Polycyclic Aromatic Compounds Research Articles

Tracking the history of polycyclic aromatic compounds in London through a River Thames sediment core and ultrahigh resolution mass spectrometry

Polycyclic aromatic compounds (PACs), including polycyclic aromatic hydrocarbons (PAHs) and heteroatom-containing analogues, constitute an important environmental contaminant class. For decades, limited numbers of priority PAHs have been routinely targeted in pollution investigations, however, there is growing awareness for the potential occurrence of thousands of PACs in the environment. In this study, untargeted Fourier transform ion cyclotron resonance mass spectrometry was used for the molecular characterisation of PACs in a sediment core from Chiswick Ait, in the River Thames, London, UK. Using complex mixture analysis approaches, including aromaticity index calculations, the number of molecular PAC components was determined for eight core depths, extending back to the 1930s. A maximum of 1676 molecular compositions representing PACs was detected at the depth corresponding to the 1950s, and a decline in PAC numbers was observed up the core. A case linking the PACs to London’s coal consumption history is presented, alongside other possible sources, with some data features indicating pyrogenic origins. The overall core profile trend in PAC components, including compounds with oxygen, sulfur, nitrogen, and chlorine atoms, is shown to broadly correspond to the 16 priority PAH concentration profile trend previously determined for this core. These findings have implications for other industry-impacted environments.

Distribution and Risk Assessment of 80 Polycyclic Aromatic Compounds in Surface Water and Industrial Effluent in the Upper Yangtze River, China

Distribution and Risk Assessment of 80 Polycyclic Aromatic Compounds in Surface Water and Industrial Effluent in the Upper Yangtze River, China

Distribution and transfer of organics in the coagulation–anaerobic hydrolysis–aerobic treatment process of cutting fluid wastewaters

Abstract Two kinds of real cutting fluid wastewater samples (i.e., sample A and sample B) and two kinds of coagulants (i.e., polymeric aluminum chloride (PAC) and polymeric iron sulfate (PFS)) were studied during coagulation experiment, and the coagulation effluent of sample B with PAC was utilized for subsequent anaerobic hydrolysis–aerobic treatment, and the molecular weight (MW) distribution and ultraviolet (UV) absorption spectroscopy were used to explore the distribution and transfer of organics of each treatment unit. The results showed that sample A and sample B both mainly contained macromolecular organics with MW > 100 kDa and small molecule organics with MW < 3 kDa, and PAC had significant coagulation performance for organics with MW > 100 kDa in both samples, while neither PAC nor PFS achieved good coagulation performance for the small molecule organics with MW < 3 kDa in both samples. It could be inferred by UV spectra that the coagulation effluent of sample A and B might both contain organics with conjugated double bonds, monocyclic aromatic hydrocarbons, and the coagulation effluent of sample B might also contain polycyclic aromatic hydrocarbons and heterocyclic compounds with low MW. MW distribution analysis and the UV spectra results showed that biological treatment could further remove organics with conjugated double bonds and aromatic compounds with MW < 3 kDa.

Characterization of cross-continental PM2.5: Insights into emissions and chemical composition

Atmospheric fine particulate matter (PM2.5) is a critical indicator of air quality, with substantial implications for human health. Understanding the emission sources and chemical composition of PM2.5 is crucial for mitigating possible adverse health effects. This study spans five diverse cities on three continents from north and south hemisphere: Stockholm (Sweden), Kyoto (Japan), Limeira, Ribeirão Preto, and Cáceres (Brazil). Our objective was to assess PM2.5 chemical composition and regional and long-range transport influences to identify the main sources of particulate air pollution at these cities during the winter/dry seasons. All studied cities but Kyoto exhibited PM2.5 levels above World Health Organization (WHO) guidelines, with the Brazilian cities experiencing the highest fine particle pollution levels, implying increased adverse health risks. We observed significant variations in concentrations of polycyclic aromatic compounds (PACs), monosaccharide anhydrides (MAs), and inorganic elements. Limeira exhibited the highest levels of total PACs (median level of 12.4 ng m−3), while Cáceres displayed high variability of PACs, most likely due to episodic regional wildfire events. MA concentrations were significantly higher in Limeira and Ribeirão Preto and together with elevated levels of retene and potassium (K) they suggested a substantial influence of biomass burning. Backward air mass trajectory analysis suggested widespread Amazon and Savanna wildfires along with local fires as main contributors for these sites. All source identification approaches highlighted differences among the cities, with Stockholm and Kyoto showing influence of sources related to traffic emissions, waste burning, and long-range transport, and Brazilian cities traffic, industrial, biogenic, and more evident biomass burning. This cross-continental study provides valuable insights into PM2.5 composition and emission sources, emphasizing the impact of different emissions on air quality. Our findings underscore the importance of local strategies to mitigate air pollution and protect public health, especially in regions where PM2.5 levels consistently exceed recommended guidelines.

