食用植物油中氯丙醇酯检测方法研究进展

脂肪酸氯丙醇酯是食用植物油加工过程中形成的一类污染物,进入人体胃肠道后在脂酶作用下可水解释放出具有潜在致癌性的氯丙醇类物质,食用油中氯丙醇酯污染已成为新出现的热点食品安全问题之一。建立准确、可靠、高灵敏的检测食用油中氯丙醇酯含量的方法具有重要的现实意义。目前氯丙醇酯的检测方法有直接法和间接法两种,直接法不破坏氯丙醇酯结构直接检测,间接法将氯丙醇酯转化为游离氯丙醇,以测得的氯丙醇含量反推计算出样品中氯丙醇酯的含量。本文综述了近年来国内外氯丙醇酯检测技术的研究概况,对各种检测方法的基本原理、操作步骤、仪器条件及各自的优缺点进行了比较分析,最后展望了氯丙醇酯检测方法的发展趋势和检测结果的应用。     

ASE-GC/MS分析5种蔬菜种子油中脂肪酸组成

采用ASE-GC/MS定量分析5种蔬菜种子油中脂肪酸组成。结果表明,经ASE快速溶剂提取,得到5种蔬菜种子的含油量由高到低分别为西瓜(55.74%)、西葫芦(48.97%)、白菜(36.53%)、番茄(26.26%)、辣椒(19.97%);经GC/MS分离检测,在5种蔬菜种子油中共检测出19种脂肪酸,其中不饱和脂肪酸11种,白菜种子油以芥酸为主,其他以油酸、亚油酸为主,不饱和脂肪酸相对含量超过80%。     

Monitoring of 49 Pesticides and 17 Mycotoxins in Wine by QuEChERS and UHPLC–MS/MS Analysis

An effective method for the determination of 49 pesticide residues and 17 mycotoxins in wine by a modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) method and ultrahigh‐performance liquid chromatography–tandem mass spectrometry was developed. The target compounds were extracted with 1% (v/v) formic acid–acetonitrile, and no cleanup steps were required. The extracts were separated on a C18 chromatographic column (2.1 mm × 50 mm, 1.7 µm) with acetonitrile and water with 0.2% formic acid solution and ammonium acetate (10 mM) as the mobile phases under gradient elution at a flow rate of 0.2 mL/min. The determination was conducted using electrospray ionization in positive ion mode with multiple reaction monitoring. The analytes were quantified by comparison with matrix‐matched standard solutions. The good linearities were obtained in the range of 0.05 to 500.0 µg/kg, and the correlation coefficients were all greater than 0.9935. The average recoveries of the 66 target compounds ranged from 69% to 119%, and the RSDs were in the range of 1% to 10%. The limits of detection were in the range of 0.05 to 20.0 µg/kg. The method was proved to be rapid, selective, sensitive, and stable, and it has been applied to analysis of 64 wine samples.     

LC–MS analysis of anthocyanins from purple corn cob

Liquid chromatography coupled with diode array spectrophotometry and mass spectrometry detection (LC–DAS–MS) has been applied to the study of the anthocyanin composition of a commercial extract from purple corn cob used as a colourant additive in the food industry. Nine different anthocyanins were isolated using semipreparative HPLC and identified by LC–MS and hydrolytic techniques. Useful information for the identification of compounds was also obtained from their fragmentation patterns (MS–MS spectra). Six of these anthocyanins seem to be present in the original cob, namely cyanidin‐3‐glucoside, pelargonidin‐3‐glucoside, peonidin‐3‐glucoside and their respective malonyl derivatives. The other three are produced during the industrial extraction process and have been identified as the corresponding ethylmalonyl derivatives. © 2002 Society of Chemical Industry     

食用油加工过程中3-氯丙醇酯和缩水甘油酯生成及脱除研究

研究了12种共计74批次市售食用油中3-氯丙醇酯(3-MCPDE)和缩水甘油酯(GE)污染情况,及脱臭条件对二者生成的影响,以及吸附剂和分子蒸馏对二者脱除的影响。结果发现,12种食用油中3-MCPDE和GE的检出率为100%,其中3-MCPDE含量范围为0. 234～12. 212mg/kg,GE含量范围为0. 196～10. 891 mg/kg,米糠油中3-MCPDE和GE含量最高,其次为棕榈液油。脱臭温度对3-MCPDE和GE的影响显著,3-MCPDE和GE大量生成的脱臭温度分别为大于220℃和大于200℃,并且随着脱臭时间的延长3-MCPDE和GE含量增加。GE可以通过活性炭、活性白土、硅胶和凹凸棒土等吸附剂吸附脱除,脱除率可达96%以上。3-MCPDE难以通过吸附剂吸附的方式脱除。分子蒸馏可同时脱除3-MCPDE和GE,蒸馏温度230℃时3-MCPDE和GE脱除率分别达到88%和94%。     

