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Nitrophenols (NPs) are hazardous pollutants found in various environmental matrices, including ambient fine particulate matter (PM2.5), agricultural residues, rainwater, wildfires, and industrial wastes. This study showed for the first time the effect of three pure nitrophenols and their mixture on human lung cells to provide basic understanding of the NP influence on cell elements and processes. We identified NPs in ambient PM2.5 and secondary organic aerosol (SOA) particles generated from the photooxidation of monocyclic aromatic hydrocarbons in the U.S. EPA smog chamber. We assessed the toxicity of identified NPs and their equimolar mixture in normal bronchial epithelial (BEAS-2B) and alveolar epithelial cancer (A549) lung cell lines. The inhibitory concentration-50 (IC50) values were highest and lowest in BEAS-2B cells treated with 2-nitrophenol (2NP) and 4-nitrophenol (4NP), respectively, at 24 h of exposure. The lactate dehydrogenase (LDH) assay showed that 4NP, the most abundant NP we identified in PM2.5, was the most cytotoxic NP examined in both cell lines. The annexin-V/fluorescein isothiocyanate (FITC) analysis showed that the populations of late apoptotic/necrotic BEAS-2B and A549 cells exposed to 3NP, 4NP, and NP equimolar mixture increased between 24 and 48 h. Cellular reactive oxygen species (ROS) buildup led to cellular death post exposure to 3NP, 4NP and the NP mixtures, while 2NP induced the lowest ROS buildup. An increased mitochondrial ROS signal following NP exposure occurred only in BEAS-2B cells. The tetramethylrhodamine, methyl ester, perchlorate (TMRM) assay showed that exposed cells exhibited collapse of the mitochondrial membrane potential. TMRM signals decreased significantly only in BEAS-2B cells, and most strongly with 4NP exposures. Our results suggest that acute atmospheric exposures to NPs may be toxic at high concentrations, but not at ambient PM2.5 concentrations. Further chronic studies with NP and NP-containing PM2.5 are warranted to assess their contribution to lung pathologies.
Nitrophenols (NPs) and related derivatives are industrially important chemicals, used notably to synthesize pharmaceuticals, insecticides, herbicides, and pesticides. However, NPs and their metabolites are highly toxic and mutagenic. They pose a serious threat to human health and ecosystem. Current work was undertaken to develop a suitable visible-light active catalyst for the sustainable and efficient mineralization of NPs in an aqueous environment. Nanocrystalline cellulose (NCs)-based nitrogen-doped titanium dioxide and carbonaceous material (N-TiO2/C) was synthesized by pyrolysis and sol-gel methods using NCs, polydopamine, and TiO2. The synthesized N-TiO2/C was characterized using different analytical techniques. Photocatalytic degradation of NPs under visible light indicated that acidic pH (3) was most suitable for the optimal degradation. 4-NP degradation followed both pseudo-first-order (R 2 = 0.9985) and Langmuir-Hinshelwood adsorption kinetic models (adsorption constant, K LH = 1.13 L mg-1). Gas chromatography-mass spectrometry and ion chromatography analysis confirmed the total mineralization of 4-NP into smaller molecular fragments such as acids, alcohols, and nitrates. The total organic carbon showed that 67% of total carbon present in 4-NP was mineralized into CO2 and CO. The catalyst was recycled for five consecutive cycles without losing its catalytic activities. The degradation mechanism of NPs with N-TiO2/C was also explored.
