LC-MS/MS-Based Determination and Optimization of Linoleic Acid Oxides in <i>Baijiu</i> and Their Variation with Storage Time

<b>Background</b>: Post-production storage plays a pivotal role in developing the characteristic flavor profile of <i>Baijiu</i>, a traditional alcoholic beverage in China. While aging markers remain crucial for quality authentication, the identification of reliable metabolic...

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Main Authors: Cheng Fang, Xiaotong Zhuang, Zhanguo Li, Yongfang Zou, Jizhou Pu, Dong Wang, Yan Xu
Format: Article
Language:English
Published: MDPI AG 2025-04-01
Series:Metabolites
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Online Access:https://www.mdpi.com/2218-1989/15/4/246
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author Cheng Fang
Xiaotong Zhuang
Zhanguo Li
Yongfang Zou
Jizhou Pu
Dong Wang
Yan Xu
author_facet Cheng Fang
Xiaotong Zhuang
Zhanguo Li
Yongfang Zou
Jizhou Pu
Dong Wang
Yan Xu
author_sort Cheng Fang
collection DOAJ
description <b>Background</b>: Post-production storage plays a pivotal role in developing the characteristic flavor profile of <i>Baijiu</i>, a traditional alcoholic beverage in China. While aging markers remain crucial for quality authentication, the identification of reliable metabolic indicators for chronological determination requires further exploration. <b>Methods</b>: This study establishes a novel liquid chromatography-tandem mass spectrometry (LC-MS/MS) methodology for quantifying five linoleic acid-derived oxidative metabolites in <i>Baijiu</i>: 9,12,13-trihydroxy-10(E)-octadecenoic acid (9,12,13-TriHOME), 9,10-Dihydroxy-12-octadecenoic acid (9,10-DiHOME), 9-oxo-(10E,12Z)-octadecadienoic acid (9-OxoODE), 9-hydroxy-(10E,12Z)-octadecadienoic acid (9-HODE) and 13-hydroxyoctadeca-(9Z,11E)-octadecadienoic acid (13-HODE). <b>Results</b>: The optimized protocol demonstrated exceptional sensitivity with limits of detection at 0.4 ppb through membrane-filtered direct dilution. Calibration curves exhibited excellent linearity (R<sup>2</sup> > 0.9990) across 1.0–100.0 ppb ranges. Method validation revealed satisfactory recovery rates (87.25–119.44%) at three spiking levels (10/20/50 ppb) with precision below 6.96% RSD. Application to authentic samples showed distinct temporal accumulation patterns. Light-aroma <i>Baijiu</i> exhibited storage duration-dependent increases in all five oxides. Strong aroma variants demonstrated significant positive correlations for 9,12,13-TriHOME, 9,10-DiHOME, and 9-OxoODE with aging time. <b>Conclusions</b>: These findings systematically characterize linoleic acid oxidation products as potential aging markers, providing both methodological advancements and new insights into <i>Baijiu</i> aging mechanisms.
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spelling doaj-art-c19ca9b28a494ae0aa60e1e0e262187b2025-08-20T03:13:45ZengMDPI AGMetabolites2218-19892025-04-0115424610.3390/metabo15040246LC-MS/MS-Based Determination and Optimization of Linoleic Acid Oxides in <i>Baijiu</i> and Their Variation with Storage TimeCheng Fang0Xiaotong Zhuang1Zhanguo Li2Yongfang Zou3Jizhou Pu4Dong Wang5Yan Xu6Laboratory of Brewing Microbiology and Applied Enzymology, School of Biotechnology, Jiangnan University, Wuxi 214122, ChinaLaboratory of Brewing Microbiology and Applied Enzymology, School of Biotechnology, Jiangnan University, Wuxi 214122, ChinaTechnical Research Institute, Shede Spirits Co., Ltd., Shehong 629000, ChinaTechnical Research Institute, Shede Spirits Co., Ltd., Shehong 629000, ChinaTechnical Research Institute, Shede Spirits Co., Ltd., Shehong 629000, ChinaLaboratory of Brewing Microbiology and Applied Enzymology, School of Biotechnology, Jiangnan University, Wuxi 214122, ChinaLaboratory of Brewing Microbiology and Applied Enzymology, School of Biotechnology, Jiangnan University, Wuxi 214122, China<b>Background</b>: Post-production storage plays a pivotal role in developing the characteristic flavor profile of <i>Baijiu</i>, a traditional alcoholic beverage in China. While aging markers remain crucial for quality authentication, the identification of reliable metabolic indicators for chronological determination requires further exploration. <b>Methods</b>: This study establishes a novel liquid chromatography-tandem mass spectrometry (LC-MS/MS) methodology for quantifying five linoleic acid-derived oxidative metabolites in <i>Baijiu</i>: 9,12,13-trihydroxy-10(E)-octadecenoic acid (9,12,13-TriHOME), 9,10-Dihydroxy-12-octadecenoic acid (9,10-DiHOME), 9-oxo-(10E,12Z)-octadecadienoic acid (9-OxoODE), 9-hydroxy-(10E,12Z)-octadecadienoic acid (9-HODE) and 13-hydroxyoctadeca-(9Z,11E)-octadecadienoic acid (13-HODE). <b>Results</b>: The optimized protocol demonstrated exceptional sensitivity with limits of detection at 0.4 ppb through membrane-filtered direct dilution. Calibration curves exhibited excellent linearity (R<sup>2</sup> > 0.9990) across 1.0–100.0 ppb ranges. Method validation revealed satisfactory recovery rates (87.25–119.44%) at three spiking levels (10/20/50 ppb) with precision below 6.96% RSD. Application to authentic samples showed distinct temporal accumulation patterns. Light-aroma <i>Baijiu</i> exhibited storage duration-dependent increases in all five oxides. Strong aroma variants demonstrated significant positive correlations for 9,12,13-TriHOME, 9,10-DiHOME, and 9-OxoODE with aging time. <b>Conclusions</b>: These findings systematically characterize linoleic acid oxidation products as potential aging markers, providing both methodological advancements and new insights into <i>Baijiu</i> aging mechanisms.https://www.mdpi.com/2218-1989/15/4/246<i>Baijiu</i>linoleic acid oxidesaging markersLC-MS/MS
spellingShingle Cheng Fang
Xiaotong Zhuang
Zhanguo Li
Yongfang Zou
Jizhou Pu
Dong Wang
Yan Xu
LC-MS/MS-Based Determination and Optimization of Linoleic Acid Oxides in <i>Baijiu</i> and Their Variation with Storage Time
Metabolites
<i>Baijiu</i>
linoleic acid oxides
aging markers
LC-MS/MS
title LC-MS/MS-Based Determination and Optimization of Linoleic Acid Oxides in <i>Baijiu</i> and Their Variation with Storage Time
title_full LC-MS/MS-Based Determination and Optimization of Linoleic Acid Oxides in <i>Baijiu</i> and Their Variation with Storage Time
title_fullStr LC-MS/MS-Based Determination and Optimization of Linoleic Acid Oxides in <i>Baijiu</i> and Their Variation with Storage Time
title_full_unstemmed LC-MS/MS-Based Determination and Optimization of Linoleic Acid Oxides in <i>Baijiu</i> and Their Variation with Storage Time
title_short LC-MS/MS-Based Determination and Optimization of Linoleic Acid Oxides in <i>Baijiu</i> and Their Variation with Storage Time
title_sort lc ms ms based determination and optimization of linoleic acid oxides in i baijiu i and their variation with storage time
topic <i>Baijiu</i>
linoleic acid oxides
aging markers
LC-MS/MS
url https://www.mdpi.com/2218-1989/15/4/246
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