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1.
Appl Microbiol Biotechnol ; 104(5): 1849-1857, 2020 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-31925484

RESUMO

This article summarizes the current knowledge about the presence of naproxen in the environment, its toxicity to nontarget organisms and the microbial degradation of this drug. Currently, naproxen has been detected in all types of water, including drinking water and groundwater. The concentrations that have been observed ranged from ng/L to µg/L. These concentrations, although low, may have a negative effect of long-term exposure on nontarget organisms, especially when naproxen is mixed with other drugs. The biological decomposition of naproxen is performed by fungi, algae and bacteria, but the only well-described pathway for its complete degradation is the degradation of naproxen by Bacillus thuringiensis B1(2015b). The key intermediates that appear during the degradation of naproxen by this strain are O-desmethylnaproxen and salicylate. This latter is then cleaved by 1,2-salicylate dioxygenase or is hydroxylated to gentisate or catechol. These intermediates can be cleaved by the appropriate dioxygenases, and the resulting products are incorporated into the central metabolism. KEY POINTS: •High consumption of naproxen is reflected in its presence in the environment. •Prolonged exposure of nontargeted organisms to naproxen can cause adverse effects. •Naproxen biodegradation occurs mainly through desmethylnaproxen as a key intermediate.


Assuntos
Exposição Ambiental/efeitos adversos , Naproxeno/metabolismo , Naproxeno/toxicidade , Poluentes Químicos da Água/metabolismo , Poluentes Químicos da Água/toxicidade , Anti-Inflamatórios não Esteroides/análise , Anti-Inflamatórios não Esteroides/metabolismo , Anti-Inflamatórios não Esteroides/toxicidade , Organismos Aquáticos/efeitos dos fármacos , Organismos Aquáticos/metabolismo , Bacillus thuringiensis/metabolismo , Proteínas de Bactérias/metabolismo , Biodegradação Ambiental , Redes e Vias Metabólicas/efeitos dos fármacos , Naproxeno/análogos & derivados , Naproxeno/análise , Poluentes Químicos da Água/análise
2.
Chemosphere ; 240: 124949, 2020 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-31568949

RESUMO

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 21 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.


Assuntos
Bezafibrato/análise , Biodegradação Ambiental , Diatomáceas/metabolismo , Preparações Farmacêuticas/análise , Preparações Farmacêuticas/metabolismo , Poluentes Químicos da Água/análise , Atenolol/análise , Carbamazepina/análise , Água Doce/química , Ibuprofeno/análise , Inativação Metabólica , Naproxeno/análise , Sulfametoxazol/análise
3.
Anal Chim Acta ; 1078: 78-89, 2019 Oct 31.
Artigo em Inglês | MEDLINE | ID: mdl-31358231

RESUMO

Based on a one-step combustion fabrication approach, a novel magnetic porous carbon (MPC) was fabricated using filter paper as porous carbon source and iron salts as magnetic precursors. The textural properties of the MPC were characterized by transmission electron microscopy (TEM), Fourier transform infrared spectrometry (FT-IR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), vibration sample magnetometer (VSM) and nitrogen absorption-desorption isotherms. The as-prepared MPC possessed a high specific surface area, a microstructure comprised of mesopores and strong magnetic response. It was employed as a magnetic solid-phase extraction (MSPE) adsorbent for the determination of three non-steroidal anti-inflammatory drugs (NSAIDs) in environmental water and biological samples coupled with high performance liquid chromatography (HPLC). The main parameters affecting extraction efficiency were investigated in detail and a satisfactory performance was obtained under the optimal conditions. The calibration curves were linear over the concentration ranging from 1 to 1200 µg L-1 for ketoprofen (KET) and 2-1200 µg L-1 for naproxen (NAP) and diclofenac (DCF) with determination coefficients (R2) between 0.9995 and 0.9997. The limits of detection (LODs) were in the range of 0.2-0.4 µg L-1. The intra- and inter-day relative standard deviations (RSDs) were less than 4.03% and 8.72%, respectively. The recoveries ranged from 84.67% to 113.73% with RSDs less than 7.76%. The satisfactory results confirmed the great potential of the novel MPC adsorbent for the extraction of NSAIDs from complex sample matrices.