Comprehensive Experimental and Computational Analysis of the Structural and HSA Binding Properties of Newly Synthesized Coumarin-Trimethoxybenzohydrazide Derivative

Polycyclic aromatic compounds encompass a diverse array of molecules that exhibit remarkable chemical activity and play pivotal roles across various scientific domains. Coumarins represent a diverse class of heterocyclic compounds, which exhibit a wide range of significant biological and pharmacological activities, while containing at least two aromatic rings in their structure. Because chemical, biological, as well as pharmacological properties and activities are highly dependent on the structural characteristics of the molecule, in this paper a detailed structural investigation of the monocrystal structure of newly synthesized (E)-N′-(1-(2,4-dioxochroman-3-ylidene)ethyl)-3,4,5-trimethoxybenzohydrazide was performed. The DFT model that is best suited for describing the structural parameters of coumarin-benzohydrazides was determined. Out of three tested models which were previously proven to be excellent in describing structures of organic compounds, B3LYP-D3BJ was found to be the best in describing the structure of investigated coumarin derivative in regard to the obtained X-ray and spectroscopic data. Determination of the best theoretical model allows for better structural characterization of the coumarin-benzohydrazides for which monocrystals and consequently X-ray structure cannot be obtained. Finally, both experimental and computational analysis indicated (with high mutual correlation) that investigated compound showed excellent binding potential toward the albumin, indicating good distribution through the organism.

Migration patterns and health risk assessment of polycyclic aromatic compounds in typical coal fire source.

The Wuda coal fire in Inner Mongolia, China, is a global catastrophic event. It emits a huge volume of organic pollutants, including polycyclic aromatic compounds (PACs), which are widely concerning due to their physiological toxicity and environmental persistence. However, there is no systematic study on the enrichment and migration patterns of PACs emitted from coal fires. Here, we compared samples from coal fire sponges and surrounding soil, and analyzed 47 PACs using GC × GC-TOFMS. Data analysis showed that the average content of 16 polycyclic aromatic hydrocarbons (16PAHs) in the coal fire sponge was 15400.65ng/g, which is about 4.2 times higher than that in the surrounding soil. Meanwhile, 31 PACs were detected at levels far exceeding those of 16PAHs. The distribution pattern of PACs showed that coal fire sources are more likely to produce and store 16PAHs while surrounding soils are more likely to be enriched with PAH derivatives. The cancer risk assessment revealed a significant cancer risk in both the coal fires and the surrounding soil. The formation mechanism of oxygenated PAHs was also explored, and it was found that coal fires emit 16PAHs and alkylated PAHs, which oxidize to form oxygenated PAHs during migration to surrounding soils. The value of naphthaldehyde/alkylated naphthalene (< 2) can be referenced as characteristic markers of coal fire pollution. This provides a new perspective on the sources of PACs in the current environment.

Polycyclic aromatic compounds in a northern freshwater ecosystem: Patterns, sources, and the influences of environmental factors

Polycyclic aromatic compounds (PACs) - a large group of organic chemicals naturally present in petroleum deposits (i.e., petrogenic) or released into the environment by incomplete combustion of organic materials (i.e., pyrogenic) - represent a potential risk to the health of aquatic ecosystems. In high latitude freshwater ecosystems, concentrations of PACs may be increasing, yet there are limited studies in such systems to assess change and to understand threats. Using 10 years of contemporary data from passive samplers deployed across five regions (n = 43 sites) in the Mackenzie River Basin, we (i) describe baseline levels of PACs, (ii) assess spatiotemporal patterns, and (iii) evaluate the extent to which environmental factors (fire, snowmelt, and proximity to oil infrastructure) influence concentrations in this system. Measured concentrations were low, relative to those in more southern systems, with mixtures primarily being dominated by non-alkylated, low molecular weight compounds. Concentrations were spatially consistent, except for two sites near Norman Wells (an area of active oil extraction) with increased levels. Similarly, observed annual variation was minimal, with 2014 having generally higher levels of PACs. We did not detect effects of fire, snowmelt, or oil infrastructure on concentrations. Taken together, our findings suggest that PACs in the Mackenzie River are currently at low levels and are primarily petrogenic in origin. They further indicate that ongoing monitoring and testing of environmental drivers (especially at finer spatial scales) are needed to better predict how ecosystem change will influence PAC levels in the basin and in other northern systems.

