Environmental pollutants and the immune response.

Environmental pollution is one of the most serious challenges to health in the modern world. Pollutants alter immune responses and can provoke immunotoxicity. In this Review, we summarize the major environmental pollutants that are attracting wide-ranging concern and the molecular basis underlying their effects on the immune system. Xenobiotic receptors, including the aryl hydrocarbon receptor (AHR), sense and respond to a subset of environmental pollutants by activating the expression of detoxification enzymes to protect the body. However, chronic activation of the AHR leads to immunotoxicity. KEAP1-NRF2 is another important system that protects the body against environmental pollutants. KEAP1 is a sensor protein that detects environmental pollutants, leading to activation of the transcription factor NRF2. NRF2 protects the body from immunotoxicity by inducing the expression of genes involved in detoxification, antioxidant and anti-inflammatory activities. Intervening in these sensor-response systems could protect the body from the devastating immunotoxicity that can be induced by environmental pollutants.

Relative genotoxicity of polycyclic aromatic hydrocarbons inferred from free energy perturbation approaches.

Utilizing molecular dynamics and free energy perturbation, we examine the relative binding affinity of several covalent polycyclic aromatic hydrocarbon - DNA (PAH-DNA) adducts at the central adenine of NRAS codon-61, a mutational hotspot implicated in cancer risk. Several PAHs classified by the International Agency for Research on Cancer as probable, possible, or unclassifiable as to carcinogenicity are found to have greater binding affinity than the known carcinogen, benzo[a]pyrene (B[a]P). van der Waals interactions between the intercalated PAH and neighboring nucleobases, and minimal disruption of the DNA duplex drive increases in binding affinity. PAH-DNA adducts may be repaired by global genomic nucleotide excision repair (GG-NER), hence we also compute relative free energies of complexation of PAH-DNA adducts with RAD4-RAD23 (the yeast ortholog of human XPC-RAD23) which constitutes the recognition step in GG-NER. PAH-DNA adducts exhibiting the greatest DNA binding affinity also exhibit the least RAD4-RAD23 complexation affinity and are thus predicted to resist the GG-NER machinery, contributing to their genotoxic potential. In particular, the fjord region PAHs dibenzo[a,l]pyrene, benzo[g]chrysene, and benzo[c]phenanthrene are found to have greater binding affinity while having weaker RAD4-RAD23 complexation affinity than their respective bay region analogs B[a]P, chrysene, and phenanthrene. We also find that the bay region PAHs dibenzo[a,j]anthracene, dibenzo[a,c]anthracene, and dibenzo[a,h]anthracene exhibit greater binding affinity and weaker RAD4-RAD23 complexation affinity than B[a]P. Thus, the study of PAH genotoxicity likely needs to be substantially broadened, with implications for public policy and the health sciences. This approach can be broadly applied to assess factors contributing to the genotoxicity of other unclassified compounds.

Fine-tuning an aromatic ring-hydroxylating oxygenase to degrade high molecular weight polycyclic aromatic hydrocarbon.

Rieske nonheme iron aromatic ring-hydroxylating oxygenases (RHOs) play pivotal roles in determining the substrate preferences of polycyclic aromatic hydrocarbon (PAH) degraders. However, their potential to degrade high molecular weight PAHs (HMW-PAHs) has been relatively unexplored. NarA2B2 is an RHO derived from a thermophilic Hydrogenibacillus sp. strain N12. In this study, we have identified four "hotspot" residues (V236, Y300, W316, and L375) that may hinder the catalytic capacity of NarA2B2 when it comes to HMW-PAHs. By employing structure-guided rational enzyme engineering, we successfully modified NarA2B2, resulting in NarA2B2 variants capable of catalyzing the degradation of six different types of HMW-PAHs, including pyrene, fluoranthene, chrysene, benzo[a]anthracene, benzo[b]fluoranthene, and benzo[a]pyrene. Three representative variants, NarA2B2W316I, NarA2B2Y300F-W316I, and NarA2B2V236A-W316I-L375F, not only maintain their abilities to degrade low-molecular-weight PAHs (LMW-PAHs) but also exhibited 2 to 4 times higher degradation efficiency for HMW-PAHs in comparison to another isozyme, NarAaAb. Computational analysis of the NarA2B2 variants predicts that these modifications alter the size and hydrophobicity of the active site pocket making it more suitable for HMW-PAHs. These findings provide a comprehensive understanding of the relationship between three-dimensional structure and functionality, thereby opening up possibilities for designing improved RHOs that can be more effectively used in the bioremediation of PAHs.

