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Molecules (Basel, Switzerland) May 2024In aqueous and solid media, 2-HP-β/γ-CD inclusion complexes with poly aromatic hydrocarbon (PAH) Phenanthrene (PHN), Anthracene (ANT), Benz(a)pyrene (BaP), and...
In aqueous and solid media, 2-HP-β/γ-CD inclusion complexes with poly aromatic hydrocarbon (PAH) Phenanthrene (PHN), Anthracene (ANT), Benz(a)pyrene (BaP), and Fluoranthene (FLT) were investigated for the first time. The inclusion complexes were characterized and investigated using fluorescence and HNMR spectroscopy. The most prevalent complexes consisting of both guests and hosts were those with a 1:1 guest-to-host ratio. The stability constants for the complexes of PHN with 2-HP-β-CD and 2-HP-γ-CD were 85 ± 12 M and 49 ± 29 M, respectively. Moreover, the stability constants were found to be 502 ± 46 M and 289 ± 44 M for the complexes of ANT with both hosts. The stability constants for the complexes of BaP with 2-HP-β-CD and 2-HP-γ-CD were (1.5 ± 0.02) × 10 M and (9.41 ± 0.03) × 10 M, respectively. The stability constant for the complexes of FLT with 2-HP-β-CD was (1.06 ± 0.06) × 10 M. However, FLT was observed to form a weak complex with 2-HP-γ-CD. Molecular dynamic (MD) simulations were used to investigate the mechanism and mode of inclusion processes, and to monitor the atomic-level stability of these complexes. The analysis of MD trajectories demonstrated that all guests formed stable inclusion complexes with both hosts throughout the duration of the simulation time, confirming the experimental findings. However, the flexible Hydroxypropyl arms prevented the PAHs from being encapsulated within the cavity; however, a stable exclusion complex was observed. The main forces that influenced the complexation included van der Waals interactions, hydrophobic forces, and C-H⋯π interaction, which contribute to the stability of these complexes.
PubMed: 38893410
DOI: 10.3390/molecules29112535 -
ACS Omega Jun 2024Microplastics have been detected in various food types, suggesting inevitable human exposure. A major fraction may originate from aerial deposition and could be...
Microplastics have been detected in various food types, suggesting inevitable human exposure. A major fraction may originate from aerial deposition and could be contaminated by ubiquitous pollutants such as polycyclic aromatic hydrocarbons (PAHs). While data on the sorption of pollutants to microplastics are abundant, the subsequent desorption in the gastrointestinal tract (GIT) is less understood. This prompted us to systematically investigate the release of microplastics-sorbed PAHs at realistic loadings (44-95 ng/mg) utilizing a physiology-based in vitro model comprising digestion in simulated saliva, gastric, and small and large intestinal fluids. Using benzo[]pyrene as a representative PAH, desorption from different microplastics based on low density polyethylene (LDPE), thermoplastic polyurethanes (TPUs), and polyamides (PAs) was investigated consecutively in all four GIT fluid simulants. The cumulative relative desorption (CRD) of benzo[]pyrene was negligible in saliva simulant but increased from gastric (4 ± 1% - 15 ± 4%) to large intestinal fluid simulant (21 ± 1% - 29 ± 6%), depending on the polymer type. CRDs were comparable for ten different microplastics in the small intestinal fluid simulant, except for a polydisperse PA-6 variant (1-10 μm), which showed an exceptionally high release (51 ± 8%). Nevertheless, the estimated contribution of microplastics-sorbed PAHs to total human PAH dietary intake was very low (≤0.1%). Our study provides a systematic data set on the desorption of PAHs from microplastics in GIT fluid simulants.
PubMed: 38882100
DOI: 10.1021/acsomega.3c09380 -
Environment International Jul 2024In experimental studies, several polycyclic aromatic hydrocarbons (PAHs) have shown endocrine disrupting properties, but very few epidemiological studies have examined...
BACKGROUND
In experimental studies, several polycyclic aromatic hydrocarbons (PAHs) have shown endocrine disrupting properties, but very few epidemiological studies have examined their impact on pubertal development and results have been heterogenous.
OBJECTIVE
To explore if maternal PAH exposure during pregnancy was associated with the offspring's timing of pubertal onset.