Atmospheric pressure field desorption-trapped ion mobility-mass spectrometry coupling.

While field ionization (FI) and field desorption (FD) are established soft vacuum ionization methods in mass spectrometry (MS), the technique of atmospheric pressure field desorption (APFD) has only recently been added to the repertoire. Similar to FI and FD, APFD can yield both positive even-electron ions of highly polar or ionic compounds and positive molecular ions, M+•, e.g., of polycyclic aromatic compounds. Thus, a dedicated APFD source assembly has been constructed and demonstrated to allow for robust APFD operation. This device also enabled observation of the emitter during operation and allowed for resistive emitter heating, thereby speeding up the desorption of the analytes and expanding the range of analytes accessible to APFD. While initial work was done using a Fourier transform-ion cyclotron resonance (FT-ICR) mass spectrometer, the new APFD source offered the flexibility to also be used on a trapped ion mobility-quadrupole-time-of-flight (TIMS-Q-TOF) instrument, and thus, it would be possible to be mounted to any Bruker mass spectrometer featuring an atmospheric pressure (AP) interface. Operating an APFD source at a TIMS-Q-TOF instrument called for the exploration of the combined use of APFD and TIMS. Here, operation, basic properties, and capabilities of this new atmospheric pressure field desorption-trapped ion mobility-mass spectrometry (APFD-TIMS-MS) coupling are described. APFD-TIMS-MS is employed for the separation of individual components of oligomers and for the accurate determination of their collision cross section (CCS). This work describes the application of APFD-TIMS-MS on poly(ethylene glycol) forming [M + Na]+ ions by cationization and on an amine-terminated poly(propylene glycol) yielding [M + H]+ ions. Some compounds forming molecular ions, M+•, by field ionization such as [60]fullerene and a mixture of four polycyclic aromatic hydrocarbons (PAHs) are examined. In APFD-TIMS-MS, the limits of detection (LODs) of fluoranthene and benzo[a]pyrene M+• ions are determined as ≈100pg and <1pg, respectively. Finally, [60]fullerene is analyzed by negative-ion APFD-TIMS-MS where it yields a molecular anion, M-•.

STUDY OF CATALYSTS BASED ON MESOPOROUS ALUMINOSILICATE IN THE DEAROMATIZATION PROCESS OF A MODEL MIXTURE: PHYSICO-CHEMICAL CHARACTERISTICS AND CATALYTIC ACTIVITY

The limitation on the content of aromatic hydrocarbons and sulfur is associated with environmental requirements according to Euro-5 standards. Upon combustion, these substances release highly toxic compounds into the atmosphere, adversely affecting human health and the surrounding environment. Additionally, a high concentration of aromatic hydrocarbons in diesel fuel significantly degrades its quality, leading to soot formation and reducing its cetane number. According to Euro-5 standards, the content of polycyclic aromatic hydrocarbons and sulfur compounds should not exceed 8% and 10 mg/kg, respectively. To address the challenge of producing high-quality diesel fuels, the hydrotreatment process is employed in the presence of heterogeneous catalysts.The article presents the synthesis of mesoporous aluminosilicates and bifunctional catalysts based on them to study the activity of the hydrotreatment process for a model mixture. The obtained samples were investigated using various physico-chemical methods such as SEM, low-temperature nitrogen adsorption/desorption, XRD, and FT-IR. It was established that the Ni/MAS-H-bentonite and Mo/MAS-H-bentonite catalysts exhibit high activity and selectivity in the hydrotreatment process under optimal conditions (240°C, 3 MPa, and 0.5 h-1).

