Formation of Heterocyclic Amines in a Meat Juice Model System

Bovine meat juice was used as a model system to examine the kinetics of the formation of heterocyclic amines. The formation was examined at temperatures between 100 and 225°C for 0.5-180 min. Heated samples were subjected to solid-phase extraction and HPLC analysis. IQx, MeIQx, 7,8-DiMeIQx, 4,8-DiMeIQx, PhIP, harman and norharman were identified. The formation of the IQx derivatives and PhIP followed a first-order model C_t=B(1–e^k1(t1-t0), and the temperature dependence followed the Eyring equation k=k_bT/he^ΔS/Re-^ΔH/RT. The parameters in the first-order model and the Eyring equation could be estimated from our data. The degradation of heterocyclic amines at high temperatures was analyzed and the products were found to be less mutagenic.     

常见香辛料对酱猪肉中杂环胺生成的影响

本文探讨了不同添加量的7种香辛料(桂皮、甘草、红花椒、大料、丁香、良姜、草果)对酱猪肉中杂环胺生成的影响。分别单独添加0.05%和0.10%的7种香辛料进行猪肉卤制,并用LC-MS/MS法检测酱猪肉中9种杂环胺的含量。结果表明:只用蒸馏水煮的空白猪肉,杂环胺总量很低(8.71 ng/g);用酱油、料酒、盐和糖卤煮的对照猪肉中,杂环胺总量很高(225.29 ng/g),为空白组含量的25.7倍,含量最高的两种杂环胺为Norharman和Harman(分别为84.99 ng/g和140.21 ng/g)。所选的7种香辛料在低剂量0.05%水平下,除桂皮、丁香、良姜外,其他香辛料对杂环胺的生成有显著促进作用(p<0.05);而在0.1%水平下,除红花椒外,其他杂环胺都能在一定程度上抑制杂环胺的生成(p>0.05)。结论:酱油、料酒等调味料可以明显促进杂环胺的生成,0.1%香辛料对酱猪肉中杂环胺生成有一定抑制作用,其中丁香的抑制效果最好,0.05%和0.1%的丁香对杂环胺总量的抑制率分别为25.78%和36.21%。总之,香辛料对杂环胺的生成在一定程度上有抑制作用,且不同香辛料抑制作用不尽相同。     

Heterocyclic Amines: 2. Inhibitory Effects of Natural Extracts on the Formation of Polar and Nonpolar Heterocyclic Amines in Cooked Beef

ABSTRACT: The effects of natural extracts on the formation of polar (IQ, MeIQ, MeIQx, 4,8-DiMeIQx, and PhIP) and nonpolar (norharman, harman, and AαC) heterocyclic amines (HAs) were examined in ground beef cooked at 200 and 210°C for 20 min. In experiment 1, the formation of MeIQx was effectively reduced by 77%, 75%, and 69%, respectively, for 1.0% pine bark extract (Pycnogenol®), 1.0% Oleoresin rosemary (Herbalox®), and grape seed extract (ActiVin^TM) at 200°C for 20 min. No 4,8-DiMeIQx was observed in the 1.0% ActiVin. When compared with the initial concentrations, glucose and creatine significantly decreased for all treatments and the control at 200°C after 20 min. In experiment 2, IQ was not formed in any treatment when beef was fried at 210°C for 10 min/side. The formation of MeIQx was reduced by 64% and 61% at 1.0% ActiVin and 1.0% Pycnogenol. Herbalox (1.0%) more effectively decreased the amount of nonpolar HAs than other treatments. No AαC and norharman were detected at 1.0 % Herbalox. Natural extracts, ActiVin, Pycnogenol, and Herbalox, effectively decreased the formation of polar and nonpolar HAs. The results provide valuable information to inhibit the formation of HAs in cooked meats.     