Herein, we report PAN-g-Alg@Ag-based nanocatalysts synthesis via in situ oxidative free-radical polymerization of acrylonitrile (AN) using Alg@Ag nanoparticles (Alg@Ag NPs). Various analytical techniques, including FTIR, XRD, SEM, TEM, UV-Vis, and DSC, were employed to determine bonding interactions and chemical characteristics of the nanocatalyst. The optimized response surface methodology coupled central composite design (RSM-CCD) reaction conditions were a 35-min irradiation time in a 70-mg L-1 2,4-dinitrophenol (DNP) solution at pH of 4.68. Here, DNP degradation was 99.46% at a desirability of 1.00. The pseudo-first-order rate constant (K1) values were 0.047, 0.050, 0.054, 0.056, 0.059, and 0.064 min-1 with associated half-life (t1/2) values of 14.74, 13.86, 12.84, 12.38, 11.74, 10.82, and 10.04 min that corresponded to DNP concentrations of 10, 20, 30, 40, 50, 60, and 70 mg L-1, respectively, in the presence of PAN-g-Alg@Ag (0.03 g). The results indicate that the reaction followed the pseudo-first-order kinetic model with an R2 value of 0.99. The combined absorption properties of PAN and Alg@Ag NPs on copolymerization on the surface contributed more charge density to surface plasmon resonance (SPR) in a way to degrade more and more molecules of DNP together with preventing the recombination of electron and hole pairs within the photocatalytic process.
Multidrug-resistant bacteria are one of the current biggest threats to public health and are responsible for most nosocomial infections. Herein, we report the efficient and facile synthesis of antibacterial agents aminoalkylphenols, derived from 5-nitrosalicyladehyde and prepared through a Petasis borono-Mannich multicomponent reaction. Minimum inhibitory concentrations (MICs) as low as 1.23 μM for a chlorine derivative were determined for multidrug-resistant Gram-positive bacteria, namely, Staphylococcus aureus and Enterococcus faecalis, two of the main pathogens responsible for infections in a hospital environment. The most promising antibacterial agents were further tested against eight strains of four Gram-positive species in order to elucidate their antibacterial broadness. In vitro cytotoxicity assays of the most active aminoalkylphenol revealed considerably lower toxicity against mammalian cells, as concentrations one order of magnitude higher than the determined MICs were required to induce human keratinocyte cell death. The phenol moiety was verified to be important in deeming the antibacterial properties of the analyzed compounds, although no correlation between such properties and their antioxidant activity was observed. A density functional theory computational study substantiated the ability of aminoalkylphenols to serve as precursors of ortho-quinone methides.
Nitrophenols are a group of small organic molecules with significant environmental implications from the atmosphere to waterways. In this work, we investigate a series of nitrophenols and nitrophenolates, with the contrasting ortho-, meta-, and para-substituted nitro group to the phenolic hydroxy or phenolate oxygen site (2/3/4NP or NP-), implementing a suite of steady-state and time-resolved spectroscopic techniques that include UV/Visible spectroscopy, femtosecond transient absorption (fs-TA) spectroscopy with probe-dependent and global analysis, and femtosecond stimulated Raman spectroscopy (FSRS), aided by quantum calculations. The excitation-dependent (400 and 267 nm) electronic dynamics in water and methanol, for six protonated or deprotonated nitrophenol molecules (three regioisomers in each set), enable a systematic investigation of the excited-state dynamics of these functional "nanomachines" that can undergo nitro-group twisting (as a rotor), excited-state intramolecular or intermolecular proton transfer (donor-acceptor, ESIPT, or ESPT), solvation, and cooling (chromophore) events on molecular timescales. In particular, the meta-substituted compound 3NP or 3NP- exhibits the strongest charge-transfer character with FSRS signatures (e.g., C-N peak frequency), and thus, does not favor nitroaromatic twist in the excited state, while the ortho-substituted compound 2NP can undergo ESIPT in water and likely generate nitrous acid (HONO) after 267 nm excitation. The delineated mechanistic insights into the nitro-substituent-location-, protonation-, solvent-, and excitation-wavelength-dependent effects on nitrophenols, in conjunction with the ultraviolet-light-induced degradation of 2NP in water, substantiates an appealing discovery loop to characterize and engineer functional molecules for environmental applications.
The present study introduces the process performances of nitrophenols pertraction using new liquid supported membranes under the action of a magnetic field. The membrane system is based on the dispersion of silver-iron oxide nanoparticles in n-alcohols supported on hollow microporous polypropylene fibers. The iron oxide-silver nanoparticles are obtained directly through cyclic voltammetry electrolysis run in the presence of soluble silver complexes ([AgCl2]-; [Ag(S2O3)2]3-; [Ag(NH3)2]+) and using pure iron electrodes. The nanostructured particles are characterized morphologically and structurally by scanning electron microscopy (SEM and HFSEM), EDAX, XRD, and thermal analysis (TG, DSC). The performances of the nitrophenols permeation process are investigated in a variable magnetic field. These studies show that the flux and extraction efficiency have the highest values for the membrane system embedding iron oxide-silver nanoparticles obtained electrochemically in the presence of [Ag(NH3)2]+ electrolyte. It is demonstrated that the total flow of nitrophenols through the new membrane system depends on diffusion, convection, and silver-assisted transport.
