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Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous in space and govern the interstellar chemistry. The two isomers of cyanonaphthalene (1-CNN and 2-CNN) were the first PAHs to be recently identified in the Taurus Molecular Cloud (TMC-1). Their large abundance is attributed to high photostability with nearly no photofragmentation at photon energies above the ionization potential. Here, we show that at ambient light and at densities akin to dense molecular clouds and the upper atmosphere of planets and moons, 1-CNN could undergo extensive fragmentation through a new mechanism leading to daughter cations. On UV photoexcitation, at a photon energy way below the ionization threshold, 1-CNN monomers form photoexcited dimer units. Intermolecular Coulombic decay between the two photoexcited units of the dimer leads to ionization, and the subsequent molecular rearrangements form new daughter cations. These daughter cations could react further, contributing to rich bottom-up astrochemistry, and could play a pivotal role in developmental astrobiology. Photofragmentation in atmospheric and astrophysical environments is hitherto known to be unimolecular, while the present results point a pathway involving bimolecular photofragmentation. [ABSTRACT FROM AUTHOR]

The recent discovery of cyano-substituted aromatic and two-ring polycyclic aromatic hydrocarbon molecules in Taurus Molecular Cloud-1 has prompted questions on how the electronic structure and excited-state dynamics of these molecules are linked with their existence and abundance. Here, we report a photodetachment and frequency- and angle-resolved photoelectron spectroscopy study of jet-cooled para-deprotonated benzonitrile (p-[Bzn-H]−). The adiabatic detachment energy was determined as 1.70 ± 0.01 eV, in good agreement with CCSD(T)/aug-cc-pVTZ calculations. The spectra across the first few electron-volts above threshold are dominated by prompt autodetachment processes associated with excitation of at least five short-lived (tens of femtoseconds) temporary anion shaped resonances since excitation cross sections are several orders of magnitude larger than direct photodetachment cross sections. The photoexcitation vibronic profile is dominated by a ≈640 cm−1 ring deformation mode. [Bzn-H]− lacks a valence-localized excited state situated below the detachment threshold and does not exhibit thermionic emission following excitation of the temporary anion resonances. Thus, [Bzn-H]− is unlikely to be stable in many interstellar environments. [ABSTRACT FROM AUTHOR]

Polycyclic aromatic hydrocarbons (PAHs) are widely recognized as catalysts for interstellar H2 formation. Extensive exploration into the catalytic potential of various PAHs has encompassed both theoretical investigations and experimental studies. In the present study, we focused on studying the reactivity of an imperfect aromatic molecule, indene (C9H8), and its hydrogenated counterpart, indane (C9H10), as potential catalysts for H2 formation within the interstellar medium. The reactions of these molecules with H atoms at 3.1 K were investigated experimentally using the para-H2 matrix isolation technique. Our experimental results demonstrate that both indene and indane are reactive toward H atoms. Indene can participate in H-atom-abstraction and H-atom-addition reactions, whereas indane primarily undergoes H-atom-abstraction reactions. The H-atom-abstraction reaction of indene results in the formation of the 1-indenyl radical (R1) (C9H7) and H2 molecule. Simultaneously, an H-atom-addition reaction forms the 1,2-dihydro-indene-3-yl radical (R2) (C9H9). Experiments also reveal that the H-atom-abstraction reaction of indane also produces the R2 radical. To the best of our knowledge, this study represents the first reporting of the infrared spectra of R1 and R2 radicals. The experimental results, combined with theoretical findings, suggest that indane and indene may play a role in the catalytic formation of interstellar H2. Furthermore, these results imply a quasi-equilibrium between the investigated molecules and the formed radicals via H-atom-addition and H-atom-abstraction reactions. [ABSTRACT FROM AUTHOR]

Understanding core level shifts in aromatic compounds is crucial for the correct interpretation of x-ray photoelectron spectroscopy (XPS) of polycyclic aromatic hydrocarbons (PAHs), including acenes, as well as of styrenic polymers, which are increasingly relevant for the microelectronic industry, among other applications. The effect of delocalization through π aromatic systems on the stabilization of valence molecular orbitals has been widely investigated in the past. However, little has been reported on the impact on the deeper C1s core energy levels. In this work, we use first-principles calculations at the level of many body perturbation theory to compute the C1s binding energies of several aromatic systems. We report a C1s red shift in PAHs and acenes of increasing size, both in the gas phase and in the molecular crystal. C1s red shifts are also calculated for stacked benzene and naphthalene pairs at decreasing intermolecular distances. A C1s red shift is in addition found between oligomers of poly(p-hydroxystyrene) and polystyrene of increasing length, which we attribute to ring–ring interactions between the side-chains. The predicted shifts are larger than common instrumental errors and could, therefore, be detected in XPS experiments. [ABSTRACT FROM AUTHOR]

The CH stretch overtone region (5750–6300 cm−1) of benzene and naphthalene is assigned herein using anharmonic quantum chemical computations, and the trend of how this extends to larger polycyclic aromatic hydrocarbons (PAHs) is established. The assignment of all experimental bands to specific vibrational states is performed for the first time. Resonance polyads and the inclusion of 3-quanta vibrational states are both needed to compute accurate vibrational frequencies with the proper density-of-states to match the experimental band shape. Hundreds of 3-quanta states produce the observed band structure in naphthalene, anthracene, and tetracene, and this number is expected to increase drastically for larger PAHs. The width and shape of the main peak are consistent from naphthalene to anthracene, necessitating further exploration of this trend to confirm whether it is representative of all PAHs in the CH stretch overtone region. Understanding observations of PAH sources in the 1–3 μm region from the NIRSpec instrument aboard JWST requires new computational data, and this study provides a benchmark and foundation for their computation. [ABSTRACT FROM AUTHOR]

Polycyclic aromatic hydrocarbons (PAHs) are widely recognized as catalysts for interstellar H2 formation. Extensive exploration into the catalytic potential of various PAHs has encompassed both theoretical investigations and experimental studies. In the present study, we focused on studying the reactivity of an imperfect aromatic molecule, indene (C9H8), and its hydrogenated counterpart, indane (C9H10), as potential catalysts for H2 formation within the interstellar medium. The reactions of these molecules with H atoms at 3.1 K were investigated experimentally using the para-H2 matrix isolation technique. Our experimental results demonstrate that both indene and indane are reactive toward H atoms. Indene can participate in H-atom-abstraction and H-atom-addition reactions, whereas indane primarily undergoes H-atom-abstraction reactions. The H-atom-abstraction reaction of indene results in the formation of the 1-indenyl radical (R1) (C9H7) and H2 molecule. Simultaneously, an H-atom-addition reaction forms the 1,2-dihydro-indene-3-yl radical (R2) (C9H9). Experiments also reveal that the H-atom-abstraction reaction of indane also produces the R2 radical. To the best of our knowledge, this study represents the first reporting of the infrared spectra of R1 and R2 radicals. The experimental results, combined with theoretical findings, suggest that indane and indene may play a role in the catalytic formation of interstellar H2. Furthermore, these results imply a quasi-equilibrium between the investigated molecules and the formed radicals via H-atom-addition and H-atom-abstraction reactions. [ABSTRACT FROM AUTHOR]

Polycyclic aromatic hydrocarbons (PAHs) are common atmospheric pollutants, and they are also ubiquitous in the interstellar medium. Here, we report the study of a complex O-containing PAH anion, the deprotonated 2-hydroxytriphenylene (2-OtPh–), using high-resolution photoelectron imaging and photodetachment spectroscopy of cryogenically cooled anions. Vibrationally resolved photoelectron spectra yield the electron affinity of the 2-OtPh radical as 2.629(1) eV and several vibrational frequencies for its ground electronic state. Photodetachment spectroscopy reveals bound valence excited electronic states for the 2-OtPh– anion, with unprecedentedly rich vibronic features. Evidence is presented for a low-lying triplet state (T1) and two singlet states (S1 and S2) below the detachment threshold. Single-color resonant two-photon photoelectron spectroscopy uncovers rich photophysics for the 2-OtPh– anion, including vibrational relaxation in S1, internal conversion to the ground state of 2-OtPh–, intersystem crossing from S2 to T1, and a long-lived autodetaching shape resonance about 1.3 eV above the detachment threshold. The rich electronic structure and photophysics afforded by the current study suggest that 2-OtPh– would be an interesting system for pump–probe experiments to unravel the dynamics of the excited states of this complex PAH anion. [ABSTRACT FROM AUTHOR]