Evaluating the Kinetics and Molecular Mechanism for Biomimetic Metabolic Activation of PAHs by Surface-Enhanced Raman Scattering Spectroscopy.

Biomimetic cytochrome P450 for chemical activation of environmental carcinogens is an efficient in vitro model for evaluating their mutagenicity and ultimately acquiring the metabolites that cannot be easily accessed by conventional routes of organic synthesis. Different kinds of mutagen derived from polyaromatic hydrocarbons (PAHs) by metalloporphyrin/oxidant model systems have been reported, but the underlying molecular mechanisms are poorly understood. Herein, we have for the first time demonstrated an effective surface-enhanced Raman scattering (SERS) protocol to study the dynamics and biomimetic metabolic behaviors of pyrene (Pyr) in the presence of various oxygen donors. Quantitative information on the relative concentration of Pyr and its metabolites in the biomimetic system can be extracted from the SERS spectra. On the basis of our results, we conclude that the oxidative metabolism of Pyr is highly influenced by the types and concentrations of oxygen donors, leading to the formation of 1-hydroxypyrene and dioxygenated products. Besides, the addition of an appropriate amount of an organic solvent can promote the formation of secondary oxidation products. These results offer valuable insights into the dynamics of PAHs metabolism and the regulation of their metabolic pathways in biomimetic activation. In comparison to traditional liquid chromatography-mass spectrometry, the present SERS approach is more suitable for high-throughput evaluation of the metabolic process and kinetics of PAHs. We anticipate that this approach will enable a more general and comprehensive tracking of metabolic dynamics and molecular mechanisms involved in the biomimetic activation of other xenobiotics, such as procarcinogens, promutagens, and drugs.

Viscosities and Densities of Binary and Ternary Mixtures of Aliphatic and Polyaromatic Hydrocarbons: Pyrene +1-Methylnaphthalene + Dodecane at T = (293.15 to 343.15) K. Experiment and Modeling.

This work presents new experimental viscosity and density data for aromatic and polyaromatic compounds in binary and ternary pyrene, 1-methylnaphthalene, and dodecane mixtures. The lack of experimental viscosity data for these mixtures requires the development of a new database, which is vital for understanding the behavior of mixtures in more complex systems, such as asphaltenes and fuels. The mixtures proposed in this work have been measured over a temperature range of (293.15 to 343.15) K at atmospheric pressure. Several mixture compositions have been studied at these conditions: 1.0, 2.5, 5.0, 7.5, 10.0, 12.5, and 15.0% pyrene mass fraction. The concentration of pyrene correlates with an increase in the viscosity and density values. At the lowest temperature in binary mixtures, the corresponding values reach 4.4217 mPa·s for viscosity and 1.0447 × 103 kg·m-3 for density, respectively. In ternary mixtures, the introduction of dodecane leads to the lowest maximum values of 3.5555 mPa·s for viscosity and 1.0112 × 103 kg·m-3 for density at the same temperature. The experimental data have been employed for the specific modification of viscosity models. These modifications could facilitate the prediction of the viscosity of mixtures that are more complex than those presented in this work. Various viscosity models have been employed, such as Linear, Ratcliff and Khan, modified UNIFAC-Visco, and Krieger-Dougherty. The settings in the models used reliably reproduce the experiment reliably. However, the Ratcliff model agrees excellently with the experiment, having a low standard deviation (2.0%) compared to other models. Furthermore, a model based on the equation of state of Guo is proposed to predict the viscosity values by modifying the specific parameters and adjusting them to the mixtures proposed in this work. The results from this study are compared to previous work, where pyrene, toluene, and heptane mixtures were analyzed. In this case, we find that the decrease of aggregation grade in the present systems is predicted by the model fixed in this work.

Physicochemical Characterization of Asphaltenes Using Microfluidic Analysis.

