超高效液相色谱-串联质谱法测定植物油中4种杂环胺含量

建立超高效液相色谱-串联质谱法(UPLC-MS/MS)测定植物油中4种杂环胺(MeIQx、4,8-DiMeIQx、7,8-DiMeIQx、PhIP)的分析方法。样品经含1%氨水乙腈提取、乙腈饱和的正己烷脱脂后,利用PCX固相萃取柱进行净化。净化后的样品采用乙腈和10 mmol/L甲酸铵溶液作为流动相进行梯度洗脱,在正离子模式下以电喷雾电离串联质谱对杂环胺的定量离子和定性离子进行监测,并利用内标法进行定量。结果表明：4种杂环胺在0.5～100.0 ng/mL范围内线性关系良好,相关系数均大于0.99,方法检出限为0.01～0.04μg/kg,定量限为0.03～0.13μg/kg;在1.0、5.0、10.0μg/kg的加标水平下,杂环胺的平均回收率在64.5%～96.5%之间,相对标准偏差在2.83%～8.52%之间。本方法快速、准确、灵敏,可应用于植物油中4种杂环胺的同时检测。     

Influence of food condiments on the formation of carcinogenic heterocyclic amines in cooked chicken and determination by LC-MS/MS

Heterocyclic amines (HCAs) are known to be suspected human carcinogens produced by high-temperature cooking of protein-rich foods such as meat and fish. In the present study, the influence of numerous food condiments on the formation of HCAs in cooked chicken was investigated. Chicken samples were subjected to pan-frying under controlled temperature. The levels of HCAs DMIP, MeIQx, 4,8-DiMeIQx, PhIP, harman and norharman were found to be between 0.93 and 27.52 ng g^?1, whereas IQ, MeIQ, AαC, MeAαC, Trp-P-1 and Trp-P-2 were found either below the limit of quantification or not detected in the control sample. Nevertheless, for samples cooked using food condiments, the amounts of HCAs (DMIP, MeIQx, 4,8-DiMeIQx and PhIP) were between 0.14 and 19.57 ng g^?1; harman and norharman were detected at higher concentrations up to 17.77 ng g^?1 while IQ and MeIQ were at levels below the limit of quantification; and AαC, MeAαC, Trp-P-1 and Trp-P-2 were not detected in any of the samples. The outcomes revealed that the formation of HCAs (except harman and norharman) diminished after the addition of food condiments. Edible oil contributed to the highest levels of HCA formation, followed by garlic, paprika, pepper and tomato.     

烹调食品中杂环胺检测的分析方法

杂环胺是富含蛋白质的食品在热加工过程中产生的一类多环芳香族化合物,具有致癌、致突变性。本文系统地对杂环胺的检测方法进行了综述。介绍了高效液相色谱法、气相色谱法、气相色谱-质谱法、液相色谱-质谱法、毛细管电泳法、ELISA方法和高效薄层色谱法等杂环胺定性定量的分析方法,重点讨论了检测方法的优势和特点。      

加工肉制品中杂环胺的形成与控制

煎炸熏烤肉制品容易导致杂环胺的产生。杂环胺大多具有致癌致突变性,特别是2-氨基-3-甲基咪唑并[4,5-f]喹啉(IQ),已被国际癌症研究中心列为"对人类高可疑致癌物(2A级)",对人体的健康存在极大的危害。主要对杂环胺形成的影响因素进行了分析,并提出了具体的抑制措施,以增加公众对杂环胺的认识,为健康饮食提供科学依据。     

不同添加量的大豆分离蛋白和淀粉对烤猪肉中杂环胺形成的影响

分别将2.5%、5.0%、7.5%和10.0%的大豆分离蛋白（SPI）和淀粉添加于猪肉中,采用UHPLC-MS/MS法测定其中16种杂环胺的含量,探讨其对杂环胺形成的影响。结果表明:添加2.5%的SPI和淀粉后,除喹喔啉类（Me IQx和4,8-Di Me IQx）外,各杂环胺的含量均显著增加（p<0.05）。随着添加量的增加,杂环胺的含量先升高后开始下降。当添加量达到10.0%时,SPI的添加对4,8-Di Me IQx的形成出现显著抑制作用（p<0.05）,而淀粉的添加对吡啶和喹啉/喹喔啉杂环胺的促进作用则变得不再显著（p<0.05）。由此可见,SPI和淀粉的添加对烤猪肉体系中多数杂环胺的形成具有低剂量促进,且随着剂量的增多促进效果逐渐减弱的影响规律。      

