Nitroaromatic Compounds Research Articles

Efficient Ground-State Recovery of UV-Photoexcited p-Nitrophenol in Aqueous Solution by Direct and Multistep Pathways.

Nitroaromatic compounds are found in brown carbon aerosols emitted to the Earth's atmosphere by biomass burning, and are important organic chromophores for the absorption of solar radiation. Here, transient absorption spectroscopy spanning 100 fs-8 μs is used to explore the pH-dependent photochemical pathways for aqueous solutions of p-nitrophenol, chosen as a representative nitroaromatic compound. Broadband ultrafast UV-visible and infrared probes are used to characterize the excited states and intermediate species involved in the multistep photochemistry, and to determine their lifetimes under different pH conditions. The assignment of absorption bands, and the dynamical interpretation of our experimental measurements are supported by computational calculations. After 320 nm photoexcitation to the first bright state, which has 1ππ* character in the Franck-Condon region, and ultrafast (∼200 fs) structural relaxation in the adiabatic S1 state to a region with 1nπ* electronic character, the S1 p-nitrophenol population decays on a time scale of ∼12 ps. This decay involves competition between direct internal conversion to the S0 state (∼40%) and rapid intersystem crossing to the triplet manifold (∼60%). Population in the T1-state decays by excited-state proton transfer (ESPT) to the surrounding water and relaxation of the resulting triplet-state p-nitrophenolate anion to its S0 electronic ground state in ∼5 ns. Reprotonation of the S0-state p-nitrophenolate anion recovers p-nitrophenol in its electronic ground state. Overall recovery of the S0 state of aqueous p-nitrophenol via these competing pathways is close to 100% efficient. The experimental observations help to explain why nitroaromatic compounds such as p-nitrophenol resist photo-oxidative degradation in the environment.

Porous Pd-Loaded IRMOF-9 as Highly Efficient Recyclable Material Towards the Reduction of Nitroaromatics in Aqueous Media.

Nitroaromatic compounds (NACs) cause severe hazardous impacts on human health as well as on the environment. Therefore, there is dire need to develop a robust material to reduce the toxicity of these organic pollutants. In this regard, our group developed a series of porous MOF materials viz., Pdx@IRMOF-9 (x=2 %, 5 % and 10 %) by loading different concentration of Pd(II) on IRMOF-9 and explored them towards reduction of different nitroaromatic compounds. Pd10%@IRMOF-9showed ~30 % greater efficiency for the reduction of 4-NP as compared to Pd2%@IRMOF-9. Pd10%@IRMOF-9showed excellent reduction ability (>85 %) towards 4-NP, 2-NP, 2-NA, 3-NA and 2,4-DNPH. The kinetic studies indicates that the reduction follows the pseudo-first-order kinetics. Moreover, the rate constant value for reduction of 3-NA was ~9 times higher than that of 2-NP. Based on the kinetic parameters, the t1/2 values for all the nitroaromatics have been calculated. The kinetic parameters, Km and Vmax have been calculated from double reciprocal Lineweaver-Burk plot and found to be 65.984 μM and 116×10-6 Mmin-1 respectively. Pd10%@IRMOF-9showed excellent recyclability towards the reduction of 4-NP for few consecutive cycles without any remarkable loss in its activity. Thus, highly efficient, porous and robust material for the reduction of nitroaromatic compounds in aqueous media have been demonstrated.

A multifunctional metal–organic complex fluorescent probe for highly sensitive detection of lysine, CrO42-/Cr2O72-, Fe3+ and nitro-aromatic compounds

Water contamination caused by organic and inorganic compounds represents an urgent global issue. It is meaningful to detect these compounds. A metal–organic complex (Zn-HTBA) was investigated as a multifunctional fluorescent probe which showed exceptional fluorescence characteristics. The Zn- HTBA can specifically detect lysine in water through fluorescence enhancement, and the detection limit was 0.17 μM. The Zn-HTBA also selectively detect CrO42-/Cr2O72- and Fe3+ with the detection limits of 0.014/0.022 and 0.12 μM through fluorescence quenching. In addition, the Zn-HTBA was found to sensitively detect nitroaromatic compounds in ethanol through fluorescence quenching. The possible detection mechanisms were studied in detail through UV–Vis, PXRD, XPS, etc. The mechanism of Zn-HTBA to detect CrO42-/Cr2O72-, Fe3+ and 2-nitrotoluene was energy competition, and the mechanism of Zn-HTBA to detect lysine was the formation of hydrogen bonds.

