Search Results (151)

The dissociation of the C-NO₂ bond is the initial step in the process of the detonation of nitroaromatic explosives. The strength of the C-NO₂ bond is significantly influenced by the relative position of the nitro group with respect to the aromatic ring plane since the planar arrangement enables the delocalization of electron density, which strengthens this bond. In this study, we have combined a statistical analysis of geometrical parameters extracted from crystal structures of trinitroaromatic molecules with ab initio calculations of non-covalent index plots and Wiberg bond index values for selected trinitroaromatic molecules to elucidate the influence of nearby substituents on the relative position of nitro groups with respect to the aromatic ring plane. The results of the analysis showed that neighboring substituents have a significant impact on the geometry of nitro groups. The results also showed that this influence arises from the repulsive interaction of voluminous substituents, attractive non-covalent contacts, and the electronic effects of substituents. Full article

The Metropolitan Area of Queretaro (MAQ) is a significant industrial hub in central Mexico whose air quality, including high concentrations of particulate matter (PM), poses a risk to the population. However, there have not been many studies on the sources and processes that influence the concentration of atmospheric pollutants. We used aerosol chemical composition and meteorological data from 1 January to 15 May 2022, along with back-trajectory modeling, to investigate emission sources not previously described in the region and the impact of local and regional meteorology on the chemical composition of aerosols. Furthermore, this study presents the first quantitative analysis of nitroaromatic compounds (NACs) in particulate matter in the MAQ using ultra-performance liquid chromatography coupled with high-resolution mass spectrometry. The NAC concentrations ranged from 0.086 to 3.618 ng m⁻³, with the highest concentrations occurring during a period of atmospheric stability. The secondary inorganic and organic fractions of the PM were the most abundant (50%) of the PM concentration throughout the campaign. Local and regional meteorology played a significant role in the variability of PM chemical composition, as it influenced oxidation and transport processes. The results reveal that emissions from biomass burning are a recurrent PM source, and regional emissions significantly impact the organic fraction of the PM. These results underscore the importance of considering both local and regional sources in assessing air pollution in the region. Full article

The detection of explosives is highly important for the investigation of explosion cases and public safety management. However, the detection of trace explosive residues in complex matrices remains a major challenge. Molecularly imprinted polymers (MIPs), which mimic the antigen–antibody recognition mechanism, can selectively recognize and bind target explosive molecules. They offer advantages such as high efficiency, specificity, renewability, and ease of preparation, and they have shown significant potential for the efficient extraction and highly sensitive detection of trace explosive residues in complex matrices. This review comprehensively discusses the applications of MIPs in the analysis of explosives; systematically summarizes the preparation methods; and evaluates their performance in detecting nitroaromatic explosives, nitrate esters, nitroamine explosives, and peroxide explosives. Finally, this review explores the future potential of emerging technologies in enhancing the MIP-based analysis of explosives. The aim is to support the further application of MIPs in the investigation of explosion cases and safety management, providing more effective technical solutions for public safety. Full article

Nitro-functionalized heterocycles, such as nitroimidazoles, are significant environmental contaminants and have been identified as components of secondary organic aerosols (SOA) and biomass-burning organic aerosols (BBOA). Their strong absorption in the near-UV (300–400 nm) makes photochemistry a critical aspect of their atmospheric processing. This study investigates both the direct near-UV photochemistry and hydroxyl radical (OH) oxidation of 4-nitroimidazole (4-NI). The atmospheric photolysis rate of 4-NI in the near-UV (300–400 nm) was found to be J_4-NI = 4.3 × 10⁻⁵ (±0.8) s⁻¹, corresponding to an atmospheric lifetime of 391 (±77) min under bulk aqueous conditions simulating aqueous aerosols and cloud water. Electrospray ionization mass spectrometry (ESI-MS) analysis following irradiation indicated loss of the nitro group, while NO elimination was observed as a more minor channel in direct photolysis. In addition, the rate constant for the reaction of 4-NI with OH radicals, k_NI+OH, was determined to be 2.9 × 10⁹ (±0.6) M⁻¹s⁻¹. Following OH oxidation, ESI-MS results show the emergence of a dominant peak at m/z = 130 amu, consistent with hydroxylation of 4-NI. Computational results indicate that OH radical addition occurs with the lowest barrier at the C2 and C5 positions of 4-NI. The combined results from direct photolysis and OH oxidation experiments suggest that OH-mediated degradation is likely to dominate under aerosol-phase conditions, where OH radical concentrations are elevated, while direct photolysis is expected to be the primary loss mechanism in high-humidity environments and bulk cloud water. Full article

