Article(id=1276844518947287888, tenantId=1146029695717560320, journalId=1235980609244409860, issueId=1276844393709568941, articleNumber=null, orderNo=null, doi=10.3969/j.issn.1000-2561.2024.10.021, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1710777600000, receivedDateStr=2024-03-19, revisedDate=1714147200000, revisedDateStr=2024-04-27, acceptedDate=null, acceptedDateStr=null, onlineDate=1782353055940, onlineDateStr=2026-06-25, pubDate=1729785600000, pubDateStr=2024-10-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1782353055940, onlineIssueDateStr=2026-06-25, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1782353055940, creator=13701087609, updateTime=1782353055940, updator=13701087609, issue=Issue{id=1276844393709568941, tenantId=1146029695717560320, journalId=1235980609244409860, year='2024', volume='45', issue='10', pageStart='1999', pageEnd='2242', issueExtLink='null', onlineDate='null', pubDate='1729785600000', pubDateStr='2024-10-25', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1782353026082, creator='13701087609', updateTime=1782355588483, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1276855141311574992, tenantId=1146029695717560320, journalId=1235980609244409860, issueId=1276844393709568941, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1276855141311574993, tenantId=1146029695717560320, journalId=1235980609244409860, issueId=1276844393709568941, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=2201, endPage=2212, ext={EN=ArticleExt(id=1276844520679535442, articleId=1276844518947287888, tenantId=1146029695717560320, journalId=1235980609244409860, language=EN, title=Analysis of Volatile Compounds in Coconut Meat of Deteriorated Dehusked Coconut Fruits under Different Temperature and Humidity by GC-IMS, columnId=1236286112713470633, journalTitle=Chinese Journal of Tropical Crops, columnName=Post-harvest Treatment & Quality Safety, runingTitle=null, highlight=null, articleAbstract=

Coconut meat is the main raw material for coconut products processing, which is mainly obtained by importing dehusked coconut fruits in containers, and the rate of bad fruit is high in the process of transportation and storage. In order to explore the method of rapid differentiation and identification, this study used gas chromatography-ion mobility spectrometry (GC-IMS) combined with principal component analysis (PCA) and orthogonal partial least squares discriminant analysis (OPLS-DA) to analyze the volatile compounds in coconut meat of unstored normal dehusked fresh coconut fruits (FCM) and deteriorated dehusked coconut fruits under 25 ℃/70%, 35 ℃/80% and 45 ℃/90% (DCM-25, DCM-35 and DCM-45). The results showed that 42 volatile compounds were identified in the four coconut meat, including thirteen alcohols, five acids, eight ketones, ten esters, four aldehydes, two pyrazines and three unknown compounds. The alcohols were the most (including ethanol, butanol and propanol, etc.), followed by acids (including acetic acid and 2-methylpropionic acid, etc.), ketones (including acetone, 3-hydroxy-2-butanone and cyclopentanone, etc.), esters (including butyl caproate, ethyl acetate, butyl butyrate and ethyl butyrate, etc.), aldehydes (including 3-methylbutyraldehyde, pentalaldehyde and heptyl aldehyde, etc.) and pyrazines (2-ethyl-3-methylpyrazine). After deterioration, alcohol, acid and ketone volatile compounds increased. Thirteen characteristic volatile compounds, including 3-methylbutyral, cyclopentanone, 3-methylbutanol monomer, butanol monomer, heptaldehyde, acetone, 2-methylpropanol monomer, 2-heptanone monomer, heptanic acid, butyl butyrate monomer, ethyl acetate, ethanol dimer and 2-ethyl-3-methylpyrazine monomer, were analyzed by OPLS-DA, with variable importance in projection greater than 1. The characteristic volatile compounds in FCM were cyclopentanone and butanol monomer by differential heat map. The characteristic volatile compounds in DCM-25 were 2-heptanone monomer, butyl butyrate monomer, ethyl acetate, ethanol dimer and 2-ethyl-3-methylpyrazine monomer (mainly esters, alcohols and ketones). The characteristic volatile compounds in DCM-35 was heptanoic acid (mainly acids). The characteristic volatile compounds in DCM-45 were 3-methylbutyraldehyde, heptyl aldehyde and acetone (mainly aldehydes and ketones). This study would provide theoretical basis for the screening of deteriorated dehusked coconut fruits.