The development of an efficient sustainable catalyst for effective removal of hazardous chemicals, viz. nitrophenols and organic dyes, from wastewater is a challenging task. Herein, facile synthesis of Ag/NiO composites by anchoring Ag nanoparticles (NPs) on NiO octahedrons with different amounts of Ag NPs (AN-5% (5% Ag), AN-10% (10% Ag) and AN-15% (15% Ag)) has been demonstrated. SEM (scanning electron microscopic) and TEM (transmission electron spectroscopic) images ensured the proper anchoring of spherical Ag NPs (particle size = 16.54 ± 1.88 nm) on octahedron particles of NiO, which was also ensured by XPS (X-ray photoelectron spectroscopy) analysis. Moreover, the resulting composites have an average surface area (49-52 m2g‒1) and pore size (2.39-2.26 nm). All three synthesized Ag/NiO composites (100 μL) catalyzed the complete reduction of para-np (4-nitrophenol: 0.1587 mM) within 2-3 min in the presence of 0.04 M NaBH4. Among them, AN-5% has been chosen because of the lowest anchored Ag (5%) to obtain the optimized catalyst's amount (50 μL) and concentration of para-np (0.1587 mM). AN-5% also exhibited excellent catalytic activity towards different nitro substituted phenols, viz. ortho-np (2-nitrophenol), meta-np (3-nitrophenol), para-np (4-nitrophenol) and tri-np (2,4,6-trinitrophenol). AN-5% displayed ∼100% catalytic efficiency for reducing meta-np in 2 min with the apparent first order rate constant (kapp) and normalized rate constant (Knor) as 1.99 s-1 and 398.14 s-1 g-1, respectively. Additionally, AN-5% (29.41 μg mL-1) reduced >95% of the colouring dyes (10 ppm) such as CONG-R (congo red: 95% in 6 min), METH-O (methyl orange: 97.5% in 7 min), METH-B (methylene blue: 98.3% in 10 min) and RHOD-B (rhodamine B: 99.2% in 5 min). AN-5% not only demonstrated catalytic reduction towards individual pollutants, but also showed excellent activity for reduction of the mixtures of nitrophenols/dyes and for treatment of simulated industrial effluent samples (EFF1, EFF2) and a real industrial sample (textile dye-bath effluent). AN-5% can also be reused up to several cycles with almost same efficiency and followed the Langmuir-Hinshelwood apparent first order kinetics model.
In this work, we have developed novel beads based on carboxymethyl cellulose (CMC) encapsulated copper oxide-titanium oxide (CuO-TiO2) nanocomposite (CMC/CuO-TiO2) via Al+3 cross-linking agent. The developed CMC/CuO-TiO2 beads were applied as a promising catalyst for the catalytic reduction of organic and inorganic contaminants; nitrophenols (NP), methyl orange (MO), eosin yellow (EY) and potassium hexacyanoferrate (K3[Fe(CN)6]) in the presence of reducing agent (NaBH4). CMC/CuO-TiO2 nanocatalyst beads exhibited excellent catalytic activity in the reduction of all selected pollutants (4-NP, 2-NP, 2,6-DNP, MO, EY and K3[Fe(CN)6]). Further, the catalytic activity of beads was optimized toward 4-nitrophenol with varying its concentrations and testing different concentrations of NaBH4. Beads stability, reusability, and loss in catalytic activity were investigated using the recyclability method, in which the CMC/CuO-TiO2 nanocomposite beads were tested several times for the reduction of 4-NP. As a result, the designed CMC/CuO-TiO2 nanocomposite beads are strong, stable, and their catalytic activity has been proven.