Photoinduced symmetry-breaking charge separation (SB-CS) has been extensively observed in various oligomers and aggregates, which holds great potential for robust artificial solar energy conversion systems. It attaches great importance to the precise manipulation of interchromophore electronic coupling in realizing efficient SB-CS. The emerging studies on SB-CS suggested that it could be realized in null-excitonic aggregates, and a long-lived SB-CS state was observed, which offers an advanced platform and has gathered immense attention in the SB-CS field. Here, we unveiled the null-exciton coupling induced ultrafast SB-CS in a rigid polycyclic aromatic hydrocarbon framework, triperyleno[3,3,3]propellane triimides (TPPTI), in which three chromophores were attached through a nonconjugated bridge. Through a combination of theoretical calculations and steady-state absorption results, we demonstrated that this nonconjugated TPPTI possesses negligible exciton coupling. Increased solvent polarity was found to significantly enhance state mixing between local excited and charge transfer states. Using transient absorption spectroscopy, ultrafast SB-CS was observed in highly polar dimethylformamide, facilitated by a selective hole-transfer coupling and a favorable charge separation free energy (ΔGCS). Additionally, the rate ratio between SB-CS and charge recombination was at least high to 1800 in dimethylformamide. This investigation provides profound insights into the role of null-exciton coupling in dominating ultrafast SB-CS in multichromophoric systems. [ABSTRACT FROM AUTHOR]

Resonant electron capture by aza and diaza derivatives of phenanthrene (7,8-benzoquinoline and 1,10-phenanthroline) and anthracene (acridine and phenazine) at incident free electron energies (Ee) in the range of 0–15 eV was studied. All compounds except 7,8-benzoquinoline form long-lived molecular ions (M−) at thermal electron energies (Ee ∼ 0 eV). Acridine and phenazine also form such ions at epithermal electron energies up to Ee = 1.5–2.5 eV. The lifetimes (τa) of M− with respect to electron autodetachment are proportional to the extent of aza-substitution and increase on going from molecules with bent geometry of the fused rings (azaphenanthrenes) to linear isomers (azaanthracenes). These regularities are due to an increase in the adiabatic electron affinities (EAa) of the molecules. The EAa values of the molecules under study were comprehensively assessed based on a comparative analysis of the measured τa values using the Rice–Ramsperger–Kassel–Marcus theory, the electronic structure analysis using the molecular orbital approach, as well as the density functional calculations of the total energy differences between the molecules and anions. The only fragmentation channel of M− ions from the compounds studied is abstraction of hydrogen atoms. When studying [M–H]− ions, electron autodetachment processes were observed, the τa values were measured, and the appearance energies were determined. A comparative analysis of the gas-phase acidity of the molecules and the EAa values of the [M–H]· radicals revealed their proportionality to the EAa values of the parent molecules. [ABSTRACT FROM AUTHOR]

Environmentally persistent free radicals (EPFRs) play an important role in aerosol effects on air quality and public health, but their atmospheric abundance and sources are poorly understood. We measured EPFRs contained in PM2.5 collected in Fairbanks, Alaska, in winter 2022. We find that EPFR concentrations were enhanced during surface-based inversion and correlate strongly with incomplete combustion markers, including carbon monoxide and elemental carbon (R2 > 0.75). EPFRs exhibit moderately good correlations with PAHs, biomass burning organic aerosols, and potassium (R2 > 0.4). We also observe strong correlations of EPFRs with hydrocarbon-like organic aerosols, Fe and Ti (R2 > 0.6), and single-particle mass spectrometry measurements reveal internal mixing of PAHs, with potassium and iron. These results suggest that residential wood burning and vehicle tailpipes are major sources of EPFRs and nontailpipe emissions, such as brake wear and road dust, may contribute to the stabilization of EPFRs. Exposure to the observed EPFR concentrations (18 ± 12 pmol m-3) would be equivalent to smoking ∼0.4-1 cigarette daily. Very strong correlations (R2 > 0.8) of EPFR with hydroxyl radical formation in surrogate lung fluid indicate that exposure to EPFRs may induce oxidative stress in the human respiratory tract.

BACKGROUND: Polycyclic aromatic hydrocarbons (PAHs) have been linked to adverse birth outcomes that have been reported to be induced by oxidative stress, but few epidemiological studies to date have evaluated associations between urinary PAH metabolites and oxidative stress biomarkers in pregnancy and identified critical periods for these outcomes and PAH exposures in pregnancy. METHODS: A cohort of pregnant women was recruited early in pregnancy from antenatal clinics at the University of California Los Angeles during 2016-2019. We collected urine samples up to three times during pregnancy in a total of 159 women enrolled in the cohort. A total of 7 PAH metabolites and 2 oxidative stress biomarkers [malondialdehyde (MDA), 8-hydroxy-2-deoxyguanosine (8-OHdG)] were measured in all available urine samples. Using multiple linear regression models, we estimated the percentage change (%) and 95% confidence interval (CI) in 8-OHdG and MDA measured at each sample collection time per doubling of PAH metabolite concentrations. Furthermore, we used linear mixed models with a random intercept for participant to estimate the associations between PAH metabolite and oxidative stress biomarker concentrations across multiple time points in pregnancy. RESULTS: Most PAH metabolites were positively associated with both urinary oxidative stress biomarkers, MDA and 8-OHdG, with stronger associations in early and late pregnancy. A doubling of each urinary PAH metabolite concentration increased MDA concentrations by 5.8-41.1% and 8-OHdG concentrations by 13.8-49.7%. Linear mixed model results were consistent with those from linear regression models for each gestational sampling period. CONCLUSION: Urinary PAH metabolites are associated with increases in oxidative stress biomarkers during pregnancy, especially in early and late pregnancy.

Topological phases in laterally confined low-dimensional nanographenes have emerged as versatile design tools that can imbue otherwise unremarkable materials with exotic band structures ranging from topological semiconductors and quantum dots to intrinsically metallic bands. The periodic boundary conditions that define the topology of a given lattice have thus far prevented the translation of this technology to the quasi-zero-dimensional (0D) domain of small molecular structures. Here, we describe the synthesis of a polycyclic aromatic hydrocarbon (PAH) featuring two localized zero modes (ZMs) formed by the topological junction interface between a trivial and nontrivial phase within a single molecule. First-principles density functional theory calculations predict a strong hybridization between adjacent ZMs that gives rise to an exceptionally small HOMO-LUMO gap. Scanning tunneling microscopy and spectroscopy corroborate the molecular structure of 9/7/9-double quantum dots and reveal an experimental quasiparticle gap of 0.16 eV, corresponding to a carbon-based small molecule long-wavelength infrared (LWIR) absorber.

Background and aimStudies suggest prenatal exposure to polycyclic aromatic hydrocarbons (PAHs) may influence wheezing or asthma in preschool-aged children. However, the impact of prenatal PAH exposure on asthma and wheeze in middle childhood remain unclear. We investigated these associations in socio-demographically diverse participants from the ECHO PATHWAYS multi-cohort consortium.MethodsWe included 1,081 birth parent-child dyads across five U.S. cities. Maternal urinary mono-hydroxylated PAH metabolite concentrations (OH-PAH) were measured during mid-pregnancy. Asthma at age 8-9 years and wheezing trajectory across childhood were characterized by caregiver reported asthma diagnosis and asthma/wheeze symptoms. We used logistic and multinomial regression to estimate odds ratios of asthma and childhood wheezing trajectories associated with five individual OH-PAHs, adjusting for urine specific gravity, various maternal and child characteristics, study site, prenatal and postnatal smoke exposure, and birth year and season in single metabolite and mutually adjusted models. We used multiplicative interaction terms to evaluate effect modification by child sex and explored OH-PAH mixture effects through Weighted Quantile Sum regression.ResultsThe prevalence of asthma in the study population was 10%. We found limited evidence of adverse associations between pregnancy OH-PAH concentrations and asthma or wheezing trajectories. We observed adverse associations between 1/9-hydroxyphenanthrene and asthma and persistent wheeze among girls, and evidence of inverse associations with asthma for 1-hydroxynathpthalene, which was stronger among boys, though tests for effect modification by child sex were not statistically significant.ConclusionsIn a large, multi-site cohort, we did not find strong evidence of an association between prenatal exposure to PAHs and child asthma at age 8-9 years, though some adverse associations were observed among girls.

