Search Results (17)

The extensive use of nitro compounds in agriculture, industry, armaments, and pharmaceuticals, along with their toxic effects on living organisms, necessitates efficient and environmentally sustainable analytical methods. Traditional extraction techniques often involve practices that are not eco-friendly, such as the use of large volumes of solvents, toxic chemicals, and the generation of significant waste; therefore, the single-drop microextraction technique was involved in overcoming these limitations. This study shows an environmentally friendly method for nitro compound analysis focusing on NB (Nitrobenzene), 2-NT (2-Nitrotoluene), 3-NT (3-Nitrotoluene), 4-NT (4-Nitrotoluene), 1,3-DNB (1,3-Dinitrobenzene), 1,2-DNB (1,2-Dinitrobenzene), 2,4-DNT (2,4-Dinitrotoluene), and TNT (Trinitrotoluene). To separate and to detect selected nitro compounds, gas chromatography with an electron capture detector was utilized, which is highly selective for analytes containing nitro groups. To determine optimal experimental conditions, extraction parameters were studied, including the impact of salt addition, temperature, and pH on extraction efficiency. Key performance parameters, such as limit of detection (LOD), limit of quantification (LOQ), repeatability, extraction recoveries, calibration range, and matrix effects, were assessed. The LOD values ranged from 0.01 to 0.09 μg/L in deionized water, 0.01 to 0.06 μg/L in tap water, 0.01 to 0.03 μg/L in seawater, and 0.03 to 0.11 μg/L in model forensic rinse water. The optimized method was successfully applied to the determination of nitro compounds in real environmental water samples and forensic rinse water samples. The environmental sustainability and greenness of the proposed method was evaluated with the AGREE, AGREEprep, and AESA techniques. 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

Ectomycorrhizal fungi have huge potential value, both nutritionally and economically, but most of them cannot be cultivated artificially. To better understand the influence of abiotic and biotic factors upon the growth of ectomycorrhizal fungi, mycosphere soil and bulk soil of five ectomycorrhizal fungi (Calvatia candida, Russula brevipes, Leucopaxillus laterarius, Leucopaxillus giganteus, and Lepista panaeola) were used as research objects for this study. Illumina MiSeq sequencing technology was used to analyze the community structure of the mycosphere and bulk soil bacteria of the five ectomycorrhizal fungi, and a comprehensive analysis was conducted based on soil physicochemical properties. Our results show that the mycosphere soil bacteria of the five ectomycorrhizal fungi are slightly different. Escherichia, Usitatibacter, and Bradyrhizobium are potential mycorrhizal-helper bacteria of distinct ectomycorrhizal fungi. Soil water content, soil pH, and available potassium are the main factors shaping the soil bacterial community of the studied ectomycorrhizal fungi. Moreover, from the KEGG functional prediction and LEfSe analysis, there are significant functional differences not only between the mycosphere soil and bulk soil. ‘Biosynthesis of terpenoidsand steroids’, ‘alpha-Linolenic acid metabolism’, ‘Longevity regulating pathway-multiple species’, ‘D-Arginine and D-ornithine metabolism’, ‘Nitrotoluene degradation’ and other functions were significantly different in mycosphere soil. These findings have pivotal implications for the sustainable utilization of ectomycorrhizal fungi, the expansion of edible fungus cultivation in forest environments, and the enhancement of derived economic benefits. Full article

Nitroaromatic compounds (NACs), which are widely used in pesticides, explosives, dyes, and pharmaceuticals, include nitrobenzene, nitrotoluenes, nitrophenols, and nitrobenzoates. They are also significant industrial pollutants in the environment. These substances, as well as their derivatives, frequently have toxic or mutagenic properties. Wastewater containing nitroaromatic compounds can be effectively managed by using biological treatment methods that are accessible, cost-effective, and environmentally friendly. This review highlights the latest developments in biological treatment systems for removing NACs from wastewater. The large-scale implementation of biological treatment systems will be facilitated by future studies that focus on identifying the best operational methods and that determine how co-pollutants impact the removal of NACs from wastewater. Full article

