RESUMEN
A green, sensitive, and fast spectrofluorimetric technique for the simultaneous determination of atenolol (ATN) and losartan potassium (LSR) was developed. The proposed technique relied on the implementation of a first derivative synchronous fluorescence spectroscopy for the determination of the investigated drugs simultaneously without pretreatment procedures. The synchronous fluorescence of both drugs was measured in methanol at Δλ of 100 nm, and the first derivative peak amplitudes (1D) were measured at 321 nm for ATN and 348 nm for LSR, each at the zero-crossing point of the other. The method was rectilinear over the concentration ranges of 100-1000 ng/mL and 50-500 ng/mL for ATN and LSR, respectively. The proposed technique was successfully applied for the determination of the studied drugs in their laboratory-prepared mixture and pharmaceutical formulations, demonstrating high mean recoveries of 100.54% for ATN and 100.62% for LSR, without interference from common excipients. The results were in good agreement with those obtained by the comparison method. Three recent greenness assessment tools, the Eco-Scale tool, the Green Analytical Procedure Index (GAPI) metric, and the Analytical GREEnness metric approach, were employed to affirm the greenness of the proposed method. The developed method was proven to be eco-friendly.
Asunto(s)
Atenolol , Losartán , Espectrometría de Fluorescencia , Atenolol/análisis , Atenolol/sangre , Losartán/análisis , Losartán/sangre , Losartán/química , Humanos , Tecnología Química Verde , FluorescenciaRESUMEN
Efforts to regulate and monitor emerging contaminants are insufficient because new chemicals are continually brought to market, and many are unregulated and potentially harmful. Domestic wastewater treatment plants are not designed to remove micropollutants and are important sources of emerging contaminants in the aquatic environment. In this study, non-target screening, an unbiased method for analyzing compounds without prior information, was used to identify compounds that may be emitted in wastewater treatment plant effluent and should be monitored. Nine wastewater treatment plants using different treatment methods were studied, and a non-target screening data-processing method was used. The frequencies at which the contaminants were detected and contaminant persistence through the treatment processes were considered, and then the contaminants were prioritized. The predicted no-effect concentration of each prioritized contaminant was used to determine whether further analysis and monitoring of the contaminant was necessary. Quantitative analyses of five compounds (amantadine, atenolol, benzotriazole, diphenhydramine, and sulpiride) were performed using reference standards. Probable molecular formulae and structures were proposed for 17 contaminants, and the risks posed by the contaminants were estimated using predicted no-effect concentrations. The results provide valuable insights into how unregulated micropollutants can be identified and prioritized for monitoring in future studies.
Asunto(s)
Monitoreo del Ambiente , Espectrometría de Masas , Eliminación de Residuos Líquidos , Aguas Residuales , Contaminantes Químicos del Agua , Contaminantes Químicos del Agua/análisis , Aguas Residuales/química , Aguas Residuales/análisis , Monitoreo del Ambiente/métodos , Cromatografía Liquida , Atenolol/análisis , Triazoles/análisisRESUMEN
Single-pass intestinal perfusion (SPIP) method is a widely used experimental model to determine the intestinal permeability of drugs. These studies are performed in the presence of a reference standard (metoprolol, MT) and a zero permeability marker (phenol red, PR). Therefore, it is important to develop a validated method for simultaneous determination of the investigated compound along with MT and PR. The aim of this study was to develop a reversed phase high-performance liquid chromatography (RP-HPLC) method with UV-detection for the simultaneous determination of atenolol (ATN), MT, and PR in the perfusion medium used in SPIP experiments. Separation of compounds were performed using an InertSustain C18 (250 × 4.6 mm, 5 µm) HPLC column at 35 °C. The mobile phase was a mixture of acetonitrile and phosphate buffer (pH 7.0, 12.5 mM) in gradient elution, and was delivered at a flow rate of 1 mL/min. The acetonitrile ratio of the mobile phase increased linearly from 10 to 35 % over 15 min. The injection volume was 20 µL, and ATN, MT and PR were detected at 224 nm. The retention times under optimum HPLC conditions were 5.028 min, 12.401 min, and 13.507 min for ATN, MT and PR, respectively. The developed RP-HPLC method was validated for selectivity, specificity, calibration curve and range, accuracy and precision, carry-over effect, stability, reinjection reproducibility, recovery and robustness. The method was linear for ATN (0.76-50 µg/mL), MT (1.14-50 µg/mL), and PR (0.47-20 µg/mL) with determination coefficients of 0.9999, 0.9994 and 0.9998, respectively. The results obtained for all validation parameters of the developed RP-HPLC method met the required limits of the ICH M10 Guideline.