The computation of the nuclear quantum dynamics of molecules is challenging, requiring both accuracy and efficiency to be applicable to systems of interest. Recently, theories have been developed for employing time-dependent basis functions (denoted modals) with vibrational coupled cluster theory (TDMVCC). The TDMVCC method was introduced along with a pilot implementation, which illustrated good accuracy in benchmark computations. In this paper, we report an efficient implementation of TDMVCC, covering the case where the wave function and Hamiltonian contain up to two-mode couplings. After a careful regrouping of terms, the wave function can be propagated with a cubic computational scaling with respect to the number of degrees of freedom. We discuss the use of a restricted set of active one-mode basis functions for each mode, as well as two interesting limits: (i) the use of a full active basis where the variational modal determination amounts essentially to the variational determination of a time-dependent reference state for the cluster expansion; and (ii) the use of a single function as an active basis for some degrees of freedom. The latter case defines a hybrid TDMVCC/TDH (time-dependent Hartree) approach that can obtain even lower computational scaling. The resulting computational scaling for hybrid and full TDMVCC[2] is illustrated for polyaromatic hydrocarbons with up to 264 modes. Finally, computations on the internal vibrational redistribution of benzoic acid (39 modes) are used to show the faster convergence of TDMVCC/TDH hybrid computations towards TDMVCC compared to simple neglect of some degrees of freedom. [ABSTRACT FROM AUTHOR]

Wildfires affect soils in multiple ways, leading to numerous challenges for colonizing microorganisms. Although it is thought that fire-adapted microorganisms lie at the forefront of postfire ecosystem recovery, the specific strategies that these organisms use to thrive in burned soils remain largely unknown. Through bioactivity screening of bacterial isolates from burned soils, we discovered that several Paraburkholderia spp. isolates produced a set of unusual rhamnolipid surfactants with a natural methyl ester modification. These rhamnolipid methyl esters (RLMEs) exhibited enhanced antimicrobial activity against other postfire microbial isolates, including pyrophilous Pyronema fungi and Amycolatopsis bacteria, compared to the typical rhamnolipids made by organisms such as Pseudomonas spp. RLMEs also showed enhanced surfactant properties and facilitated bacterial motility on agar surfaces. In vitro assays further demonstrated that RLMEs improved aqueous solubilization of polycyclic aromatic hydrocarbons, which are potential carbon sources found in char. Identification of the rhamnolipid biosynthesis genes in the postfire isolate, Paraburkholderia kirstenboschensis str. F3, led to the discovery of rhlM, whose gene product is responsible for the unique methylation of rhamnolipid substrates. RhlM is the first characterized bacterial representative of a large class of integral membrane methyltransferases that are widespread in bacteria. These results indicate multiple roles for RLMEs in the postfire lifestyle of Paraburkholderia isolates, including enhanced dispersal, solubilization of potential nutrients, and inhibition of competitors. Our findings shed new light on the chemical adaptations that bacteria employ to navigate, grow, and outcompete other soil community members in postfire environments.

OBJECTIVE: Prenatal exposure to polycyclic aromatic hydrocarbons (PAHs) is associated with adverse birth and developmental outcomes in children. We aimed to describe prenatal PAH exposures in a large, multisite U.S. consortium. METHODS: We measured 12 mono-hydroxylated metabolites (OH-PAHs) of 7 PAHs (naphthalene, fluorene, phenanthrene, pyrene, benzo(c)phenanthrene, chrysene, benz(a)anthracene) in mid-pregnancy urine of 1,892 pregnant individuals from the ECHO PATHWAYS consortium cohorts: CANDLE (n = 988; Memphis), TIDES (n = 664; Minneapolis, Rochester, San Francisco, Seattle) and GAPPS (n = 240; Seattle and Yakima, WA). We described concentrations of 8 OH-PAHs of non-smoking participants (n = 1,695) by site, socioeconomic characteristics, and pregnancy stage (we report intraclass correlation coefficients (ICC) for n = 677 TIDES participants). RESULTS: Exposure to the selected PAHs was ubiquitous at all sites. 2-hydroxynaphthalene had the highest average concentrations at all sites. CANDLE had the highest average concentrations of most metabolites. Among non-smoking participants, we observed some patterns by income, education, and race but these were not consistent and varied by site and metabolite. ICCs of repeated OH-PAH measures from TIDES participants were ≤ 0.51. CONCLUSION: In this geographically-diverse descriptive analysis of U.S. pregnancies, we observed ubiquitous exposure to low molecular weight PAHs, highlighting the importance of better understanding PAH sources and their pediatric health outcomes attributed to early life PAH exposure.

This work proposed an easy-to-perform but effective strategy to eliminate the ACQ effect of PAHs for ECL enhancement by coordinatively grafting PAH-derived ligands onto ultrathin MOLs, which opened a new horizon to develop high-efficiency Ru-complex-free porous ECL materials for fabricating supersensitive ECL sensing platforms. [Display omitted] • A novel ECL emitter was prepared by coordinatively grafting a new ECL luminophore PyTS on ultrathin MOL. • This work proposed a new and facile strategy to surmount the ACQ effect of PAHs. • This strategy provided significant inspiration for designing high-efficiency Ru-complex-free ECL materials. • The fabricated ECL biosensor accomplished the supersensitive detection of miRNA-21. The exploration of novel electrochemiluminescence (ECL) luminophores with excellent ECL properties is a current research hotspot in the ECL field. Herein, a novel high-efficiency Ru-complex-free ECL emitter PyTS-Zr-BTB-MOL has been prepared by using porous ultrathin Zr-BTB metal–organic layer (MOL) as carrier to coordinatively graft the cheap and easily available polycyclic aromatic hydrocarbon (PAH) derivative luminophore PyTS whose ECL performance has never been investigated. Gratifyingly, the ECL intensity and efficiency of PyTS-Zr-BTB-MOL were markedly enhanced compared to both PyTS monomers and PyTS aggregates. The main reason was that the distance between pyrene rings was greatly expanded after the PyTS grafting on the Zr 6 clusters of Zr-BTB-MOL, which overcame the aggregation-caused quenching (ACQ) effect of PyTS and thus enhanced the ECL emission. Meanwhile, the porous nanosheet structure of PyTS-Zr-BTB-MOL could distinctly increase the exposure of PyTS luminophores and shorten the diffusion paths of coreactants and electrons/ions, which effectively promoted the electrochemical excitation of more PyTS luminophores and thus achieved a further ECL enhancement. In light of the remarkable ECL property of PyTS-Zr-BTB-MOL, it was employed as an ECL indicator to build a novel high-sensitivity ECL biosensor for microRNA-21 determination, possessing a satisfactory response range (100 aM to 100 pM) and an ultralow detection limit (10.4 aM). Overall, this work demonstrated that using MOLs to coordinatively graft the PAH derivative luminophores to eliminate the ACQ effect and increase the utilization rate of the luminophores is a promising and efficient strategy to develop high-performance Ru-complex-free ECL materials for assembling ultrasensitive ECL biosensing platforms. [ABSTRACT FROM AUTHOR]

Intermolecular interactions with polycyclic aromatic hydrocarbons (PAHs) represent an important area of physisorption studies. These investigations are often hampered by a size of interacting PAHs, which makes the calculation prohibitively expensive. Therefore, methods designed to deal with large molecules could be helpful to reduce the computational costs of such studies. Recently we have introduced a new systematic approach for the molecular fragmentation of PAHs, denoted as AROFRAG, which decomposes a large PAH molecule into a set of predefined small PAHs with a benzene ring being the smallest unbreakable unit, and which in conjunction with the Molecules‐in‐Molecules (MIM) approach provides an accurate description of total molecular energies. In this contribution we propose an extension of the AROFRAG, which provides a description of intermolecular interactions for complexes composed of PAH molecules. The examination of interaction energy partitioning for various test cases shows that the AROFRAG3 model connected with the MIM approach accurately reproduces all important components of the interaction energy. An additional important finding in our study is that the computationally expensive long‐range electron‐correlation part of the interaction energy, that is, the dispersion component, is well described at lower AROFRAG levels even without MIM, which makes the latter models interesting alternatives to existing methods for an accurate description of the electron‐correlated part of the interaction energy. [ABSTRACT FROM AUTHOR]

Polycyclic aromatic hydrocarbons (PAHs) are a class of organic compounds frequently detected in the environment with widely varying toxicities. Many PAHs activate the aryl hydrocarbon receptor (AHR), inducing the expression of a battery of genes, including xenobiotic metabolizing enzymes like cytochrome P450s (CYPs); however, not all PAHs act via this mechanism. We screened several parent and substituted PAHs in in vitro AHR activation assays to classify their unique activity. Retene (1-methyl-7-isopropylphenanthrene) displays Ahr2-dependent teratogenicity in zebrafish, but did not activate human AHR or zebrafish Ahr2, suggesting a retene metabolite activates Ahr2 in zebrafish to induce developmental toxicity. To investigate the role of metabolism in retene toxicity, studies were performed to determine the functional role of cyp1a , cyp1b1 , and the microbiome in retene toxicity, identify the zebrafish window of susceptibility, and measure retene uptake, loss, and metabolite formation in vivo. Cyp1a-null fish were generated using CRISPR-Cas9. Cyp1a-null fish showed increased sensitivity to retene toxicity, whereas Cyp1b1-null fish were less susceptible, and microbiome elimination had no significant effect. Zebrafish required exposure to retene between 24 and 48 hours post fertilization (hpf) to exhibit toxicity. After static exposure, retene concentrations in zebrafish embryos increased until 24 hpf, peaked between 24 and 36 hpf, and decreased rapidly thereafter. We detected retene metabolites at 36 and 48 hpf, indicating metabolic onset preceding toxicity. This study highlights the value of combining molecular and systems biology approaches with mechanistic and predictive toxicology to interrogate the role of biotransformation in AHR-dependent toxicity. [ABSTRACT FROM AUTHOR]