New Insights into Aromaticity through Novel Delta Polynomials and Delta Aromatic Indices

We have developed novel polynomials called delta polynomials, which are, in turn, derived from the characteristic and matching polynomials of graphs associated with polycyclic aromatic compounds. Natural logarithmic aromatic indices are derived from these delta polynomials, which are shown to provide new insights into the aromaticity of polycyclic aromatic compounds, including the highly symmetric C60 buckminsterfullerene, several other fullerenes, graphene, kekulene series and other cycloarenes, such as polycyclic circumcoronaphenes and coronoids. The newly developed aromatic index yields a value of 6.77 for graphene, 6.516865 for buckminsterfullerene C60(Ih), 5.914023 for kekulene (D6h symmetry), 6.064420 for coronene (D6h), 6.137828 for circumcoronene (D6h), 6.069668 for dicronylene and so forth. Hence, the novel scaled logarithmic aromatic delta indices developed here appear to provide good quantitative measures of aromaticity, especially when they are used in conjunction with other aromatic indicators.

Robust and versatile assembly for emitter positioning, observation, and heating in atmospheric pressure field desorption mass spectrometry.

Atmospheric pressure field desorption (APFD) mass spectrometry (MS) has recently been introduced as a new variant of field desorption (FD) mass spectrometry. The development aimed at providing the basic characteristics of FD-MS in combination with instruments equipped with an atmospheric pressure (AP) interface. Hitherto, APFD has been demonstrated to yield both positive and negative even electron ions of highly polar or ionic compounds as well as to enable the generation of positive molecular ions, M+•, of polycyclic aromatic compounds. The prototype setup for APFD was based on a nano-electrospray ionization (nanoESI) source slightly modified to allow for emitter positioning in front of the AP interface of a Fourier transform-ion cyclotron resonance (FT-ICR) mass spectrometer. The entrance electrode of the interface was set to negative or positive high voltage with respect to the emitter at ground potential, thereby permitting the formation of positive or negative ions, respectively. This work describes a custom-built device for quicker and more reproducible sample loading on and positioning of field emitters at the entrance electrode of the atmospheric pressure interface of a mass spectrometer. In addition, the device provides means for observation of the emitter during operation and for resistive emitter heating as employed in traditional FD-MS. Emitter heating both speeds up the desorption of the analytes and allows for the desorption/ionization of analytes of higher molecular weight than without emitter heating. In some cases, the signal-to-noise ratio of APFD mass spectra is improved due to higher ion currents effected by compressing the entire process into shorter periods of spectral acquisition. The new setup enables robust and reliable operation in APFD-MS. Moreover, it has been designed as to allow for use on a range of instruments as it can either be used on an FT-ICR mass spectrometer or in combination with a trapped ion mobility-quadrupole-time-of-flight (TIMS-Q-TOF) instrument.

Polycyclic aromatic compounds (PACs) in industrial soils from northwestern of China: occurrence, distribution, exposure risk, and implications on risk-based controls.

Some Polycyclic Aromatic Compounds (PACs) such asnitrated-PAHs (NPAHs), oxygenated-PAHs (OPAHs) and methyl-PAHs (MPAHs) have attracted significant concern due to derivatives have greater potential to be more toxic at low environmental concentrations compared to their PPAHs, particularly in petrochemical industrial region and its surrounding areas surface soils in China.Hence, this article provides an insight into the fate, sources, impacts, and relevance to the external environment of PAH-derivatives based on important emissions source. Moreover, prospective health risk due to their exposure has also been discussed. In this study, the concentration (10-3ng/g) of Ʃ18PPAHs, Ʃ11MPAHs, Ʃ12NPAHs, and Ʃ4OPAHs in the park were 9.67 ± 1.40, 3.24 ± 0.54, 0.03 ± 0.02 and 0.19 ± 0.65, respectively, which were 4.47, 3.89, 2.04 and 1.17 times than of them surrounding the region. A decreasing trend of the low molecular weight (2-4Rings) contribution to the total amount of PAHs, while the fraction of high molecular weight (5-6Rings) species showed the opposite trend. According to the principal component analysis (PCA) and diagnostic ratios indicated PAHs in the soil samples have mixed sources from industrial activities, solid fuel combustion, and heavy traffic. Despite the high concentrations of MPAHs and OPAHs, the toxicity equivalency quotients (TEQs) of them were not calculated due to the lack of toxic equivalent factors (TEF), thus current studies on PAH and derivatives could have underestimated their exposure risks. The quality and sustainable management of soils are crucial for human health and sustainable development, while there is lack of public awareness of the severe issue of soil pollution. It is recommended to conduct more intensive monitoring and regional assessments in the future.

