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Nature Communications Apr 2024Carbaporphyrin dimers, investigated for their distinctive electronic structures and exceptional properties, have predominantly consisted of systems containing identical...
Carbaporphyrin dimers, investigated for their distinctive electronic structures and exceptional properties, have predominantly consisted of systems containing identical subunits. This study addresses the associated knowledge gap by focusing on asymmetric carbaporphyrin dimers with Janus-like characteristics. The synthesis of a Janus-type carbaporphyrin pseudo-dimer 5 is presented. It displays antiaromatic characteristics on the fused side and nonaromatic behavior on the unfused side. A newly synthesized tetraphenylene (TPE) linked bis-dibenzihomoporphyrin 8 and a previously reported dibenzo[g,p]chrysene (DBC) linked bis-dicarbacorrole 9 were prepared as controls. Comprehensive analyses, including H NMR spectral studies, single crystal X-ray diffraction analyses, and DFT calculations, validate the mixed character of 5. A further feature of the Janus pseudo-dimer 5 is that it may be transformed into a heterometallic complex, with one side coordinating a Cu(III) center and the other stabilizing a BODIPY complex. This disparate regiochemical reactivity underscores the potential of carbaporphyrin dimers as versatile frameworks, with electronic features and site-specific coordination chemistry controlled through asymmetry. These findings position carbaporphyrin dimers as promising candidates for advances in electronic structure studies, coordination chemistry, materials science, and beyond.
PubMed: 38575609
DOI: 10.1038/s41467-024-47239-y -
Food Research International (Ottawa,... Jul 2022More than 5.8 million tonnes of oil have been spilled into the oceans. Some oil disasters marked history, causing multiple social and economic consequences in addition... (Review)
Review
More than 5.8 million tonnes of oil have been spilled into the oceans. Some oil disasters marked history, causing multiple social and economic consequences in addition to catastrophic environmental impacts. Recently, Brazil and Mauritius faced oil disasters that have severely impacted seafood sanitary credibility. One of the components of the oil composition are the polycyclic aromatic hydrocarbons (PAH), which are the main contamination markers of petrogenic origin. There is enough evidence to correlate the intake of food contaminated with PAH with increased risks of developing cancer. The set PAH4, composed of benzo[a]anthracene, benzo[a]pyrene, benzo[b]fluoranthene, and chrysene, and the set PAH8, composed of benzo[a]anthracene, benzo[a]pyrene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[ghi]perylene, chrysene, dibenzo[a,h]anthracene, and indeno[1,2,3-cd]pyrene are recognized as markers of food chemical contamination. After oil disasters in the oceans, the risk to the health of seafood consumers tends to be of special concern, Countries like the European Union set maximum levels for benzo[a]pyrene (5 µg kg) and PAH4 (30 µg kg) in bivalve mollusks. Levels of concern established by countries that have faced oil disasters are given special attention in this review. Laboratory analysis of PAH in food samples is very challenging because it deals with quite different kinds of matrices. Furthermore, analytical results are usually related to the closure or reopening of cultivated areas and fishing points. Therefore, the progress of the analytical methods for PAH in seafood is covered in detail. Chemical laboratory measurements provide essential data to assess the potential risks to human health due to consumption of seafood contaminated with PAH. The main human health risk assessment approaches in a seafood contamination scenario with PAH are reviewed and discussed, providing an insightful and guiding tool to each step of the risk assessment framework.
Topics: Anthracenes; Benzo(a)pyrene; Chrysenes; Disasters; Food Safety; Humans; Petroleum Pollution; Polycyclic Aromatic Hydrocarbons
PubMed: 35761626
DOI: 10.1016/j.foodres.2022.111366 -
Molecules (Basel, Switzerland) Jan 2023Soil organic matter (SOM) and its heterogeneous nature constitutes the main factor determining the fate and transformation of organic chemicals (OCs). Thus, the aim of... (Review)
Review
Soil organic matter (SOM) and its heterogeneous nature constitutes the main factor determining the fate and transformation of organic chemicals (OCs). Thus, the aim of thus research was to analyze the influence of the molecular chemodiversity of a stable SOM (S-SOM) on the sorption potential of different groups of OCs (organochloride pesticides—OCPs, and non-chlorinated pesticides—NCPs, polycyclic aromatic hydrocarbons—PAHs). The research was conducted as a batch experiment. For this purpose, a S-SOM was separated from six soils (TOC = 15.0−58.7 gkg−1; TN = 1.4−6.6 gkg−1, pH in KCl = 6.4−7.4 and WRB taxonomy: fluvisols, luviosols, leptosols) by alkaline urea and dimethylsulphoxide with sulfuric acid. Isolated S-SOM fraction was evaluated by UV−VIS, FT-IR and EEM spectroscopy to describe molecular diversity, which allowed the assessment of its potential sorption properties regarding OCs. In order to directly evaluate the sorption affinity of individual OCs to S-SOM, the mixture of the 3 deuterated contaminants: chrysene (PAHs), 4,4′DDT (OCPs) atrazine (NCPs) were applied. The sorption experiment was carried out according to the 106 OECD Guidelines. The OCs concentration was analyzed by gas chromatography triple mass spectrometry (GC-MS/MS). OCs were characterized by different sorption rates to S-SOM fractions according to the overall trend: atrazine (87.5−99.9%) > 4,4′DDT (64−81.6%) > chrysene (35.2−79.8%). Moreover, atrazine exhibited the highest saturation dynamic with fast bounding time amounting to 6 h of contact with S-SOM. Proportionally, the chrysene showed the slowest binding time achieving an average of 55% sorption after 78 h. Therefore, S-SOM isolated from different soils demonstrated varying binding capacity to OCs (CoV = 21%, 27% and 33% for atrazine, DDT and chrysene, respectively). Results indicate that each sample contains S-SOM with different degrees of transformation and sorption properties that affect the OCs availability in soil. Spectroscopic analyses have shown that the main component of S-SOM are biopolymers at various stages of transformation that contain numerous aromatic−aliphatic groups with mostly hydrophilic substituents.