Introduction: Heavy metals (HM) and polycyclic aromatic hydrocarbons (PAHs) exposition has been associated with health problems. Therefore, this research evaluated genotoxicity induced in male mice strain CD-1 exposed to benzo[a]anthracene (B[a]A) and benzo[a]pyrene (B[a]P) and their interaction with Fe, Pb, and Al. Methods: Groups of animals were exposed intraperitoneally to HM, PAHs, and mixtures of both. Peripheral blood samples were taken from 0 to 96 h at 24 h intervals; genotoxicity was determined by micronucleus tests and comet assay. Additionally, toxicity and viability were evaluated. Results: HM and PAHs individually were genotoxic. About toxicity, only Al altered polychromatic erythrocytes number and did not change leukocytes viability. Concerning mixtures, Fe + B[a]P, Fe + B[a]A, Pb + B[a]P increased genotoxicity. There were no changes with Pb + B[a]A. Finally, Al mixtures with both PAHs damage was decreased. Conclusions: Exposure to HM and PAH caused genetic damage. Fe, Al, and B[a]A, established a genotoxic potential. Every metal can interact with PAHs in different ways. Also, the micronucleus test and the comet assay demonstrated their high capacity and reliability to determine the genotoxic potential of the compounds evaluated in this work. [ABSTRACT FROM AUTHOR]

In this study, pollution level, distribution, toxicity, molecular composition, probable sources as well as health risks of polycyclic aromatic hydrocarbons (PAHs) in urban and industrial soils of Kerman metropolis were investigated. Kerman is a fast-growing city and a fine example of an arid city in a developing country. For this purpose, concentrations of 16 individual PAHs in 30 samples taken from the city soils and its industrial zones were determined by gas chromatography/mass spectrometry. The ∑PAHs concentration in urban soil samples varied from 26.1 to 902.8 μg/kg, with the mean and median of 302.6 and 148.4 µg/kg, respectively. In comparison, ∑PAHs in industrial soils ranged from 26.8to 251.9 μg/kg, with the mean and median values of 65.9 and 42.9 µg/kg, respectively. Four-ring PAHs comprise the dominant compounds in urban soils, whereas, two- and three-ring PAHs proved to be the most abundant compounds in industrial soils. Source apportionment was conducted using ring classification, diagnostic ratios, PCA, and multilinear regression (MLR). Also, human health risk assessment was undertaken through employing US EPA standard statistical models. This survey revealed that PAH pollution in urban soils originates mainly from fossil fuel combustion and in industrial soils from petrogenic sources. On the whole, in the Kerman environment, the shares of petroleum combustion, natural gas combustion, and petrogenic sources were 45.32%, 34%, and 20.68% respectively. Based on this study, the ecological risk of PAHs was low-to-moderate, and incremental lifetime cancer risk for children and adults were 1.35 × 10−4 and 1.04 × 10−4 respectively, indicating rather high risks. [ABSTRACT FROM AUTHOR]

Benzo[a]pyrene (BaP), a polycyclic aromatic hydrocarbon, is known to cause teratogenesis. Environmental exposure of BaP has led to wide public concerns due to their potential risk of reproductive toxicity. However, the exact mechanism is still not clear. We aimed to explore the alterations of oxidative stress and DNA hydroxymethylation during BaP‐impaired reproductive function. BALB/c mice were intragastrically administered with different doses of BaP (0.01, 0.1, and 1 mg/kg/day, once a day), while control mice were administered with corn coil. Then, the reproductive function, alterations of oxidative stress, DNA methylation, and DNA hydroxymethylation of testis tissues were evaluated. We found that BaP caused obvious histopathological damages of testis tissues. As for sperm parameters after BaP administration, testis weight and the rate of teratosperm were increased, as well as sperm count and motility were decreased. In mechanism, BaP upregulated HO‐1 and MDA levels and downregulated SOD and CAT activity and GSH content in testis tissues, indicating that oxidative stress was induced by BaP. Furthermore, a significant induction of hydroxymethylation and inhibition of methylation were observed in testis tissues after BaP exposure. Collectively, BaP‐induced oxidative stress and hydroxymethylation were involved in impairing reproductive function, which may be the mechanism of the male infertility. [ABSTRACT FROM AUTHOR]

This study investigated biosurfactant production by the bacterial strain of P. aeruginosa gi |KP 163922| for a free and immobilized cells system using waste engine oil (WEO) as a substrate. The polyurethane foam (PUF) cubes (1 cm × 1 cm × 1 cm) were used as carriers for the immobilization. The batch experiments were performed in Erlenmeyer flasks and monitored at every 24‐h interval for both cell systems. The microbial population was counted using the plate count method, and the hydrocarbon degradation percentage was calculated to evaluate the bacterial activity. Surface tension was measured at regular intervals to ensure the presence of biosurfactants. The maximum reduction was 37 and 35 mN/m in a free and immobilized cells system. Immobilization of cells using PUF was found to be efficient in supporting bacterial growth, and after 48 h of incubation, the growth was 2.5 (±0.58) × 1011 CFU/mL. The chemical characterization using Fourier transform infrared (FTIR) spectroscopy confirmed the obtained product as rhamnolipid. Crude biosurfactant yield was found to be maximum in the case of the immobilized system, which was approximately 18 g/L. Scanning electron micrographs (SEM) of the used PUF cubes showed the strong adherence of biofilm to the cube surface and the potential of its reuse in multiple cycles. Gas chromatography–mass spectrometry (GC–MS) analysis confirms that the immobilized strain of P. aeruginosa exhibited superior biodegradation capabilities compared to free cells. Specifically, it was capable of reducing the concentration of polyaromatic hydrocarbons and converting more significant aliphatic compounds into metabolic byproducts such as alkanes, alkenes, cycloalkanes, and carbonyl groups. [ABSTRACT FROM AUTHOR]

In this research, for the first time, 16 polycyclic aromatic hydrocarbons (PAHs) in 33 types of honey samples have been analyzed using an efficient, sensitive and rapid high-density solvent-microextraction (HDS-ME) technique coupled to gas chromatography-mass spectrometry (GC-MS). Important parameters in the extraction process were optimized using central composite design (CCD). Good linear relationships were chosen for 16 PAHs in the range of 1–200 ng g−1, with a correlation coefficient (R2) higher than 0.94. The limits of detection and limits of quantification were 0.3–0.8 ng g−1 and 0.9–2.4 ng g−1, respectively. The relative standard deviations for six similar analyses at the optimized point were less than 9%. The recoveries of the proposed method were obtained between 86% and 102%. High recovery, low consumption of the solvent, speed, ease of use and good elimination of matrix interference compared to other methods are the advantages of the proposed method. The performance of the present work was confirmed by the standard addition method and satisfactory results were obtained. The concentrations of PAHs in honey samples were found lower than 11 ng g−1. [ABSTRACT FROM AUTHOR]

Understanding the health risks of polycyclic aromatic hydrocarbons (PAHs) in dust from city parks and prioritizing sources for control are essential for public health and pollution management. The combination of Source-specific and Monte Carlo not only reduces management costs, but also improves the accuracy of assessments. To evaluate the sources of PAHs in urban park dust and the possible health risks caused by different sources, dust samples from 13 popular parks in Kaifeng City were analyzed for PAHs using gas chromatograph-mass spectrometer (GC-MS). The results showed that the surface dust PAH content in the study area ranged from 332.34 µg·kg−1 to 7823.03 µg·kg−1, with a mean value of 1756.59 µg·kg−1. Nemerow Composite Pollution Index in the study area ranged from 0.32 to 14.41, with a mean of 2.24, indicating that the overall pollution warrants attention. Four pollution sources were identified using the positive matrix factorization (PMF) model: transportation source, transportation-coal and biomass combustion source, coke oven emission source, and petroleum source, with contributions of 33.74%, 25.59%, 22.14%, and 18.54%, respectively. The Monte Carlo cancer risk simulation results indicated that park dust PAHs pose a potential cancer risk to all three populations (children, adult male and adult female). Additionally, the cancer risk for children was generally higher than that for adult males and females, with transportation sources being the main contributor to the carcinogenic risk. Lastly, sensitivity analyses results showed that the toxic equivalent concentration (CS) is the parameter contributing the most to carcinogenic risk, followed by Exposure duration (ED). [ABSTRACT FROM AUTHOR]