, authors=null, authorsList=Yuanyuan WANG, Xiaojun SHEN, Fei SONG, Jintao KAN, Jianguo ZHANG, Yufeng ZHANG, authorCompany=null, correspAuthors=Yufeng ZHANG, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, 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=1276844522860573534, articleId=1276844518947287888, tenantId=1146029695717560320, journalId=1235980609244409860, language=CN, title=基于GC-IMS对不同温湿度贮藏条件下变质毛椰子果椰肉中挥发性物质分析, columnId=1236286112877048492, journalTitle=热带作物学报, columnName=采后处理与质量安全, runingTitle=null, highlight=null, articleAbstract=

椰肉是椰子产品加工的主要原料,获取方式以集装箱进口毛椰子果为主,在运输及贮藏过程中坏果率高。为了探寻快速区分和鉴别的方法,本研究利用气相色谱-离子迁移谱(gas chromatography-ion mobility spectrometry,GC-IMS)结合主成分分析(principal component analysis,PCA)和正交偏最小二乘法判别分析(orthogonal partial least squares discriminant analysis,OPLS-DA)对未贮藏正常毛椰子果椰肉(FCM)和25 ℃/70%、35 ℃/80%、45 ℃/90% 3种温湿度贮藏条件下变质毛椰子果椰肉(DCM-25、DCM-35和DCM-45)中挥发性物质进行分析。结果显示:在4种椰肉中均定性出42种挥发性物质,其中醇类13种,酸类5种,酮类8种,酯类10种,醛类4种,吡嗪类化合物2种,未定性的化合物3种。醇类最多(包括乙醇、丁醇和丙醇等),其次是酸类(包括乙酸和2-甲基丙酸等)、酮类(包括丙酮、3-羟基-2-丁酮和环戊酮等)、酯类(包括己酸丁酯、乙酸乙酯、丁酸丁酯和丁酸乙酯等)、醛类(包括3-甲基丁醛、戊醛和庚醛等)和吡嗪类(2-乙基-3-甲基吡嗪)物质。变质后醇、酸、酮类挥发性物质增多。利用OPLS-DA分析出3-甲基丁醛、环戊酮、3-甲基丁醇单体、丁醇单体、庚醛、丙酮、2-甲基丙醇单体、2-庚酮单体、庚酸、丁酸丁酯单体、乙酸乙酯、乙醇二聚体和2-乙基-3-甲基吡嗪单体13种变量投影重要性因子(variable importance in projection,VIP)大于1的特征挥发性物质。利用差异热图确定了在FCM中的特征挥发性物质为环戊酮和丁醇单体;DCM-25中的特征挥发性物质为2-庚酮单体、丁酸丁酯单体、乙酸乙酯、乙醇二聚体和2-乙基-3-甲基吡嗪单体(以酯、醇、酮类为主);DCM-35中的特征挥发性物质是庚酸(主要是酸类);DCM-45中的特征挥发性物质是3-甲基丁醛、庚醛和丙酮(以醛、酮类为主)。该研究结果为变质果的筛选提供了更多的理论依据。

, authors=

王媛媛(1982—),女,硕士,助理研究员,研究方向:热带农产品加工与贮藏保鲜。

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* 张玉锋(ZHANG Yufeng),E-mail:
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2.Hainan Engineering Center of Coconut Further Processing, Wenchang, Hainan 571339, China
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2.海南省椰子深加工工程技术研究中心,海南文昌 571339
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王媛媛(1982—),女,硕士,助理研究员,研究方向:热带农产品加工与贮藏保鲜。

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王媛媛(1982—),女,硕士,助理研究员,研究方向:热带农产品加工与贮藏保鲜。

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2.海南省椰子深加工工程技术研究中心,海南文昌 571339
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language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=3.椰子产业技术创新战略联盟,海南文昌 571339)])], figs=[ArticleFig(id=1276844533757375387, tenantId=1146029695717560320, journalId=1235980609244409860, articleId=1276844518947287888, language=EN, label=Fig. 1, caption=Three-dimensional (A), two-dimensional (B) and difference (C) spectrum of volatile compounds of coconut meat in deteriorated dehusked coconut fruits under different temperature and humidity storage conditions by GC-IMS, figureFileSmall=8SVNi/uwIuwlXt1VHGQZkg==, figureFileBig=GZxp2d7ivd3CGzOiUKwGkA==, tableContent=null), ArticleFig(id=1276844534038393756, tenantId=1146029695717560320, journalId=1235980609244409860, articleId=1276844518947287888, language=CN, label=图1, caption=不同温湿度贮藏条件下变质毛椰子果椰肉中挥发性物质GC-IMS三维谱图(A)、二维谱图(B)和差异谱图(C), figureFileSmall=8SVNi/uwIuwlXt1VHGQZkg==, figureFileBig=GZxp2d7ivd3CGzOiUKwGkA==, tableContent=null), ArticleFig(id=1276844534239720349, 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different temperature and humidity storage conditions by GC-IMS, figureFileSmall=RvVxy68U7mfUn8xmGQWQwg==, figureFileBig=dHJ8k7BznILeXVA2LhnhhA==, tableContent=null), ArticleFig(id=1276844534466212768, tenantId=1146029695717560320, journalId=1235980609244409860, articleId=1276844518947287888, language=CN, label=图3, caption=不同温湿度贮藏条件下变质毛椰子果椰肉中挥发性物质GC-IMS指纹谱图, figureFileSmall=RvVxy68U7mfUn8xmGQWQwg==, figureFileBig=dHJ8k7BznILeXVA2LhnhhA==, tableContent=null), ArticleFig(id=1276844534554293153, tenantId=1146029695717560320, journalId=1235980609244409860, articleId=1276844518947287888, language=EN, label=Fig. 4, caption=PCA and OPLS-DA analysis of volatile compounds of coconut meat in deteriorated dehusked coconut fruits under different temperature and humidity storage conditions and normal coconut fruits by GC-IMS

