Heterocyclic Aromatic Amines Research Articles

Evaluation of Chinese Prickly Ash and Cinnamon to Mitigate Heterocyclic Aromatic Amines in Superheated Steam-Light Wave Roasted Lamb Meat Patties Using QuEChERS Method Coupled with UPLC-MS/MS

Chinese prickly ash and cinnamon contain many antioxidants, which scavenge free radicals and can reduce many harmful compounds, such as heterocyclic aromatic amines (HAAs). Modern technologies used for cooking, such as the use of superheated steam roasting, are beneficial in decreasing the development of HAAs. The current study was based on the use of these two spices in roasted lamb patties to mitigate the formation of HAAs in superheated steam roasted patties. Results exhibited significant differences (p < 0.05) in the content of both polar and non-polar HAAs as compared to control patties. In cinnamon roasted patties, polar HAAs were reduced from 23.76 to 10.56 ng g−1, and non-polar HAAs were reduced from 21.34 to 15.47 ng g−1. In Chinese prickly ash patties, polar and non-polar HAAs were 43.60 ng g−1 and 35.74 ng g−1, respectively. Similarly, cinnamon-treated patties showed a significantly higher (p < 0.05) reduction in polar HAAs (23.52 to 12.41 ng g−1) than non-polar (16.08 to 9.51 ng g−1) at concentrations of 0.5–1.5%, respectively, as compared to the control, with 45.81 ng g−1 polar and 35.09 ng g−1 non-polar HAAs. The polar HAAs tested were PhIP, DMIP, IQx, and 8-MeIQx, while the non-polar were harman and norharman. Both spices and superheated steam controlled HAAs to a significant level in lamb meat patties.

A Short Review on Carcinogenicity

Humans are exposed to a variety of different and persistent DNA-damaging agents, some of which have been identified as carcinogens. DNA damage can occur from exposure to exogenous agents, but damage from endogenous processes is more common. That is, epidemiological studies of migrant populations from low-cancer-risk areas to high-cancer-incidence countries suggest the role of environmental factors and/or lifestyle as important players in the etiology of cancer. As a result, it can be assumed that carcinogens found in the environment or our diet are to blame. Carcinogen exposure is associated with various forms of DNA damage, including single-strand breaks, double-strand breaks, chemical DNA cross-links, oxidative stress, and DNA-DNA or DNA-protein breaks. This review focuses on DNA damage caused by the following carcinogens: polycyclic aromatic hydrocarbons, heterocyclic aromatic amines, mycotoxins, ultraviolet light, ionizing radiation, aristolochic acid, nitrosamines, and particulate matter. In addition, we discuss several cancers for which molecular epidemiological evidence suggests that these agents are etiological risk factors. The complex role that carcinogens play in the pathophysiology of cancer development remains unclear, but DNA damage remains central to this process.

The impact of temperature-controlled smoldering smoking on polycyclic aromatic hydrocarbons and heterocyclic amines contents in Frankfurter-type sausages

The impact of temperature-controlled smoldering smoking conditions on the accumulations of polycyclic aromatic hydrocarbons (PAHs) and heterocyclic amines (HAs) in Frankfurter-type sausages was investigated. Depending on the temperature, smoking can be divided into two phases: an unstable pyrolysis stage (≈ 200 s) and a stable pyrolysis stage (>200 s), which had different effects on hazardous substances contents. The unstable pyrolysis stage, which contributed 66.9 ∼ 89.6% of PAH accumulations by comparing with sausages smoked for 15 min, has significant impact on high PAH residues. By contrast, the contents of HAs showed steady increase trends with smoking time. Few types of free-HAs with low concentrations (3.05 ∼ 22.9 ng/g DW), but more types of bound-HAs with much higher levels (10.8 ∼ 396 ng/g DW) were found. In addition, the formation of some HAs followed the first-order reaction model. However, the detailed formation mechanisms of PAHs and HAs under temperature-controlled smoldering smoking conditions remain to be studied.

New heterocyclic azo-disperse dyes; their synthesis, characterization, application, photo physical properties and solvatochromic studies

In current research exploration, novel heterocyclic disperse dyes were synthesized, using 8-aminonaphthalen-2-ol as a coupling component and different heterocyclic aromatic amines e.g. sulfadiazine, sulfamethazine, sulfathiazole sodium salt, 2-aminobenzothiazole and 2-amino-6-methoxybenzothiazol as a diazonium component. Different analytical techniques including FT-IR, 1H-NMR, UV-Visible, FAB-LRMS and FAB-HRMS were used for the structural elucidation of the synthesized disperse dyes. The melting point of the synthesized compounds were also determined. The solvatochromism of these dyes was examined in six organic solvents possessing different polarity and the sensitivity of the absorption maxima (λmax) to acidic and basic pH were evaluated in methanol. Bathochromic shift was observed with increase in solvent polarity and under acidic pH. The fluorescence studies all the dyes were performed in four different solvents. The obtained chromophores were applied on polyester fabric observing different parameters like build-up profile, perspiration fastness, rubbing fastness, wash fastness, light fastness and sublimation fastness. All the dyes exhibited good to very good color yield and excellent fastness properties.