Asunto(s)
Atenolol , Cromatografía de Fase Inversa , Metoprolol , Fenolsulfonftaleína , Cromatografía Líquida de Alta Presión/métodos , Animales , Atenolol/análisis , Metoprolol/análisis , Ratas , Cromatografía de Fase Inversa/métodos , Reproducibilidad de los Resultados , Modelos Lineales , Fenolsulfonftaleína/química , Masculino , Límite de Detección , Ratas Wistar , PerfusiónRESUMEN
Simultaneous determination of atenolol (ATN), losartan potassium (LOS), and hydrochlorothiazide (HCZ) in presence of HCZ impurity B was conducted by chemometric approaches and radial basis function network (RBFN) using UV-spectrophotometry without preliminary separation. Three chemometric models namely, classical least-squares (CLS), principal component regression (PCR), and partial least-squares (PLS) along with RBFN were utilized using the ternary mixtures of the three drugs. The multivariate calibrations were obtained by measuring the zero-order absorbance of the mixtures from 250 to 270 nm at the interval of 0.2 nm. The models were built covering the concentration range of (4.0 to 20.0), (3.8 to 20.2), and (0.9 to 50.1) µg mL-1 for ATN, LOS, and HCZ, respectively. The regression coefficient was calculated between the actual and predicted concentrations of the 3 drugs using CLS, PCR, PLS and RBFN. The accuracy of the developed models was evaluated using the root mean square error of prediction (RMSEP) giving satisfactory results. The proposed methods were simple, accurate, precise and were applied efficiently for the quantitation of the three components in laboratory-prepared mixtures, and in dosage form showing good recovery values. In addition, the obtained results were compared statistically with each other using ANOVA test showing non-significant difference between them.
Asunto(s)
Atenolol , Hidroclorotiazida , Losartán , Espectrofotometría Ultravioleta , Hidroclorotiazida/análisis , Atenolol/análisis , Losartán/análisis , Espectrofotometría Ultravioleta/métodos , Análisis de los Mínimos Cuadrados , Análisis de Componente Principal , Formas de Dosificación , Reproducibilidad de los ResultadosRESUMEN
Determination of a widely used antihypertensive combination of atenolol and hydrochlorothiazide was achieved by rapid and eco-friendly high-performance liquid chromatography method combined with fluorescence detection. The response surface methodology is conducive to the complete separation of the two drugs in a shorter analysis time. The separation of the mixture was achieved using an Inertsil C18 analytical column (150 × 4.6 mm, 5 µ). The mobile phase used was ethanol: potassium dihydrogen phosphate at pH 3 (65:35 v/v) and the flow rate was 0.7 mL/min. The fluorescence detector operated at excitation and emission wavelengths of 230 and 310 nm (atenolol) and 270 and 375 nm (hydrochlorothiazide). The linearity of the developed method covered a concentration of atenolol of 0.05-5 µg/mL and a concentration of hydrochlorothiazide of 0.02-1 µg/mL. The greenness of the developed method was evaluated by analytical eco-scale and the recently reported evaluation method, that is, green analytical procedure index, and it was found to be an excellent, sensitive, and green alternative to the reported methods. The developed method was validated according to the ICH guidelines and compared with the reference method. No significant difference was found in terms of accuracy.
