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1.
J Agric Food Chem ; 72(12): 6691-6701, 2024 Mar 27.
Artículo en Inglés | MEDLINE | ID: mdl-38498985

RESUMEN

To accelerate the development of novel fungicides, a variety of N-(pyrazol-5-yl)benzamide derivatives with a diphenylamine moiety were designed and synthesized using a pharmacophore recombination strategy based on the structure of pyrazol-5-yl-aminophenyl-benzamides. The bioassay results demonstrated that most of the target compounds had excellent in vitro antifungal activities against Sclerotinia sclerotiorum, Valsa mali, and Botrytis cinerea. In particular, compound 5IIIh exhibited remarkable activity against S. sclerotiorum (EC50 = 0.37 mg/L), which was similar to that of fluxapyroxad (EC50 = 0.27 mg/L). In addition, compound 5IIIc (EC50 = 1.32 mg/L) was observed to be more effective against V. mali than fluxapyroxad (EC50 = 12.8 mg/L) and comparable to trifloxystrobin (EC50 = 1.62 mg/L). Furthermore, compound 5IIIh demonstrated remarkable in vivo protective antifungal properties against S. sclerotiorum, with an inhibition rate of 96.8% at 100 mg/L, which was close to that of fluxapyroxad (99.6%). Compounds 5IIIc (66.7%) and 5IIIh (62.9%) exhibited good in vivo antifungal effects against V. mali at 100 mg/L, which were superior to that of fluxapyroxad (11.1%) but lower than that of trifloxystrobin (88.9%). The succinate dehydrogenase (SDH) enzymatic inhibition assay was conducted to confirm the mechanism of action. Molecular docking analysis further revealed that compound 5IIIh has significant hydrogen-bonding, π-π, and p-π conjugation interactions with ARG 43, SER 39, TRP 173, and TYR 58 in the binding site of SDH, and the binding mode was similar to that of the commercial fungicide fluxapyroxad. All of the results suggest that compound 5IIIh could be a potential SDH inhibitor, offering a valuable reference for future studies.


Asunto(s)
Acetatos , Amidas , Antifúngicos , Fungicidas Industriales , Iminas , Estrobilurinas , Relación Estructura-Actividad , Antifúngicos/farmacología , Difenilamina/química , Simulación del Acoplamiento Molecular , Fungicidas Industriales/química , Benzamidas , Succinato Deshidrogenasa
2.
Anal Sci ; 40(1): 163-174, 2024 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-37845602

RESUMEN

This study reports the electrochemical monitoring and sensing of diphenylamine (DPA), an anti-scald agent on a modified pencil graphite electrode (PGE). DPA is also a potentially toxic environmental pollutant. A polymer of tyrosine synthesized by electrochemical process was utilized for the determination of DPA in real samples. The electrodes were characterized using IR, SEM, EDAX, AFM and EIS analyses. As far as we know, this is first time reporting the utilization of modified PGE via green approach for the monitoring of DPA. A dynamic linear range of 1.00-117.11 µM with a lower detection limit (LOD) of 0.7050 µM was showed by this sensor for the electrochemical quantification of DPA. The electrochemical oxidation of DPA on the modified sensor followed a mixed adsorption -diffusion controlled kinetics. The sensor also showed good anti-interference property for the determination of DPA in real samples. Furthermore, the developed sensor was applied for the selective sensing of DPA from real apple extracts with good recovery. The real sample analysis was validated with standard spectrophotometric method.