The environmental fates of chlorinated 4-nitrophenols, 2,6-dichloro-4-nitrophenol (2,6-DCNP) and 2-chloro-4-nitrophenol (2C4NP), mediated via microbial catabolism have attracted great attention due to their high toxicity and persistence in the environment. In this study, a strain of Ensifer sp. 22-1 that was capable of degrading both 2,6-DCNP and 2C4NP was isolated from a halogenated aromatic-contaminated soil sample. A gene cluster cnpBADCERM was predicted to be involved in the catabolism of 2,6-DCNP and 2C4NP based on genome sequence analysis. A two-component monooxygenase CnpAB, composed of an oxygenase component (CnpA) and a reductase component (CnpB), was confirmed to catalyze the continuous denitration and dechlorination of 2,6-DCNP and 2C4NP to 6-chlorohydroxyquinol (6-CHQ) and hydroxyquinol (HQ), respectively. Knockout of cnpA resulted in the complete loss of the capacity for strain 22-1 to degrade 2,6-DCNP and 2C4NP. Homologous modeling and docking showed that Val155~Ala159, Phe206~Pro209 and Phe446~Arg461 of CnpA participated in the formation of the FAD-binding pocket, and Arg101, Val155 and Asn447 formed hydrogen bonds with 2,6-DCNP/2C4NP in the substrate-binding pocket. This work characterized a new two-component monooxygenase for 2,6-DCNP and 2C4NP, and enriched our understanding of the degradation mechanism of chlorinated nitrophenols (CNPs) by microorganisms.
para-Nitrophenol (PNP), 3-methyl-4-nitrophenol (3M4NP), and 2-chloro-4-nitrophenol (2C4NP) are highly toxic compounds that have caused serious environmental issues. We inoculated an artificially contaminated soil with Burkholderia sp. strain SJ98, which has the ability to degrade PNP, 3M4NP, and 2C4NP, and quantified bioremediation. There was accelerated degradation of all nitrophenols in inoculated treatments compared to the un-inoculated treatments. The indigenous bacteria were able to degrade PNP, but not 3M4NP or 2C4NP. Real-time PCR targeting the catabolic gene pnpA showed that levels of strain SJ98 remained stable over the incubation period. High-throughput sequencing revealed that both contamination and bioaugmentation influenced the bacterial community structure. Bioaugmentation seemed to protect Kineosporia, Nitrososphaera, and Schlesneria from nitrophenol inhibition, as well as led to a sharp increase in the abundance of Nonomuraea, Kribbella, and Saccharopolyspora. There was a significant increase in the relative abundances of Thermasporomyces, Actinomadura, and Streptomyces in both contaminated and bioaugmented treatments; this indicated that these bacteria are likely directly related to nitrophenol degradation. To our knowledge, this is the first report of the simultaneous removal of PNP, 3M4NP, and 2C4NP using bioaugmentation. This study provides valuable insights into the bioremediation of soils contaminated with nitrophenols.
Enzymes that are capable of detoxifying halogenated phenols (HPs) and nitrophenols (NPs) are valuable for bioremediation and waste biorefining. HadA monooxygenase was found to perform dual functions of oxidative dehalogenation (hydroxylation plus halide elimination) and denitration (hydroxylation plus nitro elimination). Rate constants associated with individual steps of HadA reactions with phenol, halogenated phenols and nitrophenols were measured using combined transient kinetic approaches of stopped-flow absorbance/fluorescence and rapid-quench flow techniques. Density functional theory was used to calculate the thermodynamic and electronic parameters associated with hydroxylation and group elimination steps. These parameters were correlated with the rate constants of hydroxylation, group elimination, and overall product formation to identify factors controlling individual steps. The results indicated that the hydroxylation rate constant is higher when the pK a of the phenolic group is lower, i.e. it is more easily deprotonated, but not higher when the energy gap between the E LUMO of the C4a-hydroperoxy-FAD intermediate and the E HOMO of the phenolate substrate is lower. These data suggest that the substrate deprotonation has a higher energy barrier than the -OH transfer, and thus controls the hydroxylation step. For the group elimination, the process is controlled by the ability of the C-X bond to break. For the overall product formation (hydroxylation and group elimination combined), this analysis showed that the rate constant of product formation is dependent on the pK a value of the substrate, indicating that the overall reaction is controlled by substrate deprotonation. This step also likely has the highest energy barrier and thus controls the overall process of oxidative dehalogenation and denitration by HadA. This report is the first to identify a key mechanistic factor controlling the enzymatic processes of oxidative dehalogenation and denitration.