Expanding the Biosynthetic Toolbox: The Potential and Challenges of In Vitro Type II Polyketide Synthase Research

Type II polyketide synthase (PKS) systems are a rich source of structurally diverse polycyclic aromatic compounds with clinically relevant antibiotic and chemotherapeutic properties. The enzymes responsible for synthesizing the polyketide core, known collectively as the minimal cassette, hold potential for applications in synthetic biology. The minimal cassette provides polyketides of different chain lengths, which interact with other enzymes that are responsible for the varied cyclization patterns. Additionally, the type II PKS enzyme clusters offer a wide repertoire of tailoring enzymes for oxidations, glycosylations, cyclizations, and rearrangements. This review begins with the variety of chemical space accessible with type II PKS systems including the recently discovered highly reducing variants that produce polyalkenes instead of the archetypical polyketide motif. The main discussion analyzes the previous approaches with an emphasis on further research that is needed to characterize the minimal cassette enzymes in vitro. Finally, the potential type II PKS systems hold the potential to offer new tools in biocatalysis and synthetic biology, particularly in the production of novel antibiotics and biofuels.

Phosphorane-Promoted C-C Coupling during Aryne Annulations.

Arynes are fleeting, high-energy intermediates that undergo myriad trapping reactions by nucleophiles. Their unusual reactivity compared to other electrophiles can spur unexpected mechanistic pathways enroute to the formation of benzenoid products. Herein we explore a particularly unique case of thermally generated arynes reacting with phosphoranes to form helical dibenzothiophenes and -selenophenes. Multiple new helical polycyclic aromatic products are reported. DP4+ and X-ray crystallographic analysis were used in tandem to confirm the structural topologies of selected products and to demonstrate the utility of DP4+ for distinguishing between isomeric polycyclic aromatic compounds. Lastly, we discuss a plausible mechanism consistent with DFT computations that accounts for the product formation; namely, ligand coupling (i.e., reductive elimination) within a hypervalent, pentacarbon-ligated σ-phosphorane furnishes the dibenzothio- or dibenzoselenophene.

Phosphorane‐Promoted C−C Coupling during Aryne Annulations

AbstractArynes are fleeting, high‐energy intermediates that undergo myriad trapping reactions by nucleophiles. Their unusual reactivity compared to other electrophiles can spur unexpected mechanistic pathways enroute to the formation of benzenoid products. Herein we explore a particularly unique case of thermally generated arynes reacting with phosphoranes to form helical dibenzothiophenes and ‐selenophenes. Multiple new helical polycyclic aromatic products are reported. DP4+ and X‐ray crystallographic analysis were used in tandem to confirm the structural topologies of selected products and to demonstrate the utility of DP4+ for distinguishing between isomeric polycyclic aromatic compounds. Lastly, we discuss a plausible mechanism consistent with DFT computations that accounts for the product formation; namely, ligand coupling (i.e., reductive elimination) within a hypervalent, pentacarbon‐ligated σ‐phosphorane furnishes the dibenzothio‐ or dibenzoselenophene.

Negatively Curved Octagon-Incorporated Aza-nanographene and its Assembly with Fullerenes.

A negatively curved aza-nanographene (NG) containing two octagons was synthesized by a regioselective and stepwise cyclodehydrogenation procedure, in which a double aza[7]helicene was simultaneously formed as an intermediate. Their saddle-shaped structures with negative curvature were unambiguously confirmed by X-ray crystallography, thereby enabling the exploration of the structure-property relationship by photophysical, electrochemical and conformational studies. Moreover, the assembly of the octagon-embedded aza-NG with fullerenes was probed by fluorescence spectral titration, with record-high binding constants (Ka=9.5×103 M-1 with C60, Ka=3.7×104 M-1 with C70) found among reported negatively curved polycyclic aromatic compounds. The tight association of aza-NG with C60 was further elucidated by X-ray diffraction analysis of their co-crystal, which showed the formation of a 1 : 1 complex with substantial concave-convex interactions.