Asunto(s)
Atenolol , Hidroclorotiazida , Antihipertensivos , Atenolol/análisis , Cromatografía Líquida de Alta Presión/métodos , Hidroclorotiazida/análisisRESUMEN
Nowadays, various single-pill combinations are used as the best choice in hypertension management. However, these pills made a high challenge to analysts in terms of quality control assays. We have developed three sensitive, selective, fast, simple, green, accurate, precise, and robust isocratic high-performance liquid chromatography methods for simultaneous determination of valsartan and atenolol in dosage forms. To find the appropriate high-performance liquid chromatography conditions for the separation of the examined drugs, various columns, isocratic mobile phase systems were tried, and successful attempts were performed. The used columns proved to be indispensably applicable and gave a shorter analysis time and peak symmetries. This reduction in total run time leads to low solvent consumption and makes all methods more economical. The linearity, accuracy, and precision remained within the acceptable limits. Therefore, all developed methods are suitable for the routine quality control analysis of any pharmaceutical preparation containing the two tested drugs with the proposed chromatographic methods advantages for checking quality during stability studies of their pharmaceutical preparations.
Asunto(s)
Antihipertensivos/análisis , Atenolol/análisis , Valsartán/análisis , Cromatografía Líquida de Alta PresiónRESUMEN
Nowadays, enantioseparation of racemic pharmaceuticals in preparations is a prime concern by drug authorities across the globe. In the present work, it was attempted to develop novel enantioselective extraction method for five clinically used drugs (atenolol, propranolol, metoprolol, racecadotril, and raceanisodamine in their tablets) as racemates. The enantioselective solid-liquid extraction of these racemic drugs was carried out successfully by the use of chiral ionic liquid (CIL) in combination with a metal organic framework (MOF) for the first time. The composite CIL@MOF was synthesized from tropine based chiral ionic liquids with L-proline anion ([CnTr][L-Pro], n=3-6) and HKUST-1 type MOF, which was comprehensively characterized before being used as sorbent for enantioselective dispersive solid-liquid extraction. Preliminary selection of appropriate CIL was carried out on thin layer chromatography (TLC); under the joint participation of copper ion in the developing reagent, [C3Tr][L-Pro] ionic liquid showed better resolution performance with ΔRf value of 0.35 between the enantiomers was obtained for racemic atenolol. Moreover, the effect of copper salt dosage, amount of CIL, soli-liquid ratio and extraction time were investigated. The optimal conditions were obtained after thorough investigations; i.e. sample solution: ethanol, elution solvent: methanol, solid-liquid ratio: 12.5 mg:50 mL, amount of copper salt: 8 mg L-1, amount of impregnated CIL: 30% and extraction time of 30 min. As a result, enantiomeric excess values are 90.4%, 95%, 92%, 81.6% and 83.2% for atenolol, propranolol, metoprolol, racecadotril and raceanisodamine, respectively. The developed enantioselective method was validated following ICH guidelines and it was proved to be simple, effective and enantioselective way for separation of racemic pharmaceuticals with similar behaviors.
Asunto(s)
Líquidos Iónicos/química , Estructuras Metalorgánicas/química , Preparaciones Farmacéuticas/aislamiento & purificación , Extracción en Fase Sólida/métodos , Antagonistas Adrenérgicos beta/análisis , Antagonistas Adrenérgicos beta/aislamiento & purificación , Atenolol/análisis , Atenolol/aislamiento & purificación , Cromatografía Líquida de Alta Presión/métodos , Cobre/química , Metoprolol/análisis , Metoprolol/aislamiento & purificación , Preparaciones Farmacéuticas/análisis , Propranolol/análisis , Propranolol/aislamiento & purificación , Solventes/química , EstereoisomerismoRESUMEN
Beta-blockers are chiral compounds with enantiomers that have different bioactivity, which means that while one is active, the other can be inactive or even harmful. Due to their high consumption and incomplete degradation in waste water, they may reach surface waters and affect aquatic organisms. To address this issue we developed a chromatographic method suitable for determining beta-blocker enantiomers in surface waters. It was tested on five beta-blockers (acebutolol, atenolol, bisoprolol, labetalol and metoprolol) and validated on bisoprolol enantiomers. Good enantioseparation of all analysed beta-blockers was achieved on the Chirobiotic V column with the mobile phase composed of methanol/acetic acid/triethylamine (100/0.20/0.15 v/v/v) at a flow rate of 0.5 mL/min and column temperature of 45 °C. Method proved to be linear in the concentration range from 0.075 µg/mL to 5 µg/mL, and showed good recovery. The limits of bisoprolol enantiomer detection were 0.025 µg/mL and 0.026 µg/mL and of quantification 0.075 µg/mL and 0.075 µg/mL. Despite its limitations, it seems to be a promising method for bisoprolol enantiomer analysis in surface water samples. Further research could focus on waste water analysis, where enantiomer concentrations may be high. Furthermore, transferring the method to a more sensitive one such as liquid chromatography coupled with tandem mass spectrometry and using ammonium acetate as the mobile phase additive instead of acetic acid and triethylamine would perhaps yield much lower limits of detection and quantification.
