A qualitative and quantitative analysis of polycyclic aromatic compounds (PACs; polycyclic aromatic hydrocarbons (PAHs), oxygenated and nitrated polycyclic aromatic hydrocarbons (OPAHs and NPAHs)) present in the soluble organic fraction (SOF) of different soot samples has been carried out to determine the effect of soot-generation conditions on their composition and health effects. The soot samples were generated using a diesel engine bench powered by diesel (DS) and biodiesel (BS) fuels under different combustion conditions. To optimize the procedure, a surrogate soot (Printex-U) and a certified reference material (SRM1650b) were also tested. Different extraction methods were used to extract the PAHs, OPAHs and NPAHs, and the Soxhlet technique using pyridine:acetic acid 1 % was found to be the most suitable procedure to extract the highest concentration (ng mg) and more types of PAHs and OPAHs from the soot. The results show that the PACs identified, and their concentrations, depend on the formation and collection conditions. The predominant compounds in all soot samples studied were fluorene (Flo), phenanthrene (Phe), fluoranthene (Fla), pyrene (Pyr), 9-fluorenone (9Flo) and 9,10-anthraquinone (9,10Anq). As such, the presence of these PACs in the atmosphere of urban and rural areas can mainly be attributed to the emissions from diesel vehicles. The percentage of OPAHs with respect to total PACs was highest in the soot generated from a biofuel. These oxidized compounds favor regeneration of the diesel particulate filter (DPF). The results also indicate that the carcinogenicity of the soot depends on the combustion conditions and type of fuel.
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http://dx.doi.org/10.1016/j.scitotenv.2023.165755 | DOI Listing |
Anal Methods
January 2025
Department of Analytical Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz, Iran.
In the present research, an attempt has been made to develop a new thin film microextraction method for the extraction of several polycyclic aromatic hydrocarbons from aqueous samples collected from different industrial units prior to their analysis by gas chromatography combined with a flame ionization detector. In this approach, a thin iron mesh was modified by the formation of iron(II) oxinate on its surface and used for the extraction of analytes without an additional sorbent. For this purpose, first, the mesh was immersed in a sulfuric acid solution and then transferred into an 8-hydroxy quinoline (oxine) solution dissolved in ammonia solution.
View Article and Find Full Text PDFJ Comput Chem
January 2025
Departamento de Química, Instituto Tecnológico de Aeronáutica, São José dos Campos, Brazil.
In this work, the stability, aromaticity and radical character of pristine and eleven BN-doped armchair 5 and zigzag 5, 6, and 7 periacenes, were chosen for studying the effect of different doping schemes to stabilize the periacene, and to direct the open-shell density into specific regions of the PAH sheets. Ab initio multireference methods and different DFT functionals were used to analyze the singlet triplet (ST) energy. Moreover, a range of descriptors were used to characterize the open-shell character and aromaticity of the different doped structures.
View Article and Find Full Text PDFChemphyschem
January 2025
The University of Sheffield, school of mathematical and physical sciences, UNITED KINGDOM OF GREAT BRITAIN AND NORTHERN IRELAND.
Pentalene (C8H6) and NN- and BB-bridged heterocyclic analogues (BN)4H6, derived by replacement of CC pairs with BN, are taken as paradigms for tuning of ring-current (anti)aromaticity by variation of π charge, electronegativity and substitution pattern. Ab initio calculation of maps for the π current density induced in these model systems by a perpendicular external magnetic field exhibits the full range of tropicity, from diatropic aromatic to nonaromatic to paratropic antiaromatic, with a ready rationalisation in terms of an orbital model. Further calculations on systems of varying charge in which these motifs are embedded in extended PAH systems with naphthalene and phenanthrene 'clamps' show promise for switching between current patterns and related opto-electronic properties.
View Article and Find Full Text PDFChem Asian J
January 2025
Xiamen University, Department of Chemistry, Xiamen University, Lujiaxi Building Room 742, 361005, xiamen, CHINA.
The direct construction of polycyclic arenes through ring formation using simple building blocks is highly appealing but remains challenging in organic chemistry. In this study, we introduce an efficient cascade reaction that combines dearomatizing photocyclization with oxidative aromatization, driven by organophotocatalysis. Conducted under mild, transition-metal-free conditions, this reaction seamlessly converts styrene derivatives into a diverse array of functionalized polycyclic aromatic compounds with good yields and regioselectivity.
View Article and Find Full Text PDFChemphyschem
January 2025
Institute of Molecular Science Marseille, Département de chimie, FRANCE.
Electron delocalization is studied in the ground singlet and first excited triplet states of azulene-containing helicenes. After showing that the compounds we study can be synthesized, we show that they exhibit a charge separation in the ground state, which does not appear in their triplet excited state. Then, magnetically induced properties (IMS3D and ACID) and electron density decomposition methods (EDDB) are used to rationalize aromaticity in these systems.
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