Negatively Curved Octagon‐Incorporated Aza‐nanographene and its Assembly with Fullerenes

AbstractA negatively curved aza‐nanographene (NG) containing two octagons was synthesized by a regioselective and stepwise cyclodehydrogenation procedure, in which a double aza[7]helicene was simultaneously formed as an intermediate. Their saddle‐shaped structures with negative curvature were unambiguously confirmed by X‐ray crystallography, thereby enabling the exploration of the structure–property relationship by photophysical, electrochemical and conformational studies. Moreover, the assembly of the octagon‐embedded aza‐NG with fullerenes was probed by fluorescence spectral titration, with record‐high binding constants (Ka=9.5×103 M−1 with C60, Ka=3.7×104 M−1 with C70) found among reported negatively curved polycyclic aromatic compounds. The tight association of aza‐NG with C60 was further elucidated by X‐ray diffraction analysis of their co‐crystal, which showed the formation of a 1 : 1 complex with substantial concave‐convex interactions.

Pollution Characteristics and Health Risks of Polycyclic Aromatic Compounds (PACs) in Soils of a Coking Plant.

Coke production is an important source of environmental polycyclic aromatic compounds (PACs), including parent polycyclic aromatic hydrocarbons (PAHs) and their derivatives. The focus near coking plants has primarily been on parent-PAH contamination, with less attention given to highly toxic derivatives. In this study, soil samples were collected from both within and outside of a coking plant. The concentrations of parent-PAHs and their derivatives, including methylated-PAHs, oxygenated-PAHs, and nitrated-PAHs, were examined. Spatial interpolation was employed to determine their spatial distribution patterns. Methods for identifying potential sources and conducting incremental lifetime cancer risk analysis were used. This could achieve a comprehensive understanding of the status of PAC pollution and the associated health risks caused by coke production. The concentrations of total PACs inside the plant ranged from 7.4 to 115.8 mg/kg, higher than those outside (in the range of 0.2 to 65.7 mg/kg). The spatial distribution of parent-PAH concentration and their derivatives consistently decreased with increasing distance from the plant. A significant positive correlation (p < 0.05) among parent-PAHs and their derivatives was observed, indicating relatively consistent sources. Based on diagnostic ratios, the potential emission sources of soil PACs could be attributed to coal combustion and vehicle emissions, while principal component analysis-multiple linear regression further indicated that primary emissions and secondary formation jointly influenced the PAC content, accounting for 60.4% and 39.6%, respectively. The exposure risk of soil PACs was dominated by 16 priority control PAHs; the non-priority PAHs' contribution to the exposure risk was only 6.4%.

Palladium-Catalyzed Annulative π-Extension of Bay-Iodinated Triphenylenes to Access Polycyclic Aromatic Compounds.

A palladium-catalyzed annulative π-extension reaction of bay-iodinated triphenylenes with aryl iodides/o-chloroaromatic carboxylic acids was developed. This approach enabled the synthesis of diverse polycyclic aromatic compounds, including dibenzo[fg,op]tetracenes, azadibenzo[fg,op]tetracenes, and tribenzo[a,g,m]coronenes. Initial studies indicate that the resulting product, 2,3,8,9,14,15-hexakis(decyloxy)tribenzo[a,g,m]coronene, exhibits good liquid-crystalline properties.

Exposure to individual polycyclic aromatic compounds impairs the cardiac performance of American lobster (Homarus americanus) larvae

The potential for oil spills poses a threat to marine organisms, the toxicity of which has been attributed primarily to polycyclic aromatic compounds (PACs). Predictive tools such as the target lipid model (TLM) have been developed to forecast and assess these risks. The aim of the present study was to characterize the cardiotoxicity of 10 structurally diverse PACs in American lobster (Homarus americanus) larvae by assessing heart rate following a 48 h exposure in a passive dosing system, and subsequently use the TLM framework to calculate a critical target lipid body burden (CTLBB) for bradycardia. Exposure to 8 of the 10 PACs resulted in concentration-dependent bradycardia, with phenanthrene causing the greatest effect. The TLM was able to effectively characterize bradycardia in American lobsters, and the cardiotoxic CTLBB value determined in this study is among the most sensitive endpoints included in the CTLBB database. This study is one of the first to apply the TLM to a cardiac endpoint and will improve predictive models for assessing sublethal impacts of oil spills on American lobster populations.