A series of 20 wt.% MO₂/S catalysts (where M = Ce, Mn or Zr and S = SiO₂ or Al₂O₃) were prepared using various precursors of the active phases. The resulting catalysts were characterized using different methods (XRD, TPR and S_BET). For the first time, anhydrides were used as potential starting materials for ketone synthesis. This novel reaction was performed on various aliphatic anhydrides in the presence of catalysts within a temperature range of 523–723 K. For all anhydrides, except for pivalic anhydride, the appropriate ketones were obtained with good or very good yields. The vapor-phase catalytic ketonization of esters of benzene-1,x-dicarboxylic acids (x = 2, 3 or 4) with acetic acid were studied in the range of 673–723 K in order to obtain 1,x-diacetylbenzenes. Their yields strongly increased with an increase in the x value (0, 8 and 43% for x = 2, 3 and 4, respectively). The presence of acetophenone as a side product was always noted. In the case of ω-phenylalkanoic acids, their vapor-phase ketonization with acetic acid led to the formation of appropriate ketones with 47–49% yields. Much lower yields of ketones (3–19%) were obtained for acids and ethyl esters containing heterocycle substituents (with O or S atoms) and/or vinyl groups. In the reaction between ethyl 4-nitrophenylacetate and acetic acid, only the products of ester decomposition (p-toluidine and p-nitrotoluene) were determined. Full article

The properties of a conjugated copolymer (CP), poly[(9,9-Dioctyl-2,7-divinylenefluorenylene)-alt-co-(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene) (PDVF-co-MEH-PV), were investigated in the presence of graphene oxide (GO) and reduced graphene oxide (rGO) using absorption, fluorescence, laser, and time-resolved spectroscopy. CPs are usually dissolved in low-polar solvents. Although GO does not dissolve well, rGO and PDVF-co-MEH-PV dissolve in chloroform due to their oxygen acceptor sites. Hence, we studied rGO/PDVF-co-MEH-PV (CP/rGO), performing all experiments and simulations in chloroform. We performed simulations on PDVF-co-MEH-PV, approximate GO, and rGO using time-dependent density-functional theory calculations to comprehend the molecular dynamics and interactions at the molecular level. The simulation polymer used a tail-truncated oligomer model with up to three monomer units. The simulation and experimental results were in agreement. Further, the PDVF-co-MEH-PV exhibited fluorescence, laser quenching, rGO-mediated laser blinking, and spectral broadening effects when GO and rGO concentrations increased. The experimental and simulation results were compared to provide a plausible mechanism of interaction between PDVF-co-MEH-PV and rGO. We observed that for lower concentrations of rGO, the interaction did not considerably decrease the amplified spontaneous emissions of PDVF-co-MEH-PV. However, the fluorescence of PDVF-co-MEH-PV was considerably quenched at higher concentrations of rGO. These results could be helpful for future applications, such as in sensors, solar cells, and optoelectronic device design. To demonstrate the sensor capability of these composites, a paper-based sensor was designed to detect ethanol and nitrotoluene. An instrumentation setup was proposed that is cheap, reusable, and multifunctional. Full article

Detecting trace amounts of explosives is important for maintaining national security due to the growing threat of terror attacks. Particularly challenging is the increasing use of homemade explosives. Therefore, there is a constant need to improve existing technologies for detecting trace amounts of explosives. This paper describes the design of a stationary device (a gate) for detecting trace amounts of explosives and explosive taggants and the design of differential ion mobility spectrometers with a focus on the gas system. Nitromethane (NM), trimeric acetone peroxide (TATP), hexamine peroxide (HMTD), and explosive taggants 2,3-dimethyl-2,3-dinitrobutane (DMDNB) and 4-nitrotoluene (4NT) were used in this study. Gate measurements were carried out by taking air from the hands, pocket area, and shoes of the tested person. Two differential ion mobility spectrometers operating in two different modes were used as explosive detectors: a mode with a semi-permeable membrane to detect explosives with high vapor pressures (such as TATP) and a mode without a semi-permeable membrane (using direct introduction of the sample into the measuring chamber) to detect explosives with low vapor pressures (such as HMTD). The device was able to detect trace amounts of selected explosives/explosive taggants in 5 s. Full article

