The role of flavonoids in mitigating food originated heterocyclic aromatic amines that concerns human wellness

Meat products are an important part in our daily diet,providing valuable nutrients for the human body.However,heating processes cause the meat to become more appetizing with changes in texture,appearance,flavor,and chemical properties by the altering of protein structure and other ingredients.As one kind of cooking-induced contaminants,heterocyclic aromatic amines(HAAs)are widely present in protein aceous food products with strong carcinogenic and mutagenic properties.In order to promote the safety of traditional meat products,this review focused on the formation,metabolism,biological monitoring and inhibitory mechanism of HAA.An overview of the formation pathways,hazards,and control methods of HAAs during food processing in recent years was studied,aiming to provide some valuable information for exploring effective methods to inhibit the production of associated hazards during food processing.Systematic selection of different types of flavonoids to explore their effects on the formation of HAAs in an actual barbecue system can provide theoretical reference for effectively controlling the formation of HAAs and reducing their harm to human health.

Relationship between Structures and Carcinogenicities of Heterocyclic Amines

Semi-empirical molecular orbital calculations were performed on heterocyclic aromatic amines(HCAs). The relationship between the structures and the carcinogenicities can be rationally elucidated by the models based on the metabolism of HCAs and the Di-region theory. The degree of easiness for the formation of Di-region electrophilic centers determines the carcinogenic activity. There is a good linear relationship between the observed carcinogenicities and the PM3 calculated parameters, with r=0.973 and F=29.8>F ** 0.01 .

Comparison of the Ability of Myricetin and Quercetin to Modulate the Oxidative DNA Damage Induced by Heterocyclic Amines

The aim of the present study was to compare the ability of the myricetin and quercetin to modulate the oxidative DNA damage induced by 2-amino-3, 8- dimethylimidazo [4,5-f] quinoxaline (8-MeIQx), 2-amino- 3, 4, 8- trimethylimidazo [4, 5-f]-quinoxaline (4,8-diMeIQx) and 2-amino-1-methyl-6-phenyl-imidazo [4,5-b] pyridine (PhIP), in human hepatoma cells. DNA damage (strand breaks and oxidized purines/pyrimidines) was evaluated by the alkaline single-cell gel electrophoresis or comet assay. None of the myricetin and quercetin concentrations tested protected against 8-MeIQx, 4, 8-diMeIQx and PhIP-induced DNA strand breaks. The oxidized pyrimidines induced by 4, 8-diMeIQx and PhIP were reduced by myricetin but not by quercetin. Quercetin reduced the oxidized purines induced by 8-MeIQx and PhIP, while myricetin also reduced the induced by 4, 8-diMeIQx. One feasible mechanism by which myricetin and quercetin exert their protective effect towards HCAs-induced oxidative DNA could be related in part to the reduction of human CYP1A1. Another mechanism claimed to be responsible for the protective effect of myricetin and quercetin is the induction of phase II metabolizing enzymes such as UDP-glucuronyltrasferase (UGT). The ethoxyresorufin O-deethylation (CYP1A1) activity was moderately inhibited by myricetin, while little effect was observed by quercetin. On the contrary, quercetin showed the greatest increase on UDP-glucuronyltransferase activity. However, these are not the only mechanisms by which myricetin and quercetin exert their protective effect, other mechanisms such as stimulation of the repair of carcinogen-induced DNA damage and or the free radical scavenging efficiency have been also implicated. In conclusion, our results clearly indicate that myricetin was more efficient than quercetin to prevent DNA damage (oxidized purines and pyrimidines) induced by the three HCAs evaluated. This protective effect depends on the chemical structure of flavonoid and the mutagen studied.