Nitrobenzene oxidation was executed utilizing an innovative method, in which Ag/Pb3O4 semiconductors irradiated by visible light were used for activation of persulfate into sulfate radicals. Batch mode experiments were accomplished to elucidate the effect of persulfate concentrations and Ag/Pb3O4 dosages on the nitrobenzene oxidation behaviors. The physicochemical properties of original and reacted Ag/Pb3O4 were illustrated by X-ray diffraction analyses, UV-Vis diffuse reflectance spectra, FE-SEM images, EDS analyses, photoluminescence spectra and X-ray photoelectron spectra, respectively. The main oxidant was hypothesized to be sulfate radicals, induced from persulfate caused by photocatalysis of Ag/Pb3O4. It was clearly reflected on the scavenging experiments with addition of benzene, ethanol and methanol individually. As far as degradation pathways concerned, nitrobenzene was essentially transformed into hydroxycyclohexadienyl radicals, and sequentially converted to 2-nitrophenol, 3-nitrophenol or 4-nitrophenol simultaneously. Denitration of nitrophenols gave rise to synthesis of phenol, followed with generation of hydroquinone and p-benzoquinone.
Phenols, and especially their nitrated analogues, are ubiquitous pollutants and known carcinogens which have already been linked to forest decline. Although nitrophenols have been widely recognized as harmful to different aquatic and terrestrial organisms, we could not find any literature assessing their toxicity to terrestrial plants. Maize (monocot) and sunflower (dicot) were exposed to phenolic pollutants, guaiacol (GUA) and 4-nitroguaiacol (4NG), through a hydroponics system under controlled conditions in a growth chamber. Their acute physiological response was studied during a two-week root exposure to different concentrations of xenobiotics (0.1, 1.0, and 10 mM). The exposure visibly affected plant growth and the effect increased with increasing xenobiotic concentration. In general, 4NG affected plants more than GUA. Moreover, sunflower exhibited an adaptive response, especially to low and moderate GUA concentrations. The integrity of both plant species deteriorated during the exposure: biomass and photochemical pigment content were significantly reduced, which reflected in the poorer photochemical efficiency of photosystem II. Our results imply that 4NG is taken up by sunflower plants, where it could enter a lignin biosynthesis pathway.
In this study, the composite of aluminum metal-organic framework MIL-68(Al) and reduced graphene oxide (MA/RG) was synthesized via a one-step solvothermal method, and their performances for p-nitrophenol (PNP) adsorption from aqueous solution were systematically investigated. The introduction of reduced graphene oxide (RG) into MIL-68(Al) (MA) significantly changes the morphologies of the MA and increases the surface area. The MA/RG-15% prepared at RG-to-MA mass ratio of 15% shows a PNP uptake rate 64% and 123% higher than MIL-68(Al) and reduced graphene oxide (RG), respectively. The hydrogen bond and π - π dispersion were considered to be the major driving force for the spontaneous and endothermic adsorption process for PNP removal. The adsorption kinetics, which was controlled by film-diffusion and intra-particle diffusion, was greatly influenced by solution pH, ionic strength, temperature and initial PNP concentration. The adsorption kinetics and isotherms can be well delineated using pseudo-second-order and Langmuir equations, respectively. The presence of phenol or isomeric nitrophenols in the solution had minimal influence on PNP adsorption by reusable MA/RG composite.