Asunto(s)
Acebutolol/análisis , Antagonistas Adrenérgicos beta/análisis , Atenolol/análisis , Bisoprolol/análisis , Cromatografía Líquida de Alta Presión/métodos , Labetalol/análisis , Metoprolol/análisis , Agua/químicaRESUMEN
Herein, UV spectrophotometry assisted by multivariate chemometric analysis have been presented for quantitative determination of complex quinary therapy containing atenolol, ramipril, hydrochlorothiazide, simvastatin and aspirin without any prior separation. Such combination is very useful for treating various cardiovascular diseases (CVD) including high blood pressure, hypercholesterolemia in addition to its antiplatelet aggregating activity. Calibration (15 samples) and validation (10 samples) sets were prepared of different concentrations for these drugs via implementing partial factorial experimental design. The zero order UV spectra of these sets were recorded and then subjected for further chemometric analysis. Partial least square (PLS) with/without variable selection procedure i.e. genetic algorithm (GA) were employed to untangle the UV spectral overlapping of these mixtures. The performance of these chemometric techniques were compared in terms of accuracy and predictive abilities using cross-validation and external validation methods. It was found that PLS provides good recoveries with prompt predictive ability albeit GA-PLS exhibited better analytical performance owing to its capability to remove redundant variables i.e. the number of absorbance variables had been reduced to about 19-28%. The developed methods allowed reliable determination of such complex therapy in its laboratory prepared mixtures and pharmaceutical preparation within comparable results to those reported by HPLC method, posing these chemometric methods as valuable and indispensable analytical tools in in-process testing and quality control analysis of many pharmaceutical compounds targeting CVD.
Asunto(s)
Aspirina/análisis , Atenolol/análisis , Hidroclorotiazida/análisis , Ramipril/análisis , Simvastatina/análisis , Algoritmos , Cápsulas , Enfermedades Cardiovasculares/tratamiento farmacológico , Cromatografía Líquida de Alta Presión/métodos , Humanos , Análisis de los Mínimos Cuadrados , Espectrofotometría Ultravioleta/métodosRESUMEN
The present study is a first report about magnetic, optical and electrical as well as drug sensing properties of DyMnO3-ZnO green-nanocomposites that are synthesized by Pechini modified method. Three natural compounds containing Vitis vinifera, Hibiscus sabdariffa and rhus juices are used as green and eco-friendly reagents for synthesis of the nanostructures. The nanostructures are characterized by various techniques containing Fourier transform infrared spectra (FT-IR), X-ray diffraction (XRD), energy dispersive X-ray (EDX), field emission scanning electron microscopes (FESEM), high resolution transmission electron microscopy (HR-TEM), vibrating sample magnetometer (VSM) and diffuse reflectance spectroscopy (DRS). The calcination temperature, type of chelating agent and pH are optimized to achieve the best structural and smallest crystallite sizes of the systems via an eco-friendly approach. The studies show that the Vitis vinifera juice creates the best homogeneous sphere-like nanostructures. Therefore, the samples that are synthesized by Vitis vinifera juice are used for fabrication of a carbon paste electrode modified with DyMnO3-ZnO nanocomposites (DMZN/CPE). The nanostructured modified electrode exhibits an excellent electrocatalytic effect for determination of atenolol (ATN) using voltammetry techniques. The results reveal that the DyMnO3-ZnO green-nanocomposites have potential applications as a sensitive material in the drug analysis in biological samples.
