Assessment of the catalytic and biological potential of yttrium and samarium-modified copper ferrite nanomaterials.

The present study reports the preparation of crystalline and nanosized copper ferrite (CuFe2O4), Y3+ substituted CuFe2O4 (CuFe1.95Y0.05O4), and Sm3+ substituted CuFe2O4 (CuFe1.95Sm0.05O4) using a simple co-precipitation method. The XRD analysis confirmed the formation of the cubic spinel phase, while XPS studies validated the presence of Cu and Fe in 2+ and 3+ oxidation states respectively. Transmission electron microscopy (TEM) analysis revealed the nanoparticles with a diameter in the range of 10-60 nm. The introduction of fractional amounts of Y3+ and Sm3+ ions in the CuFe2O4 lattice enhanced the reduction of 4-nitrophenol, attributed to decreased particle size facilitating the reduction process. In the case of antimicrobial activity, Candida albican was found to be maximally sensitive to CuFe2O4 and CuFe1.95Y0.05O4, while Pseudomonas aeruginosa was inhibited by CuFe1.95Sm0.05O4. Moreover, a maximum of 61.9 ± 1.91 % anti-Pseudomonas biofilm activity and 75.7 ± 1.28 % DPPH radical scavenging activity was observed for CuFe1.95Y0.05O4 at 200 µg/ml concentration. The improvement in biological activities was attributed to the reduced particle size, crystal structure modification, and increased stability of the CuFe2O4 lattice with substitution. The enhancement in catalytic and biological performance highlighted the effectiveness of minimal Y3+ and Sm3+ concentrations in modulating the properties of CuFe2O4 nanomaterials.

Circular economical approach of extracting nanocarbons from waste pea peel for sensing of p-nitrophenol and its conversion into paracetamol.

An important paradigm shift towards the circular economy is to prioritize waste prevention, reuse, recycling, and recovery before disposal is necessary. In this context, a sustainable protocol of converting waste pea peel (wPP) into low-cost carbon nanomaterials for sensing and conversion of p-nitrophenol (p-NP) into value-added paracetamol is being reported. Two fractions of the carbonaceous nanomaterials were obtained after the hydrothermal treatment (HT) of wPP, firstly an aqueous portion containing water-soluble carbon dots (wPP-CDs) and a solid residue, which was converted into carbonized biochar (wPP-BC). Blue-colored fluorescent wPP-CDs displayed excitation-dependent and pH-independent properties with a quantum yield (QY) of 8.82 %, which were exploited for the fluorescence sensing of p-NP with 4.20 µM limit of detection. Pyrolyzed biochar acting as an efficient catalyst effectively reduces p-NP to p-aminophenol (p-AP) in just 16 min with a 0.237 min-1 rate of conversion. Furthermore, the produced p-AP was converted into paracetamol, an analgesic and antipyretic drug, to achieve zero waste theory. Thus, this study provides the execution of sustainable approaches based on the integral valorization of biowaste that can be further recycled and reused, offering an effective way to attain a profitable circular economy.

Fast and Facile Synthesis of 4-Nitrophenyl 2-Azidoethylcarbamate Derivatives from N-Fmoc-Protected α-Amino Acids as Activated Building Blocks for Urea Moiety-Containing Compound Library.

A fast and facile synthesis of a series of 4-nitrophenyl 2-azidoethylcarbamate derivatives as activated urea building blocks was developed. The N-Fmoc-protected 2-aminoethyl mesylates derived from various commercially available N-Fmoc-protected α-amino acids, including those having functionalized side chains with acid-labile protective groups, were directly transformed into 4-nitrophenyl 2-azidoethylcarbamate derivatives in 1 h via a one-pot two-step reaction. These urea building blocks were utilized for the preparation of a series of urea moiety-containing mitoxantrone-amino acid conjugates in 75-92% yields and parallel solution-phase synthesis of a urea compound library consisted of 30 members in 38-70% total yields.

Small molecule solvation changes due to the presence of salt are governed by the cost of solvent cavity formation and dispersion.