Inhibition of Heterocyclic Aromatic Amines in Pork Chops Using Complex Marinades with Natural Antioxidants

Five marinades were developed using natural antioxidants. Based on a consumer test of the appearance, three marinades were chosen for further investigation: an oregano, an acerola and a Dijon marinade, the Dijon marinade containing acerola, sumac and oregano. A barbecue and a sumac marinade were not included in the further study. In a home use test, consumers barbecued pork chops with the three marinades. Most of the consumers preferred the oregano and the Dijon marinade, while the acerola marinade was less liked. After controlled cooking using both direct and indirect heat to a core temperature of 65°C and 80°C, the content of the heterocyclic aromatic amines (HCA) PhiP, MeIQx, DiMeIQx, Harman and Norharman was analysed. All of the marinades reduced the content of MeIQx and DiMeIQx, although only with indirect heat, while PhiP was reduced using both grilling methods. Surprisingly, in particular the content of Harman—and to a lesser extent Norhaman—was very high in the Dijon-marinated chops. The results demonstrated that it was possible to develop well-liked marinades that can reduce the formation of selected HCAs.

Hydrolysis of New Transplatin Analogue Containing One Aliphatic and One Planar Heterocyclic Amine Ligand： A Density Functional Theory Study

Herein we give a theoretical study of the hydrolysis processes of a novel anticancer drug trans-[PtCl2（3-pico）（ipa）] （3-pico=3-methylpyridine, ipa=isopropylamine）. Two different models, model 1 relative to isolated reactant/product （R/P, wherein R=platinum complex＋H2O, P=platinum complex＋Cl^-） and model 2 relative to reactant complex/product complex （RC/PC, wherein RC=（platinum complex）（H2O）, PC=（platinum complex）（CI^-） are employed and the geometric structures are optimized at the B3LYP level of DFT method. It is found that the processes of the reactions follow the established theory for ligand substitution in square planar complexes; the geometries of the transition states （TS） agree with the previous related work and all of the reactions are endothermic. The effects originating from the inclusion of the attacking water/released chloride into the second coordination shell of platinum in RC/PC play an important role in the thermodynamic and kinetic profiles of the reactions, that is, the barrier heights of the reactions of model 2 are increased by -26.3 and -23.8 kJ/mol for step1 and step2 respectively, and the endothermicity is considerably decreased by -420.5 and -771.2 kJ/mol compared to model 1 in the gas phase. The consideration of the bulk solvation effects increase the barrier heights for both steps of model 1 by -27.6 and -6.7 kJ/mol respectively, whereas it reduces the barrier heights by -7.9 and -29.3 kJ/mol for model 2. The reaction energies are all decreased, especially for model i, indicating more stable complexes solvated in the bulk aqueous solution than in the gas phase. Additionally, to get an accurate energy picture of the title complex, the relative free energies derived from the DFT-SCRF （density functional theory self-consistent field） calculations are compared with the relative total energies. The results are that activation energies rise for the first hydrolysis and fall for the second hydrolysis for all the systems, and for all the systems, the barrier height of the second hydrolysis is always higher than that of the first step. The rate constants indicate that transplatin analogue is kinetically comparable to cisplatin and its analogue in the hydrolysis process.

THE REACTION OF BENZOYL SUBSTITUTED HETEROCYCLIC KETENE AMINALS WITH ARYL AZIDES.A FACILE APPROACH TO SYNTHSIZE 1,5-DIARYL-4-(2-IMIDAZOLINYL)-1,2,3-TRIAZOLES

Heterocyclic ketene aminals 1 react with aryl azides 2 to give the titled compounds 3,and in some cases also with the formation of fused heterocycles 4.

Solid-phase Synthesis of a Novel Kind of Hydroxylated Heterocyclic Ketene Aminals

An efficient solid-phase synthesis method for novel heterocyclic ketene aminals containing a hydroxyl group has been developed. The loading of the substrate on the resin through the hydroxyl group and the protection of the amine by the Schiff base were the key steps in the synthesis.