3.
Int J Mol Sci ; 24(23)2023 Nov 27.
Artículo en Inglés | MEDLINE | ID: mdl-38069128

RESUMEN

The title compounds were synthesized by the reaction of 5-oxo-1-(4-(phenylamino)phenyl)pyrrolidine-3-carbohydrazide with various aldehydes bearing aromatic and heterocyclic moieties and acetophenones, and their cytotoxicity was tested via MTT assay against human triple-negative breast cancer MDA-MB-231, human melanoma IGR39, human pancreatic carcinoma Panc-1, and prostate cancer cell line PPC-1. Furthermore, the selectivity of compounds towards cancer cells compared to fibroblasts was also investigated. Four compounds were identified as the most promising anticancer agents out of a series of pyrrolidinone-hydrazone derivatives bearing a diphenylamine moiety. These compounds were most selective against the prostate cancer cell line PPC-1 and the melanoma cell lines IGR39, with EC50 values in the range of 2.5-20.2 µM against these cell lines. In general, the compounds were less active against triple-negative breast cancer MDA-MB-231 cell line, and none of them showed an inhibitory effect on the migration of these cells. In the 'wound healing' assay, N'-((5-nitrothiophen-2-yl)methylene)-5-oxo-1-(4-(phenylamino)phenyl)pyrrolidine-3-carbohydrazide was identified as the most promising derivative that could be further developed as an antimetastatic agent. N'-(5-chloro- and N'-(3,4-dichlorobenzylidene)-5-oxo-1-(4-(phenylamino)phenyl)pyrrolidine-3-carbohydrazides most efficiently reduced the cell viability in IGR39 cell spheroids, while there was no effect of the investigated pyrrolidinone-hydrazone derivatives on PPC-1 3D cell cultures. Antioxidant activity determined via FRAP assay of N'-(1-(4-aminophenyl)ethylidene)-5-oxo-1-(4-(phenylamino)phenyl)pyrrolidine-3-carbohydrazide was 1.2 times higher than that of protocatechuic acid.


Asunto(s)
Antineoplásicos , Melanoma , Neoplasias de la Próstata , Neoplasias de la Mama Triple Negativas , Masculino , Humanos , Antioxidantes/farmacología , Hidrazonas/farmacología , Difenilamina/farmacología , Neoplasias de la Mama Triple Negativas/tratamiento farmacológico , Proliferación Celular , Antineoplásicos/farmacología , Pirrolidinonas/farmacología , Pirrolidinas/farmacología , Relación Estructura-Actividad , Línea Celular Tumoral
4.
Molecules ; 28(13)2023 Jul 03.
Artículo en Inglés | MEDLINE | ID: mdl-37446847

RESUMEN

The design of highly efficient sensitizers is one of the most significant areas in dye-sensitized solar cell (DSSC) research. We studied a series of benzothiadiazole-based D-π-π-A organic dyes, putting emphasis on the influence of the donor moiety on the DSSC's efficiency. Using (linear-response time-dependent) density functional theory ((TD)DFT)) with the CAM-B3LYP functional, different donor groups were characterized in terms of electronic absorption spectra and key photovoltaic parameters. As a reference, a dye was considered that had a benzothiadiazole fragment linked via thiophene rings to a diphenylamine donor and a cyanoacrylic-acid acceptor. The different systems were first studied in terms of individual performance parameters, which eventually aggregated into power conversion efficiency. Only the amino-substituted species showed a modest increase, whereas the dimethylamino case showed a decrease.


Asunto(s)
Energía Solar , Tiadiazoles , Modelos Moleculares , Colorantes
5.
J Mol Graph Model ; 124: 108560, 2023 11.
Artículo en Inglés | MEDLINE | ID: mdl-37423020

RESUMEN

Density functional theory calculations were employed to identify the ability of some diphenylamine-based hole-transporting materials (HTMs) for use in top-performance perovskite solar cells. The effects of donor/acceptor electron groups and the new π-bridge section in the three-part of structures were investigated thoroughly. The results indicated that adding electron-withdrawing functional groups such as CN in the phenylazo-indol moiety and substituting electron donor groups such as CH3 in the NH2 hydrogen atoms of the diphenylamine section can cause higher power conversion light-harvesting efficiency in new HTMs. Also, the replacement of thieno [3,2-b] benzothiophene as a part of the π bridge with the phenyl group according to the optical and electronic structure properties improves the efficiency of the new phenylazoindole derivatives.


Asunto(s)
Compuestos de Calcio , Difenilamina , Teoría Funcional de la Densidad , Electrónica
6.
J Exp Zool A Ecol Integr Physiol ; 339(7): 655-670, 2023 08.
Artículo en Inglés | MEDLINE | ID: mdl-37246476

RESUMEN

Diphenylamine (DPA) is an aniline derivative, used widely as an industrial antioxidant, dye mordant, and agricultural fungicide. DPA was reported as hazardous to mammals both acutely and chronically, however little is known about the toxicity of DPA and its derivatives during pregnancy. This study aimed to evaluate and explain the possible mechanism of toxicity induced by DPA on blood and spleen, as a fundamental hematopoietic target organ, in pregnant rats and their fetuses. Pregnant rats were orally administrated distilled water, corn oil, and/or DPA (400 mg/kg b.wt) from the 5th to 19th day of gestation. DPA-induced spleen toxicity was mirrored by significant upregulation of programmed death-1 (PD-1) protein expression and an increase in the percentage of apoptotic cells and a decrease in their proliferating capacity. These results have been confirmed through marked G0/G1 cell-cycle arrest that was observed by flow cytometric analysis of spleen cells. Moreover, the contents of reactive oxygen species and iron in the spleen tissue were significantly higher than that of the control group. DPA resulted in severe anemia, decreased hemoglobin and hematocrit, thrombocytopenia and leukopenia in addition to significant changes in differential leukocytic count of both mothers and fetuses. Evidently, DPA triggered serious pathological changes in the spleen tissue of both mothers and fetuses and the histochemical examination revealed a significant increase in iron expression. In conclusion, these results implicate the hemato- and splenotoxicity of DPA and the possible role of oxidative stress and apoptosis in DPA-induced toxicity in the spleen of pregnant rats and their fetuses. This in-turn suggests the urgent need to reduce exposure to DPA as possible as it can.