Crude oils are complex mixtures of organic molecules, of which asphaltenes are the heaviest component. Asphaltene precipitation and deposition have been recognized to be a significant problem in oil production, transmission, and processing facilities. These macromolecular aromatics are challenging to characterize due to their heterogeneity and complex molecular structure. Microfluidic devices are able to capture key characteristics of reservoir rocks and provide new insights into the transport, reactions, and chemical interactions governing fluids used in the oil and gas industry. Understanding the microscale phenomena has led to better design of macroscale processes used by the industry. One area that has seen significant growth is in the area of chemical analysis under flowing conditions. Microfluidics and microscale analysis have advanced the understanding of complex mixtures by providing in situ imaging that can be combined with other chemical characterization methods to give details of how oil, water, and added chemicals interface with pore-scale detail. This review article aims to showcase how microfluidic devices offer new physical, chemical, and dynamic information on the behavior of asphaltenes. Specifically, asphaltene deposition and related flow assurance problems, interfacial properties and rheology, and evaluation of remediation strategies studied in microchannels and microfluidic porous media are presented. Examples of successful applications that address key asphaltene-related problems highlight the advances of microscale systems as a tool for advancing the physicochemical characterization of complex fluids for the oil and gas industry.

Oxidation of Polycyclic Aromatic Hydrocarbons (PAHs) Triggered by a Photochemical Synergistic Effect between High- and Low-Molecular-Weight PAHs.

Photooxidation of polycyclic aromatic hydrocarbons (PAHs), which are widely observed in atmospheric particulate matter (PM), largely determines their atmospheric fate. In the environment, PAHs are highly complex in chemical composition, and a great variety of PAHs tend to co-occur. Despite extensive investigation on the photochemical behavior of individual PAH molecules, the photochemical interaction among these coexisting PAHs is still not well understood. Here, we show that during photooxidation, there is a strong photochemical synergistic effect among PAHs extracted from soot particles. We find that neither small PAHs with low molecular weights of 200-350 Da and 4-8 aromatic rings (named PAHsmall) nor large PAHs with high molecular weights of 350-600 Da and 8-14 aromatic rings (named PAHlarge) undergo photooxidation under red-light irradiation (λ = 648 nm), even though PAHlarge can absorb light with this wavelength. Interestingly, when PAHlarge is mixed with PAHsmall, substantial photooxidation is observed for both PAHlarge and PAHsmall. Comparisons of in situ infrared (IR), high-resolution mass spectrometry, and electron paramagnetic resonance analysis indicate that the presence of PAHsmall inhibits the light quenching effect arising from the π-π stacking of PAHlarge. This leads to the formation of singlet oxygen (1O2), which initiates the photooxidation. Our findings reveal a new mechanism for the photooxidation of PAHs and suggest that complex atmospheric PAHs exhibit distinct photoreactivity from simple systems.

Distinct Photochemistry of Odd-Carbon PAHs from the Even-Carbon Ones During the Photoaging and Analysis of Soot.

Polycyclic aromatic hydrocarbons (PAHs) are the primary organic carbons in soot. In addition to PAHs with even carbon numbers (PAHeven), substantial odd-carbon PAHs (PAHodd) have been widely observed in soot and ambient particles. Analyzing and understanding the photoaging of these compounds are essential for assessing their environmental effects. Here, using laser desorption ionization mass spectrometry (LDI-MS), we reveal the substantially different photoreactivity of PAHodd from PAHeven in the aging process and their MS detection through their distinct behaviors in the presence and absence of elemental carbon (EC) in soot. During direct photooxidation of organic carbon (OC) alone, the PAHeven are oxidized more rapidly than the PAHodd. However, the degradation of PAHodd becomes preponderant over PAHeven in the presence of EC during photoaging of the whole soot. All of these observations are proposed to originate from the more rapid hydrogen abstraction reaction from PAHodd in the EC-photosensitized reaction, owing to its unique structure of a single sp3-hybridized carbon site. Our findings reveal the photoreactivity and reaction mechanism of PAHodd for the first time, providing a comprehensive understanding of the oxidation of PAHs at a molecular level during soot aging and highlight the enhanced effect of EC on PAHodd ionization in LDI-MS analysis.