Topics: Soil; Atrazine; Chrysenes; Spectroscopy, Fourier Transform Infrared; DDT; Tandem Mass Spectrometry; Adsorption; Pesticides; Organic Chemicals; Soil Pollutants
PubMed: 36615617
DOI: 10.3390/molecules28010429 -
Toxicology and Applied Pharmacology Mar 2022Dibenzo[def,p]chrysene (DBC) is an environmental polycyclic aromatic hydrocarbon (PAH) that causes tumors in mice and has been classified as a probable human carcinogen...
Dibenzo[def,p]chrysene (DBC) is an environmental polycyclic aromatic hydrocarbon (PAH) that causes tumors in mice and has been classified as a probable human carcinogen by the International Agency for Research on Cancer. Animal toxicity studies often utilize higher doses than are found in relevant human exposures. Additionally, like many PAHs, DBC requires metabolic bioactivation to form the ultimate toxicant, and species differences in DBC and DBC metabolite metabolism have been observed. To understand the implications of dose and species differences, a physiologically based pharmacokinetic model (PBPK) for DBC and major metabolites was developed in mice and humans. Metabolism parameters used in the model were obtained from experimental in vitro metabolism assays using mice and human hepatic microsomes. PBPK model simulations were evaluated against mice dosed with 15 mg/kg DBC by oral gavage and human volunteers orally microdosed with 29 ng of DBC. DBC and its primary metabolite DBC-11,12-diol were measured in blood of mice and humans, while in urine, the majority of DBC metabolites were obeserved as conjugated DBC-11,12-diol, conjugated DBC tetrols, and unconjugated DBC tetrols. The PBPK model was able to predict the time course concentrations of DBC, DBC-11,12-diol, and other DBC metabolites in blood and urine of human volunteers and mice with reasonable accuracy. Agreement between model simulations and measured pharmacokinetic data in mice and human studies demonstrate the success and versatility of our model for interspecies extrapolation and applicability for different doses. Furthermore, our simulations show that internal dose metrics used for risk assessment do not necessarily scale allometrically, and that PBPK modeling provides a reliable approach to appropriately account for interspecies differences in metabolism and physiology.
Topics: Animals; Carcinogens; Chrysenes; Cystine; Female; Humans; Male; Mice; Models, Biological; Neoplasms
PubMed: 34933053
DOI: 10.1016/j.taap.2021.115830 -
The Science of the Total Environment Jun 2022The present study aimed to, for the first time, quantify the total content of 16 priority EPA PAHs in end-of-life tyre derived crumb rubber granulates and various...
The present study aimed to, for the first time, quantify the total content of 16 priority EPA PAHs in end-of-life tyre derived crumb rubber granulates and various manufactured rubberised asphalt mix designs. After identifying the availability of 16 EPA PAHs, the leaching behaviour of rubberised asphalt specimens, were evaluated using the Dynamic Surface Leaching Test (DSLT) based on CEN/TS 16637-2:2014 standard. This was prior to modelling the release mechanisms of PAHs by utilizing a mathematical diffusion-controlled leaching model. According to the results, the total content of 16 EPA PAHs in crumb rubber granulates ranged between 0.061 and 8.322 μg/g, which were associated with acenaphthene and pyrene, respectively. The total content of PAHs in rubberised asphalt specimens varied between 0.019 and 4.992 μg/g depending on the volume of crumb rubber granulates in the asphalt concrete mix design, and type of binder. Results of the leaching experiments revealed that the highest leached PAHs were benzo[b]fluoranthene, benzo[k]fluoranthene and naphthalene with a 64-days cumulative release per specimen surface area > 1 μg/m. Acenaphthylene, fluoranthene, fluorene and indeno[1,2,3-c,d]pyrene were released in cumulative concentrations between 0.1 and 1 μg/m. The PAHs with a cumulative release potential below 0.1 μg/m during DSLT were benzo[a]anthracene, benzo[a]pyrene, benzo[g,h,i]perylene and chrysene. The diffusion coefficients, which were calculated by mathematical modelling of DSLT data, revealed that the leaching process of 16 EPA PAHs from surface of rubberised asphalt concrete mix designs fitted all the criteria set by the NEN 7345 standard for diffusion-controlled leaching during all stages of leaching experiments.