Moisture‐resistant nitroaromatic explosive gas sensor based on hydrophilic pentiptycene polymer

AbstractThe detection of explosive materials, particularly nitroaromatic compounds such as 2,4,6‐trinitrotoluene (TNT), is critical for public safety and national security. Existing detection methods often require complex instrumentation, limiting their applicability for real‐time or in‐field use. Fluorescent sensors, which offer rapid and sensitive detection through fluorescence quenching, present a promising alternative. This study evaluates the performance of two pentiptycene‐based polymers, P‐1 and P‐2, in detecting explosive vapors, with a specific focus on their behavior under high‐humidity conditions. P‐2, modified with triethylene glycol groups, demonstrated significantly increased hydrophilicity compared to the commonly studied P‐1, as confirmed by contact angle measurements. Spectroscopic analysis revealed a blue shift in P‐2's UV–Vis absorption and photoluminescence spectra, indicating electronic property changes due to structural modifications. The enhanced hydrophilicity of P‐2 enabled it to maintain stable sensing performance under moist conditions, showing less than a 10% reduction in sensitivity, compared to the 20% decrease observed in P‐1. This superior moisture resistance suggests that P‐2 is a more robust and practical sensor for explosive detection in environments with variable humidity levels.

Magnetically separable Bi2O2CO3/MIL-101(Fe)/CoFe2O4 nanostructured catalysts for heterogeneous reductive remediation of nitrophenols and organic dyes

A new magnetically separable nanocomposite, Bi2O2CO3/MIL-101(Fe)/CoFe2O4, was successfully synthesized through a hydrothermal method. The composite was characterized through various analytical techniques. The nanocomposite demonstrated good catalytic efficiency in reducing nitroaromatic compounds and organic dyes by using NaBH4 reducing agent in aqueous solutions at room temperature. The apparent rate constant (kapp) values for 4-nitrophenol, 2-nitrophenol, 2-nitroaniline, and 4-nitroaniline were recorded at 0.457, 0.253, 1.52, and 0.564 min⁻¹, respectively, achieving complete conversion in just 2 to 9 min. Under similar conditions, methylene blue, methyl orange, rhodamine B, congo red, and crystal violet organic dyes were reduced to 98–100 % within 4 to 20 min, with kapp values ranging from 0.157 to 0.885 min⁻¹. Furthermore, the influence of catalyst dosage, NaBH4 concentration, and substrate concentration on the reduction process was examined. Importantly, the nanocomposite can be recovered using an external magnet and reused over four consecutive cycles without a significant reduction in catalytic efficiency.

A three-dimensional nitrogen-rich conjugated microporous polymer for solid-phase microextraction of nitroaromatic compounds from environmental water and soil samples

Nitroaromatic compounds (NACs), as a kind of important chemical intermediates, are widely used in industrial productions. However, NACs have carcinogenic effect and their residues may pose harm to human health. Therefore, there is necessity to set up effective analytical method to monitor them in some environmental samples. However, because of their low concentrations in real samples, they need to be enriched by an effective adsorbent before the subsequent instrumental detection. In this work, a three-dimensional nitrogen-rich conjugated microporous polymer (DCT-Try-CMP) was synthesized with 3,6-dichloro-1,2,4,5-tetrazine and triptycene as monomers via Friedel-Crafts reaction. It presented a good adsorption capability for the NACs. After optimization, a solid-phase microextraction with DCT-Try-CMP fiber combined with gas chromatography-flame ionization detection for the quantitation of trace NACs in environmental water and soil samples was developed. The limits of detection of the method (S/N = 3) for environmental water and soil samples were 0.08–0.30 μg L-1 and 1.00–5.00 ng g-1, and the limits of quantification (S/N = 9) were 0.27–0.90 μg L-1 and 3.00–15.0 ng g-1, respectively. The linear quantification response ranges for the analytes were 0.27–200 μg L-1 and 3.00–1000 ng g-1 for water and soil samples, respectively. For water samples at the analytes concentrations of 5.00, 50.0 and 100 μg L-1, the method recoveries ranged from 82.2% to 120% and for soil samples at the concentrations of 15.0, 200 and 400 ng g-1, the method recoveries fell in the range from 80.2% to 120%. The method provides a sensitive and effective approach for monitoring trace NACs in environmental water and soil samples.

