Article(id=1320882403187474924, tenantId=1146029695717560320, journalId=1260987677001138203, issueId=1320880138208784845, articleNumber=null, orderNo=null, doi=10.13386/j.issn1002-0306.2025070277, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1753200000000, receivedDateStr=2025-07-23, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1792852505727, onlineDateStr=2026-10-24, pubDate=1785513600000, pubDateStr=2026-08-01, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1792852505727, onlineIssueDateStr=2026-10-24, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1792852505727, creator=13701087609, updateTime=1792852505727, updator=13701087609, issue=Issue{id=1320880138208784845, tenantId=1146029695717560320, journalId=1260987677001138203, year='2026', volume='47', issue='15', pageStart='1', pageEnd='524', issueExtLink='null', onlineDate='null', pubDate='1785513600000', pubDateStr='2026-08-01', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1792851965715, creator='13701087609', updateTime=1792851965715, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext=null, issueFiles=null, downloadFileDto=null}, startPage=389, endPage=397, ext={EN=ArticleExt(id=1320882403992781294, articleId=1320882403187474924, tenantId=1146029695717560320, journalId=1260987677001138203, language=EN, title=Lipid Oxidation Patterns and Their Impact on Flavor Profile in Crisp Biscuits during Storage, columnId=1261343845820805453, journalTitle=Science and Technology of Food Industry, columnName=Storage and Preservation, runingTitle=null, highlight=null, articleAbstract=

Crisp biscuits are susceptible to lipid oxidation during storage, resulting in flavor deterioration and a decline in quality. To systematically investigate the dynamic changes in lipid oxidation indicators and their effect on product flavor, this study utilized headspace solid-phase microextraction coupled with gas chromatography-mass spectrometry (HS-SPME-GC-MS) to analyze samples stored for 0, 6, 8, 10, 12, and 14 months. Monitoring of lipid oxidation indices revealed that the acid value (AV) and peroxide value (POV) increased significantly with storage time (P<0.05). In contrast, the oxidative stability index (OSI) decreased markedly (P<0.05), with a 34.47% reduction over 14 months. A total of 44 volatile compounds were identified, including aldehydes (9), ketones (8), acids (1), esters (8), alcohols (4), hydrocarbons (7), pyrazines (6), and others (1). Flavor profiling demonstrated significant temporal variations: aldehydes (e.g., hexanal, isovaleraldehyde), ketones (e.g., hydroxyacetone), and acids (e.g., acetic acid) increased significantly during storage (P<0.05), whereas esters (e.g., ethyl acetate) decreased sharply (P<0.05), with a 93.24% reduction by month 14. Multivariate statistical analyses, including partial least squares-discriminant analysis (PLS-DA) and principal component analysis (PCA), combined with variable importance in projection (VIP>1) and statistical significance (P<0.05), identified 13 key differential volatile markers. Further screening highlighted seven compounds—hexanal, isovaleraldehyde, hydroxyacetone, acetic acid, acetamide, acetylacetone, and 2-methyltetrahydrofuran-3-one—as core markers indicative of flavor deterioration and overall quality decline in crisp biscuits. Correlation analysis confirmed lipid oxidation as the primary driver of off-flavor development and quality degradation. These findings demonstrate that HS-SPME-GC-MS combined with multivariate analysis is an effective approach for identifying critical differential flavor compounds during storage, providing a scientific and methodological basis for early prediction and quality monitoring of crisp biscuits.

, authors=Hongqing ZHOU, Xiuhang CHAI, Yuanfa LIU*, authorsList=Hongqing ZHOU, Xiuhang CHAI, Yuanfa LIU, authorCompany=null, correspAuthors=Yuanfa LIU, authorNote=null, correspAuthorsNote=null, copyrightStatement=Copyright © 2026 Science and Technology of Food Industry. All rights reserved., copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, fund=null), CN=ArticleExt(id=1320882407620854271, articleId=1320882403187474924, tenantId=1146029695717560320, journalId=1260987677001138203, language=CN, title=酥性饼干储藏过程中油脂氧化规律及其对产品风味的影响, columnId=1261343846517059923, journalTitle=食品工业科技, columnName=贮运保鲜, runingTitle=null, highlight=null, articleAbstract=

酥性饼干在储藏期间易发生油脂氧化,导致风味劣变与品质下降。为系统揭示其油脂氧化指标的动态变化规律及其对产品风味的影响,本研究采用顶空固相微萃取-气相色谱-质谱联用技术(HS-SPME-GC-MS),分析了储藏0、6、8、10、12和14个月共6个时间点的样品。油脂氧化指标监测结果显示,随着储藏时间延长,饼干油脂的AV和POV显著上升(P<0.05),而OSI显著下降(P<0.05),从0至14个月下降率达34.47%。风味分析共鉴定出44种挥发性化合物,包括醛类(9种)、酮类(8种)、酸类(1种)、酯类(8种)、醇类(4种)、烃类(7种)、吡嗪类(6种)及其他类(1种)。风味物质含量呈现显著动态变化,其中醛类(如正己醛、异戊醛)、酮类(如羟基丙酮)及酸类(冰醋酸)含量随储藏时间显著增加(P<0.05);而酯类物质(如乙酸乙酯)含量则显著降低(P<0.05),从0至14个月降幅达93.24%。基于偏最小二乘判别分析(PLS-DA)与主成分分析(PCA),结合变量重要性投影(VIP>1)及显著性差异(P<0.05)标准,筛选出13种关键差异风味物质。进一步分析确定正己醛、异戊醛、羟基丙酮、冰醋酸、乙酰胺、乙酸基丙酮和2-甲基四氢呋喃-3-酮共7种化合物为表征酥性饼干品质劣变的核心标志物。相关性分析证实,油脂氧化是诱发酥性饼干异常风味及导致其整体品质劣变的关键驱动因素。本研究结果表明,HS-SPME-GC-MS技术结合多元统计分析可有效识别酥性饼干储藏过程中的关键差异风味物质,为酥性饼干品质劣变的早期预测与监控提供了重要的科学依据和方法学支撑。

, authors=周洪庆, 柴秀航, 刘元法*, authorsList=周洪庆, 柴秀航, 刘元法, authorCompany=null, correspAuthors=刘元法, authorNote=

周洪庆(2000−),男,硕士研究生,研究方向:油脂营养安全与绿色制造,E-mail:

, correspAuthorsNote=
刘元法(1974−),男,博士,教授,研究方向:油脂营养安全与绿色制造,E-mail: 。
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周洪庆(2000−),男,硕士研究生,研究方向:油脂营养安全与绿色制造,E-mail:

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周洪庆(2000−),男,硕士研究生,研究方向:油脂营养安全与绿色制造,E-mail:

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Journal of the Science of Food and Agriculture, 1996, 70(2): 151−161., articleTitle=null, refAbstract=null)], funds=null, companyList=[AuthorCompany(id=1320882407906066944, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320882403187474924, xref=null, ext=[AuthorCompanyExt(id=1320882407918649857, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320882403187474924, companyId=1320882407906066944, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=School of Food Science and Technology, Jiangnan University, Wuxi 214122, China), AuthorCompanyExt(id=1320882407931232770, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320882403187474924, companyId=1320882407906066944, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=江南大学食品学院,江苏无锡 214122)])], figs=[ArticleFig(id=1320882411467031068, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320882403187474924, language=EN, label=Fig.1, caption=Acid value changes during storage of crisp biscuits, figureFileSmall=8Dm/SDs3RkfmtSISUP4Zxg==, figureFileBig=tQwADKuzz5yHeLlkeswMfw==, tableContent=null), ArticleFig(id=1320882411571888669, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320882403187474924, language=CN, label=图1, caption=酥性饼干储藏过程中酸价变化

