Examination of primary aromatic amines content in polylactic acid straws and migration into food simulants using SERS with LC-MS.

Polylactic acid (PLA) straws hold eco-friendly potential; however, residual diisocyanates used to enhance the mechanical strength can generate carcinogenic primary aromatic amines (PAAs), posing health risks. Herein, we present a rapid, comprehensive strategy to detecting PAAs in 18 brands of food-grade PLA straws and assessing their migration into diverse food simulants. Surface-enhanced Raman spectroscopy was conducted to rapidly screen straws for PAAs. Subsequently, qualitative determination of migrating PAAs into various food simulants (4 % acetic acid, 10 % ethanol, 50 % ethanol) occurred at 70 °C for 2 h using liquid chromatography-mass spectrometry. Three PAAs including 4,4'-methylenedianiline, 2,4'-methylenedianiline, and 2,4-diaminotoluene were detected in all straws. Specifically, 2,4-diaminotoluene in 50 % ethanol exceeded specific migration limit of 2 µg/kg, raising safety concerns. Notably, PAAs migration to 10 % and 50 % ethanol surpassed that to 4 % acetic acid within a short 2-hour period. Moreover, PLA straws underwent varying degrees of shape changes before and after migration. Straws with poly(butylene succinate) resisted deformation compared to those without, indicating enhanced heat resistance, while poly(butyleneadipate-co-terephthalate) improved hydrolysis resistance. Importantly, swelling study unveiled swelling effect wasn't the primary factor contributing to the increased PAAs migration in ethanol food simulant, as there was no significant disparity in swelling degrees across different food simulants. FT-IR and DSC analysis revealed higher PAAs content in 50 % ethanol were due to highly concentrated polar ethanol disrupting hydrogen bonds and van der Waal forces holding PLA molecules together. Overall, minimizing contact between PLA straws and alcoholic foods is crucial to avoid potential safety risks posed by PAAs.

Association between aromatic amines and serum neurofilament light chain as a biomarker of neural damage: a cross-sectional study from NHANES.

Background: Aromatic amines (AAs) are a group of compounds widely found in chemical industry, tobacco smoke, and during food processing, with established carcinogenic properties. To date, there have been no reports on the potential neurotoxic effects of adult exposure to AAs. Serum neurofilament light chain (sNfL) is a protein released into the bloodstream following nerve axon injury and has been validated as a reliable biomarker for various neurological diseases. However, there has been no research to investigate the relationship between AAs exposure and sNfL. Methods: In this study, we selected adults (aged ≥20 years) with data on both AAs and sNfL from the National Health and Nutrition Examination Survey (NHANES) conducted in 2013-2014. We used multivariable linear regression models to explore the correlation between urinary AAs and sNfL. Results: In total, 510 adult participants with an average age of 43.58 ± 14.74 years were included in the study. Our findings indicate that, based on univariate linear regression and between-group comparative analyses, 1-Aminonaphthalene (1-AN), 2-Aminonaphthalene (2-AN), 4-Aminobiphenyl (4-AN) and o-Anisidine (o-ANI) showed a positive correlation with serum neurofilament light chain (P < 0.05). However, multiple linear regression analysis revealed that only 2-AN exhibited a positive correlation with serum neurofilament light chain (P < 0.05), while the correlations of other compounds with serum neurofilament light chain became non-significant. Conclusion: Although our cross-sectional study fails to establish causal relationships or determine clinical significance, the findings indicate a potential association between adult exposure to AAs, notably 2-AN, and nerve damage. Consequently, further research is needed to explore the connection between AAs exposure, sNfL, and neurological conditions in adults.

Reactions of Tetracyanoethylene with Aliphatic and Aromatic Amines and Hydrazines and Chemical Transformations of Tetracyanoethylene Derivatives.

The significant synthetic potential and reactivity of tetracyanoethylene (TCNE) have captured the interest of numerous chemical communities. One of the most promising, readily achievable, yet least explored pathways for the reactivity of TCNE involves its interaction with arylamines. Typically, the reaction proceeds via tricyanovinylation (TCV); however, deviations from the standard chemical process have been observed in some instances. These include the formation of heterocyclic structures through tricyanovinyl intermediates, aliphatic dicarbonitriles through the cleavage of the C-C bond of a tetracyanoethyl substituent, complexation, and various pericyclic reactions. Therefore, the objective of this study is to review the diverse modes of interaction of TCNE with aromatic nitrogen-containing compounds and to focus the attention of the chemical community on the synthetic capabilities of this reagent, as well as the various biological and optical activities of the structures synthesized based on TCNE.

