间接法测定食用油中3-氯丙醇酯总量影响因素的研究进展

介绍了间接法测定食用油中3-氯丙醇酯总量的基本原理,并对间接法中各步骤操作条件对测定结果的影响进行了探讨,包括内标、催化剂、盐析试剂、衍生化试剂以及GC-MS分析等,为今后我国建立食用油中3-氯丙醇酯总量标准分析方法提供参考和依据.     

食用油中3-氯-1,2-丙二醇酯检测方法的研究进展

3-氯-1,2-丙二醇酯(3-MCPD酯)是油脂精炼过程中引入的又一潜在危害因子,它是3-氯丙醇与脂肪酸的酯化产物.目前3-MCPD酯测定方法的研究已成为当今食品安全检测的一大热点.本文综述了近几年来国内外食用油中3-MCPD酯的检测方法,包括酸催化酯交换间接测定法、碱催化酯交换间接测定法以及直接测定法,详细介绍了各种检测方法的研究现状及优缺点,并讨论了未来3-MCPD酯检测技术的研究发展方向,为今后我国建立食用油中3-MCPD酯标准分析方法提供参考和依据.     

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%。     

食用植物油中3-氯丙醇酯的研究进展

介绍了3-氯丙醇酯的定义、分类、潜在毒性及其在食用植物油加工过程中可能形成的途径,以及其在食用植物油中的含量,旨在促进对食用植物油加工污染物危害的认识和控制.     

食用油中氯丙醇酯污染及检测方法研究进展

食用油在精炼加工过程中会产生氯丙醇酯类物质,对食用油的安全造成影响,因此加强检测方法研究,提高检测水平尤为重要。对食用油中氯丙醇酯的组成、来源及危害进行了综述,对目前食用油中氯丙醇酯的检测方法(间接测定法和直接测定法)进行了介绍,其中详细分析了各种检测方法的原理及前处理过程等对检测结果的影响,并提出了今后的研究方向。以期为保证食用油安全性方面的研究提供参考。     

氯丙醇酯——油脂食品中新的潜在危害因子

氯丙醇酯是油脂食品中新近发现的一个潜在危害因子,日本Econa烹调油因高含量3-氯丙醇酯而被迫停止销售的事实表明氯丙醇酯问题已开始对油脂行业产生实质性影响,本文总结了当前国际学术界和业界对氯丙醇酯类物质的研究现状,对氯丙醇酯进行了较为明确的定义和初步的分类,分析了氯丙醇酯可能产生的潜在毒性,介绍了油脂食品中氯丙醇酯的来源、形成途径和控制措施。最后建议我国相关部门应积极介入,主动应对挑战,开展对氯丙醇酯安全问题的研究,以指导油脂食品的生产和消费,推动我国油脂食品行业的健康发展。     

气相色谱-质谱法测定食用油中3-氯丙醇酯

采用碱水解方式,基于苯基硼酸 (PBA)衍生化方法并结合气相色谱/质谱 (GC/MS) 联用仪测定了植物油中3-氯丙醇 (3-MCPD) 酯的含量。水解时间是碱水解样品前处理方法的关键因素,经优化,大豆油等不同品类的食用油的最佳水解时间为 1-6 min。另外,以大豆油为基质,考察了基于碱水解方式的分离分析方法的回收率、重复性以及检出限。其中,在 150~1500 μg/kg范围内进行3水平重复加标回收实验,回收率为 94%~105%、RSD为3.7%~10.8%、检出限为 15 μg/kg,定量限为 50 μg/kg。本方法能够满足日常样品中3-氯丙醇 (3-MCPD) 酯的检测。     

气相色谱法检测植物油中3-氯丙醇酯

目的建立气相色谱(GC)检测植物油中3-氯-1,2-丙二醇酯(3-氯丙醇酯,3-MCPD酯)含量的方法。方法不同浓度的3-MCPD标准溶液中加入苯硼酸(PBA)进行衍生化反应,正己烷萃取,进气相色谱检测,由3-MCPD的量和峰面积对应关系做标准曲线。测定4种食用油中3-MCPD酯含量。结果该法线性相关性良好,最低检出限0.025 mg/kg,定量限0.086 mg/kg。线性范围0.1~0.8 mg,回收率在79%~108%之间,精密度试验相对标准偏差(RSD)均小于5。市场上4种植物油中3-氯丙醇酯含量由低到高依次为花生油、大豆油、棕搁油、菜籽油,其3-MCPD酯的含量范围是3020~51520μg/kg。结论该分析方法操作简单,灵敏度高,能满足一般油脂中3-MCPD酯检测的要求。     