植物油中甾醇烯类物质的检测研究

建立了GC-MS测定植物油中4种甾醇烯类物质的方法。样品用石油醚提取,经硅胶柱净化,HP-5毛细管柱(5%苯基聚硅氧烷,30 m)分离,质谱检测采用SIM模式。在0.062 5～1.0 mg/L的质量浓度范围内,峰面积与质量浓度呈良好线性,线性相关系数(r)大于0.99。在特级初榨橄榄油中添加0.025、0.050 mg/kg和0.100 mg/kg水平的甾醇烯类物质,平均加标回收率为78.6%～107.3%,相对标准偏差小于8%,方法检测限可达0.010 mg/kg。本方法准确、灵敏、可靠,已应用于实际样品分析,并可作为鉴别地沟油的方法之一。     

冷冻法结合GC-MS/MS测定植物油中19种邻苯二甲酸酯类化合物

为了建立一种快速、高效、便捷测定植物油中19种邻苯二甲酸酯类化合物的检测方法,对冷冻法结合GC-MS/MS检测植物油中19种邻苯二甲酸酯类化合物含量的方法进行了研究。结果表明：（1）将前处理方法中–18℃冷冻保存24h改为–36℃冷冻保存12h,节省了样品前处理时间;（2）与LS/T6131—2018《粮油检验植物油中邻苯二甲酸酯类化合物的测定》方法相比,除了对邻苯二甲酸二甲酯、邻苯二甲酸二乙酯、邻苯二甲酸二异丁酯、邻苯二甲酸二正丁酯、邻苯二甲酸二环己酯、邻苯二甲酸二(2-乙基)己酯、邻苯二甲酸二异壬酯和邻苯二甲酸二异癸酯8种邻苯二甲酸酯类化合物的测定外,增加了对11种邻苯二甲酸酯类化合物的测定,包括邻苯二甲酸二烯丙酯、邻苯二甲酸二(2-甲氧基)乙酯、邻苯二甲酸二(4-甲基-2-戊基)酯、邻苯二甲酸二(2-乙氧基)乙酯、邻苯二甲酸二戊酯、邻苯二甲酸二己酯、邻苯二甲酸丁基苄基酯、邻苯二甲酸二(2-丁氧基)乙酯、邻苯二甲酸二苯酯、邻苯二甲酸二正辛酯和邻苯二甲酸二壬酯;（3）与LS/T6131—2018方法中外标法定量相比,增加了同位素内标法定量,比较了同位素内标法和外标法在测定植物油中邻苯...     

气相色谱-质谱联用法测定食用油中3-MCPD脂肪酸酯

本研究在德国油脂科学协会(DGF)标准检测方法的基础上进行方法优化,利用气相色谱-质谱联用(GC-MS)技术,建立了油脂中3-氯-1,2-丙二醇(3-MCPD)脂肪酸酯的分析方法。根据结果可知,该方法线性相关性良好,检出限为0.022 5 mg/kg,定量限为0.076 0 mg/kg,线性范围为0.05~5.0 mg/kg,回收率为95.36%~101.18%,相对标准偏差为1.36%~8.14%。试验中同时利用该方法对7种常见油脂中3-MCPD脂肪酸酯进行了检测。结果表明:该分析方法定性定量准确、灵敏度高、重现性好,能满足油脂中3-MCPD脂肪酸酯分析检测的要求。     

同位素内标-气相色谱-质谱法测定食用植物油中缩水甘油酯

建立了一种同位素内标-气相色谱-质谱法测定食用植物油中缩水甘油酯（GEs）的检测方法。先将GEs转化成3-溴-1,2-丙二醇（3-MBPD）单酯,再通过水解、衍生化,然后气相色谱-质谱法测定3-溴-1,2-丙二醇（3-MBPD）含量,并对衍生条件进行优化。结果表明：优化的衍生条件为GEs质量浓度为21.78 μg/mL时,苯硼酸（PBA）用量100 μL,衍生温度50 ℃,衍生时间10 min。该方法在GEs质量浓度为0.021 8~2.178 μg/mL范围内线性关系良好（R=0.999 9）,检出限为25 μg/kg,平均加标回收率为91.4%~97.0%,相对标准偏差为4.4%~86%。该方法的可操作性强、重现性好,灵敏度、准确度和精密度均能满足实际工作中食用植物油中GEs的定性定量检测。     