[Display omitted] Exposure to polycyclic aromatic hydrocarbons (PAHs) in the Chinese population was among the highest globally and associated with various adverse effects. This study examines the impact of China's two-phase clean air initiatives, namely the Air Pollution Prevention and Control Action Plan (APPCAP) in 2013–2017 and the Blue-Sky Defense War (BSDW) in 2018–2020, on PAH levels and human exposures in Beijing. To evaluate the effects of APPCAP, we measured 16 PAHs in 287 PM 2.5 samples collected in Beijing and 9 PAH metabolites in 358 urine samples obtained from 54 individuals who traveled from Los Angeles to Beijing between 2014 and 2018. The concentration of PM 2.5 -bound benzo[a]pyrene equivalents (BaPeq) decreased by 88.5% in 2014–2018 due to reduced traffic, coal, and biomass emissions. PAH metabolite concentrations in travelers' urine decreased by 52.3% in Beijing, correlated with changes in PM 2.5 and NO 2 levels. In contrast, no significant changes were observed in Los Angeles. To evaluate BSDW's effects, we collected 123 additional PM 2.5 samples for PAH measurements in 2019–2021. We observed sustained reductions in BaPeq concentrations attributable to reductions in coal and biomass emissions during the BSDW phase, but those from traffic sources remained unchanged. After accounting for meteorological factors, China's two-phase clean air initiatives jointly reduced Beijing's PM 2.5 -bound BaPeq concentrations by 96.6% from 2014 to 2021. These findings provide compelling evidence for the effectiveness of China's clean air actions in mitigating population exposure to PAHs in Beijing. [ABSTRACT FROM AUTHOR]

Hydrogen has a strong effect on the tendency of fuels to produce soot. The aim of this study is to investigate the effect of hydrogen addition on the formation of soot and its structural evolution in ethylene/oxygen inverse diffusion flames. Laser spectroscopy was used to measure the spatial distribution of soot and Raman spectroscopy was utilized to characterize the nanostructure of soot. Additionally, the influence of hydrogen addition on the soot formation pathway was analyzed using ReaxFF molecular dynamics simulations. The results indicate that increasing hydrogen addition (α) progressively delays soot formation and narrows the flame radius. At 40% hydrogen, soot peak reduction was approximately 64.7%. Raman spectra revealed an increase in both graphite particle size and amorphous carbon content during soot growth. During the evolution of soot nanostructures, the initial particles dominated by sp carbon chains are gradually reorganized to form sp2 aromatic carbon structure, which is consistent with the simultaneous increase of soot concentration and graphite crystal size. It is worth noting that the crystal size of these graphite structure particles is concentrated in the range of 1.6–2.3 nm, indicating that they are in the transition stage from amorphous to microcrystalline. However, at the flame's end, both particle size and amorphous carbon content decreased simultaneously, attributable to oxidation by OH radicals. The study confirms the influence of soot formation and oxidation processes on nanostructures within flames. Raman spectroscopy also indicated a nonlinear change in soot oxidation reactivity along the axial direction of the flame, initially governed by gradual graphitization as flame temperature rises. Molecular dynamics simulations elucidated the nucleation and growth mechanisms of initial soot from polycyclic aromatic hydrocarbons (PAHs). These simulation results show that the increase of hydrogen content in the gas phase reduces the aggregation ability of polycyclic aromatic hydrocarbons and delays the formation of initial soot particles (C41+). With the growth of soot, its morphology gradually evolved from the initial dense, curved, and rotating spindle to a planar structure. The main chemotactic effect of this hydrogen participation is to hinder the dehydrogenation reaction of unsaturated hydrocarbons (H + C m H n → C m H n-1 + H 2), thereby inhibiting the formation of soot precursors, resulting in a decrease in the overall soot concentration. • The microstructure changes of soot in different regions of flame were obtained. • The effect of increasing hydrogen concentration on initial soot generation was obtained. • The effect of hydrogen doping on the morphology change and reaction path of soot formation was obtained. • The main factors affecting soot formation by hydrogen mixing were obtained. [ABSTRACT FROM AUTHOR]

AbstractDifferent coal seams go through distinct biological, physical, and chemical processes. Polycyclic aromatic compounds (PACs) in coal may retain information about these processes, especially in low-rank bituminous coals. Three coal seams with different sulfur contents from the Ningwu Coalfield were studied to understand the relation of different sulfur contents with PAC formation in low-rank bituminous coals. Coal samples were extracted by solvent and separated using liquid chromatography. The collected aromatic hydrocarbon fractions were analyzed by gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). A total of 27 sulfur-containing PACs (SPACs) were identified in the high-sulfur samples, whereas only 8 SPACs were found in the low-sulfur coal and middle-sulfur coal. The total SPACs to total PACs ratios (T-SPACs/T-PACs) are 1.15%, 2.17%, and 10.65% in the low-sulfur, middle-sulfur, and high-sulfur coal, respectively. The variations of SPAC species and their content ratios indicate that SPAC formation is controlled by the sulfur contents in the low-rank bituminous coals. A total of 18 oxygen-containing PACs (OPACs) were identified in the low-sulfur coal and middle-sulfur coal, whereas only 11 OPACs were found in the high-sulfur samples. The average ratios of OPACs to the identified aromatic compounds (T-OPACs/T-PACs) are 9.81%, 9.62%, and 6.91% in the low-, middle-, and high-sulfur coals, exhibiting a negative correlation with sulfur contents and indicating that OPACs were also influenced by sulfur contents in low-rank bituminous coals. The ratios of total contents of polycyclic aromatic hydrocarbons (PAHs) to total PACs (T-PAHs/T-PACs) are 89.1%, 88.2%, and 82.0% in the low-, middle-, and high-sulfur coals, respectively, indicating a decreasing trend from low- and middle-sulfur coal to high-sulfur coal. This variation could be caused by the reaction of PAHs and sulfur to form SPACs. [ABSTRACT FROM AUTHOR]

Hole‐transporting materials (HTMs) are essential for optoelectronic devices, such as organic light‐emitting diodes (OLEDs), dye‐sensitized solar cells, and perovskite solar cells. Triarylamines have been employed as HTMs since they were introduced in 1987. However, heteroatoms or side chains embedded in the core skeleton of triarylamines can cause thermal and chemical stability problems. Herein, we report that hexabenzo[a,c,fg,j,l,op]tetracene (HBT), a small nonplanar nanographene, functions as a hydrocarbon HTM with hole transport properties that match those of triarylamine‐based HTMs. X‐ray structural analysis and theoretical calculations revealed effective multidirectional orbital interactions and transfer integrals for HBT. In‐depth experimental and theoretical analyses revealed that the nonplanarity‐inducing annulative π‐extension can achieve not only a stable amorphous state in bulk films, but also a higher increase in the highest occupied molecular orbital level than conventional linear or cyclic π‐extension. Furthermore, an in‐house manufactured HBT‐based OLED exhibited excellent performance, featuring superior curves for current density–voltage, external quantum efficiency–luminance, and lifetime compared to those of representative triarylamine‐based OLEDs. A notable improvement in device lifetime was observed for the HBT‐based OLED, highlighting the advantages of the hydrocarbon HTM. This study demonstrates the immense potential of small nonplanar nanographenes for optoelectronic device applications. [ABSTRACT FROM AUTHOR]

All‐benzenoid polycyclic aromatic hydrocarbons or macrocycles usually display localized aromaticity. On the other hand, incorporation of quinoidal units into the skeleton could lead to effective electron delocalization and global (anti)aromaticity. In this work, fully π‐conjugated macrocycle 1 and bismacrocycle 2 containing both para‐quinodimethane and triphenylamine units are efficiently synthesized mainly through intermolecular Friedel–Crafts alkylation reaction. They can be considered as a tetraazasuperbenzene and a hexaazasupernaphthalene, respectively, due to their similar geometry and electronic structures to the benzene and naphthalene. X‐ray crystallographic analyses reveal a largely planar geometry for both 1 and 2 and variable‐temperature NMR measurements disclose slow dynamic processes owing to restricted ring flipping of the phenyl rings. 1 and 2 can be easily oxidized into higher‐oxidation‐state species. NMR and theoretical calculations indicate that 12+ and 14+ show global anti‐aromaticity and aromaticity, respectively, with a dominant 32π and 30π conjugation pathway, while for the bismacrocycle 2, its dication 22+, tetracation 24+ and hexacation 26+ exhibit global aromaticity, antiaromaticity, and aromaticity with a 54π, 52π and 50π conjugation pathway along the outermost backbone, respectively. [ABSTRACT FROM AUTHOR]