With an aim to understand the photophysical behavior of twisted organic fluorescent molecules in their aggregated state, two twisted biaryl molecules, namely, 9,9'-bianthryl and 10,10'-dicyano-9,9'-bianthryl, have been synthesized and characterized by conventional spectroscopic methods. To understand the role of C-C bond twisting on the photophysical response of biaryl aggregates, monoaryl counterparts (anthracene and 9-anthracenecarbonitrile) of the biaryl systems are also investigated. Photophysical behaviors of these systems along with their monoaryl counterpart are investigated in both solution and aggregated state. Investigations reveal that fluorescence spectra of the biaryl compounds show blue-shifted emission upon aggregation. Interestingly, no blue shift of the emission has been observed for monoaryl aggregates. Photophysical data of biaryl systems compared to monoaryl unit reveal that change in geometry, during self-assembly process, disfavors the formation of charge-transfer state, which eventually causes blue shift in the emission upon aggregation. In addition to this, potential of these systems toward signaling of nitroaromatic explosive has also been explored. Among all of the nitroaromatics, the highest fluorescence quenching is observed for nitrophenols (say picric acid (PA)). The investigation also reveals that compared to monoaryl systems, biaryl systems are more responsive to fluorescence quenching by nitroaromatics. Perrin's model of quenching sphere action has been attributed to nitrophenol (PA) selective signaling behavior of biaryl systems.
New munition compounds have been developed to replace traditional explosives to prevent unintended detonations. However, insensitive munitions (IM) can leave large proportion of unexploded charge in the field, where it is subjected to photodegradation and dissolution in precipitation. The photolytic reactions occurring on the surfaces of IMX-101 and IMX-104 formulations and the subsequent fate of photolytic products in the environment were thoroughly investigated. The constituents of IMX-101 and IMX-104 formulations dissolve sequentially under rainfall in the order of aqueous solubility: 3-nitro-1,2,4-triazol-5-one (NTO) > nitroguanidine (NQ) > 2,4-dinitroanisole (DNAN) > 1,3,5-hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). A linear relationship between DNAN dissolution and rainwater volume was observed (r2: 0.86-0.99). It was estimated that it would take 16-228 years to completely dissolve these formulation particles under natural environmental conditions in Oracle, AZ. We used LC/MS/MS and GC/MS to examine the dissolution samples from IMX-101 and 104 particles exposed to rainfall and sunlight and found six DNAN photo-transformation products including 2-methoxy-5-nitrophenol, 4-methoxy-3-nitrophenol, 4-methoxy-3-nitroaniline, 2-methoxy-5-nitroaniline, 2,4-dinitrophenol, and methoxy-dinitrophenol, which are in good agreement with computational modeling results of bond strengths. The main DNAN photodegradation pathways are therefore proposed. Predicted eco-toxicity values suggested that the parent compound DNAN, methoxy-nitrophenols, methoxy-nitroanilines and the other two products (2,4-dinitrophenol and methoxy-dinitrophenol) would be harmful to fish and daphnid. Our study provides improved insight about the rain dissolution and photochemical behavior of IM formulations under natural conditions, which helps to form target-oriented strategies to mitigate explosive contamination in military training sites.
The global manufacturing of clothing is usually composed of multistep processes, which include a large number of chemicals. However, there is generally no information regarding the chemical content remaining in the finished clothes. Clothes in close and prolonged skin contact may thus be a significant source of daily human exposure to hazardous compounds depending on their ability to migrate from the textiles and be absorbed by the skin. In the present study, twenty-four imported garments on the Swedish market were investigated with respect to their content of organic compounds, using a screening workflow. Reversed-phase liquid chromatography coupled to electrospray ionization/high-resolution mass spectrometry was used for both suspect and non-target screening. The most frequently detected compound was benzothiazole followed by quinoline. Nitroanilines with suspected mutagenic and possible skin sensitization properties, and quinoline, a carcinogenic compound, were among the compounds occurring at the highest concentrations. In some garments, the level of quinoline was estimated to be close to or higher than 50,000 ng/g, the limit set by the REACH regulation. Other detected compounds were acridine, benzotriazoles, benzothiazoles, phthalates, nitrophenols, and organophosphates. Several of the identified compounds have logP and molecular weight values enabling skin uptake. This pilot study indicates which chemicals and compound classes should be prioritized for future quantitative surveys and control of the chemical content in clothing as well as research on skin transfer, skin absorption, and systemic exposure. The results also show that the current control and prevention from chemicals in imported garments on the Swedish market is insufficient.