液相色谱-质谱法测定食用植物油中缩水甘油酯的含量

采用液相色谱-质谱法检测食用油脂中缩水甘油酯的含量,以AOCS方法为基础,优化了前处理条件和流动相梯度洗脱程序。方法的缩水甘油酯回收率为92.42%¹09.20%,相对标准偏差RSD为4.01%⁷.52%,五种缩水甘油酯的最低检出限在9³0μg/kg之间。本方法灵敏度高,重复性好,能够满足实际工作中油脂中缩水甘油酯含量分析的需要。      

11种植物油的脂肪酸组成与抗氧化活性比较

对4种新资源食品油、2种高端食用油和5种普通植物油的脂肪酸组成和抗氧化活性进行比较研究,以评价不同类型植物油的质量。采用气-质联用色谱法测定了11种植物油的脂肪酸组成,应用DPPH、ABTS、FRAP法对不同植物油的全油以及极性部位的抗氧化活性进行测定。结果显示:新资源食品油(茶叶籽油除外)的多不饱和脂肪酸含量均大于65%,其中α-亚麻酸高达38%以上,而普通植物油以及牛油果油和橄榄油中α-亚麻酸含量仅有0.11%～8.67%; 11种植物油对DPPH·清除能力从大到小依次为杜仲籽油美藤果油玉米油大豆油葵花籽油牡丹籽油菜籽油橄榄油牛油果油花生油茶叶籽油;对ABTS+·的清除能力从大到小依次为橄榄油菜籽油杜仲籽油大豆油玉米油美藤果油花生油牛油果油茶叶籽油牡丹籽油葵花籽油;对FRAP Fe3+-TPTZ还原能力从大到小依次为杜仲籽油美藤果油菜籽油橄榄油玉米油花生油大豆油牡丹籽油葵花籽油牛油果油茶叶籽油。在脂肪酸组成方面,新资源食品油有较大优势,DPPH、ABTS、FRAP 3种方法所得的每种植物油的抗氧化活性不同,但杜仲籽油、美藤果油、菜籽油和玉米油在3种方法中均表现出较好的抗氧化活性。     

九种植物油中脂肪酸成分的比较研究

索氏提取法提取了大豆、不同产地葵花籽、白花生、黑花生、白芝麻、黑芝麻、油菜籽和棉花籽的油脂,用气相色谱-质谱法测定了这9种植物油中脂肪酸组成和相对含量。结果表明,不同种类植物油的脂肪酸组成和相对含量各不相同,同种类植物油脂肪酸组成一致,相对含量基本吻合,尽管植物油的产地和品种不同。除油菜籽油外,植物油中相对含量最高的两种脂肪酸为9,12-亚油酸和9-油酸,仅从这两种脂肪酸的相对含量之和也可区分不同种类的食用植物油。按我国推荐的食用植物油饱和脂肪酸、单不饱和脂肪酸和多不饱和脂肪酸的推荐摄入量比,花生油最吻合。      

三种食用植物油中不饱和脂肪酸含量调查

对市售大豆油、花生油、菜籽油等常见食用植物油中不饱和脂肪酸含量进行调查,调查结果表明:80个大豆油、花生油和菜籽油三种食用植物油样品中,不饱和脂肪酸的含量不符合相应国家标准规定的样品分别占相应品种调查数量的6.38%、7.14%和47.37%,部分食用植物油中存在掺杂现象。在符合国家标准规定的67个食用植物油样品中,含量较高的不饱和脂肪酸组成为大豆油中的亚油酸,花生油中的油酸和菜籽油中的油酸,平均含量分别为51.54%、42.20%、38.87%。     

塑料包装材料中邻苯二甲酸酯的LC/MS/MS测定方法研究

建立了LC/MS/MS测定塑料包装材料中邻苯二甲酸酯含量的分析方法.将塑料包装材料粉碎后索氏提取,经LC/MS/MS分析在50μg/L～400μg/L范围内呈现良好的线性关系(R2＞0.9985),方法检测限小于35μg,/kg;在50μg/kg、200μ g/kg、400μg/kg三个样品加标水平,PAEs的回收率在91.42％～99.90％之间;方法精密度实验的相对准偏差在5％之内.结果表明该方法准确可靠,精密度较高.     