Multifunctional N-fused fluorescent probes for detection of iron ions and nitro explosives

In this work, two novel probes 4a and 4b were synthesized through Suzuki-Miyaura coupling reaction, whose structures were further confirmed by 1H NMR, 13C NMR, high-resolution mass spectrometry (HRMS) and X-ray single crystal diffraction. The optical properties of the obtained molecules were investigated accordingly. Owing to different bridging fluorophores, there are certain differences in optical performance and detection ability between the two synthesized compounds. Especially, due to the subtle difference in orbitals energy and electron distribution displayed by the DFT calculations, 4a possesses the characteristics of dual-state emission (DSE) molecule, while 4b is an aggregation-induced emission (AIE) molecule. Interestingly, these two molecules can be developed into multifunctional detection probes, successfully applied for the fluorescence recognition of iron ions and common nitroaromatic compounds (NACs). At the same time, the probe molecules can also be applied to the detection of NACs in aqueous environment. What’s more, they can also be loaded on test strips and thin-films for fluorescence identification of NACs, thus being expected to be developed into portable detection tools for NACs.

Molecular characterization of atmospheric organic aerosols in typical megacities in China

Atmospheric aerosols in megacities impact air quality and public health. However, limited information exists on the detailed molecular composition of organic aerosols in urban areas. This study characterized the molecular composition of organic aerosols (OA) in Shanghai, Beijing and Guangzhou, China, during summer and winter of 2021. Liquid chromatography-orbitrap mass spectrometry detected 4536−5560 and 2067− 3489 organic molecular formulas in positive (ESI+) and negative (ESI−) electrospray ionization modes, respectively. CHO and CHON compounds accounted for over 80% and 60% of total abundance in ESI+ and ESI−, respectively, suggesting their significant contribution to urban OA. The number and abundance percentages of CHO showed obvious seasonal variation, with more CHO in summer than in winter, while CHON exhibited the opposite trend in Beijing and Shanghai. Compared with winter, a lower unsaturation degree, reduced aromaticity, and higher oxidation state of OA in summer were observed in Beijing and Shanghai, while these seasonal variations were not as obvious in Guangzhou, likely due to regional climate differences. The number percentage of common compounds between Beijing and Shanghai was higher than that between Guangzhou and Beijing (or Shanghai). Nitroaromatic compounds were more prevalent in winter than in summer. Further analysis of atmospheric formation relevance and precursor-product pairs suggested that CHON compounds are derived from the oxidization or hydrolyzation processes, revealing potential chemical transformations of these aerosols. This study characterized the chemical makeup of organic aerosols, providing insight into their sources and characteristics in these cities.

Selective Detection of Picric Acid by Benzodiazepine Containing Enaminone Core as Receptor and Its Application to Real Water Sample Analysis.

Nitroaromatic compounds are highly explosive and illegitimate substances. Over a decade, chemists have been affianced in extensive research on the selective and sensitive detection of these nitroaromatic explosives for homeland security and environmental protection. The benzodiazepine-based enaminone (BDE) receptor has been synthesized by aqueous extract of onion catalyzed three-component reaction between o-phenylenediamine, dimedone with an aldehyde. The BDE probe is well analyzed and applied to a sensor that selectively detects picric acid (PA). UV-Vis and fluorescence spectroscopy were used to investigate the photophysical responses of the receptor (BDE). From the observed results BDE found turn-off fluorescence with the addition of picric acid and the lowest limit of detection and limit of quantification was achieved about 24.6 nM and 73.8 nM. The fluorescence quantum yield was attained about 0.28. The BDE-PA adduct formation was confirmed by 1H NMR titration analysis. The Job's plot analysis was performed through 1H NMR titrations and established the binding stoichiometry ratio of the BDE-PA adduct as 1:1 ratio. Further, DFT calculations supported the observed photophysical responses of BDE-PA adduct to confirm the molecular level interactions. The receptor was effectively applied to approximate level of picric acid in real water sample analysis.