Topics: Benzo(a)pyrene; Hydrocarbons; Polycyclic Aromatic Hydrocarbons; Rubber
PubMed: 35189212
DOI: 10.1016/j.scitotenv.2022.153983 -
Genes and Environment : the Official... 2016Toxicogenomics is a rapidly developing discipline focused on the elucidation of the molecular and cellular effects of chemicals on biological systems. As a collaborative... (Review)
Review
Toxicogenomics is a rapidly developing discipline focused on the elucidation of the molecular and cellular effects of chemicals on biological systems. As a collaborative study group of Toxicogenomics/JEMS·MMS, we conducted studies on hepatocarcinogens in rodent liver in which 100 candidate marker genes were selected to discriminate genotoxic hepatocarcinogens from non-genotoxic hepatocarcinogens. Differential gene expression induced by 13 chemicals were examined using DNA microarray and quantitative real-time PCR (qPCR), including eight genotoxic hepatocarcinogens [o-aminoazotoluene, chrysene, dibenzo[a,l]pyrene, diethylnitrosamine (DEN), 7,12-dimethylbenz[a]anthracene, dimethylnitrosamine, dipropylnitrosamine and ethylnitrosourea (ENU)], four non-genotoxic hepatocarcinogens [carbon tetrachloride, di(2-ethylhexyl)phthalate (DEHP), phenobarbital and trichloroethylene] and a non-genotoxic non-hepatocarcinogen [ethanol]. Using qPCR, 30 key genes were extracted from mouse livers at 4 h and 28 days following dose-dependent gene expression alteration induced by DEN and ENU: the most significant changes in gene expression were observed at 4 h. Next, we selected key point times at 4 and 48 h from changes in time-dependent gene expression during the acute phase following administration of chrysene by qPCR. We successfully showed discrimination of eight genotoxic hepatocarcinogens [2-acetylaminofluorene, 2,4-diaminotoluene, diisopropanolnitrosamine, 4-dimethylaminoazobenzene, 4-(methylnitsosamino)-1-(3-pyridyl)-1-butanone, N-nitrosomorpholine, quinoline and urethane] from four non-genotoxic hepatocarcinogens [1,4-dichlorobenzene, dichlorodiphenyltrichloroethane, DEHP and furan] using qPCR and principal component analysis. Additionally, we successfully identified two rat genotoxic hepatocarcinogens [DEN and 2,6-dinitrotoluene] from a nongenotoxic-hepatocarcinogen [DEHP] and a non-genotoxic non-hepatocarcinogen [phenacetin] at 4 and 48 h. The subsequent gene pathway analysis by Ingenuity Pathway Analysis extracted the DNA damage response, resulting from the signal transduction of a p53-class mediator leading to the induction of apoptosis. The present review of these studies suggests that application of principal component analysis on the gene expression profile in rodent liver during the acute phase is useful to predict genotoxic hepatocarcinogens in comparison to non-genotoxic hepatocarcinogens and/or non-carcinogenic hepatotoxins.
PubMed: 27482301
DOI: 10.1186/s41021-016-0041-0 -
Foods (Basel, Switzerland) Feb 2023The physicochemical traits and an array of organic and inorganic contaminants were monitored in monofloral honeys (i.e., jujube [], sweet orange [], PGI Euphorbia [] and...
The physicochemical traits and an array of organic and inorganic contaminants were monitored in monofloral honeys (i.e., jujube [], sweet orange [], PGI Euphorbia [] and ) from the Moroccan Béni Mellal-Khénifra region (i.e., Khénifra, Beni Méllal, Azlal and Fquih Ben Salah provinces). Moroccan honeys were in line with the physicochemical standards set by the European Union. However, a critical contamination pattern has been outlined. In fact, jujube, sweet orange, and PGI Euphorbia honeys contained pesticides, such as acephate, dimethoate, diazinon, alachlor, carbofuran and fenthion sulfoxide, higher than the relative EU Maximum Residue Levels. The banned 2,3',4,4',5-pentachlorobiphenyl (PCB118) and 2,2',3,4,4',5,5'-heptachlorobiphenyl (PCB180) were detected in all samples and quantified in jujube, sweet orange and PGI Euphorbia honeys; while polycyclic aromatic hydrocarbons (PAHs), such as chrysene and fluorene, stood out for their higher contents in jujube and sweet orange honeys. Considering plasticizers, all honeys showed an excessive amount of dibutyl phthalate (DBP), when (improperly) considering the relative EU Specific Migration Limit. Furthermore, sweet orange, PGI Euphorbia and honeys were characterized by Pb exceeding the EU Maximum Level. Overall, data from this study may encourage Moroccan governmental bodies to strengthen their monitoring activity in beekeeping and to find suitable solutions for implementing more sustainable agricultural practices.