Asunto(s)
Atenolol/análisis , Cerámica/química , Técnicas Electroquímicas , Tecnología Química Verde/métodos , Compuestos de Manganeso/química , Nanocompuestos/química , Óxidos/química , Óxido de Zinc/química , Técnicas Biosensibles , Fenómenos Magnéticos , Nanocompuestos/ultraestructura , Fenómenos Ópticos , Espectrometría por Rayos X , Espectrofotometría Ultravioleta , Espectroscopía Infrarroja por Transformada de Fourier , Difracción de Rayos XRESUMEN
Water scarcity is a natural condition in the Mediterranean rim countries. In this region, reuse of reclaimed water (RW) from wastewater treatment plants (WWTPs) is becoming a potential source for highly water-demanding activities such as agriculture. However, the removal capacity of contaminants in regular WWTPs has been found to be limited. Considering a Mediterranean scenario, this research investigated the plant uptake and translocation of three representative pharmaceuticals and personal care products (PPCPs) typically present in RW samples from a WWTP located in an urban area in Spain, and assessed the potential risk to humans from plant consumption. The RW samples were collected and analyzed for three representative PPCPs (atenolol -ATN-, carbamazepine -CBZ- and triclosan -TCS-). The target contaminants were also spiked at two levels in the RW samples to consider two worst-case scenarios. Three plant models (lettuce, maize and radish) were grown outdoors and irrigated with four treatments: tap water; RW samples, and the two spiked RW samples. Generally speaking, results revealed an efficient root uptake for the three PPCPs regardless of plant species and fortification level, and suggested an interaction effect of treatment and plant organ. Different bioaccumulation and translocation potentials of the three PPCPs were seen into the aerial organs of the plants. Overall, these observations support the idea that factors including the physico-chemical properties of the PPCPs and physiological plant variables, could be responsible for the differential accumulation and translocation potentials observed. These variables could be critical for crops irrigated with RW in regions with extended dry seasons, high solar incidence and low annual rainfall such as those in the Mediterranean rim where plants are subjected to high transpiration rates. However, the results obtained from this experimental approach suggested a negligible risk to humans from consumption of edible plants irrigated with RW samples with presence of PPCPs, despite the fact that the three representative PPCPs under study accumulated efficiently in the plants.
Asunto(s)
Riego Agrícola , Atenolol/metabolismo , Carbamazepina/metabolismo , Productos Agrícolas/metabolismo , Triclosán/metabolismo , Contaminantes Químicos del Agua/metabolismo , Atenolol/análisis , Carbamazepina/análisis , Productos Agrícolas/crecimiento & desarrollo , Humanos , España , Triclosán/análisis , Aguas Residuales/química , Contaminantes Químicos del Agua/análisisRESUMEN
Pharmaceutically active compounds are of great concern due to their detection frequency in the environment and the unexpected risks. In this study, the simultaneous removal of mixed pharmaceuticals by microalgae was explored using a typical freshwater diatom Navicula sp. Results showed that Navicula sp. could efficiently remove atenolol, carbamazepine, ibuprofen and naproxen with the efficiencies of >90% after 21â¯d of exposure. As compared to the removal efficiencies of each pharmaceutical in the individual pharmaceutical treatments, the degradation of sulfamethoxazole, bezafibrate, and naproxen was improved in the mixed treatment, whereas the removal efficiencies of carbamazepine and atenolol decreased. Additionally, the presence of hydrophobic pharmaceuticals (i.e., ibuprofen and naproxen) accelerated the degradation of carbamazepine and sulfamethoxazole and inhibited the removal of atenolol in the mixture with the combination of six pharmaceuticals, while the addition of other pharmaceuticals show no significant effect on the removal of ibuprofen and naproxen. The bioaccumulation of pharmaceuticals in Navicula sp. increased as their log KOW values decreased. Four bezafibrate metabolites were identified and the degradation pathways of bezafibrate in diatom were proposed. It is the first report on the metabolism of BEZ in diatom, and further studies on the environmental risk of the metabolites should be investigated.
