10.1371/journal.pone.0051481
[31] Sköld, M., Karlberg, A., Matura, M. and Börje, A. (2006) The Fragrance Chemical β-Caryophyllene—Air Oxidation and Skin Sensitization. Food and Chemical Toxicology, 44, 538-545.
https://doi.org/10.1016/j.fct.2005.08.028
[32] Chen, G., Hackett, R., Walker, D., Taylor, A., Lin, Z. and Grierson, D. (2004) Identification of a Specific Isoform of Tomato Lipoxygenase (TomloxC) Involved in the Generation of Fatty Acid-Derived Flavor Compounds. Plant Physiology, 136, 2641-2651.
https://doi.org/10.1104/pp.104.041608
[33] Cao, J., Zou, X., Deng, L., Fan, Y., Li, H., Li, J., et al. (2014) Analysis of Nonpolar Lipophilic Aldehydes/Ketones in Oxidized Edible Oils Using HPLC-QqQ-MS for the Evaluation of Their Parent Fatty Acids. Food Research International, 64, 901-907.
https://doi.org/10.1016/j.foodres.2014.08.042
[34] Vogel, J.T., Tan, B., McCarty, D.R. and Klee, H.J. (2008) The Carotenoid Cleavage Dioxygenase 1 Enzyme Has Broad Substrate Specificity, Cleaving Multiple Carotenoids at Two Different Bond Positions. Journal of Biological Chemistry, 283, 11364-11373.
https://doi.org/10.1074/jbc.m710106200
[35] Gross, M., Friedman, J., Dudai, N., Larkov, O., Cohen, Y., Bar, E., et al. (2002) Biosynthesis of Estragole and T-Anethole in Bitter Fennel (Foeniculum vulgare Mill. Var. Vulgare) Chemotypes. Changes in SAM: Phenylpropene O-Methyltransferase Activities during Development. Plant Science, 163, 1047-1053.
https://doi.org/10.1016/s0168-9452(02)00279-0
[36] Fang, Q., Zheng, H., Fu, G., Yin, M., Jiang, L., Zhao, Y., et al. (2023) Integrated Untargeted Metabolome, Full-Length Sequencing, and Transcriptome Analyses Reveal Insights into the Fruit Quality at Different Harvest Times of Chaenomeles speciosa. Food Research International, 164, Article ID: 112314.
https://doi.org/10.1016/j.foodres.2022.112314

为你推荐