植物多酚抑制热加工肉制品中杂环胺形成机制研究进展

杂环胺（heterocyclic amines,HAs）是肉制品热加工过程中产生的一类具有极强致畸致癌活性的有毒化合物,其中2-氨基-3-甲基咪唑并[4,5-f]喹啉（2-amino-3-methyl-imidazo[4,5-f]-quinoline,IQ）和2-氨基-3,4-二甲基咪唑并[4,5-f]喹啉（2-amino-3,4-dimethyl-imidazo[4,5-f]-quinoline,MeIQ）,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）,1-甲基-9H-吡啶并[3,4-b]吲哚（1-methyl-9Hpyrido[3,4-b]indole,Harman）和9H-吡啶并[3,4-b]吲哚（9H-pyrido[3,4-b]indole,Norharman）3类HAs在热加工肉制品中较为常见且分布广泛。本文即围绕上述3类HAs,简要分析其形成的途径及机制,并详细阐述外源添加植物多酚抑制HAs形成的作用机制,最后依据现有研究归纳总结出多酚化合物抑制HAs与其化...     

熟肉制品中杂环胺的形成与抑制研究进展

杂环胺是熟肉制品中最常见的危害物,其种类繁多,形成途径复杂,抑制机制也不尽相同。本文介绍了2 类杂环胺的结构,主要阐述喹啉和喹喔啉类、2-氨基-1-甲基-6-苯基咪唑[4,5-b]吡啶、β-咔啉类（1-甲基-9H-吡啶[4,3-b]吲哚（1-methyl-9H-pyrido[4,3-b]indole,harman）、9H-吡啶[4,3-b]吲哚（9H-pyrido[4,3-b]indole,norharman））以及结合态杂环胺的形成途径,归纳减少杂环胺形成的措施及机理（控制加工条件和前体物、添加外源物质清除自由基和中间体、抑制美拉德反应等）,并对目前的研究现状进行概括。     

3种熏烤鸡肉制品中杂环胺含量的检测与比较

目的 以3种熏烤鸡肉制品(鸡胗、鸡翅、鸡爪)为研究对象, 通过高效液相色谱测定其中5种杂环胺类物质(heterocyclic aromatic amines, HAAs), 即2-氨基-3-甲基咪唑并[4,5-f]喹啉(2-Amino-3- methylimidazo(4,5-f)quinoline, IQ)、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)的含量并进行比较。方法 采用二元流动相乙腈/醋酸-醋酸铵(pH=3.4)进行梯度洗脱, 其中乙腈/醋酸-醋酸铵随时间配比为: 0 min: 10%/90%; 10 min: 20%/80%; 25 min: 50%/50%; 35 min: 10%/90%。紫外检测波长263 nm; 荧光激发波长/发射波长随时间改变为0 min: 300/440 nm; 17 min: 315/390 nm; 21 min: 335/410 nm。结果 在3种鸡肉熏烤制品中提取的5种杂环胺类物质中, PhIP的含量最高, 且在鸡胗中最为显著, 高达152.38 ng/g, 工业化生产的鸡胗中PhIP含量仅为4.23 ng/g; 各产品中Harman的含量最低, 且在鸡爪产品及工业化生产的鸡翅产品中未检出; 熏烤的鸡肉制品中提取的IQ、PhIP、Norharman、Harman、AaC的含量均高于工业化产品。结论 工业化生产的鸡胗、鸡翅、鸡爪中的5种HAAs的含量均低于3家传统熏烤产品的含量, 传统熏烤条件下鸡肉制品的食用安全系数相对较低, 工业化产品的安全性相对较高。     

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。     

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。     

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。     

油煎猪肉饼中6 种氨基咔啉类杂环胺的检测方法及加工条件对其生成的影响

建立一种同时测定油煎猪肉饼中6 种氨基咔啉类杂环胺（2-氨基-3-甲基-9H-吡啶并[2,3-b]吲哚、2-氨基-9H-吡啶并[2,3-b]吲哚、1-甲基-9H-吡啶并[3,4-b]吲哚、9H-吡啶并[3,4-b]吲哚、3-氨基-1,4-二甲基-5H-吡啶并[4,3-b]-吲哚和3-氨基-1-甲基-5H-吡啶并[4,3-b]吲哚）的超高效液相色谱-四极杆/静电场轨道阱高分辨质谱检测方法,并研究加工条件对猪肉饼中6 种氨基咔啉类杂环胺生成的影响。结果表明,待测杂环胺的最优提取和净化条件为：1 g样品中添加1.5 g NaCl、10 mL 1 mol/L NaOH溶液-乙腈（4∶6,V/V）提取,StrataTM-X-C柱净化,4 mL甲醇-氨水（90∶10,V/V）洗脱。6 种杂环胺在相应质量浓度范围内线性良好,相关系数均大于0.996,方法检出限和方法定量限分别为0.02～0.15 μg/kg和0.05～0.5 μg/kg,回收率为64%～91%。油煎5 min后生成的6 种杂环胺含量为9.50 μg/kg。选用菜籽油、复合涂层锅、猪肉饼直径4 cm加工条件下,6 种杂环胺生成量最高,分别为47.62、76.83 μg/kg和29.33 μg/kg。     