Polycyclic aromatic hydrocarbon skin permeation efficiency in vitro is lower through human than pigskin and decreases with lipophilicity.

Polycyclic aromatic hydrocarbons (PAH) are persistent environmental pollutants, which occasionally appear as contaminants in consumer products. Upon dermal contact, transfer of PAH into the stratum corneum (s.c.) and migration through the skin may occur, resulting in this class of highly toxic compounds to become bioavailable. In this study, dermal penetration through human and porcine skin of 24 PAH, comprising broad molar mass (M: 152-302 g/mol) and octanol-water partition coefficient (logP: 3.9-7.3) ranges, was evaluated via Franz diffusion cell in vitro assays. More lipophilic and potentially more toxic PAH had decreased permeation rates through the rather lipophilic s.c. into the more hydrophilic viable (epi-)dermis. Furthermore, human skin was less permeable than pigskin, a commonly used surrogate in skin penetration studies. In particular, the s.c. of human skin retains a greater share of PAH, an effect that is more pronounced for smaller PAH. Additionally, we compared the skin permeation kinetics of different PAH in pigskin. While small PAH (M < 230 g/mol, logP < 6) permeate the skin quickly and are detected in the receptor fluid after 2 h, large PAH (M > 252 g/mol, logP ≥ 6) do not fully permeate the skin up to 48 h. This indicates that highly lipophilic PAH do not become bioavailable as readily as their smaller congeners when transferred to the skin surface. Our data suggest that pigskin could be used as a surrogate for worst case scenario estimates of dermal PAH permeation through human skin.

Enhanced photocatalytic degradation of polycyclic aromatic hydrocarbons (PAHs) Using NiO nanoparticles.

The oncogenic and genetic properties of anthracene, a member of the polycyclic aromatic hydrocarbons (PAHs) family, pose a significant health threat to humans. This study aims to investigate the photocatalytic decomposition of anthracene under various conditions, such as different concentrations of PAHs, varying amounts of NiO (nickel oxide) nanoparticles, and different pH levels under ultraviolet light and sunlight. The synthesized NiO nanoparticles showed surface plasma resonance at 230 and 360 nm, while XRD and SEM analysis confirmed the nanoparticles were cubic crystalline in structure with sizes ranging between 37 and 126 nm. NiO nanoparticles exhibited 79% degradation of pyrene at 2 µg/mL of anthracene within 60 min of treatment. NiO at 10 µg/mL concentration showed significant adsorption of 57%, while the adsorption method worked efficiently (72%) at 5 pH. Photocatalytic degradation was confirmed by isotherm and kinetic studies through monolayer adsorption and pseudo-first-order kinetics. Further, the absorption process was confirmed by performing GC-MS analysis of the NiO nanoparticles. On the other hand, NiO nanoparticles showed antimicrobial activity against Gram negative and Gram-positive bacteria. Therefore, the present work is one of its kind proving the dual application of NiO nanoparticles, which makes them suitable candidates for bioremediation by treating PAHs and killing pathogenic bacteria.

A review on recent advancements in the treatment of polyaromatic hydrocarbons (PAHs) using sulfate radicals based advanced oxidation process.

Polyaromatic hydrocarbons (PAHs) are the most persistent compounds that get contaminated in the soil and water. Nearly 16 PAHs was considered to be a very toxic according US protection Agency. Though its concentration level is low in the environments but the effects due to it, is enormous. Advanced Oxidation Process (AOP) is an emergent methodology towards treating such pollutants with low and high molecular weight of complex substances. In this study, sulfate radical (SO4‾•) based AOP is emphasized for purging PAH from different sources. This review essentially concentrated on the mechanism of SO4‾• for the remediation of pollutants from different sources and the effects caused due to these pollutants in the environment was reduced by this mechanism is revealed in this review. It also talks about the SO4‾• precursors like Peroxymonosulfate (PMS) and Persulfate (PS) and their active participation in treating the different sources of toxic pollutants. Though PS and PMS is used for removing different contaminants, the degradation of PAH due to SO4‾• was presented particularly. The hydroxyl radical (•OH) mechanism-based methods are also emphasized in this review along with their limitations. In addition to that, different activation methods of PS and PMS were discussed which highlighted the performance of transition metals in activation. Also this review opened up about the degradation efficiency of contaminants, which was mostly higher than 90% where transition metals were used for activation. Especially, on usage of nanoparticles even 100% of degradation could be able to achieve was clearly showed in this literature study. This study mainly proposed the treatment of PAH present in the soil and water using SO4‾• with different activation methodologies. Particularly, it emphasized about the importance of treating the PAH to overcome the risk associated with the environment and humans due to its contamination.