Synthesis of O-Glycosides of Heteroatom Aroyl-Substituted Heterocyclic Ketene Aminals

Heteroatom aroyl-substituted heterocyclic ketene aminals 1 reacted with 2,3,4,6-tetra-O-acetyl-α-glucopyranosyl bromide 2 under the catalysis of Hg(CN)2 or CaH2 to give E- or Z-O-glycosides of heterocyclic ketene aminals 3 or 4 in moderate yields.

THE RADICAL NUCLEOPHILIC SUBSTITUTION REACTION OF HETEROCYCLIC KETENE AMINALS WITH 2,4-DINITROHALOBENZENES

The anion of heterocyclic ketene aminals reacted with 2,4-dini- tro-halobenzenes to give an arylated product through the radical nucleo- philic substitution confirmed by ESR spectroscopy,ESR-spin trapping techni- que,and depression of the reaction rate by the addition of inhibitor.

An Efficient Synthesis of Heterocyclic Substituted Ureidoalkylphosphonates

A convenient synthesis of various heterocyclic substituted ureidoalkylphosphonic acid diphenyl esters 3 is reported in this paper, alpha-Aminoalkylphosphonic acid diphenyl esters 1 reacted with triphosgene, and then treated with heterocyclic amines gave 3. Small amount of symmetric urylenediphosphonate 4 are isolated as side products.

Critical steps in the production of oil from oilseed to reduce heterocyclic aromatic amines

Contamination by the heterocyclic aromatic amines(HAAs)norharman and harman is one of the risks in vegetable oil production,so oil producers strive to decrease their content in the end products.In this study,the effects of production conditions—specifically,two pretreatment methods(roasting and microwaving),four extraction methods(two pressing and two solvent extraction)and adsorption refining(four absorbents)—of five oils(flaxseed,peanut,rapeseed,sesame,and sunflower seed)were evaluated.The results showed that microwaving as a pretreatment produced significantly fewer HAAs than roasting(P<0.05).After two pretreatments,the HAA content of oils was ranked from high to low as follows:sunflower oil,sesame oil,flaxseed oil,rapeseed oil,and peanut oil.Solvent-extracted oils(9.16–316.73μg/kg)had fewer HAAs than pressed oils(26.61–633.93μg/kg).Using adsorbents reduced HAAs in oils from the initial 21.77–484.22 to 0.31–41.58μg/kg,and the removal rate reached 99.28%.This study provides critical HAA reduction strategies for application in the oil production process to obtain safe final products.

Effect of pomegranate peel extract on the reduction of heterocyclic amines and quality characteristics of mutton meatballs

Pomegranate peel extract(PPE),rich in phenolic compounds,is an undervalued byproduct derived from processing pomegranates.However,there are very few studies on the inhibitory effect of PPE on harmful substances during meat processing.This study was intended to investigate the influence of different concentrations of PPE(0.50%,1%,and 1.50%)on the generation of heterocyclic amines(HCAs)and some quality attributes in mutton meatballs.All samples with the addition of PPE(0,0.50%,1%,and 1.50%)were fried for different lengths of time(2.5 min and 5 min)at 175±5 C,and the contents of fourteen HCAs,color,thiobarbituric acid reactive substances,and carbonyl values of fried mutton meatballs were evaluated.The results showed that samples fried at 2.5 min had a low HCA content,and the HCA content enhanced signifi-cantly when the frying time was increased from 2.5 to 5 min(P<0.05).In comparison with the control group,PPE could significantly inhibit the generation of total HCAs in fried mutton meatballs(P<0.05),and the total HCAs content decreased with increasing PPE concentration.PPE significantly reduced carbonyl andTBARS values in fried mutton meatballs(P<0.05).Moreover,PPE resulted in a significant increase in a*and b*values as well as a decrease in L*values in fried mutton meatballs(P<0.05).In conclusion,PPE could inhibit the formation of HCAs and improve the quality of mutton meatballs,and could be considered as a natural inhibitor of HCAs in fried meat products.

