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.

A universal model to predict yields of THMs and HAAs based on UV-Visible absorption spectra.

Differential absorption spectroscopy (DAS) quantifies changes in the UV-Visible absorbance of dissolved organic matter (DOM) caused by reactions of its chromophores. As a result of its precision and sensitvity, DAS serves as a powerful tool for characterizing the formation of disinfection by-products (DBPs) in generated in DOM chlorination reactions. However, the nonlinear relationship between the intensity of DAS and DBP concentrations as well as the need to develop site-specific fitting parameters limit its practical applications. This study investigated the physico-chemical nature of DAS of chlorinated DOM through experimental measurements and theoretical calculations. Results of this study provide molecular-level evidence that electrophilic substitution reactions involving DOM reactive sites result in the emergence of DAS feaures ascribed to the "fast" chromophores. The ring opening in the cyclic enones-like structures which can be present either in the original DOM or are generated as intermediates in its chlorination, leads to the emergence of DAS features associated with the "slow" chromophores and high yields of DBPs. The kinetic study of chlorination of real waters reveals a strong linear relationship (R2 > 0.91) between ln([DBP]) and the long-wavelength (λ > 325 nm) parameter of the DAS, notably (ln(-DA350)). This relationship varies among different water sources due to the differences in the heterogeneity of Band A3 whose maximum is near 350 nm. Band A3 is one of the Gaussian bands that comprise the overall UV-Visible spectrum of DOM. A new function (f(-DA350)) is proposed in this study to quantify DBP formation. This function, which is determined by the Band A3's area, allows establishing a universal linear relationship between f(-DA350) and ln([THMs]), as well as f(-DA350) and ln([HAAs]), across various water sources. The findings of this study will stimulate further development of spectroscopy-based DBP monitoring technology for monitoring and optimization of water disinfection processes.

The adsorption of 2-amino-1-methyl-6-phenyl-imidazolium [4, 5-B] pyridine (PhIP) by lactic acid bacteria 37X-15 and its peptidoglycan.

The heterocyclic amine 2-amino-1-methyl-6-phenyl-imidazolium [4, 5-B] pyridine (PhIP), commonly found in roasted meat products, is considered a potential carcinogen. This study is to explore the underlying mechanisms involved in the adsorption of PhIP by lactic acid bacteria 37X-15 and its peptidoglycan. The scanning electron microscope results suggested that the strain's adsorption on PhIP occurs on the cell wall, primarily composed of peptidoglycan. The fourier-transformed infrared spectroscopy results indicated that PhIP adsorption by both lactic acid bacteria 37X-15 and its peptidoglycan primarily involved OH and NH binding groups. Different adsorption conditions affected the adsorption rate of PhIP by peptidoglycan. The optimal values for each adsorption condition were 2 h, 37 °C, and pH 6 when the maximum adsorption rate reached. This study provides a new direction for the application of lactic acid bacteria and its peptidoglycan in food safety.

Occurrence, formation, and proteins perturbation of disinfection byproducts in indoor air resulting from chlorine disinfection.

Increased amounts of chlorine disinfectant have been sprayed to inactivate viruses in the environment since the COVID-19 pandemic, and the health risk from chemicals, especially disinfection byproducts (DBPs), has unintentionally increased. In this study, we characterized the occurrence of haloacetic acids (HAAs) and trihalomethanes (THMs) in indoor air and evaluated their formation potential from typical indoor ingredients. Subsequently, the adverse effect of chloroacetic acid on A549 cells was depicted at the proteomic, transcriptional and silico levels. The results revealed that the total concentrations of HAAs and THMs ranged from 1.46 to 4.20 µg/m3 in ten indoor environments. Both classes of DBPs could be generated during the chlorination of prevalent terpenes by competing reactions, which are associated with the volatile state of indoor ingredients after disinfection. The C-type lectin receptor signaling pathway and cellular senescence were significantly perturbed pathways, which interfered with the development of lung fibrosis. The negative effect was further investigated by molecular docking and transcription, which showed that HAAs can interact with four C-type lectin receptor proteins by hydrogen bonds and inhibit the mRNA expression of related proteins. This study highlights the potential secondary biological risk caused by intensive DBPs generated from chlorination and draws our attention to the potential environmental factors leading to chronic respiratory disease.

High-mobility spin-polarized two-dimensional electron gas at the interface of EuTiO3/SrTiO3heterostructures.