A: PCA analysis; B: OPLS-DA analysis; 1, 2, 3 and 4 represent FCM, DCM-25, DCM-35 and DCM-45, respectively. C: Random permutation test; D: Scatter plot of load; E: Characteristic volatile compound (VIP>1); F: Difference heat map of the characteristic volatile compound.

, figureFileSmall=F8GAUyqlj6fnDaRIjkSqkw==, figureFileBig=5174/bYT5pyNXOlxKQbGdg==, tableContent=null), ArticleFig(id=1276844534608819106, tenantId=1146029695717560320, journalId=1235980609244409860, articleId=1276844518947287888, language=CN, label=图4, caption=不同温湿度贮藏条件下变质与正常毛椰子果椰肉中GC-IMS挥发性物质的PCA和OPLS-DA分析

A:PCA分析;B:OPLS-DA分析;1、2、3和4分别表示FCM、DCM-25、DCM-35和DCM-45。C:随机置换检验;D:载荷散点图;E:特征挥发性物质(VIP>1);F:特征挥发性物质差异热图。

, figureFileSmall=F8GAUyqlj6fnDaRIjkSqkw==, figureFileBig=5174/bYT5pyNXOlxKQbGdg==, tableContent=null), ArticleFig(id=1276844534675927971, tenantId=1146029695717560320, journalId=1235980609244409860, articleId=1276844518947287888, language=EN, label=Tab. 1, caption=

Volatile compounds of coconut meat in deteriorated dehusked coconut fruits under different temperature and humidity storage conditions by GC-IMS

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基于GC-IMS对不同温湿度贮藏条件下变质毛椰子果椰肉中挥发性物质分析
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王媛媛 1, 2, 3 , 沈晓君 1 , 宋菲 1, 2, 3 , 阚金涛 1, 2, 3 , 张建国 1, 2, 3 , 张玉锋 1, 2, 3, *
热带作物学报 | 采后处理与质量安全 2024,45(10): 2201-2212
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热带作物学报 |采后处理与质量安全 2024 , 45 (10) : 2201 -2212
基于GC-IMS对不同温湿度贮藏条件下变质毛椰子果椰肉中挥发性物质分析
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王媛媛1, 2, 3, 沈晓君1, 宋菲1, 2, 3, 阚金涛1, 2, 3, 张建国1, 2, 3, 张玉锋1, 2, 3, *
作者信息
  • 1.中国热带农业科学院椰子研究所,海南文昌 571339
  • 2.海南省椰子深加工工程技术研究中心,海南文昌 571339
  • 3.椰子产业技术创新战略联盟,海南文昌 571339
通讯作者:
* 张玉锋(ZHANG Yufeng),E-mail:
Analysis of Volatile Compounds in Coconut Meat of Deteriorated Dehusked Coconut Fruits under Different Temperature and Humidity by GC-IMS
Yuanyuan WANG1, 2, 3, Xiaojun SHEN1, Fei SONG1, 2, 3, Jintao KAN1, 2, 3, Jianguo ZHANG1, 2, 3, Yufeng ZHANG1, 2, 3, *
Affiliations
  • 1.Coconut Research Institute, Chinese Academy of Tropical Agricultural Sciences, Wenchang, Hainan 571339, China
  • 2.Hainan Engineering Center of Coconut Further Processing, Wenchang, Hainan 571339, China
  • 3.Coconut Industry Technology Innovation Strategic Alliance, Wenchang, Hainan 571339, China
出版时间: 2024-10-25 doi: 10.3969/j.issn.1000-2561.2024.10.021
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椰肉是椰子产品加工的主要原料,获取方式以集装箱进口毛椰子果为主,在运输及贮藏过程中坏果率高。为了探寻快速区分和鉴别的方法,本研究利用气相色谱-离子迁移谱(gas chromatography-ion mobility spectrometry,GC-IMS)结合主成分分析(principal component analysis,PCA)和正交偏最小二乘法判别分析(orthogonal partial least squares discriminant analysis,OPLS-DA)对未贮藏正常毛椰子果椰肉(FCM)和25 ℃/70%、35 ℃/80%、45 ℃/90% 3种温湿度贮藏条件下变质毛椰子果椰肉(DCM-25、DCM-35和DCM-45)中挥发性物质进行分析。结果显示:在4种椰肉中均定性出42种挥发性物质,其中醇类13种,酸类5种,酮类8种,酯类10种,醛类4种,吡嗪类化合物2种,未定性的化合物3种。醇类最多(包括乙醇、丁醇和丙醇等),其次是酸类(包括乙酸和2-甲基丙酸等)、酮类(包括丙酮、3-羟基-2-丁酮和环戊酮等)、酯类(包括己酸丁酯、乙酸乙酯、丁酸丁酯和丁酸乙酯等)、醛类(包括3-甲基丁醛、戊醛和庚醛等)和吡嗪类(2-乙基-3-甲基吡嗪)物质。变质后醇、酸、酮类挥发性物质增多。利用OPLS-DA分析出3-甲基丁醛、环戊酮、3-甲基丁醇单体、丁醇单体、庚醛、丙酮、2-甲基丙醇单体、2-庚酮单体、庚酸、丁酸丁酯单体、乙酸乙酯、乙醇二聚体和2-乙基-3-甲基吡嗪单体13种变量投影重要性因子(variable importance in projection,VIP)大于1的特征挥发性物质。利用差异热图确定了在FCM中的特征挥发性物质为环戊酮和丁醇单体;DCM-25中的特征挥发性物质为2-庚酮单体、丁酸丁酯单体、乙酸乙酯、乙醇二聚体和2-乙基-3-甲基吡嗪单体(以酯、醇、酮类为主);DCM-35中的特征挥发性物质是庚酸(主要是酸类);DCM-45中的特征挥发性物质是3-甲基丁醛、庚醛和丙酮(以醛、酮类为主)。该研究结果为变质果的筛选提供了更多的理论依据。