Enhancing effect of chia seeds on heterocyclic amine generation in meatball

SummaryThe impact of using chia seeds at different rates (0%, 0.5%, 1%, and 1.5%) in meatball on the water content, pH and lipid oxidation (thiobarbituric acid reactive substances, TBARS), cooking loss and heterocyclic aromatic amines (HAAs) content of meatballs cooked at 150, 200, and 250 °C was investigated. The chia seed significantly affected water content (P < 0.01), cooking loss (P < 0.05), pH (P < 0.05) and total HAAs content (P < 0.01), whereas no significant impact (P > 0.05) was detected on TBARS value. With cooking, water content decreased (P < 0.01), while the pH and TBARS values increased (P < 0.01). Cooking temperatures significantly affected (P < 0.01) the water content, cooking loss and total HAAs content. The content of total HAAs of the meatballs increased with increasing the cooking temperature. The results illustrated that IQ, 7,8‐DiMeIQx, 4,8‐DiMeIQx, AαC and MeAαC were below the detectable limit (<LOD) in all samples, while MeIQx was the dominant compound among the detected HAAs compounds. The research indicated that the use of chia seeds increased the total HAA content, and the highest level was found in meatballs prepared with 1% chia seeds.

Simultaneous determination of heterocyclic aromatic amines and N-nitrosamines in fried bacon cubes and slices using LC-(ESI/APCI)-MS/MS

Bacon manufacturing involves several processing steps including nitrite curing, followed by cooking processes, typically frying. During these processes, harmful processing contaminants such as N-nitrosamines (NAs) and heterocyclic aromatic amines (HAAs) can be formed. Consequently, we developed and validated a multi-class method for quantification of the most frequently reported HAAs and NAs in fried bacon. Satisfactory repeatability and reproducibility with limits of quantification between 0.1 and 0.5 ng g−1 for most of the compounds were achieved. Quantification in pan-fried bacon cubes and slices revealed generally low levels of individual HAAs (≤1.5 ng g−1), except in ready-to-eat bacon (0.9–2.9 ng g−1). Differences in amounts of individual HAAs were observed in cubes and slices, most likely due to meat thickness. Among volatile NAs (VNAs), only N-nitrosopiperidine (NPIP), N-nitrosopyrolidine (NPYR), and N-nitrosodibutylamine (NDBA) were found at generally low concentrations (≤5 ng g−1). In contrast, non-volatile NAs (NVNAs) were present in all tested samples at considerably higher amounts, for example, N-nitroso-thiazolidine-4-carboxylic acid (NTCA) at 12–77 ng g−1. N-nitrosodimethylamine (NDMA), N-nitrosodiethylamine (NDEA), N-nitrosodipropylamine (NDPA) were not detected in any samples. Statistical evaluation and principal component analysis revealed some differences among tested samples. Dietary exposure estimation of the Danish population to HAAs and NAs showed the highest exposure in the teenage group (10–17 years).

Molecularly Imprinted Polymer Nanospheres with Hydrophilic Shells for Efficient Molecular Recognition of Heterocyclic Aromatic Amines in Aqueous Solution.

Heterocyclic aromatic amine molecularly imprinted polymer nanospheres with surface-bound dithioester groups (haa-MIP) were firstly synthesized via reversible addition-fragmentation chain transfer (RAFT) precipitation polymerization. Then, a series of core-shell structural heterocyclic aromatic amine molecularly imprinted polymer nanospheres with hydrophilic shells (MIP-HSs) were subsequently prepared by grafting the hydrophilic shells on the surface of haa-MIP via on-particle RAFT polymerization of 2-hydroxyethyl methacrylate (HEMA), itaconic acid (IA), and diethylaminoethyl methacrylate (DEAEMA). The haa-MIP nanospheres showed high affinity and specific recognition toward harmine and its structural analogs in organic solution of acetonitrile, but lost the specific binding ability in aqueous solution. However, after the grafting of the hydrophilic shells on the haa-MIP particles, the surface hydrophilicity and water dispersion stability of the polymer particles of MIP-HSs greatly improved. The binding of harmine by MIP-HSs with hydrophilic shells in aqueous solutions is about two times higher than that of NIP-HSs, showing an efficient molecular recognition of heterocyclic aromatic amines in aqueous solution. The effect of hydrophilic shell structure on the molecular recognition property of MIP-HSs was further compared. MIP-PIA with carboxyl groups containing hydrophilic shells showed the highest selective molecular recognition ability to heterocyclic aromatic amines in aqueous solution.