Graphene oxide (GO) was synthesised via the oxidation of graphite and was characterised using ATR FTIR, PXRD, SEM, TEM and TGA. These techniques confirmed the presence of characteristic oxygen-containing functional groups and the resulting increase in interlayer spacing in the nanostructure. GO is used as the support to form nanocomposites composed of combinations of the following: iron oxide nanoparticles (Fe3O4), carbon nanotubes (CNT) and palladium nanoparticles (Pd). The four final nanocomposites formed are: Pd/GO, Pd/Fe3O4/GO, Pd/CNT/GO, and Pd/CNT/Fe3O4/GO. Key intermediates were analysed using ATR FTIR for the confirmation of the modification. Additionally, all composites and their precursors underwent electron microscopic analysis to visually assess composite morphologies and the size distribution of deposited nanoparticles. The Fe3O4 and Pd nanoparticles were indistinguishable from each other in their spherical shape and particle diameters, which were no bigger than 32 nm. From the TGA, incorporation of Fe3O4, CNT and finally Pd into the nanocomposites increased total thermal stability in terms of mass percentage lost over the temperature programme. GO showed significant decomposition, with all nanocomposites remaining relatively stable up to 120 °C. ICP OES results showed total Pd content by mass percentage for each final composite, varied from 7.9% to 9.1% mass Pd/collective mass. XPS confirmed the expected elemental compositions of composites according to their structures and the Pd0 : PdII ratios are obtained. The nanocomposites were tested for the catalytic reduction of nitrophenols. Pd/CNT/Fe3O4/GO gave the highest TOF' for the reduction of 4-NP and 2-NP. For the reduction of 3-NP, Pd/GO showed the highest TOF'. Nitrophenol's pK a and catalyst TOF' correlated in a direct proportional relationship for Pd/GO and Pd/Fe3O4/GO. It was found that Pd0 surpassed PdII in catalytic activity. Reduction of PdII to Pd0 took place during the first catalytic cycle.
The green synthesis of silver nanoparticles (AgNPs) has currently been gaining wide applications in the medical field of nanomedicine. Green synthesis is one of the most effective procedures for the production of AgNPs. The Diospyros malabarica tree grown throughout India has been reported to have antioxidant and various therapeutic applications. In the context of this, we have investigated the fruit of Diospyros malabarica for the potential of forming AgNPs and analyzed its antibacterial and anticancer activity. We have developed a rapid, single-step, cost-effective and eco-friendly method for the synthesis of AgNPs using Diospyros malabarica aqueous fruit extract at room temperature. The AgNPs began to form just after the reaction was initiated. The formation and characterization of AgNPs were confirmed by UV-Vis spectrophotometry, XRD, FTIR, DLS, Zeta potential, FESEM, EDX, TEM and photoluminescence (PL) methods. The average size of AgNPs, in accordance with TEM results, was found to be 17.4 nm. The antibacterial activity of the silver nanoparticles against pathogenic microorganism strains of Staphylococcus aureus and Escherichia coli was confirmed by the well diffusion method and was found to inhibit the growth of the bacteria with an average zone of inhibition size of (8.4 ± 0.3 mm and 12.1 ± 0.5 mm) and (6.1 ± 0.7 mm and 13.1 ± 0.5 mm) at 500 and 1000 µg/mL concentrations of AgNPs, respectively. The anticancer effect of the AgNPs was confirmed by MTT assay using the U87-MG (human primary glioblastoma) cell line. The IC50 value was found to be 58.63 ± 5.74 μg/mL. The results showed that green synthesized AgNPs exhibited significant antimicrobial and anticancer potency. In addition, nitrophenols, which are regarded as priority pollutants by the United States Environmental Protection Agency (USEPA), can also be catalytically reduced to less toxic aminophenols by utilizing synthesized AgNPs. As a model reaction, AgNPs are employed as a catalyst in the reduction of 4-nitrophenol to 4-aminophenol, which is an intermediate for numerous analgesics and antipyretic drugs. Thus, the study is expected to help immensely in the pharmaceutical industries in developing antimicrobial drugs and/or as an anticancer drug, as well as in the cosmetic and food industries.
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