Asunto(s)
Sobrecarga de Hierro , Embarazo , Femenino , Ratas , Animales , Difenilamina/metabolismo , Bazo/metabolismo , Especies Reactivas de Oxígeno/metabolismo , Sobrecarga de Hierro/metabolismo , Hierro/metabolismo , Apoptosis , Feto , Mamíferos/metabolismo
8.
Antioxidants (Basel) ; 12(3)2023 Mar 13.
Artículo en Inglés | MEDLINE | ID: mdl-36978960

RESUMEN

4-Aminodiphenylamino derivatives were investigated for their antioxidant and hydrophobicity character, together with other biological measurements, such as antimicrobial and antibiofilm activity. Among these nine compounds used, we obtained novel derivatives via reaction of the starting material with NBD-chloride. Therefore, we performed a full structural analysis for these compounds, i.e., elemental analysis, IR, UV-Vis, 1H- and 13C-NMR, ESI-MS, X-ray diffraction on single crystal, etc. The hydrophobicity of all the compounds was measured either experimentally using the RP-TLC technique, or via calculation using the fragments method. The other structural characteristics were analyzed, and a correlation between the experimental and computed properties was found. Moreover, the results of the biological evaluation showed that some of the synthesized compounds have antimicrobial and antibiofilm activity.

9.
Spectrochim Acta A Mol Biomol Spectrosc ; 285: 121906, 2023 Jan 15.
Artículo en Inglés | MEDLINE | ID: mdl-36179570

RESUMEN

Diphenylamine (DPA) as a stabilizer component plays an important role in maintaining the chemical stability of single-base propellants (SBPs). This work investigated the feasibility of rapidly detecting the content of DPA in SBP by near-infrared reflectance spectroscopy (NIRS). The quantitative NIR model was developed by intervals selection, spectral pretreatment and factor number optimization. The optimal spectral intervals were determined to be 1081 nm âˆ¼ 1280 nm and 1378 nm âˆ¼ 1602 nm based on the characteristic spectral peaks of DPA. By comparing the performance of the developed models with different preprocessing methods, the best preprocessing method was standard normal variate transformation (SNV) + de-trending (Dr) + Smoothing. The optimal number of factors was 6 for DPA model. Partial least squares (PLS) regression was used to establish the calibration models of DPA. For the developed model, the determination coefficients of calibration and prediction (Rc2, Rp2) were 0.9907 and 0.9884, respectively. The root mean square errors of calibration and prediction (RMSEC, RMSEP) were 0.0310 and 0.0342, respectively. The samples in the prediction set were predicted by the developed model, and the average absolute error of the proposed and reference method was only 0.0265. The developed model can be applied in rapid monitor the content of DPA in SBP. In addition, vieille test have demonstrated that the chemical stability of SBP became worse with the decrease of DPA content. The content of DPA contained in the SBP with qualified chemical stability is not less than 0.8753%. Thus, the developed model can be used to judge whether the chemical stability of SBP is qualified or unqualified.


Asunto(s)
Difenilamina , Espectroscopía Infrarroja Corta , Análisis de los Mínimos Cuadrados , Espectroscopía Infrarroja Corta/métodos , Calibración
10.
Molecules ; 27(23)2022 Nov 30.
Artículo en Inglés | MEDLINE | ID: mdl-36500452