Determination of 2-amino-1-methyl-6-phenylimidazole [4, 5-b] pyridine (PhIP) and its precursors and possible intermediates in a chemical model system and roast pork

PhIP (2-amino-1-methyl-6-phenylimidazole [4, 5-b] pyridine) is a carcinogenic heterocyclic aromatic amine often generated in thermal processing of food. Methods for PhIP and its precursors and possible intermediates determination in chemical model system and roast pork were established based on HPLC-Q-Orbitrap-HRMS and GC-MS. Results showed that the linearity of 8 targets was good in a certain concentration range (R2 ≥ 0.992). LODs and LOQs were in the range of 0.3–15 μg/kg and 1–50 μg/kg, respectively. Under the model system, the recoveries of 8 target compounds ranged from 86.3% to 119.2%, with relative standard deviations (RSDs) of 0.5–6.9%. The established method was applied to 8 targets determination in roast pork, with recoveries ranging from 87.1% to 107.3% and RSDs in the range of 1.2–7.8%. The developed methods are accurate and fast, which are suitable for PhIP and its precursors and possible intermediates analysis in chemical model system and actual meat products.

Chinese quince proanthocyanidins enhance frying performance and suppress heterocyclic aromatic amine formation in soybean oil

SummaryThe aim of the study was to evaluate the effect of Chinese quince proanthocyanidins (PAs) on the deterioration and heterocyclic aromatic amine (HAA) formation in soybean oil when used for deep‐fat frying, one tea polyphenol (Tea‐PP) and two PAs (PA‐100 and PA‐140) (200 mg/kg) were added to soybean oils. While all three retarded the accumulation of oil degradation products and enhanced performance of frying oil, as well as reduced the formation of HAAs, both PA‐100 and PA‐140 performed better than Tea‐PP. Adding PA‐100 and PA‐140 not only decreased the increase in oxidation indices and lossy of tocopherols but also inhibited HAA formation by 14.82%–30.64% and 19.52%–54.24%, respectively. Multivariate analysis revealed that PA‐140 always had a stronger effect than PA‐100 in concurrently enhancing frying performance and suppressing the generation of HAAs. This study provides evidence for using PAs from Chinese quince as the stabilisers of frying oils and inhibitors of HAA formation in these oils in the food industry.

Mutagens in commercial food processing and its microbial transformation.

Mutagens are chemical molecules that have the ability to damage DNA. Mutagens can enter into our body upon consumption of improperly cooked or processed food products such as high temperature or prolonged cooking duration. Mutagens are found in the food products can be classified into N-nitroso derivatives, polycyclic aromatic hydrocarbons, and heterocyclic aromatic amines. Food products with high fat and protein content are more prone to mutagenic formation. Microorganisms were found to be a potent weapon in the fight against various mutagens through biotransformation. Therefore, searching for the microorganisms which have the ability to transform mutagens and the development of techniques for the identification as well as detection of mutagens in food products is much needed. In the future, methods for the identification and detection of these mutagens as well as the identification of new and more potent microorganisms which can transform mutagens into non-mutagens are much needed.

Vegetable extracts: Effective inhibitors of heterocyclic aromatic amines and advanced glycation end products in roasted Mackerel

The formation of hazardous substances, heterocyclic aromatic amines (HAAs) and advanced glycation end products (AGEs), in roasted mackerel with different cooking temperatures (180, 210, 240 °C) and vegetable extracts (celery, carrot and yam extracts) in a preheated oven was investigated. The results indicated that the introduction of vegetable extracts had inhibitory effects on HAAs and AGEs during thermal processing, especially celery extracts. Benefiting from the addition of vegetable extracts, the roasted mackerel keep high quality against lipid/protein oxidation, avoids nutrition loss of polyunsaturated fatty acids, and flavor is promoted. We also examined the variation of key precursors, including creatine, creatinine, reducing sugars, amino acids and attempted to explain the molecular pathway of inhibition of the formation of the hazardous substances by vegetable extracts. The results provide theoretical support to develop technologies for inhibiting hazardous substances formation during fish processing, which is important for food manufacturers and consumers for producing healthier meat products.