陈皮对烘烤牛肉干中杂环胺含量的影响

探讨陈皮对烘烤牛肉干中杂环胺生成及牛肉干质量损失率、色差、感官指标的影响.陈皮的总酚物质含量及抗氧化能力分别通过福林-酚法及DPPH法测定,牛肉干中杂环胺含量利用高压液相色谱法测定.在没有经过陈皮水提物腌制处理牛肉干中检测出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-用喹喔啉(4,8DiMeIQx)、9H-吡啶并[3,4-B]吲哚(Norharman)、1-甲基-9H-吡啶并[3,4-B]吲哚(Harman)和2-氨基-1-甲基-6-苯基-咪唑并[4,5-B]吡啶(PhIP),总含量为44.01ng/g.160mg/mL的陈皮水提物可显著降低MeIQx(34.3％),PhIP(96.5％),但是显著增加了Norharman(32.4％);且陈皮提取液浓度越高、腌制时间越长,其对牛肉干中杂环胺含量的影响越大;陈皮腌制处理对牛肉干质量损失率没有显著影响,而色泽随着陈皮浓度的升高而明显变淡;感官评价表明经过陈皮腌制的牛肉干在颜色及风味感官品质上无不良影响.因此,陈皮提取物腌制是一种较好的抑制烘烤牛肉干中杂环胺的方法.     

热加工肉制品中β-咔啉类杂环胺的形成、检测及毒性研究进展

为了提高食品感官质量和保证饮食健康,人们通常会选择热加工的烹饪方式。在食品热加工过程中,除了赋予食品独特的风味与色泽外,高温还会导致一些有害物质的生成。杂环胺(heterocyclic aromatic amines,HAAs)是一类多在食品热加工过程中产生的有毒化合物,具有致癌性和致突变性,长期摄入还可能导致一些慢性病如帕金森综合征、阿尔兹海默症的发生。β-咔啉类HAAs,9H-吡啶并[4,3-b]吲哚(Norharman)和1-甲基-9H-吡啶并[3,4-b]吲哚(Harman)是热加工肉制品中两种主要的HAAs。随着消费者对食品安全关注度的增加,关于HAAs的未知风险也得到了人们较多关注。本文从β-咔啉类杂环胺Norharman和Harman的形成途径出发,总结了这类物质的抑制方法以及近年来国内外对于β-咔啉类HAAs的分析检测方法研究进展,同时对其毒性研究进展进行了概述,以期为控制热加工肉制品中的β-咔啉类杂环胺生成以及带来的食品安全问题提供一定的理论支撑和参考。     

肉制品中PhIP的形成及抑制机理研究进展

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）是肉制品在热加工中产生的有害物——杂环胺（heterocyclic amines,HCA）的重要成分。PhIP通过肉制品介质进入人体后,有致癌和致突变的风险。为了避免或降低PhIP对人体的危害,在不影响肉制品品质的前提下合理控制PhIP的含量,是今后研究的一个重点方向。该文就PhIP的危害、形成及抑制机理进行综述,以期为有效抑制肉制品中PhIP的含量提供理论参考。     

Formation of heterocyclic amines during cooking of duck meat

Heterocyclic amines (HAs) are an important class of food mutagens and carcinogens produced in meat cooked at high temperature. In the present study, the effects of various cooking methods: boiling, microwave cooking, charcoal-grilling, roasting, deep-frying and pan-frying on the formation of HAs in duck breast were studied. The various HAs formed during cooking were isolated by solid-phase extraction and analysed by HPLC. Results showed that both the varieties and contents of HAs and the cooking loss of duck breast increase along with increasing cooking temperature and time. Pan-fried duck breasts contained the highest amount of total HAs, followed by charcoal-grilling, deep-frying, roasting, microwave cooking and boiling. 9H-pyrido[3,4-b]indole (norharman) and 1-methyl-9H-pyrido[3,4-b]indole (harman) were detected in all of the cooked duck meat, with levels in the range of 0.1–33?ng?g^?1. 2-Amino-1-methyl-6-phenylimidazo[4,5-f]pyridine (PhIP) was formed easily in duck meat cooked by pan-frying and charcoal-grilling in the range of 0.9–17.8?ng?g^?1. 2-Amino-3-methylimidazo[4,5-f]quinoline (IQ) was identified in duck meat cooked by charcoal-grilling and pan-frying, in the range of 0.4–4.2?ng?g^?1. 2-Amino-3,8-dimethyl-imidazo[4,5-f]quinoxaline (MeIQx) was detected in amounts below 4.5?ng?g^?1 in duck meat cooked by charcoal-grilling, roasting, deep-frying and pan-frying. The other HAs were detected in amounts below 10?ng?g^?1. Colour development increased with cooking temperature, but no correlation with HAs’ content was observed.     