In the current work, copper tungsten oxide (CuWO₄) nanoparticles are incorporated with carbon nanofiber (CNF) to form CNF/CuWO₄ nanocomposite through a facile hydrothermal method. The prepared CNF/CuWO₄ composite was applied to the electrochemical detection of hazardous organic pollutants of 4-nitrotoluene (4-NT). The well-defined CNF/CuWO₄ nanocomposite is used as a modifier of glassy carbon electrode (GCE) to form CuWO₄/CNF/GCE electrode for the detection of 4-NT. The physicochemical properties of CNF, CuWO₄, and CNF/CuWO₄ nanocomposite were examined by various characterization techniques, such as X-ray diffraction studies, field emission scanning electron microscopy, EDX-energy dispersive X-ray microanalysis, and high-resolution transmission electron microscopy. The electrochemical detection of 4-NT was evaluated using cyclic voltammetry (CV) the differential pulse voltammetry detection technique (DPV). The aforementioned CNF, CuWO₄, and CNF/CuWO₄ materials have better crystallinity with porous nature. The prepared CNF/CuWO₄ nanocomposite has better electrocatalytic ability compared to other materials such as CNF, and CuWO₄. The CuWO₄/CNF/GCE electrode exhibited remarkable sensitivity of 7.258 μA μM⁻¹ cm⁻², a low limit of detection of 86.16 nM, and a long linear range of 0.2–100 μM. The CuWO₄/CNF/GCE electrode exhibited distinguished selectivity, acceptable stability of about 90%, and well reproducibility. Meanwhile, the GCE/CNF/CuWO₄ electrode has been applied to real sample analysis with better recovery results of 91.51 to 97.10%. Full article

Modulating the transport route of photogenerated carriers on hollow cadmium sulfide without changing its intrinsic structure remains fascinating and challenging. In this work, a series of well-defined heterogeneous hollow structural materials consisting of CdS hollow nanocubes (CdS NCs) and graphitic C₃N₄ nanoparticles (CN NPs) were strategically designed and fabricated according to an electrostatic interaction approach. It was found that such CN NPs/CdS NCs still retained the hollow structure after CN NP adorning and demonstrated versatile and remarkably boosted photoreduction performance. Specifically, under visible light irradiation (λ ≥ 420 nm), the hydrogenation ratio over 2CN NPs/CdS NCs (the mass ratio of CN NPs to CdS NCs is controlled to be 2%) toward nitrobenzene, p-nitroaniline, p-nitrotoluene, p-nitrophenol, and p-nitrochlorobenzene can be increased to 100%, 99.9%, 83.2%, 93.6%, and 98.2%, respectively. In addition, based on the results of photoelectrochemical performances, the 2CN NPs/CdS NCs reach a 0.46% applied bias photo-to-current efficiency, indicating that the combination with CN NPs can indeed improve the migration and motion behavior of photogenerated carriers, besides ameliorating the photocorrosion and prolonging the lifetime of CdS NCs. Full article

Nitroaromatic explosives are the most common explosives, and their detection is important to public security, human health, and environmental protection. In particular, the detection of solid explosives through directly revealing the presence of their vapors in air would be desirable for compact and portable devices. In this study, amino-functionalized carbon nanotubes were used to produce resistive sensors to detect nitroaromatic explosives by interaction with their vapors. Devices formed by carbon nanotube networks working at room temperature revealed trinitrotoluene, one of the most common nitroaromatic explosives, and di-nitrotoluene-saturated vapors, with reaction and recovery times of a few and tens of seconds, respectively. This type of resistive device is particularly simple and may be easily combined with low-power electronics for preparing portable devices. Full article

In this work, ammonia cross-linked 8-armed polyethylene glycol hydrogel material was successfully synthesized and used as a template for synthesizing nanoparticles with fluorescent properties. The 8-armed polyethylene glycol hydrogel template was used to prepare molybdenum disulfide quantum dots (MoS₂ QDs). The ammonium tetrathiomolybdate functioned as a molybdenum source and hydrazine hydrate functioned as a reducing agent. The fluorescence properties of the as-prepared MoS₂ QDs were investigated. The bursting of fluorescence caused by adding different concentrations of explosive TNT was studied. The study indicated that the synthesized MoS₂ QDs can be used for trace TNT detection with a detection limit of 6 nmol/L and a detection range of 16–700 nmol/L. Furthermore, it indicated that the fluorescence-bursting mechanism is static bursting. Full article