RESUMEN

(1) Background: Methadone, along with buprenorphine, is the most commonly used drug for the treatment of opioid dependence. This study aimed to analyze methadone and its major metabolite, 2-ethylidene-1,5-dimethyl-3,3-diphenyl pyrrolidine (EDDP), in the urine and plasma of opiate addicts. The study group consisted of drug users voluntarily admitted to the detoxification center C.E.T.T.T. "St. Stelian" of Bucharest. Secondly, the study aimed to identify whether urine or plasma provides better results for the proposed method. (2) Methods: A GC-MS method, using an internal standard (diphenylamine) in the FULL-SCAN and SIM modes of operation and using the m/z = 72 ion for methadone and the m/z = 277 ion for EDDP, combined with a liquid-liquid extraction procedure was performed. (3) Results: The applied procedure allows the detection and quantification of methadone in both urine and plasma samples. EDDP was identified in patients with higher levels of methadone. Higher levels of methadone were detected in urine than in plasma samples. (4) Conclusions: This procedure can be used in clinical laboratories for the rapid determination of methadone levels in urine rather than in plasma. The procedure can be applied for the monitoring of methadone substitution treatment.


Asunto(s)
Buprenorfina , Trastornos Relacionados con Opioides , Humanos , Metadona/uso terapéutico , Metadona/metabolismo , Cromatografía de Gases y Espectrometría de Masas/métodos , Buprenorfina/uso terapéutico , Trastornos Relacionados con Opioides/tratamiento farmacológico , Pirrolidinas
11.
Polymers (Basel) ; 14(21)2022 Oct 22.
Artículo en Inglés | MEDLINE | ID: mdl-36365473

RESUMEN

In this work, new information concerning the optical properties of black phosphorus (BP) sheets chemically/electrochemically functionalized with diphenyl amine (DPA) and its macromolecular compound (poly(diphenylamine) (PDPA)) in the absence/presence of phosphotungstic acid (PTA) is reported. Raman scattering and FTIR spectroscopy studies indicate that the interaction of BP with PTA leads to the elimination of the PxOy layer onto the surface of the BP sheets. In the case of the chemical interaction of BP with DPA, the reaction product corresponds to DPA chemically functionalized BP sheets having an imino-phosphorane (IP) structure. The electrochemical oxidation of BP sheets chemically functionalized with DPA in the presence of PTA leads to an increase in the weight of P-N bonds as a consequence of the generation of PDPA doped with the PTA heteropolyanions, as shown by FTIR spectroscopy and Raman scattering. This process is evidenced by a shift of the Raman line from 362 cm-1 to 378 cm-1, assigned to the A1g mode. This change was explained by taking into account the compression of the layers containing P atoms, which is induced by PDPA macromolecular chains. The decrease in the intensity of the PL spectra of DPA as well as PDPA, in the presence of BP, indicates that BP acts as a PL quenching agent for these compounds. A preferential orientation of the PDPA doped with the PTA heteropolyanions on the surface of BP sheets is highlighted by the variation of the binding angle of the PDPA on the surface of BP sheets from 44.7° to 39.9°.

12.
Environ Pollut ; 315: 120407, 2022 Dec 15.
Artículo en Inglés | MEDLINE | ID: mdl-36228860

RESUMEN

Many organisms are consuming food contaminated with micro- and nanoparticles of plastics, some of which absorb persistent organic pollutants (POPs) from the environment and acting as carrier vectors for increasing the bioavailability in living organisms. We recently reported that polymethylmethacrylate (PMMA) nanoparticles at low concentrations are not toxic to animal models tested. In this study, the toxicity of diphenylamine (DPA) incorporated PMMA nanoparticles are assessed using barnacle larvae as a model organism. The absorption capacity of DPA from water for commercially available virgin PMMA microparticles is relatively low (0.14 wt%) during a 48 h period, which did not induce exposure toxicity to barnacle nauplii. Thus, PMMA nanoparticles encapsulated with high concentrations of DPA (DPA-enc-PMMA) were prepared through a reported precipitation method to achieve 40% loading of DPA inside the particles. Toxicity of DPA-enc-PMMA nanoparticles were tested using freshly spawned acorn barnacle nauplii. The observed mortality of nauplii from DPA-enc-PMMA exposure was compared to the values obtained from pure DPA exposure in water. The mortality among the exposed acorn barnacle nauplii did not exceed 50% even at a high concentration of DPA inside the PMMA nanoparticles. The results suggest that the slow release of pollutants from polymer nanoparticles may not induce significant toxicity to the organism living in a dynamic environment. The impact of long-term exposure of DPA absorbed plastic nanoparticles need to be investigated in the future.