Precision picric acid detection via a fluorenone-amide functionalized fluorescent micellar probe

Detection of picric acid (PA) in aqueous solutions is crucial for pollution control, extending beyond national security and military applications. Herein, a binary ensemble AM@SDS has been assembled by encapsulating a fluorenone functionalized amide-based probe (AM) within the micelles of an anionic surfactant, sodium dodecyl sulphate (SDS) in an aqueous medium. A range of spectroscopic techniques, including high-resolution transmission electron microscopy (HRTEM), dynamic light scattering (DLS), and fluorescence spectroscopy (FL), have been employed to characterize the formation of micelles of AM@SDS. A remarkable increase in fluorescence intensity was observed upon interactions of AM with the microenvironment of SDS micelles. Conversely, the fluorescence intensity at 358 nm was significantly quenched in the presence of PA compared to other nitroaromatic compounds (NACs). The detection limit for PA was found to be 368 nM. Furthermore, the binary ensemble AM@SDS has demonstrated remarkable efficacy in detecting PA in real water samples from diverse sources such as lake, river, and tap water, achieving an exceptional recovery rate of up to 99.9 %.

Ag nanoparticles on arginine-cyanoguanidine functionalized magnetic g-C3N4: A catalyst for nitroaromatic hydrogenation and regioselective click reactions

This study describes the development of a novel hybrid nanocatalyst that was obtained by doping magnetic g-C3N4 with Ag nanoparticles and modifying it with arginine and cyanoguanidine (Ag@Fe3O4-g-C3N4-Arg-CG). Comprehensive characterization of the nanocatalyst using techniques such as FTIR, XRD, SEM, and TGA confirmed its structural and morphological properties. The catalytic efficiency of the synthesized nanostructure was evaluated in two key reactions: the reduction of nitroaromatic compounds and a click reaction for 1,2,3-triazole synthesis. The results demonstrate that Ag@Fe3O4-g-C3N4-Arg-CG effectively reduced various nitroaromatic compounds to substituted anilines at room temperature using NaBH4 as the reducing agent. Nitrobenzene reduction did not proceed in aprotic solvents such as acetonitrile, CH2Cl2, and dimethylformamide, whereas it exhibited a high reaction yield in protic solvents such as ethanol and water. The highest yield (100 %) was observed in water at 50 °C using H2O solvent. Additionally, the nanohybrid exhibited significant potential for “green” click chemistry by efficiently synthesizing 1,2,3-triazoles under mild conditions, with low catalyst loading. Its magnetic properties facilitated easy recovery, and the catalyst maintained high activity over six cycles, making it suitable for sustainable applications in organic transformations.

Luminescent yttrium organic frameworks: Cell imaging, gas adsorption and nitro sensing applications

The flexibility of ligand (L) yield, two different yttrium organic frameworks, denoted as {[Y(L)2(H2O)4]·Cl3·DMF·(H2O)3·(S)}n (MOF-1) and {[Y(L)3/2(H2O)2]·(NO3)3·(S)}n (MOF-2), where L denotes 9,10-bis((4-carboxylatopyridinium-1-methylene)anthracene and S denotes the disordered solvent molecules. Detailed single crystal X-ray study established a one dimensional (1D) chain for MOF-1 and a three dimensional (3D) frameworks with one channel voids structure for MOF-2, respectively, due to different conformation of the ligand. In both MOFs, Y(III) have bicapped trigonal prismatic geometry. The phase purity of both MOFs has been confirmed by powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA) and IR spectroscopic studies. MOF-1, with its particle size in nano range, good fluorescence property and solubility in water, is a suitable candidate for cell imaging study. In contrast, three dimensional framework of MOF-2, with small voids, makes it well suited for gas adsorption and sensing of nitro aromatics compounds.