注:图中不同小写字母表示其统计学差异显著(P<0.05);图2、图3同。

, figureFileSmall=8Dm/SDs3RkfmtSISUP4Zxg==, figureFileBig=tQwADKuzz5yHeLlkeswMfw==, tableContent=null), ArticleFig(id=1320882411802575390, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320882403187474924, language=EN, label=Fig.2, caption=Changes in peroxide value during storage of crisp biscuits, figureFileSmall=PfJGc3lxfj0t90szHVo5mw==, figureFileBig=/EwOHtjVQi3byINdWSaEWA==, tableContent=null), ArticleFig(id=1320882411911627295, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320882403187474924, language=CN, label=图2, caption=酥性饼干储藏过程中过氧化值变化, figureFileSmall=PfJGc3lxfj0t90szHVo5mw==, figureFileBig=/EwOHtjVQi3byINdWSaEWA==, tableContent=null), ArticleFig(id=1320882411995513376, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320882403187474924, language=EN, label=Fig.3, caption=Changes in oxidative stability index during storage of crisp biscuits, figureFileSmall=5W6LScbMwJZtBgCeLsOJjQ==, figureFileBig=NTSi6ihtPm9Mp749fJsr0Q==, tableContent=null), ArticleFig(id=1320882412058427937, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320882403187474924, language=CN, label=图3, caption=酥性饼干储藏过程中氧化稳定性指数变化, figureFileSmall=5W6LScbMwJZtBgCeLsOJjQ==, figureFileBig=NTSi6ihtPm9Mp749fJsr0Q==, tableContent=null), ArticleFig(id=1320882412150702626, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320882403187474924, language=EN, label=Fig.4, caption=Sensory evaluation of crisp biscuits, figureFileSmall=q2ZXKjDTVlGGnJ8Lcmhxmg==, figureFileBig=Mx3XxCl0MsfSeCxj2vgL2g==, tableContent=null), ArticleFig(id=1320882412242977315, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320882403187474924, language=CN, label=图4, caption=酥性饼干的感官评价, figureFileSmall=q2ZXKjDTVlGGnJ8Lcmhxmg==, figureFileBig=Mx3XxCl0MsfSeCxj2vgL2g==, tableContent=null), ArticleFig(id=1320882412335252004, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320882403187474924, language=EN, label=Fig.5, caption=PLS-DA scatter plot of crisp biscuits at different storage times, figureFileSmall=jNKGwWd8IL7lf6fN7puKzg==, figureFileBig=Wv2GD64bhVx04AlIkE9D/Q==, tableContent=null), ArticleFig(id=1320882412410749477, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320882403187474924, language=CN, label=图5, caption=不同储藏时间的酥性饼干的PLS-DA散点图, figureFileSmall=jNKGwWd8IL7lf6fN7puKzg==, figureFileBig=Wv2GD64bhVx04AlIkE9D/Q==, tableContent=null), ArticleFig(id=1320882412507218470, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320882403187474924, language=EN, label=Fig.6, caption=Permutation test plot of the PLS-DA model, figureFileSmall=pXga3FwyFkEfT47ZtbWyAg==, figureFileBig=NOgXo8CnVYYdOZHhwBjoGQ==, tableContent=null), ArticleFig(id=1320882412582715943, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320882403187474924, language=CN, label=图6, caption=PLS-DA模型置换验证图, figureFileSmall=pXga3FwyFkEfT47ZtbWyAg==, figureFileBig=NOgXo8CnVYYdOZHhwBjoGQ==, tableContent=null), ArticleFig(id=1320882412670796328, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320882403187474924, language=EN, label=Fig.7, caption=Principal component analysis loadings plot for crisp biscuit samples at different storage times, figureFileSmall=GJ9Tq23nUVbEKptBulv5uA==, figureFileBig=InqEFJgHrd2oyuzCigXZ8Q==, tableContent=null), ArticleFig(id=1320882412754682409, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320882403187474924, language=CN, label=图7, caption=不同储藏时间酥性饼干样品主成分分析载荷图, figureFileSmall=GJ9Tq23nUVbEKptBulv5uA==, figureFileBig=InqEFJgHrd2oyuzCigXZ8Q==, tableContent=null), ArticleFig(id=1320882412830179882, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320882403187474924, language=EN, label=Fig.8, caption=Correlation analysis among lipid oxidation indicators, key flavor compounds, and sensory characteristics, figureFileSmall=oJtsCqPZxjFhNPEhC26Vwg==, figureFileBig=+5hkWttuKyhfzGAFv6HTpg==, tableContent=null), ArticleFig(id=1320882412918260267, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320882403187474924, language=CN, label=图8, caption=油脂氧化指标与关键性风味化合物、感官特性的相关性分析

注:*P<0.05,**P<0.01,***P<0.001,颜色深浅代表相关系数r值的大小,红色表示正相关,蓝色代表负相关。

, figureFileSmall=oJtsCqPZxjFhNPEhC26Vwg==, figureFileBig=+5hkWttuKyhfzGAFv6HTpg==, tableContent=null), ArticleFig(id=1320882412997952044, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320882403187474924, language=EN, label=Table 1, caption=

Sensory evaluation criteria for crisp biscuit

, figureFileSmall=null, figureFileBig=null, tableContent=
项目描述得分
甜味甜味微弱,几乎无法感知0~3分
甜味较淡,但可辨识4~7分
甜味适中,口感协调,无甜腻感8~10分
香味香气微弱,几乎无法感知0~3分
香味适中,具有产品应有的浓郁风味4~7分
香味非常浓郁,风味突出8~10分
哈喇味哈喇味非常明显,产品不可接受0~3分
可感知哈喇味,但程度较轻4~5分
无油脂氧化产生的哈喇味6~10分
陈味陈旧味突出,产品感官品质显著下降0~3分
可感知明显陈旧味4~5分
基本无陈旧味6~10分
), ArticleFig(id=1320882413077643821, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320882403187474924, language=CN, label=表1, caption=

酥性饼干感官评分标准

, figureFileSmall=null, figureFileBig=null, tableContent=
项目描述得分
甜味甜味微弱,几乎无法感知0~3分
甜味较淡,但可辨识4~7分
甜味适中,口感协调,无甜腻感8~10分
香味香气微弱,几乎无法感知0~3分
香味适中,具有产品应有的浓郁风味4~7分
香味非常浓郁,风味突出8~10分
哈喇味哈喇味非常明显,产品不可接受0~3分
可感知哈喇味,但程度较轻4~5分
无油脂氧化产生的哈喇味6~10分
陈味陈旧味突出,产品感官品质显著下降0~3分
可感知明显陈旧味4~5分
基本无陈旧味6~10分
), ArticleFig(id=1320882413203472942, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320882403187474924, language=EN, label=Table 2, caption=