Kinetics analysis of PAHs degradation using SiO2-ZnO nanoparticles and evaluating their antibacterial and antibiofilm efficacy.

The adsorption of Polycyclic aromatic hydrocarbons (PAHs) using nanoparticles is gaining significant attention due to the rapid removal or treatment rates. In this study, Silicon Dioxide-Zinc Oxide nanoparticles (SiO2-ZnO NPs) were synthesized to adsorb pyrene. Physicochemical characterization of SiO2-ZnO NPs showed plasmon resonance at 323 nm, agglomeration, irregular dispersion, and diameters of 90-100 nm. FT-IR analysis identified major functional groups on SiO2-ZnO NPs, including alkyne, amine, and isothiocyanate. SiO2-ZnO NPs demonstrated significant pyrene adsorption at pH 5, with 10 µg/mL of SiO2-ZnO NPs and 2 µg/mL of PAHs, performing better under UV irradiation. Two isotherm models, adsorption isotherm and kinetics adsorption, were used to analyze the PAHs adsorption by SiO2-ZnO NPs. Additionally, SiO2-ZnO NPs were tested for antibacterial and antibiofilm activities against both Gram-negative and Gram-positive bacteria. At a concentration of 150 µg/mL, SiO2-ZnO NPs produced inhibition zones of 21.57 mm, 20.30 mm, 19.30 mm, and 11.30 mm against Staphylococcus aureus, Escherichia coli, Bacillus subtilis, and Klebsiella pneumoniae, respectively. They also inhibited and disrupted biofilms of Micrococcus luteus and Acinetobacter baumannii. Furthermore, SiO2-ZnO NPs exhibited photocatalytic degradation of lead, achieving 68.24% degradation within 5 h of treatment. Therefore, SiO2-ZnO NPs are efficient candidates for multiple applications, including pyrene adsorption, bacterial biofilm disruption, and lead degradation under sunlight.

Estimating Binding Energies of π-Stacked Aromatic Dimers Using Force Field-Driven Molecular Dynamics.

π-π stacking are omnipresent interactions, crucial in many areas of chemistry, and often studied using quantum chemical methods. Here, we report a simple and computationally efficient method of estimating the binding energies of stacked polycyclic aromatic hydrocarbons based on steered molecular dynamics. This method leverages the force field parameters for accurate calculation. The presented results show good agreement with those obtained through DFT at the ωB97X-D3/cc-pVQZ level of theory. It is demonstrated that this force field-driven SMD method can be applied to other aromatic molecules, allowing insight into the complexity of the stacking interactions and, more importantly, reporting π-π stacking energy values with reasonable precision.

Eco-Friendly Inorganic Binders: A Key Alternative for Reducing Harmful Emissions in Molding and Core-Making Technologies.

Many years of foundry practice and much more accurate analytical methods have shown that sands with organic binders, in addition to their many technological advantages, pose risks associated with the emission of many compounds, including harmful ones (e.g., formaldehyde, phenol, benzene, polycyclic aromatic hydrocarbons, and sulfur), arising during the pouring of liquid casting alloys into molds, their cooling, and knock-out. The aim of this research is to demonstrate the potential benefits of adopting inorganic binders in European iron foundries. This will improve the environmental and working conditions by introducing cleaner and more ecological production methods, while also ranking the tested binders studied in terms of their harmful content. The article pays special attention to the analysis of seven innovative inorganic binders and one organic binder, acting as a reference for emissions of gases from the BTEX (benzene, toluene, ethylbenzene, and xylenes) and PAHs (polycyclic aromatic hydrocarbons) groups and other compounds such as phenol, formaldehyde, and isocyanates (MDI and TDI) generated during the mold pouring process with liquid metals. The knowledge gained will, for the first time, enrich the database needed to update the Reference Document on The Best Available Techniques for the Smitheries and Foundries Industry (SF BREF).