Microbiota and other detrimental metabolites in colorectal cancer.

Increasing scientific evidence demonstrates that gut microbiota plays an essential role in the onset and development of Colorectal cancer (CRC). However, the mechanisms by which these microorganisms contribute to cancer development are complex and far from completely clarified. Specifically, the impact of gut microbiota-derived metabolites on CRC is undeniable, exerting both protective and detrimental effects. This paper examines the effects and mechanisms by which important bacterial metabolites exert detrimental effects associated with increased risk of CRC. Metabolites considered include heterocyclic amines and polycyclic aromatic hydrocarbons, heme iron, secondary bile acids, ethanol, and aromatic amines. It is necessary to delve deeper into the mechanisms of action of these metabolites in CRC and identify the microbiota members involved in their production. Furthermore, since diet is the main factor capable of modifying the intestinal microbiota, conducting studies that include detailed descriptions of dietary interventions is crucial. All this knowledge is essential for developing precision nutrition strategies to optimise a protective intestinal microbiota against CRC.

Probabilistic Health Risk Assessment of Primary Aromatic Amines in Polyamide Cooking Utensils in China by Monte Carlo simulation.

The migration of primary aromatic amines (PAAs) from food contact materials raises significant public health concerns. In this study, the migration levels of 26 PAAs were analyzed in 242 nylon cooking utensils using ultra-performance liquid chromatography-tandem mass spectrometry. A total of 18 PAAs were detected, of which 14 were quantified, with 4,4'-diaminodiphenylmethane (4,4'-MDA) and aniline being the most prevalent ones. The compliance rates for nylon kitchenware were similar under both legislation of European Commission (76.9%) and Chinese legislation (77.9%). Probabilistic non-carcinogenic and carcinogenic risk assessment were conducted using Monte Carlo simulation, with read-across approach applied to fill the gap of toxicity data. The hazard quotients for 18 PAAs were calculated, revealing that 17 PAAs (excluding 4,4'-MDA) had acceptable hazard quotients (<1). Lifetime cancer risks for 17 PAAs were determined, with 15 PAAs (excluding benzidine and 4,4'-MDA) showing acceptable cancer risks (<10-4). The study suggests that the non-carcinogenic and carcinogenic health risks posed by PAAs migrating from FCMs can be effectively mitigated by promptly identifying non-compliant products and reducing exposure to high-risk PAAs such as 4,4'-MDA and benzidine. Enhancing the understanding of PAA hazard characterization and implementing measures to minimize health risks associated with PAA migration from FCMs is hence recommended.

Thermally-stable single-site Pd on CeO2 catalyst for selective amination of phenols to aromatic amines without external hydrogen.

Developing a new route to produce aromatic amines as key chemicals from renewable phenols is a benign alternative to current fossil-based routes like nitroaromatic hydrogenation, but is challenging because of the high dissociation energy of the Ar-OH bond and difficulty in controlling side reactions. Herein, an aerosolizing-pyrolysis strategy was developed to prepare high-density single-site cationic Pd species immobilized on CeO2 (Pd1/CeO2) with excellent sintering resistance. The obtained Pd1/CeO2 catalysts achieved remarkable selectivity of important aromatic amines (yield up to 76.2%) in the phenols amination with amines without external hydrogen sources, while Pd nano-catalysts mainly afforded phenyl-ring-saturation products. The excellent catalytic properties of the Pd1/CeO2 are closely related to high-loading Pd single-site catalysts with abundant surface defect sites and suitable acid-base properties. This report provides a sustainable route for producing aromatic amines from renewable feedstocks.

Effect of air-frying on formation and correlations of polycyclic aromatic hydrocarbons, acrylamide, and heterocyclic aromatic amines in foods and risk assessment.