A new hyphenated technique using thin-layer chromatography (TLC) to separate analytes in mixtures, coupled with mid-infrared (MIR) laser spectroscopy for identification and quantification, is presented. The method, which provides a means for rapid screening of analytes that is practical, low-cost, fast, robust, and reproducible, was tested using nitroaromatic and aliphatic nitro high explosives (HEs) as target analytes. HEs are anthropogenic contaminants containing an -NO₂ group. For validation of the new technique, a direct comparison of the 2,4,6-trinitrotoluene (TNT) spectrum, obtained by attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy coupled with TLC, was carried out. The MIR laser spectroscopy-based method was evaluated by calculating the analytical figures of merit regarding the calibration curves’ linearity and the method’s sensitivity and precision. The TNT spectrum obtained by the MIR laser method showed two prominent and characteristic bands of the explosive at approximately 1350 cm⁻¹ and 1550 cm⁻¹ compared to the spectrum acquired by ATR-FTIR. The detection limit calculated for TNT was 84 ng, while the quantification limit was 252 ng. Multivariate analysis was used to evaluate the spectroscopic data to identify sources of variation and determine their relation. Partial least squares (PLS) regression analysis and PLS combined with discriminant analysis (PLS-DA) were used for quantification and classification. The new technique, TLC-QCL, is amenable to a smaller footprint with further developments in MIR laser technology, making it portable for fieldwork. Full article

Understanding the factors that affect the detonation performance of high-energy molecules (HEMs) is crucial for the design of novel explosives and fuels with desirable characteristics. While molecular factors, such as the presence of specific functional groups that give organic molecules explosive properties, are key determinants of detonation characteristics, other factors like the geometry of molecules in crystal structures can also affect the high-energy properties of materials. Although it is known that slight deviations in the crystal structure geometry affect the sensitivity of nitroaromatic explosives, the influence of these variations on detonation performance remains unknown. In this study, we extracted different crystal structures of the same high-energy nitroaromatic molecules from the Cambridge Structural Database and calculated their detonation velocities and pressures using the Kamlet–Jacobs equations. Results indicated that different geometries of the same crystal structure can lead to non-negligible differences in detonation velocities and pressures. In the case of the 2,4,6-triamino-1,3,5-trinitrobenzene molecule, discrepancies in detonation pressures among different crystal structures were calculated to be 7.68%. Analysis of geometrical arrangements showed that these differences are mainly the consequence of diverse non-covalent bonding patterns that affect crystal densities. Full article

Nitroaromatic-explosives (NEs) not only threaten global security but are also recognized as a highly toxic pollutant. Metal–organic framework Zn-M_s (Zn-M₁, Zn-M₂) were synthesized in this study via the coordination-driven self-assembly of Zn ions and a carbazole-based ligand L containing an aldehyde group. They inherited the excellent fluorescence performance of ligand L and could work as a fluorescent sensor for detecting picric acid (PA) at low concentrations. Zn-M_s showed an emission at 450 nm and exhibited a higher fluorescence quenching efficiency toward PA than other related NEs. The results suggest that the fluorescent response might be attributed to the inner filter effect (IFE); Förster resonance energy transfer (FRET); and possibly, photo-induced electron transfer (PET). In addition, the critical role of the aldehyde group as a recognition site was corroborated using a post-modification strategy. Full article