Asunto(s)
Bezafibrato/análisis , Biodegradación Ambiental , Diatomeas/metabolismo , Preparaciones Farmacéuticas/análisis , Preparaciones Farmacéuticas/metabolismo , Contaminantes Químicos del Agua/análisis , Atenolol/análisis , Carbamazepina/análisis , Agua Dulce/química , Ibuprofeno/análisis , Inactivación Metabólica , Naproxeno/análisis , Sulfametoxazol/análisisRESUMEN
An eco-friendly corncob biochar based montmorillonite composite (Cc-Mt) was synthesized for the single adsorption and co-adsorption of lead (Pb(II)) and a pharmaceutical emerging organic contaminant Atenolol (ATE). In single adsorption system, the maximum equilibrium capacity of Cc-Mt for Pb (II) and ATE were 139.78â¯mgâ¯g-1 and 86.86â¯mgâ¯g-1, respectively, but for montmorillonite just 98.69â¯mgâ¯g-1 and 69.68â¯mgâ¯g-1, for corncob biochar just 117.54â¯mgâ¯g-1 and 47.29â¯mgâ¯g-1. Meanwhile,co-adsorption properties of ATE and Pb(II) on Cc-Mt composite were performed and found that the influence of ATE on the adsorption of Pb(II) was greater than the effect of Pb(II) on that of ATE. Moreover, Multiwfn program based on quantum chemical calculation was used to quantitatively analyze electrostatic potential (ESP) distribution, average local ionization energy (ALIE) distribution and their minimum points on neutral ATE and protonated ATE (PATE) molecules to reveal the microscopic adsorption mechanism of Cc-Mt composite to ATE, the results showed that the amino N and amide oxygen atom were easier to provide lone pair of electrons, generating hydrogen bonds or strong electrostatic interactions with functional groups on the surface of Cc-Mt, meanwhile hydroxyl O atom was also a possible reaction site. For PATE molecules, only the oxygen atom of the amide group was the most likely reactive site.
Asunto(s)
Atenolol/análisis , Bentonita/química , Carbón Orgánico/química , Plomo/análisis , Contaminantes Químicos del Agua/análisis , Adsorción , Iones , Cinética , Modelos Teóricos , Propiedades de Superficie , Purificación del Agua/métodosRESUMEN
A rapid and accurate method for the sensitive detection of illegal drug additives including atenolol (ATN), metformin hydrochloride (MET), and phenformin hydrochloride (PHE) in health products using solvent microextraction (SME) combined with surface-enhanced Raman spectroscopy (SERS) was developed. Various illegal drug additives in different health products were separated via microextraction and then detected in situ using a portable Raman spectrometer with Ag colloids acting as SERS-active substrates. The effects of experimental parameters on the detection sensitivity and producibility were evaluated, and the applications of illegal additives spiked into samples were systematically investigated with SME-SERS. It was demonstrated that the mixture of CH3OH and CHCl3 (v/v = 1 : 4) as the extractant was suitable for the rapid microextraction separation of illegal drug additives and also induced the distribution of the Ag colloids (2 M) on the CHCl3 surface. More importantly, CH3OH can carry the drug molecules to enter into the inter-particles of the Ag colloids in this process, and then significantly improve the detection sensitivity of illegal drug additives. Furthermore, the high-throughput and real-time detection of illegal drug additives spiked into health products with SME-SERS in multi-well 96 plates were achieved with the level of 0.1 µg mg-1. The results reveal that this rapid and convenient method could be used for the effective separation and sensitive detection of illegal additives in complex specimen.
Asunto(s)
Atenolol/análisis , Hipoglucemiantes/análisis , Microextracción en Fase Líquida/métodos , Metformina/análisis , Fenformina/análisis , Espectrometría Raman/métodos , Cloroformo/química , Coloides/química , Contaminación de Medicamentos , Límite de Detección , Nanopartículas del Metal/química , Metanol/química , Reproducibilidad de los Resultados , Plata/química , Solventes/químicaRESUMEN
Persulfate (PS) activation reaction, which forms sulfate radical (SO4-), can be used to degrade organic pollutants in water. However, a drawback of this reaction is that the regeneration of ferrous ions requires a high concentration of hydrogen peroxide (Fenton-like reaction) or use of UV radiation. Catechin (CAT), a non-toxic antioxidant of natural origin from tea, is used in this work to improve the sulfate radical-mediated degradation of atenolol (ATL, a model pollutant) in water using relatively low concentrations of reactive chemical species (less than 100⯵M). To the best of the author's knowledge, the direct effect of CAT on the oxidation state of iron, which is promoted by the reduction of ferric into ferrous ions with the enhancement of SO4- formation in the presence of PS, is demonstrated for the first time. The enhancement versus inhibition effect of CAT and the chemical mechanism of the iron-based activation process are explained. Results show that UVA radiation, which is representative of solar light, accelerates the initial degradation of ATL by more than 30% through ferric iron photolysis. Finally, a reaction mechanism leading to the formation of hydroxyl radicals (HO) and SO4- is proposed considering the implication of different activation/reaction chemical steps.