We are interested in the free energies of transferring nonpolar solutes into aqueous NaCl solutions with salt concentrations upwards of 2 M, the Hofmeister regime. We use the semi-explicit assembly (SEA) computational model to represent these electrolyte solutions. We find good agreement with experiments (Setschenow coefficients) on 43 nonpolar and polar solutes and with TIP3P explicit-solvent simulations. Besides being much faster than explicit solvent calculations, SEA is more accurate than the PB models we tested, successfully capturing even subtle salt effects in both the polar and nonpolar components of solvation. We find that the salt effects are mainly due to changes in the cost of forming nonpolar cavities in aqueous NaCl solutions, and not mainly due to solute-ion electrostatic interactions.

Prediction model based on decision tree analysis for laccase mediators.

A Structure Activity Relationship (SAR) study for laccase mediator systems was performed in order to correctly classify different natural phenolic mediators. Decision tree (DT) classification models with a set of five quantum-chemical calculated molecular descriptors were used. These descriptors included redox potential (ɛ°), ionization energy (E(i)), pK(a), enthalpy of formation of radical (Δ(f)H), and OH bond dissociation energy (D(O-H)). The rationale for selecting these descriptors is derived from the laccase-mediator mechanism. To validate the DT predictions, the kinetic constants of different compounds as laccase substrates, their ability for pesticide transformation as laccase-mediators, and radical stability were experimentally determined using Coriolopsis gallica laccase and the pesticide dichlorophen. The prediction capability of the DT model based on three proposed descriptors showed a complete agreement with the obtained experimental results.

Photochemical transformation of anionic 2-nitro-4-chlorophenol in surface waters: laboratory and model assessment of the degradation kinetics, and comparison with field data.

Anionic 2-nitro-4-chlorophenol (NCP) may occur in surface waters as a nitroderivative of 4-chlorophenol, which is a transformation intermediate of the herbicide dichlorprop. Here we show that NCP would undergo efficient photochemical transformation in environmental waters, mainly by direct photolysis and reaction with OH. NCP has a polychromatic photolysis quantum yield Φ(NCP)=(1.27±0.22)·10(-5), a rate constant with OH k(NCP,)(OH)=(1.09±0.09)·10(10) M(-1) s(-1), a rate constant with (1)O(2)k(NCP,1O2)=(2.15±0.38)·10(7) M(-1) s(-1), a rate constant with the triplet state of anthraquinone-2-sulphonate k(NCP,3AQ2S*)=(5.90±0.43)·10(8) M(-1) s(-1), and is poorly reactive toward CO(3)(-). The k(NCP,3AQ2S*) value is representative of reaction with the triplet states of chromophoric dissolved organic matter. The inclusion of photochemical reactivity data into a model of surface-water photochemistry allowed the NCP transformation kinetics to be predicted as a function of water chemical composition and column depth. Very good agreement between model predictions and field data was obtained for the shallow lagoons of the Rhône delta (Southern France).

Zeolitic bagasse fly ash as a low-cost sorbent for the sequestration of p-nitrophenol: equilibrium, kinetics, and column studies.

PURPOSE: The purpose of the research is to investigate the application of bagasse fly ash, a sugar industry solid waste for the synthesis of zeolites and their behavior for the sorption of p-nitrophenol (p-NP). METHODS: Zeolitic materials were prepared from bagasse fly ash using alkaline hydrothermal (CZBFA) and fusion (FZBFA) treatment. Comparative batch sorption studies of prepared zeolitic material and virgin material were undertaken to determine their capacities for removal of p-nitrophenol. RESULTS: PXRD patterns revealed that zeolite P and analcime were the dominant contents of synthesized zeolitic material. Chemical composition, morphology, and crystalline nature of CZBFA and FZBFA were characterized by XRF, FTIR, and SEM. The Langmuir, Freundlich, Dubinin Redushkwich, and Temkin sorption isotherms were applied to compare the sorption nature and capacity of synthesized CZBFA and FZBFA with virgin BFA. For each sorbent-p-NP system, a pseudo-second-order kinetic model described the sorption kinetics accurately. The thermodynamics of the p-NP-sorbent systems exhibit an exothermic sorption process. Intraparticle diffusion model shows that the sorption rate was controlled by film diffusion followed by pore diffusion. Regeneration of sorbents was carried out by desorption studies with HCl, NaOH, and SDS detergent. The column studies were performed for the practical utility of sorbents, and breakthrough curve were obtained, which exhibit higher sorption capacity than batch method. CONCLUSION: The sorption capacities of the synthesized zeolites had improved sorption capacities for the sequestration of p-NP and can be utilized as low-cost sorbents for treatment of p-nitrophenolic wastewater.