前体物含量对杂环胺形成的影响

将牛、猪、羊、鸡、鸭和鹅肉分别在200℃下煎烤10 min,分析其原料肉中前体物的含量与加工肉制品中杂环胺的形成量,以探讨不同动物原料肉中杂环胺的形成量及原料肉中前体物的含量对杂环胺形成的影响。结果表明,6种原料肉中前体物含量差异较大,肌酸与葡萄糖的摩尔浓度比在0.89～9.84之间。加工肉制品中共检测出10种杂环胺,其中9H-吡啶并[3,4-b]吲哚(Norharman)与1-甲基-9H-吡啶并[3,4-b]吲哚(Harman)在加工肉品中含量最高,分别在10.90～24.16 ng/g与4.64～14.04 ng/g之间。而2-氨基-3,8-二甲基咪唑并[4,5-f]喹喔啉(MeIQx)在牛肉中形成量较高,达3.55 ng/g,2-氨基-1-甲基-6-苯基-咪唑并[4,5-b]吡啶(PhIP)在禽肉中易于产生,其中鸡肉中含量最高,达15.26 ng/g。PhIP与肌酸和葡萄糖的摩尔浓度比存在相关性(P<0.05),随着葡萄糖浓度的增高,PhIP的形成量减少。     

煎炸肉制品中杂环胺的控制技术及体内代谢调控研究进展

杂环胺是富含蛋白质的食物在烹饪加工过程中产生的一类有害物质。由于煎炸过程温度较高,反应复杂,导致煎炸肉制品中杂环胺生成量较多。杂环胺具有较强的生物毒性,是一种潜在的致癌、致突变物质,长期摄入富含杂环胺的煎炸肉制品会对人体产生不良影响。本文对煎炸肉制品中的杂环胺进行了简介,包括其分类、结构以及生物毒性,综述了影响煎炸肉制品中杂环胺生成的因素和控制杂环胺生成的方法,并根据杂环胺的消化吸收和代谢机制,探讨了其在体内代谢的调控方式。     

Effect of Marinades on the Formation of Heterocyclic Amines in Grilled Beef Steaks

ABSTRACT:  Heterocyclic amines (HCAs) are suspected human carcinogens formed in muscle foods during high temperature grilling or cooking. Inhibition of HCAs by commercial marinades rich in polyphenolic antioxidant containing spices was evaluated with beef round steaks cooked at 204 °C (400 °F). Treatment effects on the levels of 4 HCAs were investigated: 2-amino-3,8-dimethylimidazo[4,5- f ]quinoxaline (MeIQx), 2-amino-1-methyl-6-phenyl-imidazo[4,5- b ]pyridine (PhIP), 1-methyl-9H-pyrido[4,3- b ]indol (harman), and 9H-pyrido[4,3- b ]indol (norharman). The marinades were formulated according to the package label instruction in an oil, water, and vinegar mixture, and the steaks were treated for 1 h prior to grilling. All 3 marinades, Caribbean, Southwest, and herb, significantly decreased the imidazo-azaarene HCAs (MeIQx, PhIP) as contrasted to controls and liquid blanks. The Caribbean mixture showed the highest decrease in the total HCA content (88%), followed by the herb (72%) and Southwest (57%). With a few exceptions there were significant decreases in HCAs for treatments with only the marinade bases (ingredients without any spices/herbs). As measured by high-performance liquid chromatography (HPLC), the marinades contained considerable amounts of the polyphenolic antioxidants carnosic acid, carnosol, and rosmarinic acid with Caribbean being the highest. Commonly available spice-containing marinades can be effective inhibitors of HCA formation and provide reduced exposure to some of the carcinogens formed during grilling.     

Kinetics of Formation of Polar Heterocyclic Amines in a Meat Model System

A model system was used to examine kinetics of formation of polar heterocyclic amines by heating the precursors creatinine, glucose and amino acids in proportions similar to those in bovine meat but at higher concentrations. Formation of heterocyclic amines was studied between 150 and 225°C for 0.5–120 min, depending on temperature. Heated samples were subjected to solid phase extraction and HPLC analysis, with photodiode array detection for identification and quantification of heterocyclic amines. IQx, MeIQx, 7,8-DiMeIQx, 4,8-DiMeIQx, PhIP, harman and norharman were identified. A first-order reaction model and the Eyring equation were fitted to the formation of polar heterocyclic amines to obtain rate constants and their temperature dependence.     