烤肉制品中杂环胺的研究进展

杂环胺(heterocyclic aromatic amines,HAAs)是一类有致癌和致突变作用的化合物,肉制品烤制的烹调方法会产生杂环胺。随着人们对健康安全的要求越来越高,杂环胺的检测以及控制杂环胺形成越来越受到人们的关注。本文对国内外烤肉制品中产生的杂环胺的最新研究进展进行综述,主要对烤肉制品中杂环胺形成的影响因素、检测方法、新型绿色工艺方式等方面进行了阐述,并对未来的研究进行展望。     

Effects of breeds on the formation of heterocyclic aromatic amines in smoked lamb

Heterocyclic aromatic amines (HAAs) are mutagenic and carcinogenic compounds, which are commonly detectable in cooked meat products. The objective of this study was to evaluate the effect of sheep breeds on the formation of HAAs in smoking cooked lamb. The results showed that HAAs in smoked lamb meat products were generally low (2.74–5.42 ng g^?1), with most being Harman and Norharman. IQ, MeIQx, 4,8‐DiMeIQx, Trp‐p‐2, PhIP and MeAaC were not detected in smoked lamb meat products in the present study. The total content of HAAs differed between meat products of different sheep breeds, but no difference in the order of magnitude was determined. Smoking altered the content of protein, fat, moisture and free amino acids in lamb meat products, which was probably mostly contributed by the reduction in meat moisture. Free tryptophan decreased in all breeds after smoking, which was probably used to synthesise HAAs. In summary, HAAs were low in smoked lamb meat products of all sheep breeds; thus, consumption of smoked lamb meat products should contribute very limited intake of HAAs.     

加工肉制品中杂环胺的检测方法及抑制措施的研究进展

杂环胺是肉类等高蛋白食品在烹调过程中产生一类具有致癌、致突变作用的化合物。目前已经从高温肉制品中发现近三十种的杂环胺。美国国家毒理学计划在第十一届癌症报告中将五种杂环胺列入潜在的人类致癌物质,且国际癌症研究中心也将三种杂环胺列入潜在的人类致癌物质。鉴于杂环胺可能对人类的健康带来极大危害,本文结合过去多年的文献研究,介绍了杂环胺的提取及检测方法,并对肉制品中杂环胺的抑制措施进行了概述,以期为将来研究提供科学参考。      

烧烤肉制品加工中多环芳烃和杂环胺形成途径及其防控方法研究进展

烧烤肉制品因具有独特的色泽、香气和口感受到消费者的喜爱,但传统烤制通常是在高温条件下进行,肉制品在高温下会发生脂肪裂解、美拉德反应等生成多环芳烃、杂环胺等有害物质。该文综述了烧烤肉制品中多环芳烃、杂环胺等有害物质形成途径、影响因素、抑制方法的研究进展,主要阐述了烧烤肉制品通过HAVA机理和Diels-Alder机理形成多环芳烃,通过自由基途径及美拉德反应形成杂环胺,并为此提出合理控制烤制温度和烤制时间,合理选择烤制技术,添加外源物质抑制有害物质的生成等防控方法,为优化烧烤肉制品加工工艺,促进肉制品行业的绿色安全发展提供理论基础。     

A study of the aroma of fried bacon and fried pork loin

Aroma compounds in the headspace volatiles of fried bacon and fried pork loin were identified. The concentrations of volatiles in bacon were much lower than those in pork loin, except for nitrogen compounds. It is likely that these differences were caused by the presence of nitrite in bacon. Characteristic aromas for fried bacon, described variously as bacon‐, fried meat‐, roast meat‐ and cooked meat‐like, were found through olfactory testing. These aromas were not present in the pork loin samples. Compounds such as pyrazines, pyridines and furans are thought to be responsible for these meaty aromas. Copyright © 2004 Society of Chemical Industry     

Potential carcinogenic heterocyclic aromatic amines (HAAs) in foodstuffs: Formation,extraction, analytical methods,and mitigation strategies

During the heat treatment of proteinaceous food, heterocyclic aromatic amines (HAAs), a kind of strong mutagens/carcinogens are formed. HAAs can be classified into two major groups based on the heating temperature, which are thermic HAAs generally formed in 150 to 300 °C and pyrolytic HAAs produced above 300 °C. This review focuses on the formation mechanisms of HAAs and identifies different mechanisms of the formation of HAAs in foodstuffs. Moreover, an overview of the available extraction, purification methods, and instrumental analytical methods in the last two decades is shown to determine the HAAs in various foodstuffs. Finally, based on the factors that affect the formation of HAAs in heat‐processed foodstuffs, such as the cooking method, food type, the recipe, and the content of substances with enhancing or inhibiting effects on the formation of HAAs, this review also highlights the most promising strategies for mitigating HAAs, which include adjusting cooking methods or process conditions, adding natural product extracts, antioxidants or other compounds, or reasonable selection of types of foodstuff. The review intends to provide a broad but comprehensive understanding of the formation, extraction, purification, analytical methods, and possible mitigation strategies for isolated and identified HAAs.     