Spin polarization of two-dimensional electron gas (2DEG) at the interface of EuTiO3/SrTiO3(STO) heterostructures has been theoretical predicted and experimentally observed via x-ray magnetic circular dichroism and polarized x-ray absorption spectroscopy, which, however, is lack of magnetotransport evidence. Here, we report the fabrication of high-quality EuTiO3/STO heterostructures by depositing antiferromagnetic insulating EuTiO3thin films onto STO substrates. Shubnikov-de Haas oscillation, Hall, and magnetoresistance (MR) measurements show that the interface is not only highly conducting, with electron mobility up to5.5×103cm2V-1s-1at 1.8 K, but also shows low-field hysteretic MR effects. MR of ∼9% is observed at 1.8 K and 20 Oe, which is one order of magnitude higher than those observed in other spin-polarized 2DEG oxide systems. Moreover, the heterostructures show ferromagnetic hysteresis loops. These results demonstrate that the high-mobility 2DEG is spin polarized, whose origin is attributed to the interfacial Ti3+-3dstates due to oxygen deficiency and the exchange interactions between interfacial Eu spins and itinerant Ti-3delectrons.

Heterocyclic aromatic amines in meat: Formation mechanisms, toxicological implications, occurrence, risk evaluation, and analytical methods.

Heterocyclic aromatic amines (HAAs) are detrimental substances can develop during the high-temperature cooking of protein-rich foods, such as meat. They are potent mutagens and carcinogens linked to an increased risk of various cancers. HAAs have complex structures with nitrogen-containing aromatic rings and are formed through chemical reactions between amino acids, creatin(in)e, and sugars during cooking. The formation of HAAs is influenced by various factors, such as food type, cooking temperature, time, cooking method, and technique. HAAs exert their toxicity through mechanisms like DNA adduct formation, oxidative stress, and inflammation. The research on HAAs is important for public health and food safety, leading to risk assessment and management strategies. It has also led to innovative approaches for reducing HAAs formation during cooking and minimizing related health risks. Understanding HAAs' chemistry and formation is crucial for developing effective ways to prevent their occurrence and protect human health. The current review presents an overview about HAAs, their formation pathways, and the factors influencing their formation. Additionally, it reviews their adverse health effects, occurrence, and the analytical methods used for measuring them.

The Einstein-de Haas effect in an Fe15cluster.

Classical models of spin-lattice coupling are at present unable to accurately reproduce results for numerous properties of ferromagnetic materials, such as heat transport coefficients or the sudden collapse of the magnetic moment in hcp-Fe under pressure. This inability has been attributed to the absence of a proper treatment of effects that are inherently quantum mechanical in nature, notably spin-orbit coupling (SOC). This paper introduces a time-dependent, non-collinear tight binding model, complete with SOC and vector Stoner exchange terms, that is capable of simulating the Einstein-de Haas (EdH) effect in a ferromagnetic Fe15cluster. The tight binding model is used to investigate the adiabaticity timescales that determine the response of the orbital and spin angular momenta to a rotating, externally appliedBfield, and we show that the qualitative behaviors of our simulations can be extrapolated to realistic timescales by use of the adiabatic theorem. An analysis of the trends in the torque contributions with respect to the field strength demonstrates that SOC is necessary to observe a transfer of angular momentum from the electrons to the nuclei at experimentally realisticBfields. The simulations presented in this paper demonstrate the EdH effect from first principles using a Fe cluster.

Landau Diamagnetism and de Haas-van Alphen Oscillations, Formed in Single Crystals of Y3Fe5O12, in Local Nanodimensional-Sized 2D Phase Separation Regions, Located inside Layered Domain Walls at Room Temperature and T = 77 K.

This paper presents results of the magnetic dynamics study (the microwave power absorptions at the fixed frequencies during magnetic field sweeping) in samples of Y3Fe5O12 single crystals in the form of plates and spheres of various sizes, at frequencies exceeding 30 GHz, in magnetic fields up to 18 kOe, at room temperature, and T = 77 K. It was found that in this case, the inhomogeneity's of the magnetic state manifested itself in the Y3Fe5O12 samples as 2D local phase separation regions. Such 2D phase separation regions formed inside layered domain walls representing superlattices with sizes of 700-900 Å. Depending on the shape and size of the studied plates and spheres, Landau diamagnetism or de Haas-van Alphen oscillations were observed in the 2D phase separation regions at room temperature and T = 77 K.