变质毛椰子果  /  挥发性物质  /  气相色谱-离子迁移谱  /  正交偏最小二乘法判别分析

Coconut meat is the main raw material for coconut products processing, which is mainly obtained by importing dehusked coconut fruits in containers, and the rate of bad fruit is high in the process of transportation and storage. In order to explore the method of rapid differentiation and identification, this study used gas chromatography-ion mobility spectrometry (GC-IMS) combined with principal component analysis (PCA) and orthogonal partial least squares discriminant analysis (OPLS-DA) to analyze the volatile compounds in coconut meat of unstored normal dehusked fresh coconut fruits (FCM) and deteriorated dehusked coconut fruits under 25 ℃/70%, 35 ℃/80% and 45 ℃/90% (DCM-25, DCM-35 and DCM-45). The results showed that 42 volatile compounds were identified in the four coconut meat, including thirteen alcohols, five acids, eight ketones, ten esters, four aldehydes, two pyrazines and three unknown compounds. The alcohols were the most (including ethanol, butanol and propanol, etc.), followed by acids (including acetic acid and 2-methylpropionic acid, etc.), ketones (including acetone, 3-hydroxy-2-butanone and cyclopentanone, etc.), esters (including butyl caproate, ethyl acetate, butyl butyrate and ethyl butyrate, etc.), aldehydes (including 3-methylbutyraldehyde, pentalaldehyde and heptyl aldehyde, etc.) and pyrazines (2-ethyl-3-methylpyrazine). After deterioration, alcohol, acid and ketone volatile compounds increased. Thirteen characteristic volatile compounds, including 3-methylbutyral, cyclopentanone, 3-methylbutanol monomer, butanol monomer, heptaldehyde, acetone, 2-methylpropanol monomer, 2-heptanone monomer, heptanic acid, butyl butyrate monomer, ethyl acetate, ethanol dimer and 2-ethyl-3-methylpyrazine monomer, were analyzed by OPLS-DA, with variable importance in projection greater than 1. The characteristic volatile compounds in FCM were cyclopentanone and butanol monomer by differential heat map. The characteristic volatile compounds in DCM-25 were 2-heptanone monomer, butyl butyrate monomer, ethyl acetate, ethanol dimer and 2-ethyl-3-methylpyrazine monomer (mainly esters, alcohols and ketones). The characteristic volatile compounds in DCM-35 was heptanoic acid (mainly acids). The characteristic volatile compounds in DCM-45 were 3-methylbutyraldehyde, heptyl aldehyde and acetone (mainly aldehydes and ketones). This study would provide theoretical basis for the screening of deteriorated dehusked coconut fruits.