Asunto(s)
Contaminantes Ambientales , Nanopartículas , Thoracica , Contaminantes Químicos del Agua , Animales , Microplásticos , Polimetil Metacrilato/toxicidad , Plásticos/toxicidad , Nanopartículas/toxicidad , Agua , Contaminantes Químicos del Agua/toxicidad
13.
Anal Sci ; 38(9): 1181-1188, 2022 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-35829921

RESUMEN

Metal-organic frameworks (MOFs) including cucurbit[7]uril block (Q[7]·HAuCl4) were employed to develop a diphenylamine (DPA) sensor in electrochemical method, the presence of HAuCl4 improved the conductivity of the macrocyclic compound. To further enhance of the sensitivity, Au nanoparticles were inserted between the surface of glassy carbon electrode and Q[7]·HAuCl4 MOFs (GCE-AuNPs-Q[7]·HAuCl4). Cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and differential pulse voltammetry (DPV) were applied for evaluation on the electrochemical behavior. For the electrochemical inertness of DPA, a label-free electrochemical sensor in 5 mM K3[Fe(CN)6] solution was achieved, to produce a limit of detection as low as 4.6 µM in a linear range of 5-1000 µM with good reproducibility, high stability and acceptable anti-interference ability. Application of the proposed electrode for the quantitative determination of DPA in tap water and apple juice confirms its real value.


Asunto(s)
Técnicas Biosensibles , Nanopartículas del Metal , Difenilamina , Técnicas Electroquímicas , Electrodos , Oro , Límite de Detección , Reproducibilidad de los Resultados
14.
Eur J Med Chem ; 237: 114372, 2022 Jul 05.
Artículo en Inglés | MEDLINE | ID: mdl-35447432

RESUMEN

A novel series of diphenylamine derivatives were designed and synthesized, and their biological activities were evaluated. The anti-proliferative activities of the derivatives were tested against five human cancer cell lines (MCF-7, MDA-MB-231, A549, HeLa and HT29). Among them, compound 5f exhibited the promising anti-proliferative activity against HT29 cell lines with the IC50 value of 23 nM. Further biological studies depicted that compound 5f inhibited cancer cell migration, colony formation and angiogenesis. Besides, dynamics studies and molecular docking studies revealed that compound 5f inhibited tubulin polymerization which may be a result of the compound binding to the colchicine site of tubulin. Furthermore, compound 5f arrested HT29 cell cycle at G2/M phase, and induced HT29 cell apoptosis by upregulating cyclin B1, Bcl-2, Bax, Cleaved-caspase9, Cleaved-caspase3, PARP, Cleaved-PARP proteins, and downregulating p-cdc25c (S216), p-cdc2 (T15) proteins. Mitochondrial membrane potential (MMP) and reactive oxygen species (ROS) were also determined to confirm the cell apoptosis process. Finally, compound 5f greatly inhibited the tumor growth in HT29 xenograft mice by 75.5% at 10 mg/kg. Meanwhile, compound 5f owned the good pharmacokinetic properties. All the results promised that 5f is of potential to act as an antitumor candidate and worthy of further investigation.


Asunto(s)
Antineoplásicos , Moduladores de Tubulina , Animales , Antineoplásicos/química , Sitios de Unión , Línea Celular Tumoral , Proliferación Celular , Colchicina/farmacología , Difenilamina/farmacología , Ensayos de Selección de Medicamentos Antitumorales , Humanos , Ratones , Simulación del Acoplamiento Molecular , Inhibidores de Poli(ADP-Ribosa) Polimerasas/farmacología , Polimerizacion , Tubulina (Proteína)/metabolismo , Moduladores de Tubulina/química
15.
Environ Res ; 212(Pt B): 113291, 2022 09.
Artículo en Inglés | MEDLINE | ID: mdl-35421390

RESUMEN

Incompetent governance of post-harvest horticultural crops especially apples and pears lead to numerous physiological storage disorders. In order to manage this issue, diphenylamine (DPA) is widely used as an antioxidant and anti-scald agent to preserve fruits from superficial scalds and degradation during storage. As a result, this research focuses on utilizing disposable electrodes constructed with sphere-shaped iron-manganese layered double hydroxide (FeMn-LDH) entrapped tungsten carbide (WC) nanocomposite on its electrochemical performances towards emergent food contaminant, DPA. The importance of the current work is the selection and design of hierarchically structured functional materials especially layered double hydroxides, in virtue of their outstanding properties. These multi-dimensional structures when introduced to form a composite with the highly beneficial tungsten carbide offer excellent characteristics such as exceptional accessibility to active sites, enhanced surface area, and high mass transport and diffusion which serves as advantageous for the electrochemical quantification of DPA. Furthermore, the synergy between FeMn-LDH and WC nanomaterials contributes to the higher active surface area, increased electrical conductivity, fast electron transportation, and ion diffusion, resulting in static properties including a wide linear range (0.01-183.34 µM), low detection limit (1.1 nM), greater sensitivity, selectivity, and reproducibility thus confirming the potential capability of the WC@FeMn-LDH sensor towards the interference-free determination of DPA which validates its practicality and feasibility in real-time. Hence, this work aims to stimulate the fabrication of various advanced hierarchical structures by a simple hydrothermal approach that can have veracity of potential applications.