Aroma compounds content in crisp biscuits at different storage durations

, figureFileSmall=null, figureFileBig=null, tableContent=
CAS号中文名气味描述[25−26]含量(ng/g)VIP值P-value
0 M6 M8 M10 M12 M14 M
醛类
590-86-3异戊醛木香味、苦味、油味14.26±0.23d13.57±0.19e15.00±0.18d17.09±0.05c35.26±0.37b79.8±0.10a1.277≤0.01
66-25-1正己醛刺激性的风味43.54±0.59f61.79±0.09e72.78±0.01d80.27±0.41b77.55±0.34c95.43±1.25a1.211≤0.01
124-19-6壬醛柑橘味2.82±0.10a3.79±1.19a3.1±0.76a3.69±0.73a4.36±0.17a5.69±0.28a0.3600.16
100-52-7苯甲醛苦杏仁味6.59±0.01cd5.58±0.18d6.12±0.02d7.3±0.09c16.02±0.24b35.01±0.73a0.834≤0.01
98-01-1糠醛面包、坚果、焦糖−−−−8.73±0.18b14.89±0.62a0.572≤0.01
96-17-32-甲基丁醛麦芽味7.32±0.03de8.12±0.03cd8.73±0.36c6.49±0.30e14.63±0.27b31.16±0.25a0.801≤0.01
124-13-0正辛醛脂味,刺激性气味−−−3.28±0.17a2.15±0.13b1.62±0.04c0.508≤0.01
111-71-7庚醛油脂味、青草味3.52±0.30e6.23±0.56d5.99±0.07d12.54±0.38b8.80±0.11c14.04±0.21a0.623≤0.01
121-33-5香兰素奶香味、香草味249.05±17.06c322.82±33.48ab328.82±30ab385.95±12.75a277.85±9.13bc259.42±0.92bc2.1890.02
酮类
116-09-6羟基丙酮焦糖香气6.40±0.57f36.99±1.72e42.995±2.99d47.48±5.70c200.66±1.86b261.64±2.44a2.415≤0.01
600-14-62,3-戊二酮奶油、焦糖香气−−−−3.92±0.05b6.71±0.03a0.384≤0.01
3188-00-92-甲基四氢呋喃-3-酮面包、坚果香气−−−−12.04±0.06b45.95±0.67a1.118≤0.01
513-86-03-羟基-2-丁酮油脂香味−−−−23.87±0.12b43.89±0.64a0.975≤0.01
592-20-1乙酸基丙酮刺激性气味−−−1.68±0.13c15.53±0.15b48.88±0.97a1.101≤0.01
5077-67-81-羟基-2-丁酮甜味−−−−−5.26±0.030.479≤0.01
497-23-42(5H)-呋喃酮黄油味−−−−2.51±0.07a2.39±0.13a0.306≤0.01
110-43-02-庚酮水果香味−−−−−3.33±0.010.381≤0.01
酸类
64-19-7冰醋酸强烈刺激气味62.84±0.21f73.57±2.49e89.19±2.43d107.69±2.82c149.87±3.28b191.65±5.69a1.726≤0.01
酯类
141-78-6乙酸乙酯水果香味42.34±0.91a24.91±0.30b23.51±1.06c22.23±0.18d5.35±0.10e2.86±0.07f1.069≤0.01
109-60-4乙酸丙酯水果香80.49±0.12a56.17±0.30c48.61±0.56d64.2±0.37b46.81±0.40e40.61±2.32f1.320≤0.01
123-86-4乙酸丁酯水果香味3.68±0.15−−−−−0.450≤0.01
106-65-0丁二酸二甲酯甜香味17.36±0.01a17.43±0.51a15.35±0.01b14.03±0.17c16.46±0.15a13.8±0.40c0.628≤0.01
96-48-0γ-丁内酯焦糖、甜味1.77±0.06e3.28±0.04c2.45±0.01d2.87±0.22cd13.25±0.18b19.27±0.38a0.632≤0.01
119-40-0戊二酸二甲酯微香气,酯香花香62.2±1.19a57.9±3.24ab30.38±1.23d42.99±0.91c62.89±0.05a55.55±0.65b1.176≤0.01
627-93-0己二酸二甲酯温和的坚果味13.77±0.54a11.68±1.89a10.78±2.23a7.3±0.47b13.92±0.76a11.3±0.34a0.551≤0.01
108-65-6丙二醇甲醚醋
酸酯
浅香甜味−−−−23.65±0.33a24.05±0.53a0.926≤0.01
醇类
71-41-0正戊醇杂醇油气味3.93±0.13e9.86±0.51cd7.22±0.01de13.89±0.28b12.85±0.14bc21.74±2.62a0.794≤0.01
123-96-6仲辛醇不愉快芳香气味71.29±3.32b121.05±9.08a121.57±4.64a106.76±4.50a74.78±3.5b82.63±1.14b1.806≤0.01
98-00-0糠醇苦辣气味2.67±0.01d3.73±0.08d3.31±0.01d6.03±0.43c29.26±0.52b47.63±0.95a0.977≤0.01
100-51-6苯甲醇微弱香气2.33±0.04−−−−−0.358≤0.01
吡嗪类
109-08-02-甲基吡嗪爆米花5.64±0.12cd5.87±0.49cd3.10±0.70d9.57±1.58bc11.42±0.05b19.21±2.10a0.733≤0.01
290-37-9吡嗪青草、坚果、烘烤−−−3.76±1.39c10.77±0.04b21.5±0.03a0.679≤0.01
123-32-02,5-二甲基吡嗪蒸米饭,焙烤、甜味−−−−12.79±0.01b34.17±2.40a0.895≤0.01
108-50-92,6-二甲基吡嗪蒸米饭,焙烤、甜味−−−−13.18±0.02b34.17±0.93a0.891≤0.01
13925-00-32-乙基吡嗪花生酱、木头−−−−2.34±0.05b7.5±0.22a0.435≤0.01
13925-03-62-乙基-6-甲基吡嗪蒸米饭,焙烤、甜味−−−−−5.57±0.350.551≤0.01
烃类
593-45-3正十八烷−−−−−5.03±0.20b7.62±0.27a0.419≤0.01
2216-34-44-甲基辛烷特殊气味17.97±0.24c17.59±0.76c9.38±0.09e13.99±0.18d19.17±0.21b21.29±0.07a1.267≤0.01
17312-54-83,7-二甲基癸烷轻微汽油味10.03±0.39c8.80±0.21d11.37±0.02b6.60±0.28e21.78±0.25a12.23±0.34b0.985≤0.011
17302-01-13-乙基-3-甲基庚烷−2.87±0.14d4.35±1.12c1.54±0.02e6.6±0.28a5.89±0.28b3.36±0.11d0.891≤0.01
2213-23-22,4-二甲基庚烷轻微油味27.55±0.66b22.64±0.73bc19.55±0.59c29.10±4.60b26.71±0.03b42.21±0.32a0.941≤0.01
100-42-5苯乙烯甜味,刺激性气味5.20±0.19a3.72±0.84bc3.72±0.02bc4.74±0.12b2.63±0.04cd1.81±0.04d0.3420.012
31295-56-42,6,10-三甲基十二烷无味−2.43±0.14a1.95±0.07b1.68±0.06c1.97±0.01b2.01±0.04b0.456≤0.01
其他
60-35-5乙酰胺酸味28.62±0.09c21.58±0.61d18.47±3.43d44.36±0.35b46.23±0.36b60.74±1.98a1.277≤0.01
), ArticleFig(id=1320882414923137583, tenantId=1146029695717560320, journalId=1260987677001138203, articleId=1320882403187474924, language=CN, label=表2, caption=