The levels of acrylamide (AA), four polycyclic aromatic hydrocarbons (PAH4), and heterocyclic aromatic amines (HAAs) in 184 air-fried agricultural, fishery, and animal products were measured using GC-MS and UPLC-MS/MS. Among the tested samples, sea algae exhibited the highest levels of PAH4 and eight specific HAAs (HAA8), while root and tuber crops had the greatest amount of AA. Agricultural and fisheries products had higher levels of all three contaminants, while livestock products had an inverse correlation between PAH4 and HAA8. The margin of exposure in the Korean population is considered "unlikely a concern" for all samples for PAH4 and HAA8, however, that for AA in cereal, vegetable, and root and tuber crops is deemed "may be a concern", with a value < 10,000 in all age groups. These findings suggest a need to evaluate dietary AA exposure in certain food categories and further research to minimize AA formation during air frying. Supplementary Information: The online version contains supplementary material available at 10.1007/s10068-024-01639-4.

Optimizing intermittent micro-aeration as a strategy for enhancing aniline anaerobic biodegradation: kinetic, ecotoxicity, and microbial community dynamics analyses.

Groundwater and soil contamination by aromatic amines (AAs), used in the production of polymers, plastics, and pesticides, often results from improper waste disposal and accidental leaks. These compounds are resistant to anaerobic degradation; however, micro-aeration can enhance this process by promoting microbial interactions. In batch assays, anaerobic degradation of aniline (0.14 mM), a model AA, was tested under three micro-aeration conditions: T30, T15, and T10 (30, 15, and 10 min of micro-aeration every 2 h, respectively). Aniline degradation occurred in all conditions, producing both aerobic (catechol) and anaerobic (benzoic acid) byproducts. The main genera involved in T30 and T15 were Comamonas, Clostridium, Longilinea, Petrimonas, Phenylobacterium, Pseudoxanthomonas, and Thiobacillus. In contrast, in T10 were Pseudomonas, Delftia, Leucobacter, and Thermomonas. While T30 and T15 promoted microbial cooperation for anaerobic degradation and facultative respiration, T10 resulted in a competitive environment due to dominance and oxygen scarcity. Despite aniline degradation in 9.4 h under T10, this condition was toxic to Allium cepa seeds and exhibited cytogenotoxic effects. Therefore, T15 emerged as the optimal condition, effectively promoting anaerobic degradation without accumulating toxic byproducts. Intermittent micro-aeration emerges as a promising strategy for enhancing the anaerobic degradation of AA-contaminated effluents.

A magnetic carboxyl-functionalized covalent organic framework for the efficient enrichment of foodborne heterocyclic aromatic amines prior to UPLC-MS analysis.

Foodborne heterocyclic aromatic amines (HAAs) are potent mutagens and carcinogens, posing significant health risks. Existing enrichment methods for HAAs need better adsorption selectivity and capacity for daily exposure assessment. This study hypothesized that introducing carboxylic groups into magnetic covalent organic frameworks (m-COFs) would improve HAAs adsorption by providing additional binding sites. Hence, we prepared a novel magnetic adsorbent, termed as Fe3O4@DOPA-TpPa-(COOH)2 capable of enhancing the HAAs detection through magnetic solid-phase extraction (MSPE) coupled with UPLC-MS. This sorbent demonstrated a large specific surface area (130.7 m2/g), high magnetic responsivity (21.05 emu/g), and robust stability, with an adsorption capacity (Qm[cal]: 81.82 mg/g) driven by electrostatic, LP - π/C-H - π interactions, and hydrogen bonding. Optimal MSPE conditions provided sensitive detection with a broad linear range (5-500 ng/mL), low limits of detection (0.01-7.01 ng/g), and excellent repeatability. Application to Cantonese mooncake samples showed satisfactory recoveries (62.12%-126.86%). This method offers a more accurate tool for detecting HAAs.

Simultaneous mitigation of heterocyclic aromatic amines and advanced glycation end products in roasted beef patties by plasma-activated water: Effects and mechanisms.