Asunto(s)
Difenilamina , Nanocompuestos , Difenilamina/análisis , Difenilamina/química , Técnicas Electroquímicas/métodos , Hidróxidos/química , Hierro , Manganeso , Nanocompuestos/química , Reproducibilidad de los Resultados , Tungsteno , Compuestos de Tungsteno
16.
Chemosphere ; 292: 133400, 2022 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-34974048

RESUMEN

Herein, the facile synthesis of copper(II) and benzene-1,3,5-tricarboxylate (Cu-BTC) and copper nanoporous carbon (Cu@NPC) for the electrochemical detection of diphenylamine (DPA) was systematically investigated. The Cu-BTC and Cu@NPC materials structural, morphological, and thermal stability were evaluated and confirmed using FE-SEM, HR-TEM, XRD, FT-IR, and TGA. The electrocatalytic behavior of sensor materials was examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). It is presumed that the structural stability and synergic effect exhibited in Cu@NPC are favorable for enhanced sensitivity and selectivity towards the detection of DPA. The Cu@NPC exhibited a wide linear range (0.09-396.82 µM) and the lowest limit of detection (5 nM). Furthermore, the real sample analysis of the sensor for the detection of DPA in apples and pears confirms its potential capability in practical application.


Asunto(s)
Carbono , Nanoporos , Antioxidantes , Cobre , Difenilamina , Técnicas Electroquímicas , Electrodos , Frutas , Límite de Detección , Espectroscopía Infrarroja por Transformada de Fourier
17.
J Hazard Mater ; 424(Pt A): 127378, 2022 02 15.
Artículo en Inglés | MEDLINE | ID: mdl-34879572

RESUMEN

Toxic substances, such as heavy metals, toxins, pesticides, pathogens, and veterinary drug residues in food are hazardous to consumer health. The variety and quantity of food consumption have increased owing to developments in the agricultural and food industries. Food safety has a substantial socioeconomic impact, and an increasing number of consumers have become aware of its importance. Therefore, simple and cost-effective analytical methods are required to quantify the safety of preservatives. Herein, we report an electrochemical method using double-shelled carbon-confined Ni/NiO (C@Ni/NiO) hollow microspheres to detect diphenylamine (DPA). The microspheres were synthesized by a self-templating hydrothermal method followed by calcination. The hydrothermal temperature and precursor ratio were optimized systematically to prepare double-shelled C@Ni/NiO hollow microspheres. The excellent electrocatalytic activity and electron transport properties of a C@Ni/NiO-modified glassy carbon electrode (GCE) were exploited in the electrochemical oxidation of DPA. Interestingly, the engineered C@Ni/NiO/GCE has a wide dynamic linear range (0.02-473 µM) and a DPA detection limit of 0.007 µM. In addition, the DPA sensor exhibited good selectivity, reproducibility, repeatability, and stability. The practical feasibility of the DPA sensor was evaluated in fruit samples (sweet tomatoes, apples, and red grapes), with considerable recovery.


Asunto(s)
Carbono , Difenilamina , Frutas , Microesferas , Níquel , Reproducibilidad de los Resultados
18.
Talanta ; 238(Pt 2): 123039, 2022 Feb 01.
Artículo en Inglés | MEDLINE | ID: mdl-34801896