Heterocyclic aromatic amines in fried poultry meat

 Heterocyclic aromatic amines are mutagenic compounds that are formed during heating of meat and fish. These substances are products of the reaction of creatine with amino acids and carbohydrates. It is recommended that exposure to these probable human carcinogens should be minimised. In fried boneless lean turkey breast meat five heterocyclic aromatic amines {2-amino-1-methyl-imidazo[4,5-f]quinoline (IQ), 2-amino-3,8-dimethyl-imidazo-[4,5-f]quinoline (MeIQ), 2-amino-3,8-dimethyl-imidazo[4,5-f]quinoxaline (MeIQx), 2-amino-3,4,8-trimethyl-imidazo[4,5-f]quinoxaline (4,8-DiMeIQx) and 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP)} were found. The temperature regime which was applied for frying resulted in a surface temperature of about 140°C. Clean-up was done by acid-base partition followed by solid-phase extraction (SPE) using blue cotton. HPLC analysis was carried out using electrochemical detection for IQ- and IQx-type compounds and fluorescence detection for PhIP. The low temperatures used during frying yielded comparably lower amounts of heterocyclic aromatic amines. The concentrations of the aromatic amines were as follows: IQ 1.1 μg/kg, MeIQ 0.9 μg/kg, MeIQx μg/kg, 4,8-DiMeIQx 0.4 μg/kg, and PhIP 3.8 μg/kg. Received: 19 February 1997 / Revised version: 21 April 1997     

煎香肠中杂环胺的生成规律研究

目的 考察不同煎制温度、时间和不同食用油对煎香肠中杂环胺(heterocyclic amines, HAs)生成的影响, 并进一步探究几种常见香辛料对煎香肠中HAs生成的抑制效果。方法 采用超高效液相色谱-串联四极杆质谱法(ultra performance liquid chromatography-tandem mass spectrometry, UPLC-MS/MS)对煎香肠中游离和结合态HAs进行定量分析, 评价各因素对煎香肠HAs生成的影响。结果 煎香肠中游离态HAs总量随煎制温度或时间的增加而逐渐增加, 结合态HAs总量随煎制温度升高而增加, 随煎制时间延长先减少后增加。相比于不采用食用油煎制, 添加大豆油对煎香肠游离态HAs抑制效果最好, 抑制率达37.25%; 同时对结合态HAs促进作用最小, 仅促进7.13%。辣椒粉和大蒜能显著促进煎香肠游离态和结合态HAs生成(P<0.05), 而添加0.5%黑胡椒粉时对游离态和结合态HAs的抑制率分别为25.49%和25.32%。结论 相比于时间, 温度对煎香肠HAs影响更为显著(P<0.05); 采用大豆油煎制的同时添加黑胡椒可明显抑制煎香肠中游离和结合态HAs的生成。     

高效液相色谱法测定烧烤制品中5种杂环胺的含量

目的 建立高效液相色谱法检测烧烤制品中5种杂环胺(heterocyclic aromatic amines, HAAs)含量的方法。方法 样品经乙酸乙酯、三乙胺、氨水提取, 丙基磺酸(propanesulfonic acid, PRS)和C18固相萃取小柱净化, 采用TSK-gel ODS-80TM色谱柱分析, 以乙腈和0.05 mol/L醋酸-醋酸铵缓冲液(pH=3.4)为流动相进行梯度洗脱, 紫外-荧光检测器的串联方式检测杂环胺含量。结果 2-氨基-1-甲基-6-苯基-咪唑并[4,5-b]吡啶(2-amino-1-methyl-6-phenylimidazo(4,5-b)pyridine, PhIP)、9H-吡啶并[4,3-b]吲哚(9H-pyrido[4,3-b]indole, Norharman)、1-甲基-9H-吡啶并[4,3-b]吲哚(1-methyl-9H-pyrido[4,3-b]indol, Harman)、2-氨基-9H-吡啶并[2,3-b]吲哚(2-amine-9H-pyrido[2,3-b]indol, AaC)在0.1~500 μg/L范围呈良好的线性关系, 2-氨基-3-甲基咪唑并[4,5-f]喹啉(2-amino-3-methylimidazo(4,5-f)quinoline, IQ)在0.1~1000 μg/L范围呈良好的线性关系, 相关系数r2均大于99.3%, 加标回收率为74.06%~93.77% (n=6), 相对标准偏差(relative standard deviation, RSD)为3.41%~5.93% (n=6)。结论 该方法简便快速、结果准确、灵敏度高, 适合于肉制品中的杂环胺含量的检测。通过检测结果可知不同原料中5种杂环胺含量不同, 相同原料烧烤条件不同, 产生的杂环胺含量也不相同。     