In order to detail the antiplasmodial effects of quinones (Q) and nitroaromatic compounds (ArNO₂), we investigated their reduction mechanism by Plasmodium falciparum flavoenzyme type II NADH:ubiquinone oxidoreductase (PfNDH2). The reactivity of Q and ArNO₂ (n = 29) follows a common trend and exhibits a parabolic dependence on their single-electron reduction potential ($E_7^1$), albeit with significantly scattered data. The reactivity of quinones with similar $E_7^1$ values increases with their lipophilicity. Quinones are reduced by PfNDH2 in a two-electron way, but ArNO₂ are reduced in a single-electron way. The inhibition studies using NAD⁺ and ADP-ribose showed that quinones oxidize the complexes of reduced enzyme with NADH and NAD⁺. This suggests that, as in the case of other NDH2s, quinones and the nicotinamide ring of NAD(H) bind at separate sites. A scheme of PfNDH2 catalysis is proposed, consistent with both the observed ‘ping-pong’ mechanism and the presence of two substrate binding sites. Molecular docking showed that Q and ArNO₂ bind in a similar manner and that lipophilic quinones have a higher affinity for the binding site. One may expect that PfNDH2 can be partially responsible for the previously observed enhanced antiplasmodial activity of aziridinylbenzoquinones caused by their two-electron reduction, as well as for the redox cycling and oxidative stress-type action of ArNO₂. Full article

Nitroaromatic compounds (NACs) have adverse effects on human health and climate. Daily PM_2.5 samples were collected in winter and summer of 2022 in two cities, Chengdu (CD) and Mianyang (MY), located in Sichuan Basin of southwestern China. Four types of NACs in PM_2.5, containing nitrophenols, nitrocatechols, nitrosalicylic acids, and nitronaphthol, were analyzed. The mean concentration of a total of 10 NACs (ΣNACs) in winter at the suburban MY site (71.7 ± 35.6 ng m⁻³) was higher than that in urban CD (29.5 ± 16.2 ng m⁻³), while in summer, the mean concentrations of ΣNACs in the two cities were similar, around 2.2 ng m⁻³. The much higher concentrations of ΣNACs in winter were attributed to the impact of biomass burning. 4-Nitrocatechol (4NC) was the most abundant species during the sampling period, accounting for 35–56% of ΣNACs mass. In winter, the mean light absorption coefficient of methanol-soluble brown carbon (Abs_365,M) was 10.5 ± 3.4 and 13.6 ± 4.3 Mm⁻¹ in CD and MY, respectively, which was about 4–7 times that of summer. The contributions of light absorption of ΣNACs at 365 nm to Abs_365,M were 1.6–3.6% in winter and 0.5–0.7% in summer, with 4NC contributing the most to brown carbon among all NACs. The geographical origins of potential sources of NACs at both sites were mainly distributed within the basin. Full article

2,2′,4,4′,6,6′-hexanitrostilbene (HNS) is a heat-resistant, low-sensitivity energetic material with widespread applications in pliable linear-shaped charges, high-temperature-resistant oil well perforating charges, and rocket propellants. However, the presence of highly toxic and mutagenic nitroaromatic compounds in HNS wastewater necessitates efficient and accurate detection methods. Unfortunately, the existing analytical methods for HNS detection are outdated and incompatible with modern equipment. This limits their application due to issues with detection range, accuracy, and cost. To address this gap, an improved method was developed using an Ultimate 3000 UHPLC system with methanol and water as the mobile phase and UV-Vis detection at 271 and 226 nm wavelengths. The results indicate that the optimal detection conditions are achieved with a methanol-to-water ratio of 70:30 and a flow rate of 0.5 mL/min, providing high accuracy and efficiency. Compared to traditional methods, this approach reduced the detection time by nearly 70%, with the shortest analysis time ranging from 6 to 6.5 min, significantly lowering the cost of HNS detection. The method demonstrated excellent linearity (R² > 0.9999) and high sensitivity within the concentration range of 0.50–150.00 mg/L, with precise and reliable results. This work provides both theoretical insights and experimental validation for the detection and analysis of HNS in wastewater. Full article

We performed a theoretical investigation of the fluorinated compounds’ morphology and stability. The research was conducted using the widely adopted DFT approach, specifically the B3LYP method and the cc-pVTZ basis set, aiming to design high-energy materials that exhibit low sensitivity, toxicity, instability, and reduced proneness to decomposition or degradation over a short period. In the paper, we presented the investigation results for the compounds whose total energy is the lowest. Their thermal and chemical stability was evaluated based on stability indicators such as cohesion, chemical hardness, and softness. The oxygen–fluorine balance is assessed to determine the sensitivity of these advanced materials. The density, detonation pressure, and velocity of the selected conformers were theoretically obtained to reveal the influence of -CF₃, -OCF₃, and cyclic -O(CF₂)nO- fragments on the energetic properties of nitroaromatics as well as their stability and resistance to shock stimuli. The results enable the prediction of advanced energetic materials that achieve a favorable balance between power and stability. Based on the results achieved, we put forward CF3N2, OCF3N2, C2F6N2, 1CF2N2/O2CF2N2, and 2CF4N2/O2C2F4N2 for practical usage because these compounds possess greater stability compared to tetryl and better explosive properties than TNT. Full article