The high dose of biochar reduces polycyclic aromatic hydrocarbons losses during co-composting of sewage sludge and wheat straw.

The aim of the study was to investigate the effect of the biochar (BC) dose on solvent extractable (Ctot) and freely dissolved (Cfree) polycyclic aromatic hydrocarbons (PAHs) content during co-composting. A significantly better reduction of Σ16 Ctot PAHs after 98 days occurred during composting with BC (for 1% of BC - 44% and for 5% of BC - 23%) than in the control (15%). Despite the relatively high reduction of Ctot PAHs in the experiment with 5% BC rate, the content of the PAHs was still the highest compared to other variants. Regarding Cfree PAHs, 5% rate of BC resulted in the best reduction of PAHs, while the 1% BC dose resulted in a lower reduction of Cfree than the control. For 1% BC, PAHs losses was more effective, and sequestration processes played a less significant role than in the experiment with 5% dose of BC. The total and dissolved organic carbon, and ash were predominantly responsible for Ctot and Cfree losses, and additionally pH for Cfree. The results of the experiment indicate that BC performs a crucial role in composting, affecting the Ctot and Cfree PAHs in the compost but the final effect strictly depends on the BC dose.

Laccase immobilization and its degradation of emerging pollutants: A comprehensive review.

The chronic lack of effective disposal of pollutants has resulted in the detection of a wide variety of EPs in the environment, with concentrations high enough to affect ecological health. Laccase, as a versatile oxidase capable of catalyzing a wide range of substrates and without producing toxic by-products, is a potential candidate for the biodegradation of pollutants. Immobilization can provide favorable protection for free laccase, improve the stability of laccase in complex environments, and greatly enhance the reusability of laccase, which is significant in reducing the cost of industrial applications. This study introduces the properties of laccase and subsequently elaborate on the different support materials for laccase immobilization. The research advances in the degradation of EDs, PPCPs, and PAHs by immobilized laccase are then reviewed. This review provides a comprehensive understanding of laccase immobilization, as well as the advantages of various support materials, facilitating the development of more economical and efficient immobilization systems that can be put into practice to achieve the green degradation of EPs.

Cardiolipin Membranes Promote Cytochrome c Transformation of Polycyclic Aromatic Hydrocarbons and Their In Vivo Metabolites.

The catalytic properties of cytochrome c (Cc) have captured great interest in respect to mitochondrial physiology and apoptosis, and hold potential for novel enzymatic bioremediation systems. Nevertheless, its contribution to the metabolism of environmental toxicants remains unstudied. Human exposure to polycyclic aromatic hydrocarbons (PAHs) has been associated with impactful diseases, and animal models have unveiled concerning signs of PAHs' toxicity to mitochondria. In this work, a series of eight PAHs with ionization potentials between 7.2 and 8.1 eV were used to challenge the catalytic ability of Cc and to evaluate the effect of vesicles containing cardiolipin mimicking mitochondrial membranes activating the peroxidase activity of Cc. With moderate levels of H2O2 and at pH 7.0, Cc catalyzed the oxidation of toxic PAHs, such as benzo[a]pyrene, anthracene, and benzo[a]anthracene, and the cardiolipin-containing membranes clearly increased the PAH conversions. Our results also demonstrate for the first time that Cc and Cc-cardiolipin complexes efficiently transformed the PAH metabolites 2-hydroxynaphthalene and 1-hydroxypyrene. In comparison to horseradish peroxidase, Cc was shown to reach more potent oxidizing states and react with PAHs with ionization potentials up to 7.70 eV, including pyrene and acenaphthene. Spectral assays indicated that anthracene binds to Cc, and docking simulations proposed possible binding sites positioning anthracene for oxidation. The results give support to the participation of Cc in the metabolism of PAHs, especially in mitochondria, and encourage further investigation of the molecular interaction between PAHs and Cc.

Analysis and Formation of Polycyclic Aromatic Hydrocarbons in Canned Minced Chicken and Pork during Processing.