AbstractOwing to the production of lignin-modifying enzymes (LMEs), white-rot fungi (WRF) such as polypores are potent organisms in the biodegradation of xenobiotic pollutants. The nonspecific function of LMEs including laccase and manganese peroxidase (MnP), has enabled the use of WRF in biotechnological applications, particularly in bioremediation. In this study, 12 strains from nine white-rot basidiomycete genera viz., Ganoderma, Inocutis, Irpex, Lentinus, Lenzites, Oxyporus, Peniophora, Sanghuangporus, and Trametes were isolated from Iran and identified using morphological and molecular tools. The enzyme activity of laccase and manganese peroxidase that directly correlated with the biodegradation were determined, and the strains with the highest enzyme activities were evaluated for their ability to degrade 400 mg/L of anthracene over 28 days. Gas chromatography with flame ionization detector (GC-FID) revealed that four polypores viz., Trametes versicolor v21te, T. versicolor v22da, T. hirsuta, and Oxyporus sp. degraded 64%, 52%, 34%, and 20% of the anthracene, respectively. According to our analysis, the examined indigenous WRF are potentially useful candidates for the development of new mycoremediation techniques to degrade polycyclic aromatic hydrocarbons (PAHs). [ABSTRACT FROM AUTHOR]

In this study, we introduce a novel index called the modified inverse sum indeg (MISI) energy as an extension of the traditional inverse sum indeg (ISI) energy and neighbor degree sum energy. We devised an algorithm that employs the simplified molecular input line entry system (SMILES) formula of compounds to compute the MISI energy of polycyclic aromatic hydrocarbon (PAH). Additionally, we established the bounds of the MISI energy for certain classes of graphs with fixed number of vertices. A strong correlation between the MISI energy and the total π-electron energy of PAHs is observed through regression analysis. Remarkably, this correlation outperforms that achieved by the classical ISI energy. These findings highlight the enhanced effectiveness of the MISI energy as a descriptor for capturing significant molecular properties. Moreover, our study establishes a foundation for further theoretical extensions and practical applications in the field of chemical graph theory. [ABSTRACT FROM AUTHOR]

Millions of United States (U.S.) troops deployed to the Middle East and Southwest Asia were exposed to toxic airborne hazards and/or open-air burn pits. Burn pit emissions contain particulate matter combined with toxic gasses and heavy metals. Ongoing research has demonstrated that exposures to the airborne hazards from military burn pits have profound and lasting health and wellness consequences. Research on the long-term health consequences of exposure to open burn pits has been limited. Work continues to understand the scope of the health impacts and the underlying pathobiology following exposures and to establish care standards. The U.S. Sergeant First Class Heath Robinson Honoring our Promise to Address Comprehensive Toxics (PACT) Act was signed into law August 2022. This act expands the benefits and services to U.S. Veterans exposed to toxicants, requires the Veterans Health Administration to provide toxic exposure screening, and supports increased research, education, and treatment due to toxic occupational exposures. This review highlights the state of the science related to military burn pit exposures research with an emphasis on pulmonary health. Clinical data demonstrate areas of reduced or delayed pulmonary ventilation and lung pathologies such as small airways scarring, diffuse collagen deposition and focal areas of ossification. Identification and characterization of foreign matter deposition in lung tissues are reported, including particulate matter, silica, titanium oxides, and polycyclic aromatic hydrocarbons. These data are consistent with toxic exposures and with the symptoms reported by post-deployment Veterans despite near-normal non-invasive pulmonary evaluations. On-going work toward new methods for non-invasive pulmonary diagnoses and disease monitoring are described. We propose various studies and databases as resources for clinical and health outcomes research. Pre-clinical research using different burn pit modeling approaches are summarized, including oropharyngeal aspiration, intranasal inhalation, and whole-body exposure chamber inhalation. These studies focus on the impacts of specific toxic substances as well as the effects of short-term and sustained insults over time on the pulmonary systems. [ABSTRACT FROM AUTHOR]

Polycyclic aromatic hydrocarbons (PAHs) are among the most widespread organic contaminants in the environment, and anthropogenic activities can produce PAHs through a variety of pyrogenic or petrogenic means. Knowing the concentrations and sources of PAHs helps evaluate ecosystem health and manage natural resources. In this study, 16 US Environmental Protection Agency priority PAHs were analyzed in water and sediment samples collected from September 2021 to September 2023 in four bay systems along the south and central Texas coast, which are a hotpot of crude oil transportation in the United States. Our results indicated that the total concentration of PAHs ranged from 1.9 to 8.3 ng/mL in surface waters (< 0.5 m) and from 520 to 1257 ng/g in surface sediments (top 5 cm). Grain size analysis revealed that the sediment was dominated by silt (4 - 63 μm), followed by clay (< 4 μm) and sand (> 63 μm) fractions. Both organic carbon and clay content were shown to play a significant role in controlling the PAH content in sediments. Diagnostic ratios indicated that PAHs were primarily sourced via pyrolytic processes, such as the combustion of fossil fuels. Additional sampling at Port Bay, a shallow, secondary bay in the Mission-Aransas National Estuarine Research Reserve, implicated a strong role of resuspension in the distribution and composition of PAHs in the bay systems studied. Overall, these data offer insights into the concentration levels and sources of PAHs in this key region housing oil production and transportation in the United States. [ABSTRACT FROM AUTHOR]

A simple, rapid, and sensitive procedure is developed for the determination of hydroxylated polycyclic aromatic hydrocarbons (2-hydroxynaphthalene, 2-hydroxyfluorene, 9-hydroxyphenanthrene, 3-hydroxyphenanthrene, 2-hydroxyphenanthrene, 1-hydroxypyrene, and 6-hydroxychrysene) in urine by gas chromatography–mass spectrometry. Sample preparation is based on dispersive liquid–liquid microextraction with trichloromethane in an acidic medium. Derivatization is carried out in a heated injector port using the reagent N,O-bistrimethylsilyltrifluoroacetamide. The type of dispersing solvent is experimentally selected and the optimal ratio of the following factors, i.e., pH value, volume of dispersing solvent, and extraction time, is found using a three-factor experiment. A high-temperature capillary column NT-8 is used in a temperature gradient mode for analysis by gas chromatography–mass spectrometry. The linearity range of the calibration function is found to be 0.5–100 ng/mL. The developed procedure for determining hydroxylated PAH in urine is tested on urine samples from aluminum production workers. [ABSTRACT FROM AUTHOR]

The test samples are polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs), highly toxic and widely prevalent organic pollutants in natural waters. The feasibility of using dispersive liquid–liquid microextraction (DLLME) for extracting PCBs and PAHs, followed by their determination by GC–MS, was assessed in the presence of both contaminants. A DLLME method employing a binary dispersing agent was proposed, ensuring the simultaneous extraction of analytes with efficiency ranging from 80 to 97%. The proposed procedure enabled the GC–MS determination of 16 PAHs and 7 PCBs in natural waters in a wide concentration range of 2.0 × 10–5–0.04 µg/mL with an average error of 7–18% for PAHs and 11–18% for PCBs. The relative standard deviations for repeatability and reproducibility were found to be 3.1–6.5 and 4.3–7.7%, respectively, for PAHs, and 2.8–5.3 and 3.4–6.0%, respectively, for PCBs. [ABSTRACT FROM AUTHOR]

A new naphthalene diimides extended‐pillar[6]arene 1 with a large cavity and rich host‐guest complexation properties was synthesized in high yield. It can not only form 1 : 2 complexes with large size polycyclic aromatic hydrocarbons but also form 1 : 1 : 1 ternary complex with perylene and 2,7‐diazapyrenium. Moreover, the supramolecular exchange reaction from a 1 : 2 host‐guest complex 1 ⋅ (G3)2 formed by 1 and perylene to a 1 : 1 : 1 ternary complex 1 ⋅ G3 ⋅ G5 formed by 1 with perylene and 2,7‐diazapyrenium salt was also investigated by 1H NMR experiments as well as theoretically calculations. [ABSTRACT FROM AUTHOR]