Assuntos
Anti-Inflamatórios não Esteroides/análise , Carbono/química , Diclofenaco/análise , Cetoprofeno/análise , Naproxeno/análise , Adsorção , Anti-Inflamatórios não Esteroides/sangue , Anti-Inflamatórios não Esteroides/urina , Diclofenaco/sangue , Diclofenaco/urina , Química Verde/métodos , Cetoprofeno/sangue , Cetoprofeno/urina , Limite de Detecção , Nanopartículas de Magnetita/química , Naproxeno/sangue , Naproxeno/urina , Porosidade , Rios/química , Extração em Fase Sólida/instrumentação , Extração em Fase Sólida/métodos , Poluentes Químicos da Água/análise
4.
Ecotoxicol Environ Saf ; 181: 180-186, 2019 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-31185432

RESUMO

This study examined the distribution of pharmaceuticals in Yeongsan River and at point sources (PSs) in the associated water system, and performed a risk assessment based on our findings. The samples included effluents collected from three sewage treatment plants (PS1, PS2, and PS3) and two industrial complexes (PS4 and PS5) as well as surface water collected from seven mainstreams and 11 tributaries of the river. The target pharmaceuticals were acetylsalicylic acid, carbamazepine, clarithromycin, naproxen, sulfamethazine, sulfamethoxazole, sulfathiazole, and trimethoprim, which were detected by liquid chromatography-tandem mass spectrometry. All pharmaceuticals except acetylsalicylic acid and sulfathiazole were found in PS1, PS2, and PS3 samples, whereas acetylsalicylic acid, carbamazepine, sulfamethazine, and sulfamethoxazole were found in PS4, most of the pharmaceuticals were not present in PS5. The rank order of pharmaceutical concentration in surface water was carbamazepine (97.2%, 0.2067 µg/L) > sulfamethoxazole (88.9%, 0.1132 µg/L) > naproxen (51.4%, 0.0516 µg/L) > clarithromycin (43.1%, 0.0427 µg/L). The distribution of pharmaceuticals in the Yeongsan River at PSs and non-PSs differed, and higher concentrations of human pharmaceuticals were detected in upstream and midstream areas whereas higher concentrations of animal pharmaceuticals were found downstream. Hazard quotients (HQs) evaluated at each sites based on mean concentration and 95% upper confidence limits (95% UCLs) were all less than one, indicating a low risk of toxicity. The findings of this study are expected to be useful for risk assessment of aquatic ecosystems.


Assuntos
Preparações Farmacêuticas/análise , Rios/química , Poluentes Químicos da Água/análise , Carbamazepina/análise , Cromatografia Líquida , Claritromicina/análise , Ecossistema , Monitoramento Ambiental , Naproxeno/análise , República da Coreia , Medição de Risco , Sulfametoxazol/análise , Espectrometria de Massas em Tandem , Águas Residuárias/química
5.
Mikrochim Acta ; 186(5): 297, 2019 04 23.
Artigo em Inglês | MEDLINE | ID: mdl-31016399

RESUMO

Layered double hydroxides (LDHs) of nickel and iron were hydrothermally prepared by co-precipitation using urea hydrolysis. The Ni-Fe LDH nanostructures were characterized by X-ray diffraction, FT-IR spectroscopy, scanning electron microscopy, thermogravimetric and energy dispersive X-ray analysis. The LDHs are shown to be a viable sorbent for micro solid phase extraction by packed sorbent of the nonsteroidal anti-inflammatory drugs (NSAIDs) diclofenac, ibuprofen, mefenamic acid and naproxen from human urine. Adsorption and desorption parameters were optimized using a central composite design. Following desorption with a methanol/water mixture (95:5 v:v) containing 0.1% formic acid, the NSAIDs were quantified by HPLC with UV detection. Under the optimal conditions, response is linear in the 10-1000 ng.mL-1 NSAID concentration range. Limits of detection and intra-day and inter-day RSDs are <10 ng.mL-1 and 10.2%, respectively. The method was successfully applied to the determination of NSAIDs in some positive human urine samples. Relative recoveries from spiked samples range from 94.8 to 113%. Graphical abstract Layered double hydroxides of nickel and iron were synthesized and packed in a spinal syringe for micro solid phase extraction of non-steroidal anti-inflammatory drugs.