deteriorated dehusked coconut fruit  /  volatile compound  /  GC-IMS  /  OPLS-DA
王媛媛, 沈晓君, 宋菲, 阚金涛, 张建国, 张玉锋. 基于GC-IMS对不同温湿度贮藏条件下变质毛椰子果椰肉中挥发性物质分析. 热带作物学报, 2024 , 45 (10) : 2201 -2212 . DOI: 10.3969/j.issn.1000-2561.2024.10.021
Yuanyuan WANG, Xiaojun SHEN, Fei SONG, Jintao KAN, Jianguo ZHANG, Yufeng ZHANG. Analysis of Volatile Compounds in Coconut Meat of Deteriorated Dehusked Coconut Fruits under Different Temperature and Humidity by GC-IMS[J]. Chinese Journal of Tropical Crops, 2024 , 45 (10) : 2201 -2212 . DOI: 10.3969/j.issn.1000-2561.2024.10.021
椰肉是椰子产品的主要加工原料,其营养丰富、风味独特。获取的主要方式是进口毛椰子果,毛椰子果贮藏品质直接影响椰肉品质。在长时间、远距离进口运输过程中毛椰子果被封闭在集装箱内,容易产生高温高湿环境而使毛椰子果坏果率增加。为了保障加工产品的质量需要对变质果加以剔除,在前期的研究中发现变质果与正常果品质存在较大差异,变质果椰肉油脂的酸价高、脂肪酸含量低[1]。贮藏温湿度越高、时间越长,毛椰子果中椰肉油脂的酸价就越高、脂肪酸含量也越低。为了探索变质果挥发性物质的差异,前期利用顶空固相微萃取-气相色谱-质谱联用(headspace solid-phase microextraction-gas chromatography-mass spectrometry,HS-SPME-GC-MS)和电子鼻(electronic nose,E-nose)技术对未贮藏正常新鲜毛椰子果和不同温湿度贮藏条件下变质毛椰子果的椰肉挥发性物质进行了研究,筛选出特征挥发性物质[2]。变质果椰肉在电子鼻W2W(对芳香成分和有机硫化物敏感)传感器的响应值显著高于未贮藏正常新鲜毛椰子果椰肉。
气相色谱-离子迁移谱(gas chromatography-ion mobility spectrometry,GC-IMS)技术是气相色谱和离子迁移谱联用的技术。该技术利用色谱突出的分离特性,对待测样品的挥发性组分进行预分离,使其成为单一组分,再通过离子迁移进行二次分离,获得漂移时间、保留时间和信号强度的三维谱图,从而大大提高了检测的精度[3]。与常规色谱相比,该技术无需对样品进行蒸馏、萃取等繁琐的前处理,即使痕量的挥发性风味化合物也能在很短的时间内完成,检测操作简便,风味损失小,能更真实地保存样品真正的风味。对同分异构体和极性相近的物质具有理想的鉴别能力,特别适用于醛、醇、酮、酯类和芳香族化合物等高质子亲和力和高电负性的食品风味组分的现场快速分析。相比于HS-SPME-GC-MS技术,GC-IMS鉴定的挥发性物质种类和数量均相对较少,但是由于检测的挥发性物质的沸点比GC-MS的低,对高挥发性物质更敏感,近年来GC-MS已被广泛应用于食品贮藏过程挥发性物质分析等领域[4-6]
因此,为了更全面探究变质果在挥发性物质方面的差异,本文采用GC-IMS技术对未贮藏正常毛椰子果椰肉和3种不同温湿度(25 ℃/70%、35 ℃/80%和45 ℃/90%)贮藏条件下的变质毛椰子果椰肉进行分析。采用正交偏最小二乘法判别分析(orthogonal partial least squares discriminant analysis,OPLS-DA)构建模型,依据变量投影重要性因子(variable importance in projection,VIP)分析变质毛椰子果椰肉中特征挥发性物质,为变质果的鉴别和筛选提供更多的方法和技术。
参考王媛媛等[1]的方法,选用可用于加工、未经贮运的海南本地高种成熟老椰子果为研究对象,剥去外部椰衣,修整成与国外进口的毛椰子果相同的形态,分别贮藏于25 ℃/70%、35 ℃/80%和45 ℃/90% 3种不同温湿度条件下。取未经贮藏正常毛椰子果和3种不同温湿度条件下变质毛椰子果(25 ℃/70%条件下贮藏6周;35 ℃/80%条件下贮藏至4周;45 ℃/90%条件下贮藏至3周),破壳后削去种皮,取肉,分别标注为FCM、DCM-25、DCM-35和DCM-45,用粉碎机粉碎后存放于-80 ℃冰箱中待检。