RESUMEN

The overall aim of the work was to advance electrochemical devices capable of analysis of forensically relevant residues using rapid electrochemical sensor technology. In order to achieve this, electrochemical detection of the propellant stabiliser diphenylamine (DPA) was achieved via voltammetry with signal enhancement realised in the presence of iron oxide nanoparticle modified transducers. This allowed both mechanistic and analytical evaluation with the aim to achieve the required selectivity and sensitivity for reliable detection. DPA electrochemistry was examined at glassy carbon electrodes in aqueous (3:7 methanol: sodium acetate pH 4.3) electrolyte via potential sweeping, with an irreversible wave at Ep = 0.67 V vs. Ag/AgCl. The diffusion coefficient (D) for the oxidation process was calculated as 1.43 × 10-6 cm2 s-1 with αna = 0.7. DPA electrochemistry in a non aqueous methanol/acetonitrile electrolyte resulted in a D value of 5.47 × 10-8 cm2 s-1 with αna = 0.5. Electrochemical preparation of magnetic iron oxide nanoparticles was achieved via electrooxidation of an iron anode in the presence of an amine surfactant followed by characterisation with SEM/EDX, XRD, FTIR and thermal analysis. A surface confined layer of these magnetic nanoparticles served to positively influence the response to DPA while impeding formation of surface confined oxidation products, with generation of an improved analytical signal - sensitivity 1.13× 10-3 A cm-2 mM-1 relative to bare electrode response (9.80 × 10-4 A cm-2 mM-1) over the range 0.5-50 µM DPA using differential pulse voltammetry, with LOD 3.51 × 10-6 M and LOQ 1.17 × 10-5 M. Real sample analysis involved recovery and differential pulse voltammetry of unburnt and burnt gunshot residue with DPA qualitative and quantitative analysis.


Asunto(s)
Difenilamina , Nanopartículas de Magnetita , Carbono , Electroquímica , Electrodos
19.
Pesqui. vet. bras ; 42: e07038, 2022. tab, ilus
Artículo en Inglés | LILACS, VETINDEX | ID: biblio-1487703

RESUMEN

We report two outbreaks of nitrate and nitrite poisoning in Paraíba, Northeast Brazil. The first, due to Pennisetum purpureum (elephant grass), and the second, due to P. purpureum and Brachiaria spp. (brachiaria grass), both occurred during a prolonged drought. In the first outbreak, the irrigation of the pastures with wastewater and sewage contributed to nitrate accumulation. The second outbreak occurred in pastures cultivated in the border of a dam, that had been submerged for long time accumulating large amounts of organic matter in the soil. Other probably risk factors for nitrate accumulation included the use of chemical fertilizers and herbicides and burning of the vegetation. In the first outbreak, four calves out of a total of 42 cattle died, and in the second outbreak 49 out of 243 cattle, including adults, yearlings, and a 2-day-old calf died. The clinical signs included dyspnea, cyanosis, ataxia, and falls, leading to death. The presence of nitrates was detected in both outbreaks using the diphenylamine test. Quantitative tests were performed in the second outbreak using a portable nitrate meter, and high nitrate concentrations were found. The characteristic macroscopic findings and absence of microscopic lesions and response to treatment with methylene blue were key to the diagnosis of poisoning by nitrates and nitrites. We conclude that poisoning by nitrates and nitrites in ruminants in the semiarid region of Northeastern Brazil is frequent due to the cultivation of grasses in the border of dams that had been covered by water for long periods or in areas irrigated by wastewater and/or sewage. In addition, the use of a portable measuring device is an effective alternative for the quantification of nitrates in pastures.


Relatamos dois surtos de intoxicação por nitrato e nitrito na Paraíba, Nordeste do Brasil. O primeiro por Pennisetum purpureum (capim-elefante), e o segundo por P. purpureum e Brachiaria spp. (capim braquiária); ambos ocorreram durante uma estiagem prolongada. No primeiro surto, a irrigação das pastagens com água poluída e esgoto contribuiu para o acúmulo de nitrato. O segundo surto ocorreu em pastagens cultivadas na borda de uma barragem, que há muito tempo ficavam submersas, acumulando grande quantidade de matéria orgânica no solo. Outros prováveis fatores de risco para o acúmulo de nitrato incluíram o uso de fertilizantes químicos e herbicidas e a queima da vegetação. No primeiro surto, quatro bezerros de um total de 42 bovinos morreram, e no segundo surto 49 de 243 bovinos, incluindo adultos, jovens de um ano e um bezerro de 2 dias de idade morreram. Os sinais clínicos incluíram dispneia, cianose, ataxia e quedas, levando à morte. A presença de nitratos foi detectada em ambos os surtos pelo teste de difenilamina. Testes quantitativos foram realizados no segundo surto usando um medidor portátil de nitrato, e altas concentrações de nitrato foram encontradas. Os achados macroscópicos característicos e a ausência de lesões microscópicas e a resposta ao tratamento com azul de metileno foram fundamentais para o diagnóstico de intoxicação por nitratos e nitritos. Concluímos que a intoxicação por nitratos e nitritos em ruminantes na região semiárida do Nordeste do Brasil é frequente devido ao cultivo de gramíneas nas bordas de barragens que estiveram cobertas por água por longos períodos ou em áreas irrigadas por água poluída e/ou esgoto. Além disso, o uso de medidor portátil é uma alternativa eficaz para a quantificação de nitratos em pastagens.