Two new Tb(III) metal–organic frameworks based on 4,7-dimethylphenanthroline (dmphen) and flexible ligand trans-1,4-cyclohexanedicarboxylate (chdc²⁻) were synthesized and characterized. Their crystallographic formulae are [Tb₂(dmphen)₂(H₂O)₂(chdc)₃]·2DMF (1; DMF = N,N-dimethylformamide) and [Tb₂(dmphen)₂(NO₃)₂(chdc)₂]·2DMF (2). Among some differences in their synthetic conditions, the most important one is apparently the using of terbium(III) nitrate instead of terbium(III) chloride as a metal precursor in the synthesis of 2, providing a nitrate coordination to Tb³⁺, and its subsequent notable structural differences to 1. Compound 1 was found to have a layered hcb structure with intralayer windows ca. 10 × 8 Ų in size. Its layer-to-layer packing leaves narrow channels running across these windows, with 18% as a total solvent-accessible volume in the coordination structure. Compound 2 was found to have a layered sql structure with smaller intralayer windows of ca. 8 × 6 Ų in size. Methyl substituents on the phen ligands do not affect the topology of the framework but seem to have a substantial effect on the packing density, as well as the pore volume of the resulting MOF. A high 18.4% luminescence quantum yield was found for 2. Its emission lifetime of 0.695(12) ms belongs to a typical range for phosphorescent Tb(III)-carboxylate complexes. A quenching of its emission by different nitroaromatic molecules was found. A linear concentration dependence on 3-nitrotoluene and 4-nitro-m-xylene at micromolar concentrations was found during luminescent titration experiments (LOD values ca. 350 nM), suggesting this MOF to be a viable and highly sensitive luminescent sensor for such substrates. Full article

Thin films of poly(arylene ethynylene)-conjugated polymers, including low-energy-gap donor–acceptor polymers, can be prepared via stepwise polymerization utilizing surface-confined Sonogashira cross-coupling. This robust and efficient polymerization protocol yields conjugated polymers with a precise molecular structure and with nanometer-level control of the organization and the uniform alignment of the macromolecular chains in the densely packed film. In addition to high stability and predictable and well-defined molecular organization and morphology, the surface-confined conjugated polymer chains experience significant interchain electronic interactions, resulting in dominating intermolecular π-electron delocalization which is primarily responsible for the electronic and spectroscopic properties of polymer films. The fluorescent films demonstrate remarkable performance in chemosensing applications, showing a turn-off fluorescent response on the sub-ppt (part per trillion) level of nitroaromatic explosives in water. This unique sensitivity is likely related to the enhanced exciton mobility in the uniformly aligned and structurally monodisperse polymer films. Full article

Chlorinated and fluorinated nitrophenols (HNCs) are widely used in agriculture and industry, with a global market valued at USD $25 billion, one which is expected to grow by 5% by 2030. However, these compounds pose significant environmental risks; they are classified as toxic by the International Agency for Research on Cancer (IARC). Existing treatment methods include advanced oxidation, adsorption, and bioremediation, though to date, there has been only limited research on fungal remediation of these halogenated pollutants. This study aims to explore a sustainable approach by using fungi’s potential to degrade HNCs in minimal media. Ten fungi were selected through literature screening; Caldariomyces fumago and Curvularia sp. were highly effective, degrading over 50% of 2-chloro-4-nitrophenol (2C4NP) and 80% of 5-fluoro-2-nitrophenol (5F2NP) within 24 and 48 h, respectively. Additionally, five strains showed degradation potential for fluorinated compounds. Further studies revealed C. fumago could degrade up to 1 mM of chlorinated compounds and 12 mM of fluorinated compounds, far exceeding any known environmental concentrations of HNCs; importantly, ecotoxicology tests demonstrated reductions in toxicity of 77% and 85%, respectively. This work highlights fungi’s underexplored ability to degrade toxic HNCs, offering a sustainable mycoremediation strategy and positioning mycology as a critical tool for future environmental remediation efforts. Full article