MGC-450HP人工气候箱,上海一恒科学仪器有限公司;FlavourSpec®气相离子迁移谱联用仪,德国G.A.S.公司。
GC-IMS分析:称取椰肉样品1.0 g,置于20 mL顶空瓶中,80 ℃孵育15 min后利用FlavourSpec®气相离子迁移谱联用仪进行检测。
自动顶空进样条件:孵育温度80 ℃,孵育时间15 min,进样体积500 µL,进样针温度85 ℃,孵化转速500 r/min。
GC条件:美国RESTEK公司色谱柱,WAX柱(30 m×0.53 mm,1.0 µm),色谱柱温度60 ℃,载气N2(纯度≥99.999%)。载气流速:初始流速0~2 min,2 mL/min;2~10 min,2~10 mL/min;10~20 min,10~100 mL/min;20~30 min,100 mL/min;分析时间:30 min。
IMS检测条件:漂移管长度98 mm,管内线性电压500 V/cm,漂移管温度45 ℃,漂移气流量150 mL/min(高纯氮气,纯度≥99.999%),放射源β射线(氚,3H),正离子模式。
定性与定量:利用正构酮C4~C9(正丁酮、正戊酮、正己酮、正庚酮、正辛酮、正壬酮)建立保留时间和保留指数的校准曲线,通过目标物的保留时间计算该物质的保留指数,并采用VOCal软件内置的IMS数据库和NIST2020数据库对物质进行定性;利用Reporter插件和Gallery Plot插件绘制不同样品的差异图谱和指纹图谱。
每个样品进行3次重复试验。利用Office Excel对所有数据进行处理和分析;利用IBM SPSS Statistics 25.0软件进行差异显著性检验(P<0.05);应用SIMCA14.1和Origin9.0软件进行绘图;利用SIMCA14.1软件进行主成分分析(PCA)和正交偏最小二乘判别分析(OPLS-DA)。
基于Reporter插件程序获取不同温湿度贮藏条件下毛椰子果椰肉中挥发性物质的GC-IMS三维谱图、二维俯视图和差异谱图。不同温湿度贮藏条件下毛椰子果椰肉中挥发性物质的三维谱图如图1A所示。整个图背景为蓝色,x轴方向表征离子迁移时间,y轴方向表征气相色谱保留时间。颜色代表物质的浓度,白色表示含量较低,红色表示含量较高,颜色越深表示含量越高。
与GC-IMS三维谱图相对应的二维俯视图如图1B所示,RIP峰两侧的每一个点代表一种风味特征物质,其颜色深浅和面积大小代表物质浓度的高低[7]。图中大部分数据位于迁移时间1.0~2.0和保留时间100~1600 s的区域。为更明显地比较4种毛椰子果椰肉的挥发性物质成分差异,通过Reporter插件以FCM样品图为参照,其他样品谱图做颜色抵消,如图1C所示,当风味特征物质浓度高于参照时颜色呈现红色,反之呈现蓝色[8]
运用NIST气相保留指数数据库与IMS迁移时间数据库资料,根据挥发性物质气相色谱保留时间和IMS迁移时间对挥发性组分进行定性分析,如表1所示,共定性出42种挥发性物质。其中醇类化合物13种,酸类化合物5种,酮类化合物8种,酯类化合物10种,醛类化合物4种,吡嗪类化合物2种,未定性的化合物3种。醇类物质峰体积最大(图2A),占比最多(54.86%~78.64%),包括乙醇、丁醇、丙醇、2-甲基丙醇、3-甲基丁醇、己醇、戊醇。其次是酸类(7.60%~20.23%)和酮类(8.20%~17.36%),包括乙酸、2-甲基丙酸、庚酸以及丙酮、3-羟基-2-丁酮、环戊酮、2-丁酮、2-庚酮和4-甲基3-戊烯-2-酮。检测到的酯类物质占比为1.90%~8.77%,包括己酸丁酯、乙酸乙酯、丁酸丁酯、丁酸乙酯、2-甲基丁酸乙酯、2-甲基戊酸乙酯、2-羟基丙酸乙酯和丙酸乙酯。醛类物质占比在0.38%~1.68%之间,包括3-甲基丁醛、戊醛、庚醛和己醛。吡嗪类是2-乙基-3-甲基吡嗪(0.31%~1.91%)。未定性的物质占比为0.50%~2.60%(图2B)。
为进一步探索不同温湿度贮藏条件下变质毛椰子果椰肉与未贮藏正常毛椰子果椰肉中挥发性物质的差异,采用GalleryPlot插件制得指纹图谱(图3)。每一行代表同一样品的全部信号峰,每一列代表同一挥发性物质在不同样品中的信号离子峰,颜色深浅代表其浓度高低。通过指纹图谱的比较可作为辨别不同毛椰子果椰肉中挥发性物质的依据[9]。这种可视化有助于辨别样品中挥发性有机化合物及其标志性风味分子的差异。
