目的 比较不同发酵时间六神曲样品挥发性成分的组成和含量差异，阐明六神曲独特气味的物质基础以及明确赋予其主体特征香味的关键成分。方法 以不同发酵时间的六神曲为研究对象，采用电子鼻表征其整体气味轮廓，结合气相色谱-质谱联用（gas chromatography-mass spectrometry，GC-MS）技术分析具体挥发性成分；通过化学计量学筛选不同发酵时段的差异组分，借助相对气味活度值（relative odor activity value，ROAV）揭示六神曲气味差异及其气味形成的物质基础。结果 根据电子鼻W5S、W1W、W2W传感器检测结果，可将六神曲发酵过程明确划分为T1～T4（发酵初期）、T5～T8（发酵中期）、T9～T12（发酵后期）3个阶段。GC-MS技术共鉴定出120个挥发性成分。主成分分析（principal component analysis，PCA）和正交最小偏二乘法-判别分析（orthogonal partial least squares-discriminant analysis，OPLS-DA）证实，不同发酵时间六神曲的挥发性成分存在明显差异，以变量重要性投影（variable importance in projection，VIP）值＞1且P＜0.05为标准，筛选得到49个差异性成分。结合ROAV法确定对主体特征性香味贡献最大的成分为5-羟甲基糠醛；2-已烯、反式-9-十八烯酸戊酯、3,5-二羟基-1-十九烷基苯、2-甲氧基-5-十六碳烯酸甲酯对特征性香味具有重要修饰作用。结论 通过电子鼻技术、GC-MS技术结合ROAV法可较好地分析六神曲发酵过程中挥发性成分的差异，为六神曲的鉴定和质量评价提供科学依据。

Objective To compare the composition and content differences of volatile components in Liushenqu (六神曲, Massa Medicata Fermentata, MMF) samples with different fermentation times, clarify the material basis of the unique aroma of MMF, and identify the key components that give it its main characteristic aroma. Methods Taking MMF fermented for different durations as the research object, and electronic nose was used to characterize its overall odor profile, and gas chromatography-mass spectrometry (GC-MS) was combined to analyze the specific volatile components. Chemometrics was applied to screen the differential components at different fermentation stages, and the relative odor activity value (ROAV) was used to reveal the odor differences of MMF and the material basis for its odor formation. Results Based on the detection results of the W5S, W1W, and W2W sensors of the electronic nose, the fermentation process of MMF was clearly divided into three stages: T1—T4 (initial fermentation), T5—T8 (middle fermentation), and T9—T12 (late fermentation). A total of 120 volatile components were identified by GC-MS. Principal component analysis (PCA) and orthogonal partial least squares-discriminant analysis (OPLS-DA) confirmed that there were significant differences in the volatile components of MMF at different fermentation times. A total of 49 differential components were screened out according to the criteria of variable importance in projection (VIP) > 1 and P < 0.05. Combined with the relative odor activity value method, 5-hydroxymethylfurfural was identified as the component contributing the most to the characteristic aroma of the main body. 2-Hexene, pentyl (9E)-octadec-9-enoate, 3,5-dihydroxy-1-nonadecylbenzene, and methyl 2-methoxy-5-hexadecenoate played important modifying roles in the characteristic aroma. Conclusion The differences in volatile components during the fermentation of MMF can be effectively analyzed by electronic nose, GC-MS, combined with the relative odor activity value method, which provides a scientific basis for the identification and quality evaluation of MMF.

R283.6

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