METHODS
We studied 582 mother-daughter dyads originating from a population-based cohort in a rural setting in Bangladesh. Maternal urinary samples, collected in early pregnancy (on average, gestational week 8), were analyzed for monohydroxylated metabolites of phenanthrene (1-OH-Phe, Σ2-,3-OH-Phe, and 4-OH-Phe), fluorene (Σ2-,3-OH-Flu), and pyrene (1-OH-Pyr) using liquid chromatography with tandem mass spectrometry (LC-MS/MS). The girls were interviewed on two separate occasions concerning date of menarche, as well as breast and pubic hair development according to Tanner. Associations were assessed using Kaplan-Meier analysis and multivariable-adjusted Cox proportional hazards regression or ordered logistic regression.
RESULTS
In early pregnancy, the mothers' median urinary concentrations of Σ1-,2-,3-,4-OH-Phe, Σ2-,3-OH-Flu, and 1-OH-Pyr were 3.25 ng/mL, 2.0 ng/mL, and 2.3 ng/mL respectively. At the second follow-up, 78 % of the girls had reached menarche, and the median age of menarche was 12.7 ± 0.81 years. Girls whose mothers belonged to the second and third quintiles of ΣOH-Phe metabolites had a higher rate of menarche, indicating a younger menarcheal age (HR 1.39; 95 % CI 1.04, 1.86, and HR 1.41; 95 % CI 1.05, 1.88, respectively), than girls of mothers in the lowest quintile. This trend was not observed in relation to either breast or pubic hair development. None of the other maternal urinary PAH metabolites or the sum of all thereof in early pregnancy were associated with age at menarche or pubertal stage.
CONCLUSIONS
Indications of non-monotonic associations of prenatal phenanthrene exposure with the daughters' age of menarche were found, warranting further investigation.
Topics: Humans; Female; Pregnancy; Polycyclic Aromatic Hydrocarbons; Bangladesh; Maternal Exposure; Rural Population; Adult; Prenatal Exposure Delayed Effects; Adolescent; Puberty; Child; Longitudinal Studies; Environmental Pollutants; Menarche; Cohort Studies; Young Adult
PubMed: 38875814
DOI: 10.1016/j.envint.2024.108798 -
Chemical Science Jun 2024Controlling chemical functionalization and achieving stable electrode-molecule interfaces for high-performance electrochemical energy storage applications remain...
Controlling chemical functionalization and achieving stable electrode-molecule interfaces for high-performance electrochemical energy storage applications remain challenging tasks. Herein, we present a simple, controllable, scalable, and versatile electrochemical modification approach of graphite rods (GRs) extracted from low-cost Eveready cells that were covalently modified with anthracene oligomers. The anthracene oligomers with a total layer thickness of ∼24 nm on the GR electrode yield a remarkable specific capacitance of ∼670 F g with good galvanostatic charge-discharge cycling stability (10 000) recorded in 1 M HSO electrolyte. Such a boost in capacitance is attributed mainly to two contributions: (i) an electrical double-layer at the anthracene oligomer/GR/electrolyte interfaces, and (ii) the proton-coupled electron transfer (PCET) reaction, which ensures a substantial faradaic contribution to the total capacitance. Due to the higher conductivity of the anthracene films, it possesses more azo groups (-N[double bond, length as m-dash]N-) during the electrochemical growth of the oligomer films compared to pyrene and naphthalene oligomers, which is key to PCET reactions. AC-based electrical studies unravel the in-depth charge interfacial electrical behavior of anthracene-grafted electrodes. Asymmetrical solid-state supercapacitor devices were made using anthracene-modified biomass-derived porous carbon, which showed improved performance with a specific capacitance of ∼155 F g at 2 A g with an energy density of 5.8 W h kg at a high-power density of 2010 W kg and powered LED lighting for a longer period. The present work provides a promising metal-free approach in developing organic thin-film hybrid capacitors.
PubMed: 38873075
DOI: 10.1039/d4sc00611a -
RSC Advances Jun 2024The aim of this study was to develop a new method for sampling and analyzing polycyclic aromatic hydrocarbons in the air. This was achieved by utilizing a needle trap...