Heterocyclic aromatic amines (HAAs) and advanced glycation end products (AGEs) are hazardous substances produced when food is heated. In this study, the ability of plasma-activated water (PAW) to simultaneously mitigate production of HAAs and AGEs in roasted beef patties was investigated. Assays of free radicals, lipid peroxidation, and active carbonyls were used to analyze the mechanisms. PAW treatment decreased the contents of free HAAs, free AGEs, bound HAAs, and bound AGEs to 12.65 ng/g, 0.10 µg/g, 297.74 ng/g, and 4.32 µg/g, with the inhibition rates of 23.88%, 23.08%, 11.02%, and 8.47%, respectively. PAW treatment decreased HAAs and AGEs and mitigated their increase during storage. The decrease of HAAs and AGEs in PAW-treated samples was correlated with the enhancement of antioxidant capacity. The increase of free radical scavenging ability by PAW treatment led to the decrease of lipid peroxidation and the decrease of active carbonyls, HAAs, and AGEs in meat products.

Trioctylphosphine oxide-based hydrophobic magnetic deep eutectic solvent as a novel extractant for the enrichment of primary aromatic amines from juice and environmental water.

In this study, a novel technique utilizing vortex-assisted dispersive liquid-liquid microextraction with magnetic deep eutectic solvents (MDESs) was established and coupled with HPLC-UV to analyze six primary aromatic amines (PAAs). A novel hydrophobic MDES prepared from trioctylphosphine oxide, octanol, and CoCl2 was used as the extractant, which could be dispersed uniformly during extraction, then floated onto the sample surface and re-aggregated into a single drop spontaneously after the extraction. The variables influencing the efficiency of the extraction process were investigated. When performing under the optimal extraction conditions, this method exhibited excellent linearity, low limits of detection (0.2-0.9 ng mL-1), and high precision (RSD ≤ 8.3 %). The enrichment factors ranged from 56 to 182. Satisfactory recoveries in the range of 91.6-109.2 % with RSDs < 7.1 % were obtained from three apple juices and three environmental water samples. The greenness and practicality of the developed method were assessed by AGREE, AGREEprep, and blue applicability grade index metric tools. Overall, the established procedure demonstrated its simplicity, speediness, environmental friendliness, and effectiveness in analyzing PAAs from aqueous matrices.

Bitter melon extract mitigates heterocyclic aromatic amine formation in chicken thigh meat.

The purpose of the present research was to study the impact of bitter melon extract (BME) on the generation of heterocyclic aromatic amines (HAAs) in chicken thigh meat. Raw chicken samples were marinated overnight with various levels (0%, 0.5%, and 1%) of BME, and pan-fried at 150, 200, and 250°C for a total of 10 min. IQx, IQ, MeIQx, MeIQ, 7,8-DiMeIQx, 4,8-DiMeIQx, PhIP, AαC, and MeAαC were detected in quantities that varied according to the cooking temperature and the concentration of BME. Notably, IQx, MeIQx, MeIQ, 7,8-DiMeIQx, 4,8-DiMeIQx, and AαC levels were reduced through the application of the marinade. Cooking at higher temperatures led to elevated levels of total HAAs. Total HAA levels were 0.98 ± 1.12 ng/g, 3.82 ± 2.12 ng/g, and 6.25 ± 3.35 ng/g in samples cooked at 150, 200, and 250°C, respectively (p < .01). BME demonstrated its effectiveness in mitigating total HAA levels, showing reductions ranging from 25.9% to 69.9%. The most effective concentration of BME in reducing total HAAs was 1% for all cooking temperatures, which might be attributed to its antioxidant activity. These results carry substantial implications for potentially incorporating natural extracts such as BME into chicken products as a viable strategy to reduce HAAs, thus enhancing the safety and quality of meat products.

Understanding the heterocyclic aromatic amines: An overview and recent findings.

Heterocyclic aromatic amines (HAAs) constitute a group of highly toxic organic compounds strongly associated with the onset of various types of cancer. This paper aims to serve as a valuable resource for food scientists working towards a better understanding of these compounds including formation, minimizing strategies, analysis, and toxicity as well as addressing existing gaps in the literature. Despite extensive research conducted on these compounds since their discovery, several aspects remain inadequately understood, necessitating further investigation. These include their formation pathways, toxic mechanisms, effective mitigation strategies, and specific health effects on humans. Nonetheless, recent research has yielded promising results, contributing significantly to our understanding of HAAs by proposing new potential formation pathways and innovative strategies for their reduction.