PubMed: 36900486
DOI: 10.3390/foods12050969 -
RSC Advances Sep 2018The composition and physical properties of spilled oil undergo great changes during a serious weathering process. This causes great difficulties for identifying the...
Evaluation of diagnostic ratios of phenanthrenes and chrysenes for the identification of severely weathered spilled oils from the simulation weathering and the Sinopec pipeline explosion at Huangdao, 2013.
The composition and physical properties of spilled oil undergo great changes during a serious weathering process. This causes great difficulties for identifying the source of an oil spill. So stable and trustworthy diagnostic ratios (DRs) for the accurate identification of severely weathered spilled oils are very important. An explosion in the Sinopec pipeline happened on November 22, 2013 at Qingdao, China. Local beaches at Jiaozhou Bay were polluted by spilled oils. After the accident we collected original spilled oil samples from an area free from human interference near the oil leakage point. Synchronized with actual beach weathering, laboratory experiments were conducted to simulate oil weathering for 360 days by using the collected original spilled oil samples. Based on the -test and the repeatability limit method, 46 diagnostic ratios (DRs) of phenanthrenes and chrysenes were screened. 18 DRs maintained remarkable stability during the simulated weathering experiments and field weathering process. These stable ratios can retain the characteristics of the oil source during weathering. They are very beneficial for improving the accuracy of identifying the source of severely weathered oil and can be used as an effective supplement to the existing index system for source identification.
PubMed: 35547522
DOI: 10.1039/c8ra03154a -
Angewandte Chemie (International Ed. in... Aug 2021Two subvalent, redox-active diborane(4) anions, [3] and [3] , carrying exceptionally high negative charge densities are reported: Reduction of 9-methoxy-9-borafluorene...
Two subvalent, redox-active diborane(4) anions, [3] and [3] , carrying exceptionally high negative charge densities are reported: Reduction of 9-methoxy-9-borafluorene with Li granules without stirring leads to the crystallization of the B(sp )-B(sp ) diborane(5) anion salt Li[5]. [5] contains a 2,2'-biphenyldiyl-bridged B-B core, a chelating 2,2'-biphenyldiyl moiety, and a MeO substituent. Reduction of Li[5] with Na metal gives the Na salt of the tetraanion [3] in which two doubly reduced 9-borafluorenyl fragments are linked via a B-B single bond. Comproportionation of Li[5] and Na [3] quantitatively furnishes the diborane(4) dianion salt Na [3], the doubly boron-doped congener of 9,9'-bis(fluorenylidene). Under acid catalysis, Na [3] undergoes a formal Stone-Wales rearrangement to yield a dibenzo[g,p]chrysene derivative with B=B core. Na [3] shows boron-centered nucleophilicity toward n-butyl chloride. Na [3] produces bright blue chemiluminescence when exposed to air.
PubMed: 34161639
DOI: 10.1002/anie.202106980 -
Frontiers in Cell and Developmental... 2023Polyaromatic hydrocarbons (PAHs) are considered as redox active environmental toxicants inducing oxidative stress (OS) mediated injury to cells. Oxidative predominance...
Polyaromatic hydrocarbons (PAHs) are considered as redox active environmental toxicants inducing oxidative stress (OS) mediated injury to cells. Oxidative predominance is reported in 30%-80% of idiopathic male infertility (IMI) patients. Hence, this work aims to unravel correlation, if any, between seminal PAH exposome and sperm function in IMI patients through a proteomic approach. Seminal PAH exposome was analyzed in 43 fertile donors and 60 IMI patients by HPLC and receiver operating characteristic (ROC) curve was applied to find out the cut-off limits. Spermatozoa proteome was analyzed by label free liquid chromatography mass spectroscopy (LC-MS/MS) followed by molecular pathway analysis using bioinformatic tools. Validation of key proteins' expression and protein oxidative modifications were analyzed by western blot. Of the 16 standards toxic PAH, 13 were detected in semen. Impact of the different PAHs on fertility are Anthracene < benzo (a) pyrene < benzo [b] fluoranthene < Fluoranthene < benzo (a) anthracene
PubMed: 37261076
DOI: 10.3389/fcell.2023.1117155