Potentiometric determination of α-L-fucosidase enzyme by using 2-chloro-4-nitrophenol-rhodamine B ion pair chemical recognition in PVC membrane sensor.

The activity of the α-L-fucosidase (AFU) enzyme represents an excellent test for diagnosis of hepatocellular carcinoma (HCC) and fucosidosis recognized in inborn disorder of metabolism and increases the sensitivity of detection to 95.5% in patients with HCC. Therefore, the determination of the activity of AFU enzyme is very important and can be used as a screening tool for the early diagnosis of tumors for HCC patients. A simple, accurate, and sensitive potentiometric method was developed for measuring the activity of AFU. The method was based upon measuring the concentration of 2-chloro-4-nitrophenol (2-chloro-4-NP) using a 2-chloro-4-NP-rhodamine B ion pair in a PVC membrane sensor. The electrode shows a linear, reproducible, and stable potentiometric response with an anionic Nernstian slope of -51.13 ± 0.6 mV/decade over a wide range of concentrations 10(-5)-10(-2) M and a detection limit of 1.0 × 10(-6) M of 2-chloro-4-NP. The membrane exhibits a fast response time of 30 s, over a pH range of 4.0-6.5. The selectivity coefficients indicate excellent selectivity for 2-chloro-4-NP over a number of interfering species, e.g., chloride, nitrate, sulfate, chromate urea, albumin, glucose, uric acid, and total protein. The prepared sensor has been used successfully for the determination of 2-chloro-4-NP produced from the hydrolysis of 2-chloro-4-NP-α-L-fucopyranoside substrate. It was also applied for the determination α-L-fucosidase enzyme of 33 serum samples of healthy subjects and patients. The average recoveries ± RSD for the healthy subjects, cirrhosis of chronic hepatitis C and B, and HCC serum samples were 102.6 ± 1.01%, 101.5 ± 0.95%, and 100.1 ± 1.1%, respectively. The results obtained are in good agreement with those obtained by standard methods.

Assessment of the genotoxic and carcinogenic risks of p-nitrophenol when it is present as an impurity in a drug product.

According to the 2008 US FDA (draft) and 2006 EMEA guidance documents for genotoxic impurities, an impurity that is positive in an in vitro genotoxicity study, in the absence of in vivo genotoxicity or carcinogenicity data, should be treated as genotoxic and typically controlled to 1.5 microg/day for chronic use. For p-nitrophenol (PNP), existing study results (i.e., positive in vitro clastogenicity in mammalian cells, no information on its in vivo genotoxicity, and negative with respect to carcinogenicity in a dermal mouse study with no confirmation of systemic exposure) indicated that it should be considered genotoxic and exposure as a drug impurity limited. Therefore, to more completely characterize the genotoxic potential of PNP (consistent with the guidance documents), in vivo mouse micronucleus and dermal pharmacokinetic bridging studies were conducted. In the micronucleus study, PNP was negative, demonstrating that the reported in vitro clastogenicity is not present in vivo. In the pharmacokinetic study, PNP was well absorbed dermally, validating the negative dermal carcinogenicity assessment. These results indicate that PNP should be considered a non-genotoxic impurity and, as a drug impurity, a threshold limit of 4 mg/day would be set (per ICH Q3C). This threshold limit is higher than the EPA reference dose (listed in the 2006 Edition of the Drinking Water Standards and Health Advisories), so if present at such levels, the specification limits for PNP should be determined on a case-by-case basis, based on risk-benefit.

Final report on the safety assessment of amino nitrophenols as used in hair dyes.