图3中A区域内所示,在FCM中峰体积较高的挥发性物质主要是环戊酮和丁醇单体2种。乙酸二聚体、丁醇二聚体、己酸丁酯单体和二聚体、戊醇单体和二聚体、2-庚酮二聚体、2-甲基丙醇二聚体、4-甲基-3-戊烯-2-酮、2-甲基戊酸乙酯、丁酸乙酯、2-甲基丁酸乙酯、戊醛、己醛、2-乙基-3-甲基吡嗪单体和二聚体、2-羟基丙酸乙酯、2-丁酮、丙酸乙酯、己醇单体和二聚体、丁酸丁酯单体和二聚体、3-甲基丁醇二聚体(24种)以及3种未定性物质在DCM-25中峰体积高于其他毛椰子果椰肉,而2-甲基丙醇单体、3-羟基-2-丁酮单体和乙醇单体在DCM-25中峰体积较低。3-羟基-2-丁酮二聚体、丙酮和乙酸乙酯在DCM-25和DCM-45中的峰体积均较高(C区域内)。如红色箭头所示,庚酸在DCM-35中的峰体积最高。3-甲基丁醛和3-甲基丁醇单体在DCM-45中的峰体积高于其他处理(D区域内)。
指纹图谱仅对不同温湿度贮藏条件下变质毛椰子果和正常果椰肉中挥发性成分进行粗略区分。较难精确地确定是哪种挥发性化合物造成了差异,PCA和OPLS-DA能够有效区分不同组间的观测值,发现导致各组间差异的重要变量。样本间的异同可以通过模型的分值图直观地表示出来[10]。如图4A所示,以前2个主成分绘制得分图,方差贡献率分别为68.5%和15.6%,累计方差贡献率为84.1%(≥80%),说明PCA分析可以将FCM与DCM-25、DCM-35和DCM-45中检测出的挥发性物质种类进行有效区分。FCM与DCM-45在一个象限内其挥发性物质相似,DCM-35与DCM-45均在不同的象限其差异较大。为了进一步提高识别能力,采用了监督化学计量技术,进行OPLS-DA分析,如图4B所示,与PCA结果一致,FCM和DCM-45位于同一个象限,较为相似,与其余2种位于不同空间位置,彼此保持一定的距离,实现了很好的分离。表明DCM-45虽然贮藏温湿度高但到达变质的时间较短,与正常果挥发性物质的差异也较小。OPLS-DA模型的拟合参数(R2=1,Q2=0.970)表明该模型具有很强的解释和预测能力。同样,进行200次重复排列检验以评估OPLS-DA模型的稳健性,如图4C所示,R2=0.275,Q2=-0.999,证明该模型是可靠的,不存在过拟合,能够用来描述4种毛椰子果椰肉中挥发性化合物的差异。根据挥发性物质载荷散点图(图4D),丁醇单体在FCM的峰体积高于其他样品;己醛、戊醇二聚体、2-羟基丙酸乙酯、4-甲基3-戊烯-2-酮、未知物质3、2-乙基-3-甲基吡嗪单体和二聚体、2-丁酮和2-甲基丁酸乙酯等在DCM-25的峰体积高于其他样品;庚酸在DCM-35的峰体积高于其他样品;3-甲基丁醛在DCM-45的峰体积高于其他样品。
图4E可见,VIP大于1的特征挥发性物质共有13种,分别为:3-甲基丁醛、环戊酮、3-甲基丁醇单体、丁醇单体、庚醛、丙酮、2-甲基丙醇单体、2-庚酮单体、庚酸、丁酸丁酯单体、乙酸乙酯、乙醇二聚体和2-乙基-3-甲基吡嗪单体。通过绘制特征挥发性物质含量的差异热图可知(图4F),在FCM中的特征挥发性物质为环戊酮和丁醇单体;DCM-25中的特征挥发性物质为2-庚酮单体、丁酸丁酯单体、乙酸乙酯、乙醇二聚体和2-乙基-3-甲基吡嗪单体;DCM-35中的特征挥发性物质是庚酸;DCM-45中的特征挥发性物质是3-甲基丁醛、庚醛和丙酮。
与GC-MS相比,利用GC-IMS对样品处理和分析的温度更低,能够检测到一些热稳定性差和分子量较小的挥发性物质[11-12]。本研究利用GC-IMS检测出DCM-25的挥发性物质峰体积最大,而HS-SPME-GC-MS分析DCM-45的挥发性物质含量最多[2],说明在25 ℃/70%正常温湿度条件下,由于贮藏时间长(6周),毛椰子果发生了较为严重的脂质氧化降解[1],生成了较多分子量小的脂质氧化降解产物,可被GC-IMS检测出来。毛椰子果椰肉中的醇、酸、酮类挥发性物质较多,且变质后均增加。醇类中增加较为明显的为丙醇、2-甲基丙醇二聚体和3-甲基丁醇二聚体等。醇类物质主要来源于脂肪酸的降解、氨基酸代谢、碳水化合物发酵和甲基酮还原等多种途径[13],在感官分析上具有较高的阈值。酸类物质形成与乳酸发酵、糖类和蛋白质代谢有关[14]。酮类中增加较为明显的是3-羟基-2-丁酮二聚体和2-丁酮等。酮类物质大多来源于脂肪氧化、热降解、氨基酸降解作用以及微生物代谢等,其香气阈值较高[15]。此外,利用GC-IMS还分析出2-乙基-3-甲基吡嗪化合物,且变质后增加。