不同储藏时间的酥性饼干香气物质含量

, figureFileSmall=null, figureFileBig=null, tableContent=
CAS号中文名气味描述[25−26]含量(ng/g)VIP值P-value
0 M6 M8 M10 M12 M14 M
醛类
590-86-3异戊醛木香味、苦味、油味14.26±0.23d13.57±0.19e15.00±0.18d17.09±0.05c35.26±0.37b79.8±0.10a1.277≤0.01
66-25-1正己醛刺激性的风味43.54±0.59f61.79±0.09e72.78±0.01d80.27±0.41b77.55±0.34c95.43±1.25a1.211≤0.01
124-19-6壬醛柑橘味2.82±0.10a3.79±1.19a3.1±0.76a3.69±0.73a4.36±0.17a5.69±0.28a0.3600.16
100-52-7苯甲醛苦杏仁味6.59±0.01cd5.58±0.18d6.12±0.02d7.3±0.09c16.02±0.24b35.01±0.73a0.834≤0.01
98-01-1糠醛面包、坚果、焦糖−−−−8.73±0.18b14.89±0.62a0.572≤0.01
96-17-32-甲基丁醛麦芽味7.32±0.03de8.12±0.03cd8.73±0.36c6.49±0.30e14.63±0.27b31.16±0.25a0.801≤0.01
124-13-0正辛醛脂味,刺激性气味−−−3.28±0.17a2.15±0.13b1.62±0.04c0.508≤0.01
111-71-7庚醛油脂味、青草味3.52±0.30e6.23±0.56d5.99±0.07d12.54±0.38b8.80±0.11c14.04±0.21a0.623≤0.01
121-33-5香兰素奶香味、香草味249.05±17.06c322.82±33.48ab328.82±30ab385.95±12.75a277.85±9.13bc259.42±0.92bc2.1890.02
酮类
116-09-6羟基丙酮焦糖香气6.40±0.57f36.99±1.72e42.995±2.99d47.48±5.70c200.66±1.86b261.64±2.44a2.415≤0.01
600-14-62,3-戊二酮奶油、焦糖香气−−−−3.92±0.05b6.71±0.03a0.384≤0.01
3188-00-92-甲基四氢呋喃-3-酮面包、坚果香气−−−−12.04±0.06b45.95±0.67a1.118≤0.01
513-86-03-羟基-2-丁酮油脂香味−−−−23.87±0.12b43.89±0.64a0.975≤0.01
592-20-1乙酸基丙酮刺激性气味−−−1.68±0.13c15.53±0.15b48.88±0.97a1.101≤0.01
5077-67-81-羟基-2-丁酮甜味−−−−−5.26±0.030.479≤0.01
497-23-42(5H)-呋喃酮黄油味−−−−2.51±0.07a2.39±0.13a0.306≤0.01
110-43-02-庚酮水果香味−−−−−3.33±0.010.381≤0.01
酸类
64-19-7冰醋酸强烈刺激气味62.84±0.21f73.57±2.49e89.19±2.43d107.69±2.82c149.87±3.28b191.65±5.69a1.726≤0.01
酯类
141-78-6乙酸乙酯水果香味42.34±0.91a24.91±0.30b23.51±1.06c22.23±0.18d5.35±0.10e2.86±0.07f1.069≤0.01
109-60-4乙酸丙酯水果香80.49±0.12a56.17±0.30c48.61±0.56d64.2±0.37b46.81±0.40e40.61±2.32f1.320≤0.01
123-86-4乙酸丁酯水果香味3.68±0.15−−−−−0.450≤0.01
106-65-0丁二酸二甲酯甜香味17.36±0.01a17.43±0.51a15.35±0.01b14.03±0.17c16.46±0.15a13.8±0.40c0.628≤0.01
96-48-0γ-丁内酯焦糖、甜味1.77±0.06e3.28±0.04c2.45±0.01d2.87±0.22cd13.25±0.18b19.27±0.38a0.632≤0.01
119-40-0戊二酸二甲酯微香气,酯香花香62.2±1.19a57.9±3.24ab30.38±1.23d42.99±0.91c62.89±0.05a55.55±0.65b1.176≤0.01
627-93-0己二酸二甲酯温和的坚果味13.77±0.54a11.68±1.89a10.78±2.23a7.3±0.47b13.92±0.76a11.3±0.34a0.551≤0.01
108-65-6丙二醇甲醚醋
酸酯
浅香甜味−−−−23.65±0.33a24.05±0.53a0.926≤0.01
醇类
71-41-0正戊醇杂醇油气味3.93±0.13e9.86±0.51cd7.22±0.01de13.89±0.28b12.85±0.14bc21.74±2.62a0.794≤0.01
123-96-6仲辛醇不愉快芳香气味71.29±3.32b121.05±9.08a121.57±4.64a106.76±4.50a74.78±3.5b82.63±1.14b1.806≤0.01
98-00-0糠醇苦辣气味2.67±0.01d3.73±0.08d3.31±0.01d6.03±0.43c29.26±0.52b47.63±0.95a0.977≤0.01
100-51-6苯甲醇微弱香气2.33±0.04−−−−−0.358≤0.01
吡嗪类
109-08-02-甲基吡嗪爆米花5.64±0.12cd5.87±0.49cd3.10±0.70d9.57±1.58bc11.42±0.05b19.21±2.10a0.733≤0.01
290-37-9吡嗪青草、坚果、烘烤−−−3.76±1.39c10.77±0.04b21.5±0.03a0.679≤0.01
123-32-02,5-二甲基吡嗪蒸米饭,焙烤、甜味−−−−12.79±0.01b34.17±2.40a0.895≤0.01
108-50-92,6-二甲基吡嗪蒸米饭,焙烤、甜味−−−−13.18±0.02b34.17±0.93a0.891≤0.01
13925-00-32-乙基吡嗪花生酱、木头−−−−2.34±0.05b7.5±0.22a0.435≤0.01
13925-03-62-乙基-6-甲基吡嗪蒸米饭,焙烤、甜味−−−−−5.57±0.350.551≤0.01
烃类
593-45-3正十八烷−−−−−5.03±0.20b7.62±0.27a0.419≤0.01
2216-34-44-甲基辛烷特殊气味17.97±0.24c17.59±0.76c9.38±0.09e13.99±0.18d19.17±0.21b21.29±0.07a1.267≤0.01
17312-54-83,7-二甲基癸烷轻微汽油味10.03±0.39c8.80±0.21d11.37±0.02b6.60±0.28e21.78±0.25a12.23±0.34b0.985≤0.011
17302-01-13-乙基-3-甲基庚烷−2.87±0.14d4.35±1.12c1.54±0.02e6.6±0.28a5.89±0.28b3.36±0.11d0.891≤0.01
2213-23-22,4-二甲基庚烷轻微油味27.55±0.66b22.64±0.73bc19.55±0.59c29.10±4.60b26.71±0.03b42.21±0.32a0.941≤0.01
100-42-5苯乙烯甜味,刺激性气味5.20±0.19a3.72±0.84bc3.72±0.02bc4.74±0.12b2.63±0.04cd1.81±0.04d0.3420.012
31295-56-42,6,10-三甲基十二烷无味−2.43±0.14a1.95±0.07b1.68±0.06c1.97±0.01b2.01±0.04b0.456≤0.01
其他
60-35-5乙酰胺酸味28.62±0.09c21.58±0.61d18.47±3.43d44.36±0.35b46.23±0.36b60.74±1.98a1.277≤0.01
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酥性饼干储藏过程中油脂氧化规律及其对产品风味的影响
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周洪庆 , 柴秀航 , 刘元法 *
食品工业科技 | 贮运保鲜 2026,47(15): 389-397
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食品工业科技 |贮运保鲜 2026 , 47 (15) : 389 -397
酥性饼干储藏过程中油脂氧化规律及其对产品风味的影响
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周洪庆 , 柴秀航, 刘元法*
作者信息
  • 江南大学食品学院,江苏无锡 214122
通讯作者:
刘元法(1974−),男,博士,教授,研究方向:油脂营养安全与绿色制造,E-mail: 。
作者简介:

周洪庆(2000−),男,硕士研究生,研究方向:油脂营养安全与绿色制造,E-mail:

Lipid Oxidation Patterns and Their Impact on Flavor Profile in Crisp Biscuits during Storage
Hongqing ZHOU , Xiuhang CHAI, Yuanfa LIU*
Affiliations
  • School of Food Science and Technology, Jiangnan University, Wuxi 214122, China
出版时间: 2026-08-01 doi: 10.13386/j.issn1002-0306.2025070277
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酥性饼干在储藏期间易发生油脂氧化,导致风味劣变与品质下降。为系统揭示其油脂氧化指标的动态变化规律及其对产品风味的影响,本研究采用顶空固相微萃取-气相色谱-质谱联用技术(HS-SPME-GC-MS),分析了储藏0、6、8、10、12和14个月共6个时间点的样品。油脂氧化指标监测结果显示,随着储藏时间延长,饼干油脂的AV和POV显著上升(P<0.05),而OSI显著下降(P<0.05),从0至14个月下降率达34.47%。风味分析共鉴定出44种挥发性化合物,包括醛类(9种)、酮类(8种)、酸类(1种)、酯类(8种)、醇类(4种)、烃类(7种)、吡嗪类(6种)及其他类(1种)。风味物质含量呈现显著动态变化,其中醛类(如正己醛、异戊醛)、酮类(如羟基丙酮)及酸类(冰醋酸)含量随储藏时间显著增加(P<0.05);而酯类物质(如乙酸乙酯)含量则显著降低(P<0.05),从0至14个月降幅达93.24%。基于偏最小二乘判别分析(PLS-DA)与主成分分析(PCA),结合变量重要性投影(VIP>1)及显著性差异(P<0.05)标准,筛选出13种关键差异风味物质。进一步分析确定正己醛、异戊醛、羟基丙酮、冰醋酸、乙酰胺、乙酸基丙酮和2-甲基四氢呋喃-3-酮共7种化合物为表征酥性饼干品质劣变的核心标志物。相关性分析证实,油脂氧化是诱发酥性饼干异常风味及导致其整体品质劣变的关键驱动因素。本研究结果表明,HS-SPME-GC-MS技术结合多元统计分析可有效识别酥性饼干储藏过程中的关键差异风味物质,为酥性饼干品质劣变的早期预测与监控提供了重要的科学依据和方法学支撑。

酥性饼干  /  风味物质  /  油脂氧化  /  气相色谱-质谱(GC-MS)  /  关键风味物质

Crisp biscuits are susceptible to lipid oxidation during storage, resulting in flavor deterioration and a decline in quality. To systematically investigate the dynamic changes in lipid oxidation indicators and their effect on product flavor, this study utilized headspace solid-phase microextraction coupled with gas chromatography-mass spectrometry (HS-SPME-GC-MS) to analyze samples stored for 0, 6, 8, 10, 12, and 14 months. Monitoring of lipid oxidation indices revealed that the acid value (AV) and peroxide value (POV) increased significantly with storage time (P<0.05). In contrast, the oxidative stability index (OSI) decreased markedly (P<0.05), with a 34.47% reduction over 14 months. A total of 44 volatile compounds were identified, including aldehydes (9), ketones (8), acids (1), esters (8), alcohols (4), hydrocarbons (7), pyrazines (6), and others (1). Flavor profiling demonstrated significant temporal variations: aldehydes (e.g., hexanal, isovaleraldehyde), ketones (e.g., hydroxyacetone), and acids (e.g., acetic acid) increased significantly during storage (P<0.05), whereas esters (e.g., ethyl acetate) decreased sharply (P<0.05), with a 93.24% reduction by month 14. Multivariate statistical analyses, including partial least squares-discriminant analysis (PLS-DA) and principal component analysis (PCA), combined with variable importance in projection (VIP>1) and statistical significance (P<0.05), identified 13 key differential volatile markers. Further screening highlighted seven compounds—hexanal, isovaleraldehyde, hydroxyacetone, acetic acid, acetamide, acetylacetone, and 2-methyltetrahydrofuran-3-one—as core markers indicative of flavor deterioration and overall quality decline in crisp biscuits. Correlation analysis confirmed lipid oxidation as the primary driver of off-flavor development and quality degradation. These findings demonstrate that HS-SPME-GC-MS combined with multivariate analysis is an effective approach for identifying critical differential flavor compounds during storage, providing a scientific and methodological basis for early prediction and quality monitoring of crisp biscuits.