The magnetic layered double hydroxide/zeolitic imidazolate framework-8 nanocomposite coupled with HPLC-MS/MS for the detection of heterocyclic aromatic amines in thermally processed meat.

In this research, a novel magnetic nanocomposite (Fe3O4@Zn/Al-LABSA-LDH/ZIF-8) was synthesized using Fe3O4 as the magnetic core, layered double hydroxide (LDH) with linear alkylbenzene sulfonic acid (LABSA) intercalation and zeolitic imidazolate framework-8 (ZIF-8) as the shell. Benefiting from the intercalation of LABSA into LDH combined with ZIF-8, the multiple interactions, including π-π stacking, hydrogen bonding, and electrostatic interactions, conferred high selectivity and good extraction capability to the material towards heterocyclic aromatic amines (HAAs). Fe3O4@Zn/Al-LABSA-LDH@ZIF-8 was used as an adsorbent for magnetic solid-phase extraction (MSPE) to enrich HAAs in thermally processed meat samples, followed by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) detection. The method exhibited a low detection limit (0.021-0.221 ng/g), good linearity (R2 ≥ 0.9999), high precision (RSD < 7.2 %), and satisfactory sample recovery (89.7 % -107.5 %). This research provides a promising approach for developing novel adsorbents in sample preparation and improving analytical performance.

Effect of free and bound proanthocyanidins from Chinese quince on heterocyclic aromatic amine formation and quality in fried chicken.

The abilities of Chinese quince free proanthocyanidins (FP) and bound proanthocyanidins (BP) at different levels (0.1%, 0.15%, and 0.3%) to mitigate heterocyclic aromatic amine (HAA) formation in fried chicken patties were investigated for the first time and compared with vitamin C (Vc). FP and BP reduced HAAs in a dose-dependent manner. Significantly, high concentrations of FP (0.3%) resulted in a reduction of PhIP, harman, and norharman levels by 59.84%, 22.91%, and 38.21%, respectively, in chicken patties. The addition of proanthocyanidins significantly (p < 0.05) reduced the weight loss of fried chicken patties. Furthermore, a positive correlation was observed among pH, weight loss, and total HAA formation in all three groups (FP, BP, and Vc). Multivariate analysis showed that FP had a more pronounced effect than BP from the perspective of enhancing the quality of fried chicken patties and reducing the formation of HAAs. These results indicate that proanthocyanidins, both BP and FP, but especially FP, from Chinese quince can inhibit the formation of carcinogenic HAAs when added to protein-rich foods that are subsequently fried.

Theoretical exploration of the phenolic compounds' inhibition mechanism of heterocyclic aromatic amines in roasted beef patties by density functional theory.

The ability of spices (bay leaf, star anise, and red pepper) and their characteristic phenolic compounds (quercetin, kaempferol, and capsaicin) to inhibit Heterocyclic aromatic amines (HAAs) in roasted beef patties were compared. Density functional theory (DFT) was used to reveal phenolic compounds interacting with HAAs-related intermediates and free radicals to explore possible inhibitory mechanisms for HAAs. 3 % red chili and 0.03 % capsaicin reduced the total HAAs content by 57.09 % and 68.79 %, respectively. DFT demonstrated that this was due to the stronger interaction between capsaicin and the ß-carboline HAAs intermediate (Ebind = -32.95 kcal/mol). The interaction between quercetin and phenylacetaldehyde was found to be the strongest (Ebind = -17.47 kcal/mol). Additionally, DFT indicated that capsaicin reduced the carbonyl content by transferring hydrogen atoms (HAT) to eliminate HO·, HOO·, and carbon-centered alkyl radicals. This study provided a reference for the development of DFT in the control of HAAs.

The Risk of Oral Cancer and the High Consumption of Thermally Processed Meat Containing Mutagenic and Carcinogenic Compounds.