Asunto(s)
Atenolol/química , Catequina/química , Sulfatos/química , Contaminantes Químicos del Agua/química , Purificación del Agua/métodos , Atenolol/análisis , Peróxido de Hidrógeno , Radical Hidroxilo , Hierro/química , Contaminantes Químicos del Agua/análisisRESUMEN
In this study, we investigated the transformation of atenolol (ATL) by the naturally occurring laccase from Trametes versicolor in aqueous solution. Removal efficiency of ATL via laccase-catalyzed reaction in the presence of various laccase mediators was examined, and found that only the mediator 2, 2, 6, 6-tetramethyl-1-piperidinyloxy (TEMPO) was able to greatly promote ATL transformation. The influences of TEMPO concentration, laccase dosage, as well as solution pH and temperature on ATL transformation efficiency were tested. As TEMPO concentrations was increased from 0 to 2000⯵M, ATL transformation efficiency first increased and then decreased, and the optimal TEMPO concentration was determined as 500⯵M. ATL transformation efficiency was gradually increased with increasing laccase dosage. ATL transformation was highly pH-dependent with an optimum pH of 7.0, and it was almost constant over a temperature range of 25-50⯰C. Humic acid inhibited ATL transformation through competition reaction with laccase. The presence of anions HCO3- and CO32- reduced ATL transformation due to both anions enhanced solution pHs, while Cl-, SO42-, and NO3- at 10â¯mM showed no obvious influence. The main transformation products were identified, and the potential transformation pathways were proposed. After enzymatic treatment, the toxicity of ATL and TEMPO mixtures was greatly reduced. The results of this study might present an alternative clean strategy for the remediation of ATL contaminated water matrix.
Asunto(s)
Atenolol/análisis , Óxidos N-Cíclicos/química , Lacasa/metabolismo , Contaminantes Químicos del Agua/análisis , Purificación del Agua/métodos , Atenolol/metabolismo , Catálisis , Sustancias Húmicas/análisis , Oxidación-Reducción , Temperatura , Trametes/enzimología , Contaminantes Químicos del Agua/metabolismoRESUMEN
A method based on gas chromatography-mass spectrometry (GC-MS) is described for the determination of bisoprolol and atenolol in human bone. After the addition of lobivolol as internal standard, pulverized samples were incubated in acetonitrile for 1 h under ultrasounds. After adjusting the pH of the samples to 6, they were centrifuged, and the supernatants were subjected to solid phase extraction. Elution was achieved by using 3 mL of 2% ammonium hydroxide in 80:20 dichloromethane:isopropanol solution. Eluted samples were evaporated and derivatized. Chromatography was performed on a fused silica capillary column and analytes were determined in the selected-ion-monitoring (SIM) mode. The assay was validated in the range 0.1-0.3 ng/mg (depending on the drug) to 150 ng/mg, the mean absolute recoveries were 60% for bisoprolol and 106% for atenolol, the matrix effect was 69% for bisoprolol and 70% for atenolol and process efficiency was 41% for bisoprolol and 80% for atenolol. The intra- and inter-assay accuracy values were always better than 12%. The validated method was then applied to bone samples from two real forensic cases in which toxicological analysis in blood were positive for atenolol in the first case (0.65 µg/mL) and bisoprolol in the second case (0.06 µg/mL). Atenolol was found in bone samples from the corresponding case at the approximate concentration of 148 ng/mg and bisoprolol was found at 8 ng/mg.