crisp biscuits  /  flavor substances  /  lipid oxidation  /  gas chromatography-mass spectrometry (GC-MS)  /  key flavor compounds
周洪庆, 柴秀航, 刘元法. 酥性饼干储藏过程中油脂氧化规律及其对产品风味的影响. 食品工业科技, 2026 , 47 (15) : 389 -397 . DOI: 10.13386/j.issn1002-0306.2025070277
Hongqing ZHOU, Xiuhang CHAI, Yuanfa LIU. Lipid Oxidation Patterns and Their Impact on Flavor Profile in Crisp Biscuits during Storage[J]. Science and Technology of Food Industry, 2026 , 47 (15) : 389 -397 . DOI: 10.13386/j.issn1002-0306.2025070277
随着全球烘焙食品市场的持续扩张,饼干作为便捷食品的代表,其消费需求呈现显著增长态势,其中酥性饼干因其独特的酥松质地和丰富风味,已经成为许多人在加餐或正餐中不可或缺的一部分[1]。但其高油脂含量(通常>20%)在储藏过程中易引发油脂氧化酸败,成为制约产品货架期与市场接受度的核心问题。油脂氧化经历链式反应:初期生成氢过氧化物(过氧化值POV可量化其积累),进一步降解形成醛、酮、酸等小分子挥发性次级产物(气相色谱-质谱GC-MS可直接鉴定其种类)。这些氧化产物,尤其是短链醛类(如正己醛、戊醛)和酮类,是导致饼干产生“哈败味”等异常风味的直接诱因,同时也伴随着酸价(Acid value,AV)升高,氧化稳定性指数(Oxidation stability index,OSI)下降等理化劣变特征[2]。
当前,国内外对烘焙食品储藏期的研究多聚焦单一或者少数指标,缺乏对酥性饼干多维度氧化指标协同演变的系统监测。邹晴晴等[3]仅以过氧化值为劣变指标建立货架期模型,未考量酸价和氧化稳定性指数的变化,更未能建立整合多指标的综合关联模型。郑艺梅等[4]仅仅测定了储藏期内饼干的酸价和过氧化值,但未涉及OSI等,监测体系指标覆盖不全。更重要的是,上述研究依赖的传统油脂氧化指标存在一定的局限性,它们通常在氧化进行到一定阶段后才发生显著变化,灵敏度相对较低,对早期劣变的预警能力有限。相比之下,油脂氧化过程中产生的挥发性风味物质(如醛、酮、酸等)具有更高的灵敏度,这些化合物种类和浓度的动态变化更能敏锐地反映油脂氧化的起始和进程。尽管酸价和过氧化值等关键理化指标仍符合国家标准(GB 2716-2018)的限值要求,但产品的风味品质已经发生显著劣变,达到消费者不可接受的程度。但是目前酥性饼干油脂氧化进程与GC-MS定量分析的挥发性风味物质关联解析不足。王雨萌等[5]应用气相色谱-离子迁移谱联用技术(GC-IMS)系统分析了文冠果饼干的挥发性风味物质组成,明确了文冠果油与文冠果茶粉对饼干中酯类、醛类等风味物质的增强作用,但却忽略了系统建立油脂氧化指标与定量分析的特定氧化衍生风味物质之间的动态关联模型。因此有必要探究酥性饼干在储藏过程中油脂氧化指标的动态变化规律及其对风味品质的影响。
顶空固相微萃取-气相色谱-质谱联用技术(HS-SPME-GC-MS)在风味富集过程实现自动化,具有快速、便捷等优点,因此通常用于检测和鉴定分析[6−7]。本研究以酥性饼干为对象,系统探究其储藏期油脂氧化规律和产品风味演变机制,揭示油脂氧化与产品风味之间的关系,为酥性饼干的产品开发与储藏品质控制提供了理论依据。
棕榈油、低筋小麦粉 益海嘉里食品科技有限公司;糖粉 佛山鑫丰食品有限公司;白砂糖、食用盐、香草精、小苏打 市售;石油醚、氢氧化钠、酚酞指示剂、标准硫代硫酸钠溶液(0.01 mol/L)、三氯甲烷、冰乙酸、乙醇、碘化钾、可溶性淀粉等化学试剂 分析纯,国药集团化学试剂有限公司。
TQ8040NX GC-MS 日本岛津;SOX406脂肪测定仪 海能仪器;RE212-B旋转蒸发器 日本雅马拓;Metrohm Ranchman743型油脂氧化稳定性测定仪 瑞士万通公司;HBWO-3003-ZS3欧式烤炉 上海韩焙机械科技有限公司;KT-7500和面机 美国凯膳怡。
基础配方:低筋面粉100 g,棕榈油50 g,白砂糖8 g,糖粉40 g,小苏打1 g,香草精1 g,水16 g,食用盐0.8 g。
制备过程如下:首先将棕榈油置于恒温水浴(40±2 ℃)中软化至膏状,转移至和面机搅拌缸内,加入香草精以低速混合30 s至均匀分散;随后将过筛(80目筛网)的低筋小麦粉与白砂糖、糖粉、小苏打、食用盐预先干混均匀,分两次加入搅拌缸,同时逐次注入配方水量;启动和面机以低速搅拌1 min,至混合物呈松散团聚状且无干粉即停止。将拌合后的面团移出,分割为8 g/个的剂子,用模具压制成型。成型坯体置于烤盘,放入预热至上火175 ℃,下火170 ℃的烤箱中烘烤20 min。
为研究储藏时间对酥性饼干的影响,将规格一致(尺寸与形状相同)的酥性饼干样品用铝箔包装袋包装后经封口机密封,置于恒温恒湿箱(25 ℃,75%RH)中贮藏。基于市售同类产品的保质期普遍设定为9个月以上,因此分别于0个月(0 M)、6个月(6 M)、8个月(8 M)、10个月(10 M)、12个月(12 M)、14个月(14 M)取样,涵盖保质期内、临近保质期与超过保质期三个关键阶段,通过测定其风味物质、酸价、过氧化值、油脂氧化稳定性指数,以系统评估储藏时间对酥性饼干的影响。
参考国家标准GB 5009.6-2016《食品中脂肪的测定》中的索氏抽提法提取酥性饼干中的油脂。将饼干尽可能碾碎,取100 g于滤纸筒中用石油醚浸泡抽提,然后旋转蒸发除去溶剂,置于烘箱干燥,最后称重,并将其用于之后的实验分析。
参照国家标准GB 5009.229-2016《食品安全国家标准 食品中酸价的测定》和GB 5009.227-2023《食品安全国家标准 食品中过氧化值的测定》,测定酥性饼干中提取油脂的酸价和过氧化值。
氧化稳定性指数采用Rancimat方法测试(GB/T 21121-2007)。酥性饼干提取的油样称3.00 g于测试管中。测试条件为:空气流量20 L/min,氧化温度120 ℃。
本实验从酥性饼干的风味维度对酥性饼干进行评价。酥性饼干的感官评定参考GB/T 20980-2021《饼干质量通则》和渠琦等[8]方法。实验通过15名经培训的人员(8名女性和7名男性,平均年龄为24±3岁)作为测试员进行酥性饼干的感官评价,满分为10分,最后得分取15个人的平均值,感官评价标准如表1所示。
样品前处理:取不同储藏时间点的酥性饼干样品,破碎磨成粉末状,分别称取2 g置于顶空瓶中,加入5 μL 4-甲基-2-戊酮作为内标,其质量浓度为90 μg/mL。
固相微萃取条件:顶空瓶密封后50 ℃水浴平衡30 min,后将萃取头取出再插入250 ℃进样口解吸5 min。
色谱条件:毛细管色谱柱DB-WAX,柱长60 m,内径0.25 mm,膜厚0.25 μm。初温40 ℃,保持6 min,以5 ℃/min速率升至200 ℃,以10 ℃/min速率升至240 ℃,保持10 min。
质谱条件:电子轰击(EI)离子源,电子能量70 eV,离子源温度230 ℃,接口温度250 ℃。采用全扫描模式采集信号,扫描范围40~500 m/z。
挥发性物质定性定量分析:HS-SPME-GC-MS检测的化合物基于NIST14的谱库进行比对,保留匹配度大于80的化合物,定量通过化合物的峰面积与内标化合物的峰面积进行比较,得到风味物质的含量,其计算公式为:
$ \rm C_i=S_i/S_{内标}\times C_{内标} $
式中,Ci为待测物质的质量分数,ng/g;Si代表未知物的峰面积;S内标代表内标化合物的峰面积;C内标为内标物的质量分数,ng/g。
采用Excel 2019和SPSS 27.0软件进行数据处理以及单因素分析;SIMCA 14.1软件进行偏最小二乘判别分析(Partial least squares-discriminant analysis,PLS-DA),计算预测变量重要性投影(Varible importance in projection,VIP);Origin 2021软件绘制图像,所有数据用平均值±标准差表示。显著性分析使用标记字母法表示,P<0.05表示存在显著性差异,以上实验均进行3次重复。