苹果与葡萄对烤牛肉饼体外消化过程杂环胺释放的影响

研究外源添加物在消化过程中对蛋白结合态杂环胺（heterocyclic aromatic amines,HAAs）释放的影响。在烤牛肉饼的体外消化实验中以加入新鲜苹果和葡萄泥作为实验组,以未添加新鲜苹果和葡萄泥为对照组,消化液中的游离HAAs和蛋白结合态HAAs分别通过乙酸乙酯和盐酸水解提取,经固相萃取后使用超高效液相色谱-质谱联用仪测定。结果表明：苹果与葡萄的添加并未引起总HAAs含量的显著变化,但都不同程度促进了蛋白结合态HAAs向游离态HAAs的转化,且转化效果随新鲜苹果和葡萄泥添加量增加呈增强趋势。     

葡萄籽提取物对烤羊肉中杂环胺形成的影响

将0.05%VE,0.1%与0.5%葡萄籽提取物,0.1%与0.5%槲皮素分别添加于羊肉表面,在200℃下煎烤10 min,利用固相萃取-配备二极管阵列检测器和荧光检测器的高效液相色谱分析烤羊肉中15种杂环胺的形成量,以探讨天然提取物对烤羊肉中杂环胺形成量的影响。结果表明:烤羊肉中共检测出10种杂环胺,其中极性杂环胺4种,非极性杂环胺6种,总量达51.68 ng/g。在极性杂环胺中2-氨基-1-甲基-6-苯基-咪唑并[4,5-b]吡啶(PhIP)的形成量较高,达10.50 ng/g;非极性杂环胺中9H-吡啶并[3,4-b]吲哚(Norharman)与1-甲基-9H-吡啶并[3,4-b]吲哚(Harman)的形成量较高,分别达19.66 ng/g与12.23 ng/g。烤羊肉中添加天然抗氧化剂只对极性杂环胺有抑制作用,其中添加0.5%葡萄籽提取物可以显著抑制2-氨基-3甲基咪唑并[4,5-f]喹啉(IQ),2-氨基-3,8-二甲基咪唑并[4,5-f]喹喔啉(MeIQx),2-氨基-3,4,8-三甲基咪唑并[4,5-f]喹喔啉(4,8-DiMeIQx)与PhIP 4种极性杂环胺的形成(P<0.05),其生成量分别减少36.65%,67.73%,35.63%与30%。天然抗氧化剂对烤羊肉中非极性杂环胺的抑制作用不明显。     

Kinetics of Heterocyclic Amines Formation in Meat Emulsion at Different Fat Contents

The objectives of the study were to investigate the yield of heterocyclic amines (HA) in meat emulsion during heating as in cooking at different temperatures using the kinetic modeling approach and to determine the influence of fat content on the formation of HAs. Meat emulsion with two different fat contents namely extra lean (6 g/100 g) and regular (19 g/100 g) were used in the study. The samples were heated at 160, 180 and 200°C for times, varying from 5 to 40 mins. HAs namely IQx, MeIQx, and PhIP were identified and quantified using the HPLC. Formation of HAs was dependent on temperature, time, and fat content. It followed the first-order kinetics. Increasing fat content of samples resulted in lower HAs concentrations and lower activation energy of reaction. Fat enhanced formation of HAs in meat but apparently diluted available precursors for reactions.     

Determination of Heterocyclic Amines in Meat Matrices Using Enhanced Matrix Removal‐Lipid Extraction and Liquid Chromatography–Tandem Mass Spectrometry

A simple, fast, and efficient method, “enhanced matrix removal of lipids” (EMR‐lipid), was proposed, optimized, and validated for identifying five polar heterocyclic amines (HCAs) in meat samples that ranged from high‐protein (beef and chicken) to high‐fat (pork bacon) matrices. The protocol involves an initial solid–liquid phase extraction followed by a rapid dispersive solid‐phase extraction using EMR‐lipid sorbents and salting‐out partitioning. Acetonitrile containing formic acid at two levels (1% and 2%) efficiently extracted HCAs from different meat matrices. Liquid chromatography–tandem mass spectrometry (MS/MS) with selective reaction monitoring mode was developed for qualitative and quantitative analysis. The highest MS/MS responses and better peak separation of analytes were achieved by adjusting mobile phases to pH 3.0 with instrumental detection limits between 0.01 and 0.05 ng/mL. Good linearity of standard curves was obtained in both pure solvents and postspiked meat extracts between 0.5 and 50.0 ng/mL. The validation results showed good precision, accuracy, and sensitivity for detecting HCAs in spiked meat samples. Satisfactory recoveries of four HCAs were achieved: 65% to 111% in beef, 71% to 106% in bacon, and 42% to 77% in chicken. Matrix effects were also assessed and showed less than –20% of ion suppression in bacon extract, while a medium to high signal suppression was observed in beef (–37% to –55%) and chicken (–28% to –52%). This optimized EMR‐lipid method provides acceptable results and advantages for determining trace level HCAs in complex meat matrices.     