The aim of this study was to develop a new method for sampling and analyzing polycyclic aromatic hydrocarbons in the air. This was achieved by utilizing a needle trap device packed with a modified porous aromatic framework coated with magnetic nanoparticles (PAF-6-MNPs). The modified adsorbent underwent qualitative evaluation using Fourier-transform infrared spectroscopy and X-ray diffraction, as well as scanning and transmission electron microscopy. The optimal conditions for sampling polycyclic aromatic hydrocarbons compounds were determined using a dynamic atmosphere chamber. The method was validated by taking various samples from the standard chamber, and then analyzed under different environmental sampling conditions using a gas chromatography device. The limit of detection (LOD) and limit of quantification (LOQ) values for the analytes of interest, including naphthalene, anthracene, and pyrene, ranged from 0.0034-0.0051 and 0.010-0.015 μg L, respectively. Also, the repeatability and reproducibility of the method expressed as relative standard deviation, for the mentioned analyses were found to be in the range of 17.8-20.5% and 20-22.9%. The results indicated that over a 20 day storage period (with the needle trap device containing the analytes of interest kept in the refrigerator), there was no significant decrease in the amount of analytes compared to the initial amount. These findings suggest that, the needle trap packed with the proposed adsorbent offers a reliable, highly-sensitive, easy-to-use, and cost-effective method for sampling polycyclic aromatic hydrocarbons in the air compared to the conventional method recommended by the National Institute of Occupational Safety and Health (NIOSH), method 5515.
PubMed: 38860255
DOI: 10.1039/d4ra01651c -
Scientific Reports Jun 2024This study investigates the environmental impact of burning herbicide-contaminated biomass, focusing on atrazine (ATZ) and diuron (DIU) sprayed on rice straw prior to...
This study investigates the environmental impact of burning herbicide-contaminated biomass, focusing on atrazine (ATZ) and diuron (DIU) sprayed on rice straw prior to burning. Samples of soil, biomass residues, total suspended particulate (TSP), particulate matter with an aerodynamic diameter ≤ 10 µm (PM), and aerosols were collected and analyzed. Soil analysis before and after burning contaminated biomass showed significant changes, with 2,4-dichlorophenoxyacetic acid (2,4-D) initially constituting 79.2% and decreasing by 3.3 times post-burning. Atrazine-desethyl, sebuthylazine, and terbuthylazine were detected post-burning. In raw rice straw biomass, terbuthylazine dominated at 80.0%, but burning ATZ-contaminated biomass led to the detection of atrazine-desethyl and notable increases in sebuthylazine and terbuthylazine. Conversely, burning DIU-contaminated biomass resulted in a shift to 2,4-D dominance. Analysis of atmospheric components showed changes in TSP, PM, and aerosol samples. Linuron in ambient TSP decreased by 1.6 times after burning ATZ-contaminated biomass, while atrazine increased by 2.9 times. Carcinogenic polycyclic aromatic hydrocarbons (PAHs), including benzo[a]anthracene (BaA), benzo[a]pyrene (BaP), and benzo[b]fluoranthene (BbF), increased by approximately 9.9 to 13.9 times after burning ATZ-contaminated biomass. In PM, BaA and BaP concentrations increased by approximately 11.4 and 19.0 times, respectively, after burning ATZ-contaminated biomass. This study sheds light on the environmental risks posed by burning herbicide-contaminated biomass, emphasizing the need for sustainable agricultural practices and effective waste management. The findings underscore the importance of regulatory measures to mitigate environmental contamination and protect human health.
Topics: Atrazine; Oryza; Herbicides; Biomass; Soil; Diuron; Soil Pollutants; Air Pollutants; Environmental Monitoring; Particulate Matter
PubMed: 38858445
DOI: 10.1038/s41598-024-64291-2 -
Nature Communications Jun 2024Tobacco smoking (TS) is implicated in lung cancer (LC) progression through the development of metabolic syndrome. However, direct evidence linking metabolic syndrome to...
Tobacco smoking (TS) is implicated in lung cancer (LC) progression through the development of metabolic syndrome. However, direct evidence linking metabolic syndrome to TS-mediated LC progression remains to be established. Our findings demonstrate that 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone and benzo[a]pyrene (NNK and BaP; NB), components of tobacco smoke, induce metabolic syndrome characteristics, particularly hyperglycemia, promoting lung cancer progression in male C57BL/6 J mice. NB enhances glucose uptake in tumor-associated macrophages by increasing the expression and surface localization of glucose transporter (GLUT) 1 and 3, thereby leading to transcriptional upregulation of insulin-like growth factor 2 (IGF2), which subsequently activates insulin receptor (IR) in LC cells in a paracrine manner, promoting its nuclear import. Nuclear IR binds to nucleophosmin (NPM1), resulting in IR/NPM1-mediated activation of the CD274 promoter and expression of programmed death ligand-1 (PD-L1). Restricting glycolysis, depleting macrophages, or blocking PD-L1 inhibits NB-mediated LC progression. Analysis of patient tissues and public databases reveals elevated levels of IGF2 and GLUT1 in tumor-associated macrophages, as well as tumoral PD-L1 and phosphorylated insulin-like growth factor 1 receptor/insulin receptor (pIGF-1R/IR) expression, suggesting potential poor prognostic biomarkers for LC patients. Our data indicate that paracrine IGF2/IR/NPM1/PD-L1 signaling, facilitated by NB-induced dysregulation of glucose levels and metabolic reprogramming of macrophages, contributes to TS-mediated LC progression.