酥性饼干中油脂含量在20%以上,由于光照、热以及水分等因素的影响,油脂会发生氧化酸败,引起产品中的游离脂肪酸含量的增加[9],不仅引发不良风味化合物的生成,还可能产生潜在毒性物质,从而影响产品的品质。如图1所示,酥性饼干的酸价随储藏时间延长呈上升趋势,从储藏0 M的0.59±0.01 mg/g上升到储藏14 M的0.85±0.02 mg/g,增幅44.07%。该现象表明,储藏过程中油脂氧化程度不断加剧。油脂氧化会促使甘油三酯分解,进而导致游离脂肪酸含量增加,这是酸价升高的直接原因[10]。本研究中酸价随时间的变化规律,与陆婷婷[11]关于咖啡果皮粉对曲奇饼干酸价影响规律的研究结论一致。在整个储藏期间,酸价均符合国家标准≤5.0 mg/g。
油脂在储藏过程中氧化,首先生成不稳定的初级氧化产物—氢过氧化物。氢过氧化物不稳定,不仅可通过酸催化发生分子重排,还能进一步降解形成醛、酮、游离脂肪酸等次级氧化产物[12],使得醛、酮、酸类物质含量不断增加。作为衡量油脂初级氧化程度的关键指标,过氧化值(POV)直接反映了氢过氧化物的积累量,是评判油脂变质初期程度的重要依据[13]。图2数据显示,酥性饼干的POV随储藏时间显著上升,这清晰地表明储藏期间油脂的氧化反应持续进行,氢过氧化物不断生成并积累。在储藏8 M后,POV显著提升(P<0.05),表明此阶段氧化进程可能加速。在储藏10~14 M期间,过氧化值变化不显著,这可能与氢过氧化物的分解速率与其生成速率达到动态平衡有关。在储藏14 M后,过氧化值为0.033±0.00 g/100 g,尽管POV呈上升趋势,但在整个研究期内,均符合国家标准≤0.25 g/100 g,表明产品在规定的储藏期内氧化程度处于安全可控的范围。
氧化稳定性指数是评价油脂氧化稳定性的直观指标。从图3中可知,酥性饼干中的油脂在120 ℃下的OSI值随储藏时间延长而持续下降。具体而言,氧化稳定性指数由储藏初期的21.18±0.52 h显著下降至储藏14 M时的13.88±0.10 h(P<0.05),降幅达34.47%。原因在于储藏期间,酥性饼干中油脂的酸价升高,游离脂肪酸增多;过氧化值升高,油脂氧化的中间产物积累,均会加速酥性饼干中油脂氧化的进程[14],最终导致氧化稳定性快速下降。
感官评价是对产品货架期判断的重要手段,也是对产品品质描述的直观指标。如图4所示,不同储藏周期酥性饼干的感官雷达图清晰揭示了风味维度的动态演变趋势。随着储藏时间的延长,代表产品初始品质的良好风味(如甜味、香味)得分显著下降,甜味得分从储藏初始0 M的8.01±1.10分逐渐降至储藏14 M的6.14±0.85分,香味得分从5.12±1.02分降至2.33±0.78分,反映出产品原有风味逐渐丧失。与此同时,与品质劣变相关的异常风味属性(哈喇味、陈旧味)也呈现明显变化,哈喇味得分从4.83±0.22分下降至0.98±0.02分,陈味得分从7.43±1.23分降至1.12±0.22分,说明不良风味感知逐渐增加。
上述风味变化与储藏过程中发生的化学变化密切相关。异常风味的增加与油脂氧化程度加剧一致,具体表现为AV和POV上升、OSI下降。已有研究表明,油脂氧化过程中生成的不饱和醛、酮等次级氧化产物,即使微量存在,因其较低的感官阈值也极易被消费者感知为典型的油脂哈败特征[15]。同时,伴随氧化进程的加剧,油脂中游离脂肪酸含量增加,可能引起酯类等愉悦风味成分的损失或转化,从而导致产品原有的甜香、果香等良好风味逐渐减弱。因此,酥性饼干储藏期间感官品质的劣变,尤其是哈喇味和陈味的增强以及甜味和香味的消退,主要归因于油脂氧化程度的不断加剧。
本研究采用HS-SPME-GC-MS技术,对6个不同储藏时间点的酥性饼干风味物质进行了系统分析。经NIST14库对比定性及分类统计,共检测到44种风味化合物,涵盖醛类(9种)、酮类(8种)、酸类(1种)、酯类(8种)、醇类(4种)、烃类(7种)、吡嗪类(6种)及其他(1种)。检测到的风味物质种类随储藏时间延长,总体呈上升趋势(0 M的27种到14 M的42种),这一现象表明了储藏期间复杂化学反应的持续进行,尤其是以油脂氧化为主导的劣变过程。
由表2可知,醛类、酮类、酸类和酯类化合物是酥性饼干中含量较高的风味组分。醛类物质含量在储藏过程中呈现显著上升趋势,这与油脂氧化进程高度一致。酥性饼干的油脂含量通常在20%(w/w)以上,储藏期间产生的不良风味(如金属味、油漆味、酸败味、陈味)主要源于不饱和脂肪酸(如亚油酸)自动氧化,其初级氢过氧化物分解直接产生大量挥发性醛类[16]。公认的脂质氧化标志物正己醛含量从43.54±0.59 ng/g上升到95.43±1.25 ng/g,增长率为119.18%,异戊醛从储藏0 M的14.26±0.23 ng/g上升至14 M的79.8±0.10 ng/g,印证了AV和POV上升所反映的氧化程度加剧和游离脂肪酸增多,以及OSI下降所预示的氧化稳定性丧失。不饱和醛类物质通常具有较低的阈值和强烈的气味特征[17],是导致“哈喇味”的关键贡献者。虽然香兰素(含量最高的醛类)作为外源增香剂提供香草味、奶香味,但其存在并不会干扰通过醛类物质的总体水平来判断油脂氧化的程度。本研究观察到的醛类增长趋势与Maire等[18]在关于烘焙制品脂质氧化中所阐述的结论一致,共同指向不饱和脂肪酸在光照、氧气条件下自发氧化降解的普遍机制。
酮类是油脂深度氧化的典型产物。羟基丙酮在所有样品中均被检出,且其含量随储藏时间延长呈显著上升趋势。该变化趋势与氧化稳定性指数的持续下降及过氧化值的升高有关,表明其生成与油脂氧化进程密切相关。油脂氧化产生的醛类(如正己醛)可与氨基酸发生Strecker等次级反应,生成羟基丙酮等前体物[19]。羟基丙酮在储藏后期浓度较高,且具有刺激性风味,使饼干产生明显的哈喇味和陈味。在储藏后期(12 M和14 M)样品中检测到多种特征性酮类化合物,如2,3-戊二酮、2(5H)-呋喃酮、2-甲基四氢呋喃-3-酮及3-羟基-2-丁酮等酮类化合物,以及仅仅在14 M样品中检测出的1-羟基-2-丁酮和2-庚酮。这些化合物的出现是油脂氧化进入深度阶段的象征。它们主要来源于前期积累的氢过氧化物(POV升高的直接体现)的进一步分解(如β-裂解)以及更复杂的氧化反应途径(如脂肪酸的β-氧化[20])。这些深度氧化产物的检出与OSI显著下降,共同表明酥性饼干中的油脂发生了深度氧化。
尽管适量的酸类物质能够增强样品的风味特性,但过高的酸类物质含量会导致样品产生过于刺激的气味,从而降低其感官评价得分[21]。检测出的唯一酸类物质是冰醋酸,含量从62.84±0.21 ng/g显著上升到191.65±5.69 ng/g(P<0.05),增长率为204.98%,这一增长趋势紧密关联于AV的上升,是油脂水解(产生游离脂肪酸)和游离脂肪酸进一步氧化(生成短链羧酸如冰醋酸)双重作用的结果。虽然冰醋酸具有强烈的刺激气味,但其气味阈值相对较高,且适量时可使饼干风味更加丰富[22],但含量的显著升高仍是体系酸败程度加剧的一个重要化学指标。
具有愉悦水果香气的酯类物质含量在储藏过程中呈现显著下降趋势,与醛、酮、酸的上升相反。乙酸乙酯含量从初始0 M样品的42.34±0.91 ng/g显著降至14 M样品的2.86±0.07 ng/g(P<0.05),下降率93.24%,乙酸丙酯也下降49.55%,乙酸丁酯更是在储藏初期(0 M)后消失。主要是油脂氧化所导致游离脂肪酸积累与体系酸度增加,在饼干低水分活度条件下协同催化酯键水解,生成乙醇和乙酸。因此,酯类的快速消耗不仅是风味愉悦感丧失的直接原因,也是氧化反应的间接体现。
在所有检测样品中,2-甲基吡嗪是唯一普遍存在的吡嗪类化合物。这类物质因其特有的烘烤香气和爆米花风味特征,在烘焙食品中广泛存在,是赋予食品坚果、咖啡及巧克力等典型风味的关键组分。研究证实,吡嗪类化合物是形成烘焙产品特征焦香风味的主要物质基础[23]。其中,2,5-二甲基吡嗪和2,6-二甲基吡嗪仅在贮藏12 M和14 M的样品中被检出,这主要与油脂深度氧化密切相关。在储藏后期,前期积累的大量脂质氧化产物(如醛类、酮类)可与氨源结合,通过次级反应生成吡嗪类化合物[24]。因此,特定吡嗪的出现可视为油脂深度氧化(OSI低、POV和AV值高)并触发新的风味形成途径的重要标志。