Asunto(s)
Atenolol/análisis , Bisoprolol/análisis , Huesos/química , Toxicología Forense , Cromatografía de Gases y Espectrometría de Masas , Humanos , Reproducibilidad de los Resultados , Extracción en Fase SólidaRESUMEN
BiOCl@Fe3O4 photocatalyst was synthesized to activate peroxymonosulfate (PMS) for atenolol (ATL) degradation under simulated sunlight irradiation in present study. XRD, SEM, adsorbability and pore size distribution of BiOCl@Fe3O4 were analyzed. Magnetic BiOCl performed high activity in PMS activation and could be easily solid-liquid separation by applying an external magnetic field. Many parameters were inspected, including scavengers, PMS concentration, catalyst dosage, pH, anions (Cl- and CO3-). h+, SO4-, HO, O2-, SO5- were involved in ATL degradation in BiOCl@Fe3O4/PMS/sunlight system. The second-order rate constant of the reaction between ATL and SO4- (kATL, SO4-) was estimated via laser flash photolysis experiments. Moreover, ATL mineralization was followed by TOC analyzer. Twelve possible intermediate products were identified through LC-QTOF-MS analysis, and six ATL degradation pathways were concluded. This type of magnetic photocatalyst is characterized by ease of separation, high activation and good reusability. It may have application potential in refractory organic pollutants degradation.
Asunto(s)
Atenolol/metabolismo , Bismuto/química , Óxido Ferrosoférrico/química , Peróxidos/química , Contaminantes Químicos del Agua/metabolismo , Purificación del Agua/métodos , Atenolol/análisis , Atenolol/química , Catálisis , Cinética , Contaminantes Químicos del Agua/análisis , Contaminantes Químicos del Agua/químicaRESUMEN
A total of 58 samples were collected from hospitals, municipal wastewater treatment plants (WWTPs), a receiving water body (Dagu Drainage Canal, DDC), and adjacent farmland in Tianjin City, China, in May and November 2013 and were analyzed for five common ß-blockers (atenolol, sotalol, metoprolol, propranolol, and nadolol) to elucidate their source, occurrence and fate in a typical city in China. The profiles of the enantiomers of the ß-blockers in some samples were examined. Sotalol, metoprolol and propranolol were frequently detected, atenolol was less frequently detected, and nadolol was mostly not detected. Generally, the concentrations in hospital wastewaters occurred from Asunto(s)
Antagonistas Adrenérgicos beta/análisis
, Monitoreo del Ambiente
, Eliminación de Residuos Líquidos
, Aguas Residuales/química
, Contaminantes Químicos del Agua/análisis
, Atenolol/análisis
, China
, Metoprolol/análisis
, Propranolol/análisis
, Suelo
, Estereoisomerismo
RESUMEN
In this report recycled LiFePO4 (LFP) from exhaust batteries was utilized to form B@C3N4/LiFePO4/CuFe2O4 (BLC) nano-junction as a visible active photocatalyst. The junction synthesized by two routes: Using as extracted LFP and forming LFP by extracted FePO4 and Li2CO3 via in-situ deposition method. The two ternary junctions BLC and BLC (E) (utilizing as extracted LFP) were utilized for visible and solar powered degradation of beta-blocker drug Atenolol (ATL). Varying the loading of CuFe2O4 (CF) which possesses lowest band gap, BLC (10%), BLC-3 (30%), BLC-5 (50%) and BLC-E (30% CF and as extracted LFP) were produced with BLC-3 exhibiting remarkable activity. The optical band gaps of BLC-3 (2.40â¯eV) and BLC (E) (2.46â¯eV) and photocurrent responses reveal high visible absorption and highly diminished recombination. 99.5% and 85.3% of ATL (20â¯mgâ¯L-1) could be degraded by BLC-3 and BLC (E) (0.3â¯gâ¯L-1) respectively in 60â¯min of exposure to Xe lamp and retaining of high activity in natural sunlight. Band-junction analysis, effect of scavengers and effect on teraphthalic acid and nitroblue tetrazolium reveal O2- and OH radicals as active species and mineralization was confirmed by liquid chromatography-mass spectrometer (LC-MS). Cyto-toxicity studies on human peripheral blood cells and effect on growth of Pseudomonas aeruginosa confirm the complete mineralization. The BLC photocatalyst is a promising multi-functional catalyst utilizing LFP (rarely used as photocatalyst) for treatment of pharmaceutical waste water and other environmental applications.