Topics: Animals; Lung Neoplasms; Male; Humans; Mice, Inbred C57BL; Receptor, Insulin; Mice; B7-H1 Antigen; Hyperglycemia; Benzo(a)pyrene; Nucleophosmin; Insulin-Like Growth Factor II; Disease Progression; Nuclear Proteins; Nitrosamines; Tumor-Associated Macrophages; Cell Line, Tumor; Paracrine Communication; Gene Expression Regulation, Neoplastic; Smoking; Macrophages
PubMed: 38851766
DOI: 10.1038/s41467-024-49199-9 -
Nature Communications Jun 2024Developing highly active materials that efficiently utilize solar spectra is crucial for photocatalysis, but still remains a challenge. Here, we report a new...
Developing highly active materials that efficiently utilize solar spectra is crucial for photocatalysis, but still remains a challenge. Here, we report a new donor-acceptor (D-A) covalent organic framework (COF) with a wide absorption range from 200 nm to 900 nm (ultraviolet-visible-near infrared light). We find that the thiophene functional group is accurately introduced into the electron acceptor units of TpDPP-Py (TpDPP: 5,5'-(2,5-bis(2-ethylhexyl)-3,6-dioxo-2,3,5,6-tetrahydropyrrolo [3,4-c]pyrrole-1,4-diyl)bis(thiophene-2-carbaldehyde), Py: 1,3,6,8-tetrakis(4-aminophenyl)pyrene) COFs not only significantly extends its spectral absorption capacity but also endows them with two-photon and three-photon absorption effects, greatly enhancing the utilization rate of sunlight. The selective coupling of benzylamine as the target reactant is used to assess the photocatalytic activity of TpDPP-Py COFs, showing high photocatalytic conversion of 99% and selectivity of 98% in 20 min. Additionally, the TpDPP-Py COFs also exhibit the universality of photocatalytic selective coupling of other imine derivatives with ~100% conversion efficiency. Overall, this work brings a significant strategy for developing COFs with a wide absorption range to enhance photocatalytic activity.
PubMed: 38849337
DOI: 10.1038/s41467-024-49036-z -
Inorganic Chemistry Jun 2024Three novel bismuth-organic compounds, with the general formula [Bi(HPDC)(PDC)]·(arene)·2HO (HPDC = 2,6-pyridinedicarboxylic acid; arene = pyrene, naphthalene, and...
Three novel bismuth-organic compounds, with the general formula [Bi(HPDC)(PDC)]·(arene)·2HO (HPDC = 2,6-pyridinedicarboxylic acid; arene = pyrene, naphthalene, and azulene), that consist of neutral dinuclear Bi-pyridinedicarboxylate complexes and outer coordination sphere arene molecules were synthesized and structurally characterized. The structures of all three phases exhibit strong π-π stacking interactions between the Bi-bound PDC/HPDC and outer sphere organic molecules; these interactions effectively sandwich the arene molecules between bismuth complexes and thereby prevent molecular vibrations. Upon UV irradiation, the compounds containing pyrene and naphthalene displayed red and green emission, respectively, with quantum yields of 1.3(2) and 30.8(4)%. The emission was found to originate from the T → S transition of the corresponding arene and result in phosphorescence characteristic of the arene employed. By comparison, the azulene-containing compound displayed very weak blue-purple phosphorescence of unknown origin and is a rare example of T → S emission from azulene. The pyrene- and naphthalene-containing compounds both display radioluminescence, with intensities of 11 and 38% relative to bismuth germanate, respectively. Collectively, these results provide further insights into the structure-property relationships that underpin luminescence from Bi-based materials and highlight the utility of Bi-organic molecules in the realization of organic emission.
PubMed: 38823026
DOI: 10.1021/acs.inorgchem.4c00606