醇类物质只检测出4种,其中苯甲醇仅在储藏初期(0 M)被检出,具有微弱的香气。正戊醇、仲辛醇和糠醇在所有的样品中均被检出,仲辛醇在醇类物质中含量最高,且在不同储藏期间含量呈现较大波动。
本研究的烃类化合物基本为烷烃类物质,该类化合物通常不具有明显风味特征,对酥性饼干整体香气的形成贡献较小。在所有样品中均检出的烃类包括4-甲基辛烷、3,7-二甲基癸烷、3-乙基-3-甲基庚烷、2,4-二甲基庚烷及苯乙烯,具有特殊气味、汽油味、轻油味、刺激性气味。
为了进一步明确不同储藏时间酥性饼干中的关键差异成分,本研究采用偏最小二乘法-判别分析(PLS-DA)。该方法基于样本分类信息,能够有效凸显组间差异并建立判别模型,适用于识别不同储存阶段的特征性风味化合物[27−28]。
以挥发性物质作为因变量,不同储藏时间的酥性饼干样品作为自变量,通过PLS-DA(图5),可以实现不同储藏时间酥性饼干样品的有效区分,此次分析中,自变量拟合指数(R2X)为0.997,因变量指数(R2Y)为0.996,模型预测指数为0.986,R2和Q2均大于0.5,表明模型拟合结果可以接受。
而后,为了进一步验证模型的可靠性,将模型经过200次置换检验(Permutation test),最右侧的R2和Q2大于左侧,Q2回归线与纵轴交点小于0(图6),表明模型不存在过拟合,模型验证有效,认为该结果可用于判断6种不同储藏时间的饼干样品的差异性化合物。
变量重要性分析值(VIP)可以量化PLS-DA的每个变量对分类的贡献度,以便筛选出重要的分类变量,根据VIPs>1且P<0.05的标准[29],VIP值越大,代表着该变量在不同储藏时间差异越显著。根据结果显示,按VIP值大小排序,羟基丙酮(2.415)、香兰素(2.189)、仲辛醇(1.806)、冰醋酸(1.726)、乙酸丙酯(1.320)、乙酰胺(1.277)、异戊醛(1.277)、4-甲基辛烷(1.267)、正己醛(1.211)、戊二酸二甲酯(1.176)、2-甲基四氢呋喃-3-酮(1.118)、乙酸基丙酮(1.101)、乙酸乙酯(1.069),这13种物质满足VIP值>1,P<0.05,对不同储藏时间的酥性饼干有显著的影响,是区分不同储藏时间的主要差异性物质。
对不同储藏时间的酥性饼干关键风味成分进行主成分分析[30]。如图7所示,主成分1(PC1)和主成分2(PC2)的贡献率分别为62.9%和23.5%。在PC1轴上,短期储藏样品(如前四个时间点)主要分布于负轴区域,而长期储藏样品(12 M和14 M)则多集中于正轴区域。
该结果表明,基于风味物质组成,不同储藏时间的酥性饼干样品在PCA空间中能清晰区分,且无重叠现象。这表明在储藏过程中,酥性饼干的风味物质组成发生了显著变化,所筛选出的13种风味化合物能有效鉴别其储藏时间。图中箭头代表各风味物质,其指向特定样品群的距离越近,表明该物质与该组样品的相关性越高。PCA结果显示,乙酸乙酯和乙酸丙酯与0 M和6 M样品相关性较高;仲辛醇和香兰素则与8 M和10 M样品相关性较高;而正己醛、异戊醛、冰醋酸、乙酰胺、羟基丙酮、乙酸基丙酮及2-甲基四氢呋喃-3-酮等物质与12 M和14 M样品表现出较强相关性。结合感官评价及风味描述分析发现,具有果香风味的物质(如乙酸乙酯、乙酸丙酯)随储藏时间延长呈显著下降趋势,该趋势与感官评价中香味和甜味得分的降低一致。相反,具有油脂味和刺激性气味的物质(如正己醛、冰醋酸、异戊醛)则呈现上升趋势,这与感官评价中陈味、哈喇味得分降低的趋势相符。此外,鉴于醛类物质普遍具有较低的感觉阈值[31],其对饼干整体气味的贡献尤为重要。因此,所筛选出的醛类等关键差异化合物对饼干储藏前后风味的演变具有显著影响。综上,正己醛、异戊醛、冰醋酸、乙酰胺、羟基丙酮、乙酸基丙酮及2-甲基四氢呋喃-3-酮是表征酥性饼干在储藏过程中品质劣变的关键风味化合物。
为系统解析酥性饼干储藏过程中油脂氧化、关键风味化合物及感官特性之间的内在联系,本研究进行了全面的相关性分析,结果如图8所示。结果显示,筛选出的7种关键劣变风味化合物与酸价(AV)、过氧化值(POV)呈正相关,而与氧化稳定指数(OSI)呈负相关。这印证了氧化程度加剧直接促进了这些关键风味化合物的生成。其中正己醛与AV呈极显著正相关(r=0.96,P<0.01),羟基丙酮和冰醋酸与AV呈显著正相关(r=0.84,0.91,P<0.05);正己醛与POV呈显著正相关(r=0.92,P<0.05);冰醋酸与OSI呈极显著负相关(r=−0.93,P<0.01),羟基丙酮和乙酰胺与OSI呈显著负相关(r=−0.87,−0.81,P<0.05)。感官评价分析进一步强化了上述分析结论,酥性饼干储藏过程中陈味得分与酸价(r=−0.94,P<0.01)和过氧化值(r=−0.81)呈显著负相关关系,而与OSI(r=0.88,P<0.05)呈显著正相关关系。哈喇味得分与酸价(r=−0.94,P<0.01)和过氧化值(r=−0.91,P<0.05)呈显著负相关关系,与OSI(r=0.94,P<0.01)呈显著正相关关系。相关性分析结果证实,油脂氧化进程是诱导酥性饼干中关键劣变风味化合物生成的主要驱动因素,油脂氧化引发的风味化合物的变化,直接导致了陈味和哈喇味的产生,因此油脂氧化是酥性饼干在储藏过程中发生品质劣变并最终达到不可接受状态的关键原因。
本研究系统揭示了酥性饼干在长期储藏(0 M~14 M)过程中油脂氧化稳定性与产品风味的协同演变规律,阐明了油脂氧化对产品风味劣变的主导作用。结果表明,随着储藏时间延长,酸价与过氧化值显著升高,而氧化稳定性指数持续下降,说明油脂氧化不断加剧。HS-SPME-GC-MS分析共检测到44种挥发性化合物,其中正己醛、异戊醛、羟基丙酮和冰醋酸等氧化产物显著增加,而乙酸乙酯等酯类化合物明显减少。这些变化与感官评价中“哈喇味”和“陈味”的增强以及“甜味”和“香味”的减弱呈显著相关。通过PLS-DA和PCA分析共筛选出13种关键差异风味物质,并进一步确定正己醛、异戊醛、羟基丙酮、冰醋酸、乙酰胺、乙酸基丙酮及2-甲基-四氢呋喃-3-酮共7种化合物为表征酥性饼干品质劣变的核心风味标志物。相关性分析进一步证实,油脂氧化是诱导这些关键异味物质生成并导致感官品质劣变的首要驱动因素。本研究不仅明确了酥性饼干储藏过程中油脂氧化与风味劣变的耦合机制,而且提出了可用于表征品质劣变的核心风味标志物,为酥性饼干品质变化的早期预测、货架期判定及储藏品质监控提供了新的科学依据和方法学支撑。

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2026年第47卷第15期
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doi: 10.13386/j.issn1002-0306.2025070277
  • 接收时间:2025-07-23
  • 首发时间:2026-10-24
  • 出版时间:2026-08-01
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  • 收稿日期:2025-07-23
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    江南大学食品学院,江苏无锡 214122

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刘元法(1974−),男,博士,教授,研究方向:油脂营养安全与绿色制造,E-mail: 。
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2种不同金属材料的力学参数
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鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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