食品中3-氯丙醇酯的研究现状

食品中的3-氯丙醇酯在人体内会水解为游离的3-氯丙醇而影响人体健康,已成为国际普遍关注的食品安全问题之一。本文主要综述了3-氯丙醇酯的几条生成途径,包括氯离子直接亲核进攻途径、环酰氧鎓离子中间体途径和缩水甘油酯中间体途径、环氧化物环自由基途径,3-氯丙醇酯的生成主要受加热温度和时间、pH、含水量、氯化钠含量及金属离子等因素的影响。最后从精炼植物油和食品加工两个过程提出了控制食品中3-氯丙醇酯含量的措施,并对食品中3-氯丙醇酯未来研究方向进行了展望。     

食用油中3-氯-1,2-丙二醇酯的研究进展

近些年国际上关于食用油污染物——3-氯-1,2丙二醇酯的话题屡见不鲜。作为一种对于人体具有潜在危害的非营养成分,研究食用油中3-氯-1,2丙二醇脂的形成机理以及危害对食用油的安全性有着重要的意义。本文主要阐述食用油中的污染物——3-氯-1,2丙二醇脂的来源、检测方法、形成机理以及去除方法。      

食用植物油中3-MCPD酯GC-MS测定方法研究

建立了甲醇钠-甲醇水解,固相萃取柱净化,HFBI衍生结合气相色谱-质谱(GC-MS)方法对食用植物油中3-MCPD酯含量进行测定。该方法在0.50～2. 50 mg/L范围内线性关系良好(r~2=0.988 5),检出限为0. 025 5 mg/kg,定量限为0. 093 3 mg/kg。3-MCPD酯的平均加标回收率在94. 80%～104. 62%之间,RSD 1.47%～5.23%。本方法操作简单、灵敏度高、重复性好,能够很好地适用于食用植物油中3-MCPD酯的检测。采用该方法对新疆几种市售食用植物油中的3-MCPD酯进行测定。新疆市售的几种食用植物油中均检测出浓度不等的3-MCPD酯。其中菜籽油、亚麻籽油、番茄籽油、花生油以及葡萄籽油受3-MCPD酯污染严重,3-MCPD酯含量都高于0.4 mg/kg。而核桃油、大豆油、红花籽油中3-MCPD酯的含量都低于0.4mg/kg。     

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。     

Occurrence of 3-MCPD and glycidyl esters in edible oils in the United States

Fatty acid esters of 3-monochloropropanediol (3-MCPD) and glycidol are processing contaminants found in a wide range of edible oils. While both 3 MCPD and glycidol have toxicological properties that at present has concerns for food safety, the published occurrence data are limited. Occurrence information is presented for the concentrations of 3-MCPD and glycidyl esters in 116 retail and/or industrial edible oils and fats using LC-MS/MS analysis of intact esters. The concentrations for bound 3-MCPD ranged from below the limit of quantitation (<LOQ) to 0.09 mg kg^?1 (ppm) in 22 unrefined oils and from 0.005 to 7.2 mg kg^?1 (ppm) in 94 refined oils. The concentrations for bound glycidol ranged from <LOQ to 0.03 mg kg^?1 (ppm) in unrefined oil samples and from <LOQ to 10.5 mg kg^?1 (ppm) in processed oil samples. The highest concentrations for both 3-MCPD and glycidol were seen in refined palm oil and palm olein samples. Palm olein samples also contained a higher percentage of 3-MCPD in mono-ester form than any other type of oil.     