超高效液相色谱-串联质谱法快速检测预制调理羊肉串中15种杂环胺

目的基于超高效液相色谱-串联质谱法(ultra performance liquid chromatography-tandem mass spectroscopy,UPLC-MS/MS)建立预制调理烤制羊肉串样品中15种杂环胺(heterocyclic aromatic amines,HAAs)的高通量快速检测方法。方法将预制调理羊肉串烤制后,对固相萃取柱萃取法(Oasis PRiME HLB柱和OasisMCX柱)、分散固相萃取法(QuEChERS)的净化效率进行评估;得到净化物后经T3色谱柱(150 mm×2.1 mm,1.8μm)分离,以乙腈和15 mmol/L甲酸铵溶液为流动相,梯度洗脱分离,采用串联三重四极杆质谱法对15种HAAs进行定量分析。结果在一定检测范围内,15种HAAs的线性良好,相关系数(r^(2))在0.9979~0.9997之间,检出限和定量限分别是0.002~0.017 ng/g和0.008~0.050 ng/g,加标回收率为81.3%~113.2%,相对标准偏差(relative standard deviations,RSDs)不大于11.9%。结论该方法前处理效率高,灵敏度高,重现性好,可用于预制调理烤制羊肉串样品中15种HAAs的快速检测,为日后建立预制食品国家标准与法规提供方法依据。

新疆烤羊肉串中杂环胺的生成规律研究进展

烤羊肉串,作为新疆特色美食,以其引人入胜的外观和独特的风味深受广大消费者追捧。然而,这类经过高温加工的食品容易产生多种致癌物质,其中之一就是杂环胺。杂环胺主要源自富含蛋白质的动物性食品,具有强烈的致癌和致突变特性。过量摄入将会提高人体患癌风险,对人体健康构成严重威胁。杂环胺的生成与反应底物、加工方式以及加工条件等密切相关。本文总结了杂环胺在热加工肉类中的分布状况及其生成的主要因素,重点综述了新疆特色美食烤羊肉串中杂环胺的生成规律以及抑制策略,旨在为今后新疆烤羊肉串的绿色加工以及杂环胺的减控方法提供科学理论依据,对消费者的健康饮食具有重要的指导意义。

不同烟熏时间鸡腿肉香气化合物与危害物及相关前体物研究

为探究不同熏制时间下熏鸡风味成分和危害物的变化及其与前体物的关系,利用色谱质谱等技术对香气化合物、杂环胺(HAs)、晚期糖基化终末产物(AGEs)、多环芳烃(PAHs)、还原糖、游离氨基酸与脂肪酸等进行定性定量分析。结果表明,在熏鸡腿中共鉴定出67种香气化合物,气味活性值(OAVs)>1的香气化合物有24种,以愈创木酚贡献率最大。随着熏制时间增加,酚类化合物、HAs、AGEs和4种多环芳烃(PAH4)含量显著升高(P<0.05),而水分、肌酐和葡萄糖则逐渐减少。9H-吡啶并[3,4-b]吲哚(Norharman)、羧甲基赖氨酸(CML)、羧乙基赖氨酸(CEL)和?(Chr)是熏鸡中主要潜在危害物,熏制12 h后的含量分别为37.38 ng·g^(-1)、123.94μg·g^(-1)、180.13μg·g^(-1)和41.10μg·kg^(-1)。最佳熏制时间为6 h,长时间熏制不利于熏鸡香气化合物的保持且伴生大量危害物。相关性分析表明,壬醛、1-辛烯-3-醇、2,5-二甲基吡嗪等关键香气化合物含量与还原糖、部分游离氨基酸和不饱和脂肪酸含量显著负相关;Norharman、CEL和PAH4等含量与多种游离氨基酸、水分等含量显著或极显著负相关;苯丙氨酸、甲硫氨酸、酪氨酸和色氨酸等含量同时与香气化合物和危害物含量显著(P<0.05)或极显著正/负相关(P<0.01)。本研究揭示了熏鸡熏制过程中香气化合物与危害物协同伴生关系,可为熏鸡风味保持和危害物消减提供数据基础。