Effects of Rosemary Extracts on the Reduction of Heterocyclic Amines in Beef Patties

ABSTRACT:  The effects of rosmarinic acid and a rosemary antioxidant powder were evaluated on the reduction and mutagenicity of MeIQx, PhIP, and comutagens norharman and harman in beef patties fried at 375 °F for 5 min each side and 400 °F for 7.5 min each side. Both rosemary extracts were found to effectively decrease the formation and overall mutagenic activity of heterocyclic amines (HCAs) due to their antioxidative characteristics. At the lower temperature, rosmarinic acid was able to reduce MeIQx by up to 64% and PhIP by 48%, while rosemary powder reduced the formations of MeIQx up to 69% and PhIP up to 66%. The effects of the rosemary extracts were more dramatic when cooking temperature and time were increased, as rosmarinic acid was able to reduce MeIQx formation up to 70% and PhIP up to 64%; also, rosemary powder significantly reduced MeIQx up to 57% and PhIP up to 77%. The overall mutagenic activity was evaluated by the Ames Salmonella assay and both rosemary extracts were capable of reducing mutagenicity in beef patties at the higher cooking temperature of 400 °F. At 375 °F there was an insignificant trend of the rosemary extracts decreasing the number of Salmonella revertants. There was no significant inhibiting effect by any of the rosemary extracts on the formation of either norharman and harman as measured in this study.     

牛肉菜肴中杂环胺的形成机理和抑制方法研究进展

牛肉菜肴指以牛肉为原材料烹制而成的一类即食食品。牛肉经高温处理降解生成具有一定的致癌、致突变性的杂环胺。本文阐述了两类杂环胺的分类标准及形成机理、影响杂环胺生成的因素、牛肉菜肴中杂环胺的预处理和常见检测方法、通过研究外源物质的添加和对前体物质的影响进而研究杂环胺的抑制方法,并对杂环胺研究的未来加以展望,可对牛肉菜肴烹制过程杂环胺的控制有一定的借鉴意义。     

畜禽产品加工过程中有害物质的形成机制及抑制措施--以杂环胺为例

畜禽产品加工过程中容易形成致癌性、致突变性的杂环胺. IQ型杂环胺通过非酶褐变形成,即包含肌酸、氨基酸、糖的美拉德反应;氨基咔啉主要是通过氨基酸和蛋白质在高于300℃的温度下热解产生. 研究表明,随着加工温度的升高和加工时间的延长,杂环胺含量显著上升. 一些天然植物提取物以及抗氧化剂对杂环胺的形成有一定抑制作用. 介绍了杂环胺的结构、分类、含量、影响因素等,重点对杂环胺的形成机制及抑制措施进行了分析.     

烹调肉制品中杂环胺的检测技术和控制手段研究进展

杂环胺是烹调肉和鱼等高蛋白食物过程中形成的一类致癌致突变化合物。本文概述烹调肉制品中杂环胺的前处理方法和检测技术,并重点阐述肉制品加工过程中产生杂环胺的控制手段。     

新疆传统腌制对烤羊肉食用品质及杂环胺含量的影响

为了改善烤羊肉的风味、色泽、嫩度等食用品质,减少杂环胺(heterocyclic amines,HAs)的形成,本实验以羊肉为对象,研究了不同新疆传统腌制料(红辣椒(H)、洋葱(Y)、孜然(Z)、蛋清(Q))对烤羊肉水分质量分数、持水力、色泽、嫩度、质构特性及HAs含量的影响.结果表明:不同的腌制料对烤羊肉的食用品质有...     