Replacement of C─C unit with its isoelectronic B─N unit in aromatics provides a new class of molecules with appealing properties. Herein, Five novel butterfly‐shaped furan‐fused bis‐BN dihydropyrenes (FBN) derivatives are synthesized with different push‐pull electron "wings". These compounds exhibit prominent UV‐A/B absorption, high energy levels, and p‐type characteristics. Thanks to the side‐chain engineering and BN dipole manipulation, their intramolecular dipole moments and intermolecular stacking mode are effectively regulated to improve intra‐ and inter‐molecular charge transfer, thus achieving high hole mobilities. Five FBN‐X compounds are doped with PC71BM as heterojunction photosensitive layers to fabricate solution‐processed high performance organic photodetectors (OPDs), which exhibit self‐powered effect and high sensitivity to UV‐A/B. Especially, the FBN‐CN‐based device presents a high detectivity up to 1.72 × 1012 Jones, a peak external quantum efficiency of 19.1%, and an extremely low dark current density of 8.90 × 10−10 A cm−2 under 320 nm at 0 V. To the best of authors knowledge, it is the first report of photodiode‐type UV‐OPDs containing BN‐doped polycyclic aromatic hydrocarbons as active layer to date. And the optimal device shows a significant advantage over the reported 300–380 nm UV‐OPDs. In addition, a 10 × 10 array of organic image sensor is successfully demonstrated, which showcases excellent low‐light imaging capability. [ABSTRACT FROM AUTHOR]

AbstractThis study investigated the effects of different fat contents and cooking techniques on the presence of PAHs in chicken doner kebabs, as well as the dietary exposure and potential health risks for the Turkish population. The methodology for the detection and quantification of 16 PAH compounds in chicken doner samples using high-performance liquid chromatography (HPLC-UV) was validated. The limit of detection (LOD), quantification (LOQ), recovery, and relative standard deviation (RSD) were found to be 0.44%–1.14%, 1.45%–3.56%, 63.12%–101.50%, and 0.14%–3.16%, respectively. Our findings revealed that, among the analyzed compounds, BaA was the most dominant PAH compound, and that the charcoal cooking technique resulted in the highest accumulation of both BaP and PAH4 concentrations in chicken doner kebabs. Additionally, a significant increase in PAH levels was observed in relation to higher fat content. Moreover, it was found that the estimated daily intake (EDI) of BaP and PAH4 was higher in charcoal-grilled, well-done, high-fat chicken doner samples. As a result, the fact that the Margin of Exposure (MOE) values calculated for chicken doner samples across the Turkish population are above 10,000 indicates a low level of concern. [ABSTRACT FROM AUTHOR]

We describe the synthesis of π‐extended phosphetene rings (4‐member P‐rings) flanked with PAH systems of various topologies. These compounds are fully characterized including X‐ray diffraction. The impact of both the polyaromatic platform and the P‐ring on the structure, and the optical and redox properties are investigated both experimentally and theoretically. Although neither the P centre nor the 4‐membered ring significantly takes part in the HOMO or LUMO orbitals, both structural features have an important modulating role in distorting the symmetry of the orbitals, leading to chiroptical properties. The stereogenic P‐atom is used as a remote chiral perturbator to induce circularly polarized luminescence of the polyaromatic system. The dissymmetry factor is highly dependent on the polyaromatic topology, as supported by theoretical calculations. [ABSTRACT FROM AUTHOR]

In the field of conservation of cultural heritage, one must always consider the environmental conditions in which the works of art are located and the level of atmospheric pollution to which they are exposed, especially in the case of monuments stored outdoors. The present study is focused on the detection and the quantification of polycyclic aromatic hydrocarbons (PAHs) in black crust samples from the Monumental Cemetery of Milan (Italy), and the assessment of their sources through the analysis of the distributions of the different compounds in the samples, together with the use of diagnostic ratios. Six black crust samples taken from funerary monuments were analyzed. Fourteen polycyclic aromatic hydrocarbons were identified (naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, chrysene, benzo[a]anthracene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene) by high-performance liquid chromatography with a diode-array detector (HPLC–DAD), with a total concentration from 0.72 to 3.81 μg/g (mean of 1.87 μg/g). The known carcinogenic benzo[a]pyrene accounted for 5–10% of the total polycyclic aromatic hydrocarbons in the samples analyzed, with concentrations up to 0.20 μg/g. Moreover, the study of the distribution and diagnostic ratios allowed us to confirm that anthropogenic sources such as traffic and the proximity of the train station are the major causes of the degradation of the monuments contained in this Cemetery. [ABSTRACT FROM AUTHOR]

The polycyclic aromatic hydrocarbons (PAHs) congener concentrations and risk upon human exposure to smoked bushmeat products were analyzed. GC/MS MRM and QuEChERS methods were used for the analysis. This work has become necessary due to the need for more information concerning the quantitative determination of these compounds and their health risk assessment. The 16 PAH congeners identified were acenaphthylene (ACA), naphthalene (NAP), acenaphthene (ACE), fluorene (FLU), anthracene (ANT), phenanthrene (PHE), fluoranthene (FLT), pyrene (PYR), benzo[b]fluoranthene (BBF), benzo[k]fluoranthene (BKF), benzo[a]anthracene (BAA), chrysene (CHR), indeno(1,2,3‐cd)pyrene (IND), dibenzo(a,h)anthracene (DAA), benzo(g,h,i)pyrene (BGP), and benzo[a]pyrene (BAP). At the 5% and 95% daily intake levels, BAP was at 3.34 and 17.39 μg/kg(bw)/day, ΣPAH4 was at 25.11 and 109.15 μg/kg(bw)/day, and ΣPAH8 was at 55.76 and 236.68 μg/kg(bw)/day, respectively. BAP, ΣPAH4, and ΣPAH8 concentration exceeded the European Union limits, as BAP concentration was as low as 6.09 μg/kg and as high as 34.19. The exposure values were significantly high. Specifically, the margin of exposure for BAP was as low as 2.09 × 10−2; for ΣPAH4, it was 1.36 × 10−−2; and for ΣPAH8, it was 1.95 × 10−2 all at the 95% level. These figures are substantially lower than the benchmark of 10,000, indicating a higher ILTCR. Furthermore, the ILTCR ranged from a minimum of 47.77 to a maximum of 248.53 at the 5% and 95% levels, respectively. This study makes smoked bushmeat a public health concern because the higher figures obtained indicate higher carcinogenicity upon consumption. [ABSTRACT FROM AUTHOR]

Background: The impact of polycyclic aromatic hydrocarbons (PAHs) on lung function has garnered attention, but studies mostly focus on individual effect. This study investigates urinary PAH metabolites as biomarkers of exposure and assesses the relationships between single and combined exposures to nine urinary PAH metabolites and lung function in adults. Methods: Data from 4040 adults in the 2007–2012 National Health and Nutrition Examination Survey (NHANES) were analyzed. Weighted generalized linear models estimated the effects of individual PAH metabolites on lung function. Additionally, weighted quantile sum (WQS) regression, quantile g-computation (qgcomp), and Bayesian kernel machine regression (BKMR) were employed to evaluate the combined impacts of multiple PAH metabolites. Results: Analyses of individual PAH metabolites revealed negative associations with lung function, excluding forced vital capacity (FVC). The WQS, qgcomp, and BKMR models consistently showed that exposure to multiple PAH metabolites was associated with lung function decrease. WQS indicated that 2-hydroxynaphthalene (2-NAP) was the largest contributor to the reductions in forced expiratory volume in 1 s (FEV1), FVC, peak expiratory flow (PEF), and forced expiratory flow from 25 to 75% of FVC (PEF25-75%). Additionally, 1-hydroxypyrene (1-PYR) was the primary PAH metabolite contributing to the decreases in FEV1/FVC and fractional exhaled nitric oxide (FeNO). The combined effect of urinary PAH metabolites did not affect FVC in the current smokers or FeNO in nonsmokers, but decreased FEV1/FVC in current smokers. Conclusion: This study strengthens the negative relationships between multiple PAH metabolites exposure and lung function in adults. Given the limitations of this study, including the lack of knowledge of other exposure pathways and the uncertainty of urinary metabolites, further research is necessary to explore the mechanisms underlying these associations and to address the limitations in exposure assessment. [ABSTRACT FROM AUTHOR]

This study aimed to observe changes in the diet of crab Eriphia gonagra due to the oil spill that occurred in 2019 on two beaches on the Pernambuco coast (Gaibu and Carneiros Beach) Northeastern, Brazil. Changes in the species feeding were investigated considering the periods before, during, and after of the spill and correlated with the analysis of sediment contamination Polycyclic Aromatic Hydrocarbons (PAHs) and Trace Metals (TM). 160 specimens were analysed. 24 food items were found, with a prevalence of Mollusca (fragment) and Macroalgae in the diet. There was no detection of oil fragments in the stomachs of animals, however, different patterns were observed in the feeding of the species studied in the BEF, DUR, and AFT periods of the spill. A generalist habit, it was possible to observe changes in captured items, thus we observed a diet with low nutritional levels caused mainly in impacted environments. Two factors may be prevalent in explaining the impacts caused by the feeding of E. gonagra in Carneiros Beach. The first was the decrease in prey that died after the arrival of the oil, the second was the lasting effects of contaminants on the predation capacity of the species. [ABSTRACT FROM AUTHOR]