A new,direct analytical method using LC-MS/MS for fatty acid esters of 3-chloro-1,2-propanediol (3-MCPD esters) in edible oils

A new, direct analytical method for the determination of 3-chloro-1,2-propanediol fatty acid esters (3-MCPD esters) was developed. The targeted 3-MCPD esters included five types of monoester and 20 types of diester. Samples (oils and fats) were dissolved in a mixture of tert-butyl methyl ether and ethyl acetate (4:1), purified using two solid-phase extraction (SPE) cartridges (C₁₈ and silica), then analysed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Five monoesters and five diesters with the same fatty acid group could be separated and quantified. Pairs of 3-MCPD diesters carrying the same two different fatty acid groups, but at reversed positions (sn-1 and sn-2), could not be separated and so were expressed as a sum of both compounds. The limits of quantification (LOQs) were estimated to be between 0.02 to 0.08?mg?kg^?1, depending on the types of 3-MCPD ester. Repeatability expressed as relative standard deviation (RSD_r%) varied from 5.5% to 25.5%. The new method was shown to be applicable to various commercial edible oils and showed levels of 3-MCPD esters varying from 0.58 to 25.35?mg?kg^?1. The levels of mono- and diesters ranged from 0.10 to 0.69?mg?kg^?1 and from 0.06 to 16?mg?kg^?1, respectively.     

食用植物油中4种氯丙醇脂肪酸酯的GC-MS测定方法研究

采用气相色谱-质谱(GC-MS)联用技术,建立了同时测定食用植物油中3-氯-1,2-丙二醇脂肪酸酯(3-MCPD酯)、2-氯-1,3-丙二醇脂肪酸酯(2-MCPD酯)、1,3-二氯-2-丙二醇脂肪酸酯(1,3-DCP酯)和2,3-二氯-1-丙二醇脂肪酸酯(2,3-DCP酯)含量的分析方法。该方法在0.005~0.5 mg/L范围内线性关系良好,检出限0.1 mg/kg,定量限0.2 mg/kg,加标回收率在97.2%~106.0%之间,相对标准偏差在3.4%~7.1%之间。该方法操作简便,灵敏度高,重复性好,定性定量准确,对仪器污染小,能满足食用植物油中氯丙醇酯的检测需求。     

温度以及氯离子对初榨胡麻油中3-MCPD酯生成的影响

采用气相色谱-负化学离子源-质谱(GC-NCI-MS)联用技术,建立了测定食用植物油中3-氯丙醇酯(3-MCPD酯)含量的分析方法。该方法在0.01~0.10 mg/kg范围内线性关系良好(r2=0.997 4),检出限为5 μg/kg,定量限为20 μg/kg。加标回收率在80.47%~81.68%之间,相对标准偏差在5.60%~8.35%之间。对初榨胡麻油中3-MCPD酯进行检测,结果表明：低温炒籽对于初榨胡麻油中3-MCPD酯生成没有影响。将油样加热至160 ℃~200 ℃范围内,初榨胡麻油中3-MCPD酯的生成随温度的升高以而增加,但增加不明显。将油样加热至200 ℃时,初榨胡麻油中3-MCPD酯的生成随加热时间的增加而增加,但增长不显著。但将油样加热至200 ℃时,随着氯离子含量的增加,初榨胡麻油中3-MCPD酯呈显著上升趋势。     

Identification of 3-MCPD esters to verify the adulteration of extra virgin olive oil

ABSTRACT

The adulteration of olive oil is an important issue around the world. This paper reports an indirect method by which to identify 3-monochloropropane-1,2-diol (3-MCPD) esters in olive oils. Following sample preparation, the samples were spiked with 1,2-bis-palmitoyl-3-chloropropanediol standard for analysis using gas chromatograph-tandem mass spectrometry. The total recovery ranged from 102.8% to 105.5%, the coefficient of variation ranged from 1.1% to 10.1%, and the limit of quantification was 0.125 mg/kg. The content of 3-MCPD esters in samples of refined olive oil (0.97–20.53 mg/kg) exceeded those of extra virgin olive oil (non-detected to 0.24 mg/kg). These results indicate that the oil refining process increased the content of 3-MCPD esters, which means that they could be used as a target compound for the differentiation of extra virgin olive oil from refined olive oil in order to prevent adulteration.     