Assuntos
Ligas/química , Anti-Inflamatórios não Esteroides/urina , Hidróxidos/química , Ferro/química , Nanopartículas Metálicas/química , Níquel/química , Adsorção , Técnicas Biossensoriais/instrumentação , Técnicas Biossensoriais/métodos , Cromatografia Líquida de Alta Pressão/métodos , Diclofenaco/análise , Humanos , Ibuprofeno/análise , Limite de Detecção , Ácido Mefenâmico/análise , Naproxeno/análise , Reprodutibilidade dos Testes , Microextração em Fase Sólida/instrumentação , Microextração em Fase Sólida/métodos , Propriedades de Superfície
6.
Water Sci Technol ; 79(3): 480-488, 2019 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-30924802

RESUMO

Naproxen (NPX) degradation was investigated by anodic oxidation both at constant potential and by cyclic voltammetry, using this last technique for optimizing reaction conditions and catalyst properties. Three multiwall carbon nanotubes (MWCNTs)-promoted electrodes were used (MWCNT, MWCNT-COOH and MWCNT-NH2) and a two steps oxidation process was observed in all the cases. At the optimized conditions (volume of MWCNT = 15 µL), the influence of the scan rate indicates the diffusion-adsorption control of the process. Likewise, the kinetic study of NPX degradation at fix potential, considering two different stirring speeds (250 and 500 rpm), indicates that degradation rate increases with the stirring speed. After 20 h, NPX is degraded even an 82.5%, whereas the mineralization reaches almost 70%, as it was obtained from total organic carbon analysis. The pH effect was also analysed, in the range 5-11, observing a positive effect at low pH. Concerning the surface chemistry of the electrode, MWCNT-NH2, with the highest isoelectric point (4.70), is the most promising material due to the improved interactions with the reactant. From these observations, a pathway is proposed, which includes two steps of electrochemical oxidation followed by subsequent oxidation steps, until mineralization of the NPX, attributed mainly to active chlorine species and ·OH.


Assuntos
Nanotubos de Carbono/química , Naproxeno/química , Poluentes Químicos da Água/química , Purificação da Água/métodos , Técnicas Eletroquímicas , Eletrodos , Concentração de Íons de Hidrogênio , Naproxeno/análise , Oxirredução , Poluentes Químicos da Água/análise
7.
Ecotoxicol Environ Saf ; 174: 83-91, 2019 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-30822671

RESUMO

A simple, sensitive and quick method for direct simultaneous chiral analysis of frequently used non-steroidal anti-inflammatory drugs (NSAIDs) (ibuprofen, naproxen and flurbiprofen) in river water by HPLC-MS/MS was established and validated. Chromatographic parameters including the mobile phase composition, pH values, temperature and flow rates were optimized to obtain both satisfactory sensitivity and enantiomeric resolution (Rs≥ 1.0), which suggested the composition and pH values of mobile phase played crucial influence on enantioseparations. The method demonstrated its superiority compared with previous studies regarding to the low MQLs (1.1-37.1 ng/L) and short runtime (< 20 min), enabling quantitative enantiomeric determination of trace level of emerging contaminants in water. The environmental monitoring of receiving water (34 sites along rivers) in Beijing revealed ibuprofen was the most abundant, with mean concentration of 114.9 ng/L and detection frequency of 91%, naproxen was also detectable at all sites from < MQL-43.2 ng/L, both presenting an excess of the S-(+)-enantiomer. Therefore to better understand the ecological risk posed from the trace organic contaminants on the aquatic organisms, chiral pollutants need analyzed at the enantiomeric levels. This is the first to profile the enantiospecific occurrence of NSAIDs in surface water in Beijing, China. It could provide useful information on environmental behaviors of chiral pollutants and facilitate more accurate environmental risk assessment.


Assuntos
Anti-Inflamatórios não Esteroides/análise , Cromatografia Líquida de Alta Pressão/métodos , Espectrometria de Massas em Tandem/métodos , Poluentes Químicos da Água/análise , Anti-Inflamatórios não Esteroides/química , Pequim , Monitoramento Ambiental , Flurbiprofeno/análise , Flurbiprofeno/química , Ibuprofeno/análise , Ibuprofeno/química , Naproxeno/análise , Naproxeno/química , Projetos Piloto , Rios/química , Estereoisomerismo , Poluentes Químicos da Água/química
8.
Environ Sci Pollut Res Int ; 26(33): 34301-34310, 2019 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-30746625

RESUMO

Naproxen (NAP) is a nonsteroidal anti-inflammatory drug which has been widely used and frequently detected in water environments. This study investigated the NAP degradation in the chlorination and UV/chlorine disinfection processes, which usually acted as the last barriers for water treatment. The results showed that both chlorination and UV/chlorine disinfection could remove NAP effectively. At various chlorine dosages (0.1~0.5 mM), the contributions of chlorination and reactive radicals to the degradation of NAP in the UV/chlorine process were calculated to be 50.5~56.9% and 43.1~49.5%, respectively. However, the reactive radicals dominated in NAP degradation in alkaline solutions, while chlorination dominated in acidic conditions. The HCO3- (10~50 mM) slightly inhibited, Cl- (10~50 mM) gradually promoted, and HA (1~5 mg/L) significantly reduced NAP degradation by UV/chlorine process. The degradation intermediates and products were obtained via high-performance liquid chromatography with QE-MS/MS; NAP was degraded by demethylation, acetylation, and dicarboxylic acid pathways during the chlorination and UV/chlorination processes.