One-pot bioinspired synthesis of PbO/CuO/FeO trimetallic oxide nanocomposite using Vitis vinifera fruit juice for highly sensitive electrochemical detection of 4-Nitrotoluene

The determination of explosive nitroaromatic chemicals has prompted concerns about human safety around the world. In this work, we demonstrate an electrochemical sensor based on trimetallic oxide nanocomposites modified screen-printed carbon electrode (SPCE) for the detection of nitroaromatic compounds. Trimetallic oxide nanocomposites are multiphase materials containing ternary metal oxides. Because of their high specific surface area, superior electron transport capabilities, and favourable catalytic behaviour, they are frequently employed as antibacterial materials, catalysts, and sensors. In order to combat the problems associated with high manufacturing costs, low selectivity, and low sensitivity of conventional sensors, this paper reports on the construction of an electrochemical sensor for 4-nitrotoluene (4-NT) using a trimetallic oxide nano-sensor. The nano-sensor is composed of transition metal oxides copper and iron combined with post-transition lead metal oxide. In this study, we prepared a PbO/CuO/FeO TMO NCs sample with different individual metal oxides synthesized by a green reduction method using Vitis vinifera fruit juice. SEM was used to observe and validate structural and morphological variations brought on by various metal compositions. The four bio-synthesized materials comprise dispersed multiphase matrices containing varying shapes of nanoparticles with different morphologies. The elemental and phase arrangements of the synthesized samples were investigated employing UV, FT-IR, XRD, and EDAX approaches. The findings of the electrochemical measurements indicate that the SPCE modified with PbO/CuO/FeO TMO NCs has enhanced sensing capabilities over CuO, FeO, and PbO NPs for 4-NT; the limit of detection is 4.512 nM and sensitivity is −0.531 μA nM−1 for the developed sensor. Notably, recovery values (99.2–101.7 %) in water samples showed that evaluating interfering species from different contaminants had no effect on the sensing of 4-NT. All of these findings show that the newly developed sensor performs well in terms of reproducibility, selectivity, and sensitivity for the detection of 4-NT

Co–Ni nanoparticle supported on heteroatom-doped carbon derived from garlic powder and eutectic solvent: Its application in Nitroarenes reduction

This paper presents the synthesis of a novel heterogeneous catalyst, PSN-C600-Co2:Ni1, designed for the hydrogenation of nitroaromatic compounds. The catalyst is a porous carbon substrate triply doped with nitrogen, sulfur, and phosphorus, incorporating bimetallic Co and Ni nanoparticles. A natural precursor, garlic biochar, and a biodegradable eutectic solvent were used in the synthesis. Various characterization techniques, including Scanning Electron Microscope (SEM), X-Ray Energy Diffraction Spectroscopy (EDX), Elemental Mapping Measurements (MAP), Thermogravimetric Analysis (TGA), X-Ray Diffraction (XRD), Infrared Spectrometer (FTIR), Transmission Electron Microscope (TEM), Raman Spectroscopy, and Nitrogen Adsorption and Desorption Pattern (N2 adsorption-desorption isotherm), were utilized to examine the features and properties of the synthesized PSN-C600-Co2:Ni1 catalyst.

Evidence for Cytotoxicity and Mitochondrial Dysfunction in Human Lung Cells Exposed to Biomass Burning Aerosol Constituents: Levoglucosan and 4-Nitrocatechol

Biomass burning (BB) emissions are one of the largest sources of carbonaceous aerosol, posing a significant risk as an airway irritant. Important BB markers include wood pyrolysis emissions, such as levoglucosan (LG) that is an anhydrous sugar bearing a six-carbon ring structure (i.e., 1,6-anhydro-β-D-glucopyranose). Atmospheric chemical aging of BB-derived aerosol (BBA) in the presence of nitrogen oxides (NOx) can yield nitro-aromatic compounds, including 4-nitrocatechol (4NC). There is building evidence that NOx-mediated chemical aging of BBA poses a more serious exposure effect than primary pyrolysis emissions. This study provides a comparative toxicological assessment following the exposure to important BBA marker compounds in human lung cells (i.e., A549 and BEAS-2B) to determine whether aromatic 4NC is more toxic than BBA-bound anhydrous carbohydrate (i.e., LG). We determined inhibitory concentration-50 (IC50) and examined reactive oxygen species (ROS) changes, mitochondrial dysfunction, and apoptosis induction in the two cell lines following exposure to LG and 4NC in a dose-response manner. In the BEAS-2B cells, estimated IC50 values for 4NC were 33 and 8.8 μg mL-1, and for LG were 2546 and ∼ 3 × 107 μg mL-1 at 24 h and 48 h of exposure, respectively. A549 cells exhibited a much higher IC50 value than BEAS-2B cells. LG exposures resulted in mitochondrial stress with viability inhibition, but cells recovered with increasing exposure time. 4NC exposures at 200 μg mL-1 resulted in the induction of apoptosis at 6 h. Mitochondrial dysfunction and ROS imbalance induced the intrinsic apoptotic pathway induction following 4NC exposures. While increased ROS is caused by LG exposure in lung cells, 4NC is a marker of concern during BB emissions, as we observed apoptosis and high mitochondrial ROS in both lung cells at atmospherically-relevant aerosol concentrations. It may be associated with higher airway or inhalation pathologies in higher BBA emissions, such as wildfires or during wood combustion.