The International Agency for Research on Cancer has classified the consumption of heat-processed meat as a direct human carcinogen and the consumption of red meat as a probable carcinogen. Mutagenic and carcinogenic compounds present in meat dishes include, among others, polycyclic aromatic hydrocarbons (PAHs) and heterocyclic aromatic amines (HAAs). These compounds can cause the development of gastrointestinal cancer. Oral cancer is one of the world's research priorities due to the ever-increasing incidence rate. However, the effect of diet on oral cancer is still a poorly recognized issue. The aim of this study was to assess the relationship between the risk of oral cancer and dietary ingredients with a particular emphasis on red meat and thermally processed meat. This study was conducted among patients with oral cancer in 2022 and 2023. The shortened standardized Food Frequency Questionnaire (FFQ) and a multivariate regression statistical analysis were used. The high consumption of red meat in general and thermally processed meat, especially smoked, fried, roasted and boiled, increases the risk of oral cavity cancer. Limiting the consumption of meat products and modifying the methods of preparing meat dishes may reduce exposure to carcinogenic compounds from the diet and thus reduce the risk of developing oral cancer.

In-situ growth of metal-organic frameworks on cellulose nanofiber aerogels for rapid adsorption of heterocyclic aromatic amines.

Heterocyclic aromatic amines (HAAs) are the main carcinogens produced during thermal processing of protein-rich foods. In this paper, a composite aerogel (TOCNFCa) with a stabilized dual-network structure was prepared via a template for the in-situ synthesis of UiO-66 on cellulose for the adsorption of HAAs in food. The dual-network structure of TOCNFCa provides the composite aerogel with excellent wet strength, maintaining excellent compressive properties. With the in-situ grown UiO-66 content up to 71.89 wt%, the hierarchical porosity endowed TOCNFCa@UiO-66 with the ability to rapidly adsorb HAAs molecules with high capacity (1.44-5.82 µmol/g). Based on excellent thermal stability, adsorption capacity and anti-interference, TOCNFCa@UiO-66 achieved satisfactory recoveries of HAAs in the boiled marinade, which is faster and more economical than the conventional SPE method. Moreover, TOCNFCa@UiO-66 could maintain 84.55 % of the initial adsorption capacity after 5 times of reuse.

Defective UiO-66/cellulose nanocomposite aerogel for the adsorption of heterocyclic aromatic amines.

Heterocyclic aromatic amines (HAAs), arising as chemical derivatives during the high-temperature culinary treatment of proteinaceous comestibles, exhibit notable carcinogenic potential. In this paper, a composite aerogel (AGD-UiO-66) with high-capacity and fast adsorption of HAAs was made with anchoring defective UiO-66 (D-UiO-66) mediated by lauric acid on the backbone of cellulose nanofibers (CNF). AGD-UiO-66 with hierarchical porosity reduced the mass transfer efficiency for the adsorption of HAAs and achieved high adsorption amount (0.84-1.05 µmol/g) and fast adsorption (15 min). The isothermal adsorption model demonstrated that AGD-UiO-66 belonged to a multilayer adsorption mechanism for HAAs. Furthermore, AGD-UiO-66 was successfully used to adsorb 12 HAAs in different food (roasted beef, roasted pork, roasted salmon and marinade) with high recoveries of 94.65%-104.43%. The intrinsic potential of AGD-UiO-66 demonstrated that it could be widely applicable to the adsorption of HAAs in foods.

FeMo2Ox(OH)y-based mineral hydrogels as a novel POD nanozyme for sensitive and selective detection of aromatic amines contaminants via a colorimetric sensor array.

Developing convenient pathways to discriminate and identify multiple aromatic amines (AAs) remains fascinating and critical. Here, a novel three-channel colorimetric sensor array based on FeMo2Ox(OH)y-based mineral (FM) hydrogels is successfully constructed to monitor AAs in tap water. Benefiting from the substantial oxygen vacancies (VO), FM nanozymes exhibit extraordinary peroxidase (POD)-like activities with Km of 0.133 mM and Vmax of 2.518 × 10-2 mM·s-1 toward 3,3',5,5'-tetramethylbenzidine (TMB), which are much better than horseradish peroxidase and most of POD mimics. This reveals that doping Cu and Co into FM (FM-Cu and FM-Co) can change POD activity. Based on various POD activities, TMB and H2O2 are used to generate fingerprint colorimetry signals from the colorimetry sensor array. The analytes can accurately discriminate through linear discriminant analysis, with a detection limit as low as 2.12 × 10-2-0.14 µM. The sensor array can effectively identify and discriminate AA contaminants and their mixtures and has performed well in real sample tests.