Carbonyl-trapping by phenolics and the inhibition of the formation of carcinogenic heterocyclic aromatic amines with the structure of aminoimidazoazaarene in beef patties.

Carcinogenic heterocyclic aromatic amines (HAAs) with the structure of aminoimidazoazaarene (PhIP, MeIQx, IQ, and MeIQ) are produced by reaction of creatin(in)e, ammonia, and reactive carbonyls (phenylacetaldehyde, acrolein, and crotonaldehyde). In an attempt to provide efficient methodologies for HAA reduction in beef patties, this study: identified phloroglucinol as the most efficient phenolic to reduce HAA formation (76-96% inhibition); isolated and characterized by NMR and MS phloroglucinol/phenylcetaldehyde and phloroglucinol/acrolein adducts; and determined by LC-MS/MS adduct formation in beef patties treated with phloroglucinol. Obtained results suggested that addition of trihydroxyphenols (including phloroglucinol) to beef patties should decrease HAA formation. This was confirmed by both immersing beef patties in apple (or pear) juice before cooking (>90% inhibition) and including wheat bran in patty recipe. All these results confirm the key role of reactive carbonyls in the formation of carcinogenic HAAs and propose carbonyl-trapping as a way for controlling HAA formation in food products.

NaHCO3 addition enhances water permeance and Ca/haloacetic acids selectivity of nanofiltration membranes for drinking water treatment.

The existence of disinfection by-products such as haloacetic acids (HAAs) in drinking water severely threatens water safety and public health. Nanofiltration (NF) is a promising strategy to remove HAAs for clean water production. However, NF often possesses overhigh rejection of essential minerals such as calcium. Herein, we developed highly selective NF membranes with tailored surface charge and pore size for efficient rejection of HAAs and high passage of minerals. The NF membranes were fabricated through interfacial polymerization (IP) with NaHCO3 as an additive. The NaHCO3-tailored NF membranes exhibited high water permeance up to ∼24.0 L m - 2 h - 1 bar-1 (more than doubled compared with the control membrane) thanks to the formation of stripe-like features and enlarged pore size. Meanwhile, the tailored membranes showed enhanced negative charge, which benefitted their rejection of HAAs and passage of Ca and Mg. The higher rejection of HAAs (e.g., > 90%) with the lower rejection of minerals (e.g., < 30% for Ca) allowed the NF membranes to achieve higher minerals/HAAs selectivity, which was significantly higher than those of commercially available NF membranes. The simultaneously enhanced membrane performance and higher minerals/HAAs selectivity would greatly boost water production efficiency and water quality. Our findings provide a novel insight to tailor the minerals/micropollutants selectivity of NF membranes for highly selective separation in membrane-based water treatment.

Artificial magnetism for a harmonically trapped Fermi gas in a synthetic magnetic field.

We have analytically explored the artificial magnetism for a 3D spin-polarized harmonically trapped ideal Fermi gas of electrically neutral particles exposed to a uniform synthetic magnetic field. Though polarization of the spin is necessary for trapping electrically neutral atoms in a magneto-optical trap, Pauli paramagnetism can not be studied for the spin-polarized Fermi system. However, it is possible to study Landau diamagnetism and de Haas-van Alphen effect for such a system. We have unified the artificial Landau diamagnetism and the artificial de Haas-van Alphen effect in a single framework for all temperatures as well as for all possible magnitudes of the synthetic magnetic field in the thermodynamic limit. Our prediction is testable in the present-day experimental setup for ultracold fermionic atoms in magneto-optical trap.

Gate-tunable transport in van der Waals topological insulator Bi4Br4nanobelts.

Bi4Br4is a quasi-one-dimensional van der Waals topological insulator with novel electronic properties. Several efforts have been devoted to the understanding of its bulk form, yet it remains a challenge to explore the transport properties in low-dimensional structures due to the difficulty of device fabrication. Here we report for the first time a gate-tunable transport in exfoliated Bi4Br4nanobelts. Notable two-frequency Shubnikov-de Haas oscillations oscillations are discovered at low temperatures, with the low- and high-frequency parts coming from the three-dimensional bulk state and the two-dimensional surface state, respectively. In addition, ambipolar field effect is realized with a longitudinal resistance peak and a sign reverse in the Hall coefficient. Our successful measurements of quantum oscillations and realization of gate-tunable transport lay a foundation for further investigation of novel topological properties and room-temperature quantum spin Hall states in Bi4Br4.