在FCM特征挥发性物质中环戊酮具有令人愉快的薄荷气味,丁醇具有酒味。DCM-25特征挥发性物质中2-庚酮具有奶油香和果香,主要由亚油酸氧化降解产生[16]。丁酸丁酯具有苹果、香蕉、菠萝等果香香味,在自然界存在于苹果、香蕉、葡萄、梨、草莓等水果之中[17];乙酸乙酯有酯香、果香气味[18];乙醇具有酒香的气味;2-乙基-3-甲基吡嗪则具有坚果、焙烤和甜香味道[19],是一类通过含氨基化合物和羰基化合物发生的Maillard反应形成的含氮杂环化合物,通过Streker降解反应产生[20]。在前期的报道中也发现毛椰子果长时间贮藏后会出现Maillard的褐变反应[1]。DCM-25中的特征挥发性物质以酯、醇、酮类为主。酯、醇类物质多存在于发酵型食品中尤其是酒类,丁酸丁酯、乙酸乙酯、乙醇在白酒中均有报道[21-22]。可能是因为25 ℃/70%的正常温湿度贮藏过程中,贮藏时间相对较长,毛椰子果椰肉中糖类物质代谢生成醇类,醇类进一步与酸类酯化而成酯类物质。庚酸是DCM-35中的特征挥发性物质,具有发酵香和果香,在贮藏后期产生[23]。稍高的35 ℃/80%贮藏温湿度,贮藏时间较短,抑制了醇类和酯类物质的生成,但加速了酸类物质的积累。DCM-45特征挥发性物质中3-甲基丁醛具有水果香/坚果香/奶酪香[24],主要是由亮氨酸通过生物合成和Strecker降解途径产生[25]。由于Strecker降解途径需要在一定温度下进行,本研究中的3-甲基丁醛可能主要由于45 ℃/90%的高温高湿条件发生的Strecker降解途径产生的。庚醛具有鱼腥和油脂味[26],主要由亚麻酸分解产生;丙酮则具有苦杏仁味、苹果香和梨香[27]。DCM-45中的特征挥发性物质主要为醛、酮类物质。脂肪中不饱和脂肪酸在温度较高的情况下容易被氧化生成过氧化物,继而进一步分解为风味阈值较低的醛、酮等挥发性物质。醛类在低浓度下具有特征性的脂肪香气,但高于临界值的较高浓度会产生腐烂、腐臭或其他异味[28]
综上所述,在4种椰肉样品中均定性出42种挥发性物质,其中醇类13种,酸类5种,酮类8种,酯类10种,醛类4种,吡嗪类化合物2种。醇类最多,其次是酸、酮、酯、醛和吡嗪类物质,且变质后醇、酸、酮类均增多。利用OPLS-DA分析出13种特征挥发性物质,其中FCM中的特征挥发性物质有环戊酮和丁醇单体;DCM-25中有2-庚酮单体、丁酸丁酯单体、乙酸乙酯、乙醇二聚体和2-乙基-3-甲基吡嗪单体(以酯、醇、酮为主);DCM-35中有庚酸(主要是酸类);而DCM-45中有3-甲基丁醛、庚醛和丙酮(以醛、酮类为主)。本研究为变质果的筛选提供了更多的理论依据。
  • 海南省自然科学基金项目(321MS0807; 322RC790)
  • 中央级公益性科研院所基本科研业务费专项(1630152022002)
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2024年第45卷第10期
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doi: 10.3969/j.issn.1000-2561.2024.10.021
  • 接收时间:2024-03-19
  • 首发时间:2026-06-25
  • 出版时间:2024-10-25
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  • 收稿日期:2024-03-19
  • 修回日期:2024-04-27
基金
海南省自然科学基金项目(321MS0807; 322RC790)
中央级公益性科研院所基本科研业务费专项(1630152022002)
作者信息
    1.中国热带农业科学院椰子研究所,海南文昌 571339
    2.海南省椰子深加工工程技术研究中心,海南文昌 571339
    3.椰子产业技术创新战略联盟,海南文昌 571339

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* 张玉锋(ZHANG Yufeng),E-mail:
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
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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