Visible-light induced effective and sustainable remediation of nitro organics pollutants using Pd-doped ZnO nanocatalyst

Nitroaromatic compounds represent a class of highly toxic pollutants discharged into aquatic environments by various industrial activities, posing significant threats to ecological integrity and human health due to their persistent and hazardous nature. In this study, Pd-doped ZnO nanoparticles were investigated as a potential solution for the degradation of nitro organics, offering heightened photocatalytic efficacy and prolonged stability. The synthesis of Pd-doped ZnO NPs was achieved via the hydrothermal method, with subsequent analysis through XRD spectra and XPS confirming successful Pd doping within the ZnO matrix. Characterization through FESEM and HRTEM unveiled the heterogeneous morphologies of both undoped and Pd-doped ZnO nanoparticles. Additionally, UV–vis and PL spectroscopy provided insights into the optical properties, chemical bonding, and defect structures of the synthesized Pd-doped ZnO NPs. Pd doping induces a redshift in ZnO’s absorption spectra, reducing the bandgap from 3.12 to 2.94 eV as Pd concentration rises from 0 to 0.2 wt.%. The photocatalytic degradation, following pseudo-first-order kinetics, achieved 90% nitrobenzene abatement (200 µg/L, pH 7) under visible light within 320 min with a catalyst loading of 16 µg/mL. The photocatalytic efficacy of 0.08 wt% Pd-doped ZnO (k = 0.058 min⁻1) exhibited a 25-fold enhancement compared to bare ZnO (k = 3.1 × 10–4 min-1). Subsequent quenching and ESR experiments identified hydroxyl radicals (OH•) as the predominant active species in the degradation mechanism. Mass spectrometry analysis unveiled potential breakdown intermediates, illuminating a plausible degradation pathway. The investigated Pd-doped ZnO nanoparticles demonstrated reusability for up to five successive treatment cycles, offering a sustainable solution to nitro organics contamination challenges.

Two Stable Pillar-Layered Zn-LMOFs for Highly Fluorescence Sensing of Inorganic Pollutants and Nitro Aromatic Compounds in Water.

Luminescent metal-organic frameworks (LMOFs) are a potential class of functional materials for the photoluminescent detection of a wide range of analytes as well as for the detection of pollutants in wastewater. Herein, by using the pillar-layered strategy, two new luminescence Zn-LMOFs (JLU-MOF222 and JLU-MOF223) were successfully solvothermal synthesized. The 2D layers are both consisting of Zn2+ and TPHC [TPHC = (1,1':2',1″-terphenyl)-3,3″,4,4',4″,5'-hexacarboxylic acid] ligands and then pillared by the different N-donor ligands to form the 3D Zn-LMOFs with fsh topology. Benefiting from the uncoordinated carboxylate sites, uncoordinated N atom, or -NH2 group in the pillaring ligands and excellent stability in pH = 2-13 aqueous phase, JLU-MOF222 and JLU-MOF223 not only can sensitively detect trace amounts of inorganic pollutants (Fe3+, Cr2O72-) and nitro aromatic compounds TNP and 2,4-DNP (TNP = 2,4,6- trinitrophenol, 2,4-DNP = 2,4-dinitrophenol) through luminescence quenching but also exhibit high selectivity of other anti-interference competing analytes. The two new Zn-LMOFs can be used as potential luminescent sensors for pollutant detection in water due to their high KSV and low limit of detection (LOD).