2-Amino-3-nitrophenol, 2-amino-4-nitrophenol, 2-amino-5-nitrophenol, 4-amino-3-nitrophenol, 4-amino-2-nitrophenol, 2-amino-4-nitrophenol sulfate, 3-nitro-p-hydroxyethylaminophenol, and 4-hydroxypropylamino-3-nitrophenol are substituted aromatic compounds used as semipermanent (nonoxidative) hair colorants and as toners in permanent (oxidative) hair dye products. All ingredients in this group except 2-amino-4-nitrophenol sulfate, 2-amino-5-nitrophenol, and 4-amino-2-nitrophenol have reported uses in cosmetics at use concentrations from 2% to 9%. The available toxicity studies for these amino nitrophenol hair dyes did not suggest safety concerns except for the potential carcinogenicity and mutagenicity of 4-amino-2-nitrophenol. 2-Amino-3-nitrophenol, 2-amino-4-nitrophenol, 2-amino-4-nitrophenol sulfate, 2-amino-5-nitrophenol, 4-amino-3-nitrophenol, 3-nitro-p-hydroxyethylaminophenol, and 4-hydroxypropylamino-3-nitrophenol are safe as hair dye ingredients in the practices of use and concentration as described in this safety assessment, but the data are insufficient to make a safety determination for 4-amino-2-nitrophenol.

Kinetic and safety assessment for salicylic acid nitration by nitric acid/acetic acid system.

The nitration process of salicylic acid for the production of the important intermediate 5-nitrosalicylic acid is studied from thermokinetic and safety points of view. Investigations carried out by considering, as process deviations, the loss of the thermal control point out the possibility of runaway phenomena due to the occurrence of polynitration reactions. Isothermal experiments are carried out in various conditions to assess the involved reaction network and reaction kinetics.

Polymetallic complexes in microemulsions for the hydrolysis of 4-nitrophenyl phosphate: a bio-mimetic model for decontamination of organophosphates in the environment.

Reactions of several metal ions and polymetallic complexes toward hydrolysis of 4-nitrophenyl phosphate (NPP) were investigated at 10(-3)M concentration in oil-in-water microemulsions and aqueous media. The reactions were monitored by measuring the absorbance of the nitrophenolate ion produced in the reaction aliquots with time. The order of effectiveness of the metal ions and polymetallic complexes at neutral pH toward hydrolysis of NPP was found to be Turnbull's Blue>magnetite>Fe(III)>Fe(II)>Co(II)>Ca(II)>Cu(II). The possible application of these systems for sites contaminated with chemical warfare agents such as organophosphates is discussed.

Construction and assessment of models of CYP2E1: predictions of metabolism from docking, molecular dynamics, and density functional theoretical calculations.

3D models of CYP2E1 were constructed for the purpose of structure-based prediction of 2E1 metabolism of diverse substrates based on configuration sampling of ligand-atom-oxyferryl center distances and quantum chemical criteria. Models were constructed on the basis of sequence alignments of 2E1 with templates of known structure, including rabbit CYP2C5 (3LVdH) and bacterial CYP450s. Following geometric and energetic assessments, the utility of the model was tested in structure-based predictions of metabolism. Autodock was used to dock chlorzoxazone, p-nitrophenol, N-nitrosodimethylamine, acetominophen, caffeine, theophylline, and methoxyflurane into the model CYP2E1 employing a model oxyferryl heme with charges based on density functional theoretical parametrization. In all cases, the lowest energy bound docked configurations corresponded to ones with the substrate intimately associated with the oxyferryl center. Configurations among the lowest energy docked forms of each of the ligands had orientations relative to the oxyferryl center consistent with the experimentally observed metabolites. Docking of long-chain dialkylnitrosoamines revealed no heme binding site bound configurations, in agreement with the negligible metabolism of these ligands. The lowest energy docked configurations of chlorzoxazone, p-nitrophenol, and N-nitrosodimethylamine, high-affinity substrates of 2E1, were used to initiate 300 ps molecular dynamics (MD) trajectories. The MD-sampled ligand-oxyferryl heme reactant configurations were in good accord with density functional theoretical (DFT) optimized oxyferryl-heme-ligand geometries. Analysis of the MD-sampled ligand-2E1 configurations from multiple docked orientations indicates the configurations with closest exposure of reactive centers to the oxyferryl heme to be correlated with observed metabolites with proper consideration of H-abstraction energetics. DFT assessment of relative radical energetics is directly compared with differential H-abstraction activation energetics by compound I and by a p-nitrosophenoxy radical compound I surrogate for the specific case of methoxyflurane and is shown to be in good agreement.