Efficient and harmless treatment of microplastics in soil is the current focus of microplastic pollution management. In this study, the pyrolysis effect of soil microplastics at different temperatures and holding times was analyzed. The results showed that temperature and holding time significantly affected the morphology and compositional structure of soil. Pure microplastics and product adhesion after pyrolysis at low temperature (400°C) were not easy to remove. Interestingly, compared with pure polyethylene (PE), direct pyrolysis of microplastics in soil could obtain better results, and the content of organic matter and polycyclic aromatic hydrocarbons (PAH) could be significantly reduced. However, the pyrolysis performance was very unsatisfactory even if the action time was prolonged at 400°C. Prolonged high‐temperature treatment accelerated the fragmentation of the alkane main chain of PE, thus generating more PAH, and the temperature was not high enough (400°C) for further effective degradation of PAH into carbon dioxide and water. Therefore, higher temperature and longer holding time need to be selected to ensure the pyrolysis performance. This study revealed the role and mechanism of pyrolysis in soil microplastic mixed systems, aiming to provide a basis for the treatment of microplastics in terrestrial ecosystems. [ABSTRACT FROM AUTHOR]

Splitting the five and seven‐membered rings of azulene and embedding them separately into a conjugated backbone provides azulene‐like polycyclic aromatic hydrocarbons (PAHs), which are of great interest in quantum and material chemistry. However, the synthetic accessibility poses a significant challenge. In this study, we present the synthesis of a novel azulene‐like PAH, Pery‐57, which can be viewed as the integration of a perylene framework into the split azulene. The compact structure of Pery‐57 displays several intriguing characteristics, including NIR II absorption at 1200 nm, a substantial dipole moment of 3.5 D, and head‐to‐tail alternating columnar packing. Furthermore, Pery‐57 exhibits remarkable redox properties. The cationic radical Pery‐57⋅+ readily captures a hydrogen atom. Variable‐temperature NMR (VT NMR) and variable‐temperature EPR (VT‐EPR) studies reveal that the dianion Pery‐572− possesses an open‐shell singlet ground state and demonstrates significant global anti‐aromaticity. The dication Pery‐572+ is also predicted to exhibit diradical character. Despite bearing three bulky substituents, Pery‐57 displays p‐type transport characteristics with a mobility of 0.03 cm2 V−1 s−1, attributed to its unique azulene‐like structure. Overall, this work directs interest in azulene‐like PAHs, a unique member of nonalternant PAHs showcasing exceptional properties and applications. [ABSTRACT FROM AUTHOR]

Delocalized organic π‐radicals are intrinsically amphoteric redox systems; however, achieving their multistage redox capability presents a challenge. In addition, their instability often hampers their synthesis, isolation, and characterization. Herein, we report the synthesis of a stable π‐extended nanographene π‐radical (NR1) and its isolation in the crystalline form. NR1 exhibits an unusual four‐stage amphoteric redox behavior, as revealed by cyclic voltammetry measurements. The stable charged species, including a cation and a radical dication, are characterized using spectroscopic methods. This study demonstrates that π‐extension could serve as a viable approach to unlock the multistage redox ability of delocalized organic radicals. [ABSTRACT FROM AUTHOR]

The presence of polycyclic hydrocarbons (PAHs) and microplastics (MPs) in aquatic environments affects the ecosystems and threatens human health. In this study, the abundance, composition, and morphological characteristics of MPs were determined for the first time in the inland freshwater resources of the Konya Closed Basin, Turkey. The abundance of MPs ranged from 1139 to 23,444 particles/m3 and 150 to 3510 particles/kg in the surface water and sediment, respectively. Fragments and fibers were the most abundant MP shapes in the surface waters (51%, 34%) and sediments (29%, 40%), followed by films, pellets, and foams. Transparent and white MPs were present at the highest percentage in surface waters (72%) and sediments (69%), followed by blue, grey, black, brown, and green. In addition, polyethylene, polypropylene, and cellophane were identified as the main polymers in surface waters (34%, 25%, 24%) and sediments (37%, 17%, 31%). In the Konya Closed Basin, 35% of the surface water samples and 54% of the sediment samples were exposed to very high contamination (CF ≥ 6). Surface waters (PLI: 2.51) and sediments (PLI: 1.67) in the basin were contaminated (PLI > 1) with MPs. The 16 PAHs sorbed on MPs in the surface water and sediment ranged from 394 to 24,754 ng/g and from 37 to 18,323 ng/g, respectively. Phenanthrene and fluoranthene were the most abundant PAHs sorbed on MPs in all surface waters and sediments. Two to three-ring PAH compounds sorbed on MPs were also dominantly detected in surface waters and sediments, accounting for 68% and 78% of the total 16 PAHs, respectively. The source of PAHs carried by MPs in the Konya Closed Basin was mainly of petrogenic origin. Incremental lifetime cancer risk (ILCR) results indicated that the maximum ILCR values were higher than the EPA acceptable level (10−6) for child (2.95 × 10−5) and adult (1.46 × 10−4), indicating a potential cancer risk. [ABSTRACT FROM AUTHOR]

Background: Exposure to military burn pit smoke during deployment is associated with different respiratory and non-respiratory diseases. However, information linking smoke exposure to human pulmonary health is lacking. This study examined the effects of simulated burn pit smoke condensates on human airway epithelial cells (HAECs) from twelve donors (smokers/non-smokers, biological female/male) cultured at an air-liquid interface and exposed to condensates from three simulated burn pit waste materials (cardboard, plywood, and plastic) incinerated at two combustion conditions: smoldering and flaming. Cellular gene expression was analyzed using bulk RNA sequencing, and basolateral media cytokine levels were assessed using multiplex immunoassay. Results: Flaming smoke condensates caused more significant differentially expressed genes (DEGs) with plywood flaming smoke being the most potent in altering gene expression and modulating cytokine release. Cardboard and plywood flaming condensates primarily activated detoxification pathways, whereas plastic flaming affected genes related to anti-microbial and inflammatory responses. Correlation analysis between smoke condensate chemicals and gene expression to understand the underlying mechanism revealed crucial role of oxygenated polycyclic aromatic hydrocarbons (PAHs) and aluminum, molybdenum, and silicon elements; IL6 expression was positively correlated with most PAHs. Stratification of data based on HAEC donor demographics suggests that these affect gene expression changes. Enrichment analysis indicated similarity with several deployment-related presumptive and reported diseases, including asthma, emphysema, and cancer of different organs. Conclusions: This study highlights that simulated burn pit smoke exposure of HAECs causes gene expression changes indicative of deployment-related diseases with more pronounced effects seen in smokers and females. Future studies are needed to further characterize how sex and smoking status affect deployment-related diseases. [ABSTRACT FROM AUTHOR]

The knowledge of the deposition fate of ambient polycyclic aromatic hydrocarbons (PAHs) on plant leaves is limited. To fill in this knowledge gap, this study strives to observe the intermolecular complex between the polycyclic aromatic hydrocarbons and epicuticular wax of plant leaves using laser scanning microscopy. Epicuticular wax refers to a type of organic mixture that covers the outermost layer of leaves. The leaves of 20 tree species were collected in Beijing in July 2023. The concentrations of 31 PAHs were quantified by gas chromatography–mass spectrometry. Furthermore, the intermolecular complexes of polycyclic aromatic hydrocarbons and epicuticular wax were found with a fluorescence spectrofluorometer and laser scanning microscopy. The levels of total PAHs across 20 tree species ranged from 12.4 ng g−1 to 68.4 ng g−1. Differences in the amounts of total PAHs across tree leaves were observed, which may be ascribed to the differences in leaf surface across tree types. The higher concentration of low-molecular-weight PAHs was found in leaves compared to high-molecular-weight PAHs. The fluorescence spectrofluorometer identified the formation of a new intermolecular complex with fluorescence emission at an excitation wavelength of 340 nm between PAHs and epicuticular wax relative to PAHs. We used laser scanning microscopy with a 405 nm laser for excitation to observe the new intermolecular complex of PAHs and epicuticular wax on the stomata and epicuticular wax of leaves. This study found the intermolecular complex of PAHs on the surface of leaves in situ, which provides important information about the deposition fate of ambient PAHs. [ABSTRACT FROM AUTHOR]