Esters of 3-chloro-1,2-propanediol (3-MCPD) in vegetable oils: Significance in the formation of 3-MCPD

3-Mono-chloropropane-1,2-diol (3-MCPD) is a contaminant that occurs in food in its free (diol) form as well as in an esterified (with fatty acids) form. Using a simple intestinal model, it was demonstrated that 3-MCPD monoesters and 3-MCPD diesters are accepted by intestinal lipase as substrates in vitro. Under the chosen conditions, the yield of 3-MCPD from a 3-MCPD monoester was greater than 95% in approximately 1 min. Release from the diesters was slower, reaching about 45, 65 and 95% of 3-MCPD after 1, 5 and 90 min of incubation, respectively. However, in human, the hydrolysis of 3-MCPD esters is unlikely to release 100% as 3-MCPD, as triglycerides and phospholipids are hydrolysed in the intestine liberating 2-monoglycerides. Assuming a similar metabolism for 3-MCPD esters as that known for acylglycerols in humans in vivo, the de-esterification in positions 1 and 3 would thus be favoured by pancreatic lipases. Therefore, 3-MCPD, and 3-MCPD-2 monoesters would be released, respectively, from the 1-/3-monoesters, and the diesters potentially present in food. Hence, information on the exact amounts of the partial fatty acid chloroesters, i.e. 3-MCPD mono- and diesters, is important to assess the contribution of foods to the bioavailability of 3-MCPD. Therefore, a rapid method for the determination of the ratio of 3-MCPD monoesters to diesters in fats and oils was developed using gas chromatography-mass spectrometry (GC-MS) and isotopically labelled 3-MCPD esters as internal standards. The analysis of 11 different samples of fat mixes typically employed in food manufacturing demonstrated that a maximum of about 15% of the total amount of 3-MCPD bound in esters is present in the monoesterified form. The potentially slower release of 3-MCPD from 3-MCPD diesters, and the mono- to diesters ratio suggest that 3-MCPD esters may in fact contribute only marginally to the overall dietary exposure to 3-MCPD. Further work on the bioavailability, metabolism and possible toxicity of chloroesters per se is warranted.     

Esters of 3-chloro-1,2-propanediol (3-MCPD) in vegetable oils: Significance in the formation of 3-MCPD

3-Mono-chloropropane-1,2-diol (3-MCPD) is a contaminant that occurs in food in its free (diol) form as well as in an esterified (with fatty acids) form. Using a simple intestinal model, it was demonstrated that 3-MCPD monoesters and 3-MCPD diesters are accepted by intestinal lipase as substrates in vitro. Under the chosen conditions, the yield of 3-MCPD from a 3-MCPD monoester was greater than 95% in approximately 1 min. Release from the diesters was slower, reaching about 45, 65 and 95% of 3-MCPD after 1, 5 and 90 min of incubation, respectively. However, in human, the hydrolysis of 3-MCPD esters is unlikely to release 100% as 3-MCPD, as triglycerides and phospholipids are hydrolysed in the intestine liberating 2-monoglycerides. Assuming a similar metabolism for 3-MCPD esters as that known for acylglycerols in humans in vivo, the de-esterification in positions 1 and 3 would thus be favoured by pancreatic lipases. Therefore, 3-MCPD, and 3-MCPD-2 monoesters would be released, respectively, from the 1-/3-monoesters, and the diesters potentially present in food. Hence, information on the exact amounts of the partial fatty acid chloroesters, i.e. 3-MCPD mono- and diesters, is important to assess the contribution of foods to the bioavailability of 3-MCPD. Therefore, a rapid method for the determination of the ratio of 3-MCPD monoesters to diesters in fats and oils was developed using gas chromatography-mass spectrometry (GC-MS) and isotopically labelled 3-MCPD esters as internal standards. The analysis of 11 different samples of fat mixes typically employed in food manufacturing demonstrated that a maximum of about 15% of the total amount of 3-MCPD bound in esters is present in the monoesterified form. The potentially slower release of 3-MCPD from 3-MCPD diesters, and the mono- to diesters ratio suggest that 3-MCPD esters may in fact contribute only marginally to the overall dietary exposure to 3-MCPD. Further work on the bioavailability, metabolism and possible toxicity of chloroesters per se is warranted.