Formation of Artificial Fermi Surfaces with a Triangular Superlattice on a Conventional Two-Dimensional Electron Gas.

Imposing an external periodic electrostatic potential to the electrons confined in a quantum well makes it possible to engineer synthetic two-dimensional band structures, with electronic properties different from those in the host semiconductor. Here we report the fabrication and study of a tunable triangular artificial lattice on a GaAs/AlGaAs heterostructure where it is possible to transform from the original GaAs band structure and a circular Fermi surface to a new band structure with multiple artificial Fermi surfaces simply by altering a gate bias. For weak electrostatic modulation magnetotransport measurements reveal multiple quantum oscillations and commensurability oscillations due to the electron scattering from the artificial lattice. Increasing the strength of the modulation reveals new commensurability oscillations of the electrons from the artificial Fermi surface scattering from the triangular artificial lattice. These results show that low disorder gate-tunable lateral superlattices can be used to form artificial two-dimensional crystals with designer electronic properties.

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.

Dietary intakes of trihalomethanes and haloacetic acids from ready-to-eat vegetables in taiwan.

BACKGROUND: Chlorine-based disinfectants are often used to sanitize fruit and vegetables to produce a product called ready-to-eat (RTE) vegetables. During the disinfection process, disinfection byproducts (DBPs), such as trihalomethanes (THMs) and haloacetic acids (HAAs), might be formed via chlorination. OBJECTIVE: To determine the amounts of DBPs that occur in RTE vegetables in Taiwan, an analytical method which can detect THMs and HAAs simultaneously was developed for this study. METHODS: For HAAs, dimethyl sulfate (DMS) was first added into the sample as derivatization reagent and tetrabutylammonium hydrogen sulfate (TBA-H2SO4) was used as the ion-pairing agent to improve the derivatization process. Afterwards, the solid-phase microextraction (SPME) procedure coupled with gas chromatography with tandem mass spectrometers (GC/MS/MS) was performed to measure the HAAs derivatives and THMs in the sample. RESULTS: A total of 92 single RTE ingredients were analyzed in this study. Among various THMs and HAAs, the results showed that dibromochloromethane (21%) and dichloroacetic acid (12%) had the highest detection rates, respectively. Compared with fruits, vegetables were more easily to contain DBPs. For adults in Taiwan, the maximum daily exposure of THMs and HAAs estimated via the consumption of RTE vegetables were 28.53 and 77.83 µg, respectively. SIGNIFICANCE: The findings from this study suggest that the exposure of DBPs from RTE vegetables is an important food safety issue in Taiwan.

Mechanical Detection of the De Haas-van Alphen Effect in Graphene.

In our work, we study the dynamics of a graphene Corbino disk supported by a gold mechanical resonator in the presence of a magnetic field. We demonstrate here that our graphene/gold mechanical structure exhibits a nontrivial resonance frequency dependence on the applied magnetic field, showing how this feature is indicative of the de Haas-van Alphen effect in the graphene Corbino disk. Relying on the mechanical resonances of the Au structure, our detection scheme is essentially independent of the material considered and can be applied for dHvA measurements on any conducting 2D material. In particular, the scheme is expected to be an important tool in studies of centrosymmetric transition metal dichalcogenide (TMD) crystals, shedding new light on hidden magnetization and interaction effects.

Shubnikov-de Haas oscillations and nontrivial topological states in Weyl semimetal candidate SmAlSi.

The RAlX (R = Light rare earth; X = Ge, Si) compounds, as a family of magnetic Weyl semimetal, have recently attracted growing attention due to the tunability of Weyl nodes and its interactions with diverse magnetism by rare-earth atoms. Here, we report the magnetotransport evidence and electronic structure calculations on nontrivial band topology of SmAlSi, a new member of this family. At low temperatures, SmAlSi exhibits large non-saturated magnetoresistance (MR) (as large as ∼5500% at 2 K and 48 T) and distinct Shubnikov-de Haas (SdH) oscillations. The field dependent MRs at 2 K deviate from the semiclassical (µ0H)2variation but follow the power-law relation MR∝(µ0H)mwith a crossover fromm∼ 1.52 at low fields (µ0H< 15 T) tom∼ 1 under high fields (µ0H> 18 T), which is attributed to the existence of Weyl points and electron-hole compensated characteristics with high mobility. From the analysis of SdH oscillations, two fundamental frequencies originating from the Fermi surface pockets with non-trivialπBerry phases and small cyclotron mass can be identified, this feature is supported by the calculated electronic band structures with two Weyl pockets near the Fermi level. Our study establishes SmAlSi as a paradigm for researching the novel topological states of RAlX family.