Sustainable synthesis of multifaceted copper oxide nanoparticles from Euphorbia tirucalli: Unveiling antimicrobial and catalytic potential

This work presents Euphorbia tirucalli mediated green synthesis of multi-purpose copper oxide nanoparticles (ET@CuO-NPs) exhibiting enhanced antimicrobial activity. These plant extract capped nanoparticles were characterized using sophisticated techniques such as FTIR, Raman, UV–Vis, SEM, HR-TEM, DLS, zeta potential, XPS and XRD. A uniform rod-shaped morphology was observed in HR-TEM images with size around 50 nm. Antibacterial and antifungal activity was investigated by agar well diffusion method. The bactericidal action was confirmed by zone of inhibition of 28 mm and 34 mm respectively against gram-negative and a gram-positive bacterium. The nanoparticles also show excellent antioxidant activity via free radical scavenging by DPPH. The scope of ET@CuO-NPs was extended to catalytic reduction of nitroaromatic compounds into their corresponding amino derivatives. The reduction of 4-nitrophenol, a model nitroaromatic pollutant could be completed within just 6 min with a recycling efficiency of 8 cycles. Thus, the multifaceted ET@CuO-NPs exhibited diverse therapeutic and catalytic potential.

Selectivity Modulation of Multistep Reduction Reactions by Gold Nanoclusters

The selective synthesis of valuable azo‐ and azoxyaromatic chemicals via transfer coupling of nitroaromatic compounds has been achieved by fine‐tuning the catalyst structure. Here, a direct method to modulate nitrobenzene reduction and selectively alter the product from azobenzene to azoxybenzene by employing the size effect of Au is reported. Au nanoclusters (NCs) with smaller sizes embedded in ZIF‐8 controllably converted nitrobenzene into azoxybenzene, while supported Au nanoparticles (NPs) catalyzed nitrobenzene reduction to azobenzene. X‐ray photoelectron spectroscopy (XPS) and Diffuse reflectance infrared Fourier transform spectroscopy on CO adsorption (CO‐DRIFTS) of Au NC/ZIF‐8 revealed a higher valence state and a lower electron density of Au than that of Au NP/ZIF‐8, combined with the desorption of azoxybenzene from the Au NC and Au NP surface, suggesting that the Au NCs with lower electron density exhibit stronger adsorption. Density functional theory (DFT) calculations and charge density difference maps indicated that azoxybenzene bonded to Au NC/ZIF‐8 with greater adsorption energy, resulting in more electron transfer between azoxybenzene and the generated Au sites, which inhibited further reduction of azoxybenzene and resulted in high azoxybenzene selectivity. The application of the size effect of Au particles to regulate nitrobenzene transfer coupling provided new insights into the structure‐selectivity relationships.

Selectivity Modulation of Multistep Reduction Reactions by Gold Nanoclusters.

The selective synthesis of valuable azo- and azoxyaromatic chemicals via transfer coupling of nitroaromatic compounds has been achieved by fine-tuning the catalyst structure. Here, a direct method to modulate nitrobenzene reduction and selectively alter the product from azobenzene to azoxybenzene by employing the size effect of Au is reported. Au nanoclusters (NCs) with smaller sizes embedded in ZIF-8 controllably converted nitrobenzene into azoxybenzene, while supported Au nanoparticles (NPs)catalyzed nitrobenzene reduction to azobenzene. X-ray photoelectron spectroscopy (XPS) and Diffuse reflectance infrared Fourier transform spectroscopy on CO adsorption (CO-DRIFTS) of Au NC/ZIF-8 revealed a higher valence state and a lower electron density of Au than that of Au NP/ZIF-8, combined with the desorption of azoxybenzene from the Au NC and Au NP surface, suggesting that the Au NCs with lower electron density exhibit stronger adsorption. Density functional theory (DFT) calculations and charge density difference maps indicated that azoxybenzene bonded to Au NC/ZIF-8 with greater adsorption energy, resulting in more electron transfer between azoxybenzene and the generated Au sites, which inhibited further reduction of azoxybenzene and resulted in high azoxybenzene selectivity. The application of the size effect of Au particles to regulate nitrobenzene transfer coupling provided new insights into the structure-selectivity relationships.