低共熔溶剂双水相萃取-UPLC法检测吸烟者尿液中杂环胺类化合物

为评估香烟烟气中杂环胺的暴露水平,建立了一种基于低共熔溶剂/无机盐双水相萃取-UPLC法测定吸烟者尿液中5种杂环胺(IQ,IQ[4,5-b],Harman,Norharman和Phe-P-1)的方法.制备了7种以氯化胆碱(ChCl)为氢键受体的低共熔溶剂,并对其进行了表征;系统考察了影响萃取效率的主要参数,并将该方法与其它方法进行了对比研究.结果表明,在最佳提取条件下,杂环胺(HAAs)的回收率为81.9%~106.2%,日内和日间精密度分别低于2.9%和3.2%,检出限和定量限分别为0.020~0.097 ng/g和0.19~0.39 ng/g.该方法具有操作简单、环境友好及单样品成本低等特点,为尿液中杂环胺的检测提供了一种新方法,在生物样品检测领域具有良好的开发与应用价值.

水产品中杂环胺类化合物的形成及调控研究进展

水产品肌肉组织中含有的氨基酸、葡萄糖与肌酸(肌酸酐)在加热过程中会生成有害产物杂环胺(heterocyclic aromatic amines,HAAs),大量摄入会增加人体患癌风险。本文简要介绍了HAAs的分类、形成机制和水产品中HAAs的分布,重点综述了水产品中HAAs的调控,旨在为水产制品安全性的提升提供理论参考。

食品中杂环胺在机体中的代谢机制和减控措施的研究进展

杂环胺作为一类热诱导形成的有害物,广泛存在于富含蛋白质的高温加工食品中。经体内代谢活化后具有较强的致癌和致突变性,可对机体造成严重危害。该文详细综述了杂环胺的分类、在不同食品中的含量及检测方法、代谢机制、毒性作用及其减控措施,以充分揭示食品有害物杂环胺发挥毒性作用的机理,以期为其毒性控制和探索新型减控措施提供参考。

咪唑喹啉类杂环胺的形成机制及外源物质对其抑制机理研究进展

咪唑喹啉类(Imidazoquinoline,IQ型)杂环胺是目前已知的公认致突变活性最强的杂环胺(Heterocyclic Amines,HAs),其与多种癌症和神经退行性疾病密切相关。IQ型HAs形成的前体物质是游离氨基酸、还原糖和肌酸/肌酐,其在高温条件下发生一系列化学反应生成的自由基和活性羰基化合物等中间产物是IQ型HAs形成的基础。在肉制品热加工过程中,外源添加物质能够不同程度地影响IQ型HAs的形成,外源添加物质抑制IQ型HAs的作用机制主要包括前体物竞争性抑制机制、自由基清除机制和活性羰基化合物捕获机制3种。本文围绕IQ型HAs的形成过程以及外源物质抑制其形成的作用机制展开论述,明确了IQ型HAs生成的反应途径,详细阐述了外源物质抑制IQ型HAs形成的作用机制,为有效控制肉制品热加工过程中IQ型HAs的形成提供理论指导。

活性羰基化合物及其对食品加工过程中化学危害物形成的影响

活性羰基化合物(reactive carbonyl species,RCSs)是一类活泼的醛酮类物质。RCSs在体内通过脂质氧化和糖酵解等反应形成,也可在食品加工过程中通过脂质氧化和美拉德反应形成。RCSs在体内通常维持一个低浓度水平,当过量存在时会引起机体系列病变发生。人体摄入RCSs主要源于加工食品,与此同时,食品加工过程中的RCSs还会诱导其他加工危害物的形成,因此控制食品中RCSs的形成对于营养健康至关重要。本文对RCSs的形成、生物学活性,及其对食品加工中杂环胺、晚期糖基化终末产物、丙烯酰胺以及多环芳烃等加工危害物形成的影响进行综述,以期为食品加工中RCSs及其相关食品加工安全控制提供参考。