Shubnikov-de Haas and de Haas-van Alphen oscillations in Czochralski grown CoSi single crystal.

Anisotropic transport, Shubnikov-de Haas (SdH), and de Haas-van Alphen (dHvA) quantum oscillations studies are reported on a high-quality CoSi single crystal grown by the Czochralski method. Temperature-dependent resistivities indicate the dominating electron-electron scattering. Magnetoresistance (MR) at 2 K reaches 610% forI ∥ [111]andB ∥ [011-], whereas it is 500% forI ∥ [011-] andB ∥ [111]. A negative slope in field-dependent Hall resistivity suggests electrons are the majority carriers. The carrier concentration extracted from Hall conductivity indicates no electron-hole compensation. In 3D CoSi, the electron transport lifetime is found to be approximately in the same order as the quantum lifetime, whereas in 2Delectron gas the long-range scattering drives the transport life much larger than the quantum lifetime. From MR and Hall SdH oscillations, the effective masses and Dingle temperatures have been calculated. The dHvA oscillation reveals three frequencies at 18 T (γ), 558 T (α) and 663 T (ß), whereas, SdH oscillation results in only two frequenciesαandß. Theγfrequency observed in dHvA oscillation is a tiny hole pocket at the Γ point.

Effect of Traditional Stir-Frying on the Characteristics and Quality of Mutton Sao Zi.

The effects of stir-frying stage and time on the formation of Maillard reaction products (MRP) and potentially hazardous substances with time in stir-fried mutton sao zi were investigated. Furosine, fluorescence intensity, Nε-(1-carboxymethyl)-L-lysine (CML), Nε-(1-carboxyethyl)-L-lysine (CEL), polyaromatic hydrocarbons PAHs), heterocyclic aromatic amines (HAAs), and acrylamides (AA) mainly presented were of stir-fried mutton sao zi. The furosine decreased after mixed stir-frying (MSF) 160 s due to its degradation as the Maillard reaction (MR) progressed. The fluorescent compound gradually increased with time during the stir-frying process. The CML and CEL peaked in MSF at 200 s. AA reached its maximum at MSF 120 s and then decreased. All the 5 HAAs were detected after MSF 200 s, suggesting that stir-frying mutton sao zi was at its best before MSF for 200 s. When stir-frying exceeded the optimal processing time of (MSF 160 s) 200 s, the benzo[a]pyrene peaked at 0.82 µg/kg, far lower than the maximum permissible value specified by the Commission of the European Communities. Extended stir-frying promoted MRP and some hazardous substances, but the content of potentially hazardous substances was still within the safety range for food.

Formation of Carcinogens in Processed Meat and Its Measurement with the Usage of Artificial Digestion-A Review.

Meat is a rich source of various nutrients. However, it needs processing before consumption, what in turn generates formation of carcinogenic compounds, i.a., polycyclic aromatic hydrocarbons (PAH), nitrosamines (NOCs), and the most mutagenic heterocyclic aromatic amines (HAAs). It was widely found that many factors affect the content of carcinogens in processed meat. However, it has recently been discovered that after digestion free HAAs are released, which are not detectable before enzymatic treatment. It was established that the highest percentage of carcinogens is released in the small intestine and that its amount can be increased up to 6.6-fold. The change in free HAAs content in analyzed samples was dependent on many factors such as meat type, doneness, particle size of meat, and the enzyme concentration used for digestion. In turn, introduction of bacteria naturally occurring in the human digestive tract into the model significantly decreases total amount of HAAs. Contrary, the addition of food ingredients rich in polyphenols, fiber, and water (pepper powder, onions, apples) increases free HAAs' release up to 56.06%. Results suggests that in vitro digestion should be an integral step of sample preparation. Artificial digestion introduced before chromatographic analysis will allow to estimate accurately the content of carcinogens in processed meat.