驴排、牛排和猪排中杂环胺的差异性分析

为探求相同煎炸方式下驴排、牛排和猪排在杂环胺（HAs）生成方面的差异性,通过基质固相分散-固相萃取技术对样本中HAs进行了分离、富集,利用高效液相色谱-质谱法（HPLC-MS/MS）对样本中HAs进行了定性分析,并通过高效液相色谱法对样本中IQ、Norharman、Harman、AaC、MeIQx、DMIP和PhIP等7种HAs进行了含量测定。结果表明,在相同煎炸方式（200 ℃,15 min）下,驴排、牛排和猪排中HAs具有明显差异性。其中,驴排、牛排主要是以热反应型HAs（IQ、MeIQx、DMIP、PhIP）为主,猪排主要是以热解型HAs（Norharman、Harman、AaC）为主。猪排和牛排中热反应型HAs含量（1.74 mg/g,1.73 mg/g）高于驴排（1.02 mg/g）,差异性显著（p<0.05）,而热解型HAs,猪排中最高（2.14 mg/g）,牛排次之（1.07 mg/g）,驴排最低（0.58 mg/g）。综上所述,通过揭示相同煎炸条件下驴排、牛排、猪排中HAs生成方面的差异性,可以为驴排加工过程中的食品安全研究提供参考。     

15种黄酮类化合物对烤鸡胸肉中杂环胺含量的影响

为研究15 种黄酮类化合物对烤鸡胸肉中5 种杂环胺含量的影响,将烤鸡胸肉经NaOH提取、乙酸乙酯萃取,通过Oasis MCX固相萃取小柱净化后,采用超高效液相色谱-串联质谱法对杂环胺含量进行分析,并采用主成分分析法研究黄酮类化合物对烤鸡胸肉中杂环胺形成影响的差异性。结果表明,15 种黄酮类化合物中染料木素、表没食子儿茶素没食子酸酯（epigallocatechin gallate,EGCG）和木犀草素对烤鸡胸肉中1-甲基-9H-吡啶并[3,4-b]吲哚和9H-吡啶并[3,4-b]吲哚抑制作用较好,抑制率达20%以上;EGCG、柚皮素、木犀草素和染料木素对2-氨基-1-甲基-6-苯基-咪唑并[4,5-b]吡啶抑制作用较好,抑制率达45%以上;染料木素、柚皮素和木犀草素对2-氨基-3,8-二甲基咪唑并[4,5-f]喹喔啉和2-氨基-3,4,8-三甲基-3H-咪唑并[4,5-f]喹喔啉抑制作用较好,抑制率达45%以上。主成分分析结果显示,EGCG、木犀草素和染料木素聚为一类,且对5 种杂环胺均有较强的抑制作用。通过化学结构推测得出,黄酮母核中A环同时存在5-羟基和7-羟基,B环的4’-羟基对黄酮类化合物有效抑制烤鸡胸肉中杂环胺的形成具有重要作用,而C环中3-羟基的存在会降低其对杂环胺形成的抑制作用。综上,黄酮类化合物对杂环胺的形成具有影响,EGCG、木犀草素和染料木素的抑制作用最强,可为高温肉制品安全加工提供理论参考。     

模型体系中PhIP、Norharman、Harman 3种杂环胺的形成与抑制

采用模型体系探讨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[3,4-b]吲哚(9H-pyrido[3,4-b]indole,norharman)、1-甲基-9H-吡啶并[3,4-b]吲哚(1-methyl-9H-pyrido[3,4-b]indole,harman)3种杂环胺的形成规律及抑制措施。结果表明:随着加热温度的升高与加热时间的延长,模型体系中PhIP、Norharman和Harman的形成量均不断增多,其中PhIP对加热温度较为敏感,100、125℃反应20 min不能形成PhIP,150℃加热时PhIP生成量开始逐渐增多,175～200℃加热时PhIP形成量急剧增加;单独加热色氨酸即能产生Norharman和Harman,加入葡萄糖时Norharman和Harman的形成量进一步提高;本研究建立的同时检测色氨酸、Norharman和Harman的色谱方法明确表明,色氨酸是Norharman和Harman的前体物;高良姜素及其类似物山柰酚和槲皮...