不同产地芝麻所制芝麻油中杂环胺的分析测定

芝麻油可能含有杂环胺9H-吡啶并[3,4-b]吲哚(norharman)和1-甲基-9H-吡啶并[3,4-b]吲哚(harman),为了有效检测芝麻油中杂环胺含量,建立了一种高效液相色谱-荧光检测法(HPLC-FLD),并对不同产地芝麻所制芝麻油中杂环胺含量进行对比。结果表明：所建立的HPLC-FLD能在15 min内实现对芝麻油中杂环胺的测定;在相同炒籽条件下,不同产地芝麻所制芝麻油中杂环胺含量有显著差异(p<0.05),非洲产地的芝麻所制的芝麻油中杂环胺含量(421.87μg/kg)相对高于亚洲产地的(329.32μg/kg),埃塞俄比亚产地的芝麻所制芝麻油中杂环胺含量最高,为720.81μg/kg,而苏丹和中国河南驻马店产地的芝麻所制芝麻油中杂环胺含量较低,分别为236.01μg/kg和239.63μg/kg。综上,芝麻油中杂环胺含量与芝麻原料的选择有关,选择合适的芝麻原料对减控芝麻油中杂环胺、保障芝麻油食用安全具有重要意义。     

天然抗氧化物质对肉制品中杂环胺生成的影响

杂环胺常见于如禽肉、鱼肉等富含蛋白质的热加工肉制品中,是一类杂环芳香族化合物。杂环胺具有极强的致癌致突变性,通常在肉制品于100℃及以上的高温烹制过程中产生。长期摄入具有高含量杂环胺的肉制品,会增加消费者患肿瘤患癌的风险。天然抗氧化物质具有抗氧化活性,且毒性小,安全性高,现已普遍应用于肉制品加工领域。通过添加天然抗氧化物质抑制肉制品中杂环胺的生成是当前研究热点。本文简要介绍了杂环胺的分类、形成等,并重点综述了近10年天然抗氧化物质对肉制品杂环胺形成的影响研究进展,其中,重点围绕多酚类化合物、黄酮类化合物、香辛料3类具有代表性的天然抗氧化物质对肉制品中杂环胺形成的影响进行了详尽的阐述。最后对未来的研究提出了展望。     

烹调方式对不同肉及其制品中杂环胺的影响概述

杂环胺(heterocyclic aromatic amines,HAAs)是一类杂环芳香族化合物,是富含蛋白质的食物(如肉类和鱼类等)在高温和长时间烹饪过程中产生的一类有害物质.目前已经从高温加工的肉及其制品中发现有超过30种的杂环胺.国际癌症研究机构已把2-氨基-3-甲基咪唑并[4,5-f]喹啉(IQ)等杂环胺列为...     

Steam-assisted roasting inhibits formation of heterocyclic aromatic amines and alters volatile flavour profile of beef steak

In order to evaluate the effect of steam addition during meat roasting, beef sirloin steaks were cooked at five humidities (0%, 25%, 50%, 75% and 100%) under 230 °C to a centre temperature of 71 °C. With increased humidity, heating rate generally increased and the cooked steak gradually lost the typical roasted appearance. Thiobarbituric acid-reactive substances (TBARS) values generally increased, while carbonyl groups were not affected. Increased humidity promoted the formation of volatile aldehydes and alcohols, while pyrazines decreased significantly from 0% to 25% humidity. Steam-assisted roasting inhibited the formation of heterocyclic aromatic amines (HAAs; except for IQ and Norharman). However, further increase in humidity (larger than 25%) did not have additional inhibition effect. Based on the results, it is recommended to roast beef with steam addition to reduce toxic HAAs, but the humidity should be kept at a relatively low level to maintain a typical roasted appearance and flavour profile.