超低温冷冻除脂-气相色谱串联质谱法检测食用植物油中21种邻苯二甲酸酯

建立了超低温冷冻除脂-气相色谱串联质谱(GC-MS/MS)检测食用植物油中21种邻苯二甲酸酯(PAEs)的新方法。样品用乙腈提取,经超低温(-80℃)冷冻10 min除脂,再经减压浓缩,以正己烷复溶,采用GC-MS/MS多反应监测模式进行测定。结果表明,在考察浓度范围(1~1000 ng/mL)内21种PAEs均呈现良好线性,相关系数均大于0.999,检出限为0.10~8.52 μg/kg,定量限为0.32~28.40 μg/kg,加标回收率为74.31%~116.62%,相对标准偏差为1.21%~17.82%。对市售7类19个油样的抽样检测,显示邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、邻苯二甲酸二异丁酯(DIBP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸丁基苄基酯(BBP)、邻苯二甲酸(2-丁氧基)乙酯(DBEP)、邻苯二甲酸二正庚酯(DHP)、邻苯二甲酸二(2-乙基己)酯(DEHP)和邻苯二甲酸二正辛酯(DNOP)共9种PAEs被检出,其中DMP、DBP、DBEP、DHP和DEHP检出率均大于90%,含量范围为105.57~2156.76 μg/kg。该方法操作简便,成本低,可用于食用植物油中PAEs的有效测定。     

橄榄油中脂肪酸烷基酯含量测定

采用商品化固相萃取柱净化,气相色谱-质谱联用法检测,建立了一种前处理简单快捷的橄榄油中脂肪酸烷基酯含量测定方法。该方法测定橄榄油中8种脂肪酸烷基酯的检出限均为1.0 mg/kg,加标回收率为99.05%~111.13%,相对标准偏差为0.50%~6.70%。方法重复性好,准确度高。通过测定橄榄油中脂肪酸烷基酯的含量,可以帮助区分橄榄油品质,为特级初榨橄榄油掺伪的鉴别提供技术支持。     

气相色谱-串联质谱法测定婴幼儿配方奶粉中氯丙醇酯和缩水甘油酯

目的 建立气相色谱-串联质谱法(gas chromatography-tandem mass spectrometry,GC-MS/MS)测定婴幼儿配方奶粉中3-氯-1,2-丙二醇脂肪酸酯(3-monochloropropane-1,2-diol ester,3-MCPDE)、2-氯-l,3-丙二醇脂肪酸酯(2-mon...     

An investigation of presence of 2- and 3-monochloropropanediol fatty acid esters in Canadian human milk samples

ABSTRACT

Occurrence of 2- and 3-monochloropropanediol fatty acid esters (MCPDEs) in 199 human milk samples collected from Canadian women was examined in this study. MCPDEs were determined via indirect analytical approach by using acidic hydrolysis/transesterification and derivatization with cyclohexanone using a fluorinated sulfonic acid resin as a catalyst followed by GC-MS analysis. Analyses were done by a stable isotope dilution assay (SIDA) using 3-monochloropropanediol-d₅ dipalmitate and 2-monochloropropanediol-d₅ distearate as internal standards. In all samples 2-MCPD esters were not detected, at LOD = 1 ng/g for 2-MCPD equivalent. 3-MCPD esters were not detected, at LOD = 2 ng/g for 3-MCPD equivalent, in 193 samples. Six samples had the apparent concentration of 3-MCPD equivalent in the range of 2.0–5.1 ng/g, which was likely caused by accidental contamination during processing of samples. For selected samples, these findings were confirmed by direct analysis via LC-MS/MS analysis based on SIDA for 3-MCPD dipalmitate and 2-MCPD distearate. To our best knowledge, this is the first study to analyze human milk samples for 2-MCPD esters.     

Fatty acid esters of monochloropropanediol (MCPD) and glycidol in refined edible oils

Recently, fatty acid esters of monochloropropanediol (MCPD) and that of glycidol have been reported in refined edible oils. Since then a wealth of research has been published on the factors influencing the formation of these contaminants in foods. It can be noted that the predominant precursors in a given matrix will not necessarily be the same as in other matrices. Further, proven relationships in the past between precursors responsible for free MCPD or free glycidol formation will not necessarily be valid for their fatty acid-esterified counterparts. This review attempts to summarise the current status of the literature as it pertains to the reasons surrounding the manifestation of MCPD esters and glycidyl esters in oils and fats. Recent efforts to mitigate the levels of these contaminants were highlighted and put into the context of their respective reaction matrices. As more accurate occurrence data for MCPD esters and glycidyl esters in other foods are collected, more targeted mitigation experiments can be formulated with respect to the reaction matrices under investigation.