肉制品加工过程中harman和norharman形成机制研究进展

1-甲基-9H.-吡啶[3,4-b]吲哚(harman)和9H-吡啶[3,4-b]吲哚(norharman)是肉制品加工过程中形成的一类具有潜在毒性的β-咔啉生物碱,主要在高温体系下通过氨基酸裂解形成.本文概述肉制品加工过程中harman和norharman的形成机制,重点阐述加工方式对harman、norharman的作用规律,分析harman、norharman的前体物、生成途径及抑制措施,为肉制品加工工艺的革新和营养健康肉制品的开发提供基础.     

不同前体物对酱肉中β-咔啉norhharman和harman的影响

以羊肉为原料肉制作酱肉,通过向原料肉中加入norharman（9H．吡啶[3,4-b]吲哚）和harman（1-甲基．9H．吡啶[3,4-b]吲哚）形成的潜在前体物（色氨酸、苯丙氨酸、葡萄糖和肌酸）,研究前体物对酱肉中norharman、harman形成的影响。结果表明：酱肉及肉汤中norharman、hamlan的含量随着色氨酸添加量的增加而增加,当色氨酸添加量为2．4mmol时,酱肉及肉汤中总共形成的norharman、harman分别为空白对照组的3．85倍和2．33倍;除1．2mmol的苯丙氨酸显著增加肉汤中harman含量外（P〈0．05）,其余浓度的苯丙氨酸对酱肉及肉汤中norharman、harman的形成无显著影响（P〉0．05）;与高浓度的肌酸相比,低浓度（0．12mm01）的肌酸更易促进酱肉及肉汤中norharman、harman的形成;随着葡萄糖含量的升高,酱肉及肉汤中norharman、harman的含量呈先升高后降低的趋势,当葡萄糖添加量为1．2mmol时,酱肉及肉汤中总共形成的norharman、harman分别比空白对照组升高54％、66％。     

花椒叶提取物对烤牛肉饼杂环胺形成的影响

以牛肉和花椒叶为研究对象,研究花椒叶提取物（Zanthoxylum bungeanum Maxim. leaf extract,ZME）添加量（0.015%、0.030%、0.045%）对烤牛肉饼中杂环胺（heterocyclic amines,HAs）形成的影响。结果表明,与对照组相比,ZME能够显著抑制烤牛肉饼中总HAs的形成（P＜0.05）,对其最大抑制率为39.87%,但对不同种类HAs形成的影响不同。其中,添加0.045% ZME对2-氨基-1-甲基-6-苯基咪唑并[4,5-b]吡啶、2-氨基-3-甲基咪唑并[4,5-f]喹啉、2-氨基-3,4-二甲基咪唑并[4,5-f]喹啉、1-甲基-9H-吡啶并[3,4-b]吲哚和2-氨基-9H-吡啶并[2,3-b]吲哚的抑制率分别达到71.76%、78.02%、49.07%、35.82%和100%;而0.045% ZME却促进2-氨基-3,8-二甲基咪唑并[4,5-f]喹喔啉和9H-吡啶并[3,4-b]吲哚的形成。进一步分析ZME对烤牛肉饼中HAs前体物的影响,结果显示前体物的消耗随着ZME添加量的增加呈降低趋势,相关性分析表明HAs的形成与多种游离氨基酸的消耗显著相关。上述结果表明ZME能显著抑制烤牛肉饼中HAs的形成,为其提高加工食品安全性及更广泛的应用提供理论依据。     

Analysis of heterocyclic amines and β-carbolines by liquid chromatography–mass spectrometry in cooked meats commonly consumed in Korea