Polycyclic aromatic hydrocarbons (PAHs) represent important toxic compounds formed in meat products during processing. This study aims to analyze 22 PAHs by QuEChERS coupled with GC-MS/MS in canned minced chicken and pork during processing. After marinating raw minced chicken and pork separately with a standard flavoring formula used for canning meat in Taiwan, they were subjected to different processing conditions including stir-frying, degassing and sterilizing at 115 °C/60 min (low-temperature-long-time, LTLT) and 125 °C/25 min (high-temperature-short-time, HTST). The quantitation of PAHs in these meat products revealed the formation of only three PAHs including acenaphthylene (AcPy), acenaphthene (AcP) and pyrene (Pyr) in canned minced chicken and pork during processing with no significant difference in total PAHs between the meat types. Analysis of PAH precursors showed the presence of benzaldehyde at the highest level, followed by 2-cyclohexene-1-one and trans,trans-2,4-decadienal in canned minced chicken and pork, suggesting PAH formation through the reaction of benzaldehyde with linoleic acid degradation products and of 2-cyclohexene-1-one with C4 compounds through the Diels-Alder reaction, as well as the reaction of trans,trans-2,4-decadienal with 2-butene. Monounsaturated and polyunsaturated fatty acids were present in the largest proportion in LTLT-sterilized chicken/pork, followed by HTST-sterilized chicken/pork and raw chicken/pork, and their levels did not show a high impact on PAH formation, probably due to an insufficient heating temperature and length of time. A two-factorial analysis suggested that PAH formation was not significantly affected by the sterilization condition or meat type. Principal component analysis corroborated the observed results implying the formation of PAHs in canned minced chicken/pork under different processing conditions with an insignificant difference (p > 0.05) between them, with the individual PAH content following the order of Pyr > AcPy > AcP.

Molecular Interactions Governing the Rat Aryl Hydrocarbon Receptor Activities of Polycyclic Aromatic Compounds and Predictive Model Development.

Polycyclic aromatic compounds (PACs) exhibit rat aryl hydrocarbon receptor (rAhR) activities, leading to diverse biological or toxic effects. In this study, the key amino residues and molecular interactions that govern the rAhR activity of PACs were investigated using in silico strategies. The homology model of rAhR was first docked with 90 PACs to yield complexes, and the results of the molecular dynamics simulations of 16 typical complexes showed that the binding energies of the complexes range from -7.37 to -26.39 kcal/mol. The major contribution to the molecular interaction comes from van der Waals forces, and Pro295 and Arg316 become the key residues involved in most complexes. Two QSAR models were further developed to predict the rAhR activity of PACs (in terms of log IEQ for PACs without halogen substitutions and log%-TCDD-max for halogenated PACs). Both models have good predictive ability, robustness, and extrapolation ability. Molecular polarizability, electronegativity, size, and nucleophilicity are identified as the important factors affecting the rAhR activity of PACs. The developed models could be employed to predict the rAhR activity of other reactive PACs. This work provides insight into the mechanisms and interactions of the rAhR activity of PACs and assists in the assessment of their fate and risk in organisms.

Using bioactive compounds to mitigate the formation of typical chemical contaminants generated during the thermal processing of different food matrices.

With rising consumer awareness of health and wellness, the demand for enhanced food safety is rapidly increasing. The generation of chemical contaminants during the thermal processing of food materials, including polycyclic aromatic hydrocarbons, heterocyclic aromatic amines, and acrylamide happens every day in every kitchen all around the world. Unlike extraneous chemical contaminants (e.g., pesticides, herbicides, and chemical fertilizers), these endogenic chemical contaminants occur during the cooking process and cannot be removed before consumption. Therefore, much effort has been invested in searching for ways to reduce such thermally induced chemical contaminants. Recently, the addition of bioactive compounds has been found to be effective and promising. However, no systematic review of this practical science has been made yet. This review aims to summarize the latest applications of bioactive compounds for the control of chemical contaminants during food thermal processing. The underlying generation mechanisms and the toxic effects of these chemical contaminants are discussed in depth to reveal how and why they are suppressed by the addition of certain bioactive ingredients. Examples of specific bioactive compounds, such as phenolic compounds and organic acids, as well as their application scenarios, are outlined. In the end, outlooks and expectations for future development are provided based on a comprehensive summary and reflection of references.