Asunto(s)
Animales , Bovinos , Brachiaria/envenenamiento , Intoxicación por Plantas/epidemiología , Intoxicación por Plantas/etiología , Nitratos/envenenamiento , Nitritos/envenenamiento , Pennisetum/envenenamiento , Riego Agrícola , Pastizales , Contaminación Química del Agua/efectos adversos
20.
Pesqui. vet. bras ; 42: e07038, 2022. tab, ilus
Artículo en Inglés | LILACS, VETINDEX | ID: biblio-1360627

RESUMEN

We report two outbreaks of nitrate and nitrite poisoning in Paraíba, Northeast Brazil. The first, due to Pennisetum purpureum (elephant grass), and the second, due to P. purpureum and Brachiaria spp. (brachiaria grass), both occurred during a prolonged drought. In the first outbreak, the irrigation of the pastures with wastewater and sewage contributed to nitrate accumulation. The second outbreak occurred in pastures cultivated in the border of a dam, that had been submerged for long time accumulating large amounts of organic matter in the soil. Other probably risk factors for nitrate accumulation included the use of chemical fertilizers and herbicides and burning of the vegetation. In the first outbreak, four calves out of a total of 42 cattle died, and in the second outbreak 49 out of 243 cattle, including adults, yearlings, and a 2-day-old calf died. The clinical signs included dyspnea, cyanosis, ataxia, and falls, leading to death. The presence of nitrates was detected in both outbreaks using the diphenylamine test. Quantitative tests were performed in the second outbreak using a portable nitrate meter, and high nitrate concentrations were found. The characteristic macroscopic findings and absence of microscopic lesions and response to treatment with methylene blue were key to the diagnosis of poisoning by nitrates and nitrites. We conclude that poisoning by nitrates and nitrites in ruminants in the semiarid region of Northeastern Brazil is frequent due to the cultivation of grasses in the border of dams that had been covered by water for long periods or in areas irrigated by wastewater and/or sewage. In addition, the use of a portable measuring device is an effective alternative for the quantification of nitrates in pastures.(AU)


Relatamos dois surtos de intoxicação por nitrato e nitrito na Paraíba, Nordeste do Brasil. O primeiro por Pennisetum purpureum (capim-elefante), e o segundo por P. purpureum e Brachiaria spp. (capim braquiária); ambos ocorreram durante uma estiagem prolongada. No primeiro surto, a irrigação das pastagens com água poluída e esgoto contribuiu para o acúmulo de nitrato. O segundo surto ocorreu em pastagens cultivadas na borda de uma barragem, que há muito tempo ficavam submersas, acumulando grande quantidade de matéria orgânica no solo. Outros prováveis fatores de risco para o acúmulo de nitrato incluíram o uso de fertilizantes químicos e herbicidas e a queima da vegetação. No primeiro surto, quatro bezerros de um total de 42 bovinos morreram, e no segundo surto 49 de 243 bovinos, incluindo adultos, jovens de um ano e um bezerro de 2 dias de idade morreram. Os sinais clínicos incluíram dispneia, cianose, ataxia e quedas, levando à morte. A presença de nitratos foi detectada em ambos os surtos pelo teste de difenilamina. Testes quantitativos foram realizados no segundo surto usando um medidor portátil de nitrato, e altas concentrações de nitrato foram encontradas. Os achados macroscópicos característicos e a ausência de lesões microscópicas e a resposta ao tratamento com azul de metileno foram fundamentais para o diagnóstico de intoxicação por nitratos e nitritos. Concluímos que a intoxicação por nitratos e nitritos em ruminantes na região semiárida do Nordeste do Brasil é frequente devido ao cultivo de gramíneas nas bordas de barragens que estiveram cobertas por água por longos períodos ou em áreas irrigadas por água poluída e/ou esgoto. Além disso, o uso de medidor portátil é uma alternativa eficaz para a quantificação de nitratos em pastagens.(AU)


Asunto(s)
Animales , Bovinos , Intoxicación por Plantas/etiología , Intoxicación por Plantas/epidemiología , Brachiaria/envenenamiento , Pennisetum/envenenamiento , Nitratos/envenenamiento , Nitritos/envenenamiento , Contaminación Química del Agua/efectos adversos , Pastizales , Riego Agrícola
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