Heterocyclic amines (HAs), which form in meats during heating and cooking, are recognized as mutagenic and carcinogenic compounds. In this study, 13 HAs and 2 β-carbolines (BCs) were analyzed in cooked Korean meat products, including griddled bacon, griddled pork loin, boiled pork loin, boiled chicken meat, chicken meat stock, chicken breast for salad and chicken patty. The samples were either cooked in the laboratory or purchased from local fast-food restaurants. The HAs and BCs in the samples were separated using solid-phase extraction and were analyzed by high performance liquid chromatography–mass spectrometry (HPLC–MS). The most frequently detected HAs and BCs in the cooked meats were harman (1-methyl-9H pyrido[4,3-b]indole; 990.9 ng g^?1), norharman (9H-pyrido[4,3-b]indole; 412.7 ng g^?1) and PhIP (2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine; 258.2 ng g^?1). The griddled pork loin and bacon contained higher levels of norharman, harman and PhIP than the other cooked meats. PhIP, which is classified as a Group 2B carcinogen by the International Agency for Research on Cancer, had levels of 258.2 and 168.2 ng g^?1 in the griddled pork loin and griddled bacon, respectively. The griddled bacon was the only sample containing TriMeIQx (2-amino-3,4,7,8-tetramethylimidazo[4,5-f]quinoxaline; 79.9 ng g^?1). IQ (2-amino-3-methyl imidazo[4,5-f]quinoline), 7,8-DiMeIQx (2-amino-3,7,8-trimethylimidazo[4,5-f]quinoxaline), 4,8-DiMeIQx (2-amino-3,4,8-trimethylimidazo[4,5-f]quinoxaline) and AαC (2-amino-9H-pyrido[2,3-b]indole) were detected at trace levels in all samples.     

Effects of various additives on the formation of heterocyclic amines in fried fish fibre

The effects of various additives on the formation of heterocyclic amines (HAs) in fried fish fibre (Trachinooephlus myops) were studied. Fried fish fibre was prepared by boiling raw snake fish, followed by deboning, eviscerating, separating of fish meat and pressing. The fish meat was subjected to frying, during which treatment the additives, such as sugar, monosodium glutamate (MSG), antioxidants and edible oil, were added. The HAs were analyzed by high-performance liquid chromatography (HPLC) with diode-array detection. Results showed that the formation of HAs was retarded after the addition of a high level of sugar (19%), and the amount of 9H-pyrido-[4,3-b]indole (Norharman), 1-methyl-9H-pyrido-[4,3-b]indole (Harman), 2-amino-9H-pyrido[2,3-b]indole (AαC) or 2-amino-3-methyl-9H-pyrido[2,3-b]indole (MeAαC) also decreased to a minimum. The total amount of HAs rose with increasing levels of MSG, and the individual HAs, Norharman, Harman, AαC and MeAαC showed the same trend. Antioxidants, such as vitamin C, α-tocopherol and BHT (Butylated hydroxytoluene), did not show any consistent effect of concentration on HAs formation. Coconut oil contributed to the highest levels of HAs formation, followed by lard and soybean oil.     

Formation of heterocyclic amines in fried fish fiber during processing and storage

The formation of heterocyclic amines (HAs) in fried fish fiber during processing and storage was studied. Fried fish fiber was prepared by boiling of raw fish, followed by eviscerating, pressing, chopping, and then the fish meat was subjected to frying, during which the various additives such as sugar, soybean sauce, and edible oil were added. The various HAs in fried fish fiber were analyzed by high-performance liquid chromatography with photodiode-array detection. Only four HAs, Norharman, Harman, 2-amino-9H-pyrido[2,3-b]indole, and 2-amino-3-methyl-9H-pyrido[2,3-b]indole were detected in fried fish fiber. The amount of HAs increased with increasing frying temperature. Amino acids might play a more important role for HA formation than reducing sugar during processing of fried fish fiber. During storage, the HAs increased with increasing storage temperature when the fried fish fiber was packed in an aluminum foil bag. However, the relationship between storage temperature and HAs formation was not consistent when the fried fish fiber was packed in a plastic bag.     

Lack of formation of heterocyclic amines in fumes from frying French fries

The formation of heterocyclic amines (HAs) in the fumes from frying French fries in soybean oil or lard was studied. A high-pressure liquid chromatography method was used to determine the various HAs in fumes. Results showed that the yields of fumes produced from soybean oil when heated alone for 2 or 4 h were higher than from lard; however, a reversed trend was found when frying French fries in soybean oil and lard. Most fumes from soybean oil and lard while frying French fries were adsorbed onto the condensation apparatus, while the other portions were adsorbed onto the wool and glass beads, which were incorporated in our experimental design for collecting the fumes. The fumes from soybean oil when heated alone were found to contain three HAs, namely, 2-amino-3-methylimidazo[4,5-f]quinoxaline (IQx), 2-amino-3-methylimidazo[4,5-f ]quinoline (IQ), and 1-methyl-9H-pyrido[4,3-b ]indole (Harman), whereas two more HAs, 2-amino-3,4-dimethylimidazo[4,5-f]quinoline (MeIQ) and 3-amino-1,4-dimethyl-5H-pyrido[4,3-b ]indole (Trp-P-1), were generated in lard. Lard was more susceptible to the formation of HAs than soybean oil when both were heated alone. No HAs were detected in the fumes from French fries fried in soybean oil and lard.