The paper presents the results of a numerical evaluation of limiting sensitivity of the method for detecting vapors of nitrocompounds in the atmosphere based on one-color laser fragmentation (LF)/laser-induced fluorescence (LIF) of NO fragments via A²Σ⁺ (v′ = 0) ← X²Π (v″ = 2) transition. The calculations were performed using the developed kinetic model of the one-color LF/LIF process under consideration. The calculations take into account the influence of ambient nitrogen dioxide as a limiter of the sensitivity of the method when operating in a real atmosphere. It is shown that if the nitrogen dioxide concentration in the atmosphere does not exceed a value of 10 ppb, the maximum detectable vapor concentrations of nitrobenzene and o-nitrotoluene are several ppb. It is also shown that the method of single-frequency one-color excitation usually used for the detection of nitrocompounds does not allow achieving the maximum efficiency of the LF/LIF process. Full article

MIL-100(Fe, Cr) and MIL-101(Cr) were synthesized by the hydrothermal method and applied to the adsorptions of five aromatic amines from aqueous solutions. These three metal-organic frameworks (MOFs) were well characterized by powder X-ray diffraction (PXRD), scanning electron microscope (SEM), transmission electron microscope (TEM), thermogravimetric analysis (TGA) and surface area analysis. The adsorption mechanism of three MOFs and the effects of the structures of MOFs on the adsorption of aromatic amines were discussed. The results show that the cavity system and suitable hydrogen bond acceptor were important factors for the adsorption for five aromatic amines of aniline, 1-naphthalamine, o-toluidine, 2-amino-4-nitrotoluene and 2-nitroaniline: (a) the saturated adsorption capacity of aniline, 1-naphthylamine and o-toluidine on MIL-100(Fe) were 52.0, 53.4 and 49.6 mg/g, respectively, which can be attributed to the intermolecular hydrogen bond interaction and cavity system diffusion. (b) The adsorption capacity of 2-nitroaniline and 2-amino-4-nitrotoluene on MIL-101(Cr) were 54.3 and 25.0 mg/g, respectively, which can be attributed to the more suitable pore size of MIL-101(Cr) than that of MIL-100(Fe, Cr). The MOFs of MIL-100(Fe) and MIL-101(Cr) can be potential materials for removing aromatic amines from aqueous solutions. Full article

There is great interest in understanding trinitrotoluene (TNT) and dinitrotoluene (DNT) contamination, detection and remediation in the environment due to TNT’s negative health effects and security implications. Numerous publications have focused on detecting TNT in groundwater using multiple techniques, including electrochemistry. The main degradation pathway of nitrotoluenes in the environment is reduction, frequently with biological and/or photolytic assistance. Riboflavin has also been noted to aid in TNT remediation in soils and groundwater when exposed to light. This report indicates that adding riboflavin to a TNT or DNT solution enhances redox currents in electrochemical experiments. Here AC voltammetry was performed and peak currents compared with and without riboflavin present. Results indicated that TNT, DNT and riboflavin could be detected using AC voltammetry on modified gold electrodes and the addition of riboflavin affected redox peaks of TNT and DNT. Poised potential experiments indicated that it is possible to enhance reduction of TNT in the presence of riboflavin and light. These results were dramatic enough to explain long term enhancement of bioremediation in environments containing high levels of riboflavin and enhance the limit of detection in electrochemically-based nitrotoluene sensing. Full article

A series of substituted tetraphenylporphyrin iron chloride complexes [RTPPFe(III)Cl, R=o/p-NO₂, o/p-Cl, H, o/p-CH₃, o/p-OCH₃] were synthesized by a novel universal mixed-solvent method and the spectral properties of free base porphyrins and iron porphyrin compounds were compared with each other. The experimental results showed that the one-pot mixed solvent method was superior to the two-step method in the yields, reaction time and workup of reaction mixtures for the synthesis of iron porphyrin compounds. The highest yields (28.7%-40.4%) of RTPPFe(III)Cl were obtained in the mixed solvents propionic acid, glacial acetic acid and m-nitrotoluene under reflux for 2 h. A detailed analysis of ultraviolet-visible (UV-vis), infrared (IR) and far-infrared (FIR) spectra suggested the transformation from free base porphyrins to iron porphyrins. The red shift of the Soret band in ultraviolet-visible spectra due to the presence of p-nitrophenyl substituents and the blue shift of Fe-Cl bond of TPPFeCl in far-infrared spectra were further explained by the electron transfer and molecular planarity in the porphyrin ring. Full article