Reducing effects of tea marinades on heterocyclic aromatic amines formation in chicken thigh meat: focus on white and oolong tea

Reducing effects of tea marinades on heterocyclic aromatic amines formation in chicken thigh meat: focus on white and oolong tea

Heterocyclic aromatic amines in spiced pork shoulder: content analysis and effects of soy sauce, cooking wine and sugar

SummarySpiced pork shoulder is a traditional Chinese meat product that is loved by consumers. However, heterocyclic aromatic amines (HAAs) formed by spiced pork shoulder during processing endanger human health. The present study determined the HAA contents of seven kinds of spiced pork shoulder, and examined the effects of soy sauce, cooking wine and sugar on the formation of HAAs. The total HAAs of the seven samples were between 0.10 ng/g and 56.82 ng/g. There were Harman (0.03–39.77 ng/g) and Norharman (0.06–18.76 ng/g) correlations in all samples. Not all samples had higher HAAs levels in the skin than the whole shoulder. Creatine and creatinine were more actively involved in the formation of HAAs than glucose. Soy sauce contributed the most to the formation of HAAs, followed by cooking wine and sugar. Compared to spiced pork shoulder, the soup contained more HAAs. Exogenous contamination of HAAs in soy sauce, cooking wine and soup was an important source of HAAs in spiced pork shoulder.

Advantageous Effects of Sumac Usage in Meatball Preparation on Various Quality Criteria and Formation of Heterocyclic Aromatic Amines

Heterocyclic aromatic amines (HAAs) are mutagenic/carcinogenic compounds that can be formed during the cooking process of proteinaceous foods such as meat. Therefore, it is needed to inhibit or reduce their formations in cooked meats. Hereby, the effects of sumac usage (0.5%, w/w) in beef meatball preparation on the formation of HAAs and some quality parameters (water, pH, cooking loss, and lipid oxidation values) of meatballs cooked at 150 and 250 °C were investigated. The sumac usage caused a reduction in pH (p < 0.01), cooking loss (p < 0.05), lipid oxidation level (TBARS, p < 0.01), and total HAA amount (p < 0.05) of the samples. In addition, increasing the cooking temperature significantly decreased the pH value (p < 0.01) and increased the cooking loss (p < 0.05) of the samples. Only one compound, 2-amino-3,8-dimethylimidazo [4,5-ƒ]quinoxaline (MeIQx), from nine different HAAs studied in this study, could be determined, and the levels of the other HAAs studied were lower than their detection limits. On the other hand, MeIQx was not detected in the samples cooked at 150 °C, it was only determined in the control group samples cooked at 250 °C. The sumac usage completely inhibited MeIQx formation in the samples. Due to its positive effect on cooking loss value, lipid oxidation level, and MeIQx formation, it can be suggested to use sumac powder in meatball preparation.

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

Abstract 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 (9.16–316.73 µg/kg) had fewer HAAs than pressed oils (26.61–633.93 µg/kg). Using adsorbents reduced HAAs in oils from the initial 21.77–484.22 to 0.31–41.58 µg/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.

β-Carbolines norharman and harman change neurobehavior causing neurological damage in Caenorhabditis elegans.

β-Carbolines norharman and harman, belonging to the class of heterocyclic aromatic amines (HAAs), are typical hazardous substances produced during the thermal processing of food. Compared to other HAAs, there have been limited reports on the toxicity of β-carbolines. Nevertheless, the current studies are concerned with the neurotoxic effects of norharman and harman at high doses. It is still unknown whether the relatively low dose of β-carbolines in foods induces neurotoxicity and the mechanism of the toxicity. In this study, C. elegans was exposed to a series of gradients of norharman and harman (0, 0.05, 5, and 10 mg L-1). The survival rate and indicators of ethology (locomotor behaviors, foraging behavior, and chemotaxis ability) were assessed. The antioxidant system and the contents of neurotransmitters, as well as the activity of acetylcholinesterase (AChE), were evaluated. Additionally, the RNA-seq screening of differentially expressed genes (DEGs) revealed the potential molecular mechanisms of norharman- and harman-induced toxic effects. Our results indicated that the risk of long-term exposure to norharman and harman at low doses (food-related doses) should be emphasized. Moreover, β-carbolines might induce neurotoxicity by causing oxidative damage, regulating the content of neurotransmitters, and interfering with cytochrome P450 metabolism. This study would provide a toxicological basis for the neurotoxicity of β-carbolines and lay the foundation for the risk assessment of endogenous pollutants in food.

Content of heterocyclic aromatic amines and D-enantiomers of amino acids in sausage products

Content of heterocyclic aromatic amines and D-enantiomers of amino acids in sausage products

Assessment of heterocyclic aromatic amines contents in flamed and braised chicken in Burkina Faso.

The nutritional status of meat is tarnished by its association with the induced cooking contaminants. The aim of this study was to assess the heterocyclic aromatic amines profile and contents in processed chicken in Burkina Faso. Eight polar and apolar heterocyclic aromatic amines (HAAs) including 2-mino-3-methylimidazo[4,5-f]quinolone (IQ), 3-amino-1,4-dimethyl-5H-pyrido[4, 3-b]indole (Trp-P1), 3-amino-1-methyl-5H-pyrido[4,3-b]indole (Trp-P2), 2-mino-9H-pyrido-[2,3-b]indole (AαC), 2-amino-1-methyl-6-phenylimidazo[4, 5- ]pyridine (PhIP), 2-amino-3-methyl-9H-pyrido[2,3-b] indole (MeAαC), 2-amino-3,4,8-rimethylimidazo[4,5-f]quinoxaline (4,8-DiMeIQx) and 2-amino-3,8-imethylimidazo[4,5-]quinoxaline (MeIQx) were screened by high performance liquid chromatography from 29 samples of flamed chicken and 66 samples of braised chicken collected in Ouagadougou city. Apolar HAAs and polar HAAs were respectively 12 and 3 times more abundant in flamed chickens (32.66±10 and 3.48±10.39 ng/g, respectively) than in braised chickens (2.70±9.67 and 0.92 ng/g, respectively). The maximum levels of AαC were in the same proportions in flamed (12.01 ng/g) and braised chickens (14.13 ng/g). Flamed chicken had the highest Trp-P1 content (530.31 ng/g). The 4,8-DiMeIQx was not detected in braised chicken. The AαCs were more abundant in flamed than in braised chicken. The profile and the contents of the HAAs in processed chicken are related to cooking methods. Because of the high variability observed on the obtained concentrations, investigations on the contents of precursors in raw chicken, the effect of marinating ingredients on the formation of HAAs are needed.

Sensory acceptability of antioxidant-based formulations dedicated to mitigate heterocyclic aromatic amines in cooked meat

In a previous work, we studied the inhibition of heterocyclic aromatic amine formation by natural ingredients rich in antioxidants: caper, oregano, wine and green tea. This present work aimed to assess the sensory impact of the addition of these ingredients in ground beef patties. The best liked formulations were determined by a hedonic scoring. Caper and oregano were not significantly different from the standard, the most appreciated, due to their congruency with cooked meat. Direct dissimilarity assessment was performed to evaluate the overall, gustative and odor differences between formulations. Olfactive differences were evidenced as key drivers of these differences. Standard and caper were close while oregano was found significantly different from them. A fast sensory profiling permitted to evidence that aromatic plant note was discriminant for oregano formulation. Gas chromatography-mass spectrometry/multibooth olfactometry identified the distinctive odor-active compounds of the formulations as pyrazines and sulfide for oregano formulation and ester for caper formulation.

Development of a Modified QuEChERS Method Based on Magnetic Multi-Walled Carbon Nanotubes as a Clean-Up Adsorbent for the Analysis of Heterocyclic Aromatic Amines in Braised Sauce Beef.

Heterocyclic aromatic amines (HAAs) generated during the cooking of meats cause adverse effects on human health. The purpose of the current research was to develop a modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged, Safe) method using magnetic multi-walled carbon nanotubes (Fe3O4-MWCNTs) as clean-up adsorbents for the rapid determination of HAAs in braised sauce beef. The significant parameters in extraction and clean-up processes were screened and optimized. Under optimal conditions, the LODs ranged from 3.0 ng/g to 4.2 ng/g. The recoveries (78.5−103.2%) and relative standard deviations RSDs (<4.6%) of five HAAs were obtained. These are in accordance with the validation criteria (recovery in the range of 70−120% with RSD less than 20%). Compared with conventional clean-up adsorbents (PSA or C18), Fe3O4-MWCNTs displayed equivalent or better matrix removal efficiency, while making the pretreatment process easier and more time-saving through magnetic separation. Less usage of adsorbent makes the method possess another advantage of being lower in cost per sample. The method developed was successfully applied to analyze real samples collected from local deli counters, demonstrating Fe3O4-MWCNTs could be considered as an effective alternative adsorbent with great potential in the QuEChERS process.