Assuntos
Cloro/química , Desinfetantes/química , Desinfecção , Naproxeno/química , Poluentes Químicos da Água/química , Anti-Inflamatórios não Esteroides , Halogenação , Cinética , Naproxeno/análise , Espectrometria de Massas em Tandem , Raios Ultravioleta , Poluentes Químicos da Água/análise , Purificação da Água/métodos
9.
J Sep Sci ; 42(9): 1702-1709, 2019 May.
Artigo em Inglês | MEDLINE | ID: mdl-30809939

RESUMO

Rapid, simple, and sensitive submicellar liquid chromatography with fluorescence detection was developed and validated to quantify naproxen in plasma and brain samples after oral administration of Naproxen formulations. The method used tramadol as an internal standard. Different submicellar mobile phases with organic phases ranging from 40 to 60% were studied to improve the native fluorescence of the Naproxen and decrease retention times. Separation was done in a Zorbax SB C8 column (250 × 4.6 mm, 5 µm) with a mobile phase containing acidic 0.007 M sodium dodecyl sulfate/acetonitrile (50:50, v/v) at a flow rate of 1 mL/min. Detection was performed with an excitation wavelength of 280 nm and emission of 310 nm and 360 nm for internal standard and Naproxen, respectively. The method was validated by International Conference of Harmonization standards. The method is specific, accurate, and precise (relative standard deviation <3%). Limits of detection and quantification were 0.08 and 0.25 µg/mL, respectively, for biological samples. This method was applied to analyze brain/plasma ratios in mice that had received oral administrations of Naproxen micellar formulations containing 10% w/w of sodium dodecyl sulfate, Cremophor RH 40, or Tween 80. The sodium dodecyl sulfate micelles were faster and more widely distributed in the mouse brains.


Assuntos
Anti-Inflamatórios/análise , Química Encefálica , Cromatografia Líquida/métodos , Naproxeno/análise , Plasma/química , Animais , Anti-Inflamatórios/sangue , Cromatografia Líquida/instrumentação , Fluorescência , Masculino , Camundongos , Camundongos Endogâmicos BALB C , Naproxeno/sangue
10.
Biomed Chromatogr ; 33(1): e4396, 2019 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-30246262

RESUMO

In the present study, we aimed to develop a reliable screening method based on liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) for the detection and quantification of naproxen, methyltestosterone and 17α-hydroxyprogesterone caproate residues. The target analytes were extracted from samples of eel, flatfish and shrimp using acetonitrile with 1% acetic acid, followed by liquid-liquid purification with n-hexane. Chromatographic separation was achieved on a reversed-phase analytical column using 0.1% formic acid containing 10 mm ammonium formate in distilled water (A) and methanol (B) as mobile phases. All the matrix-matched calibration curves were linear (R2 ≥ 0.99) over the concentration range of the tested analytes. Recovery at three spiking levels (0.005, 0.01 and 0.02 mg/kg) ranged from 68 to 117% with intra- and inter-day precisions <10%. Five market samples for each matrix (eel, flatfish and shrimp) were collected and tested for method application. In summary, the proposed method is feasible to screen and quantify the analytes with high selectivity in aquatic food products meant for human consumption.


Assuntos
Caproato de 17 alfa-Hidroxiprogesterona/análise , Resíduos de Drogas/análise , Metiltestosterona/análise , Naproxeno/análise , Alimentos Marinhos/análise , Caproato de 17 alfa-Hidroxiprogesterona/isolamento & purificação , Animais , Cromatografia Líquida/métodos , Enguias , Linguados , Limite de Detecção , Modelos Lineares , Extração Líquido-Líquido/métodos , Metiltestosterona/isolamento & purificação , Naproxeno/isolamento & purificação , Penaeidae , Reprodutibilidade dos Testes , Espectrometria de Massas em Tandem/métodos
11.
Chem Res Toxicol ; 32(1): 168-178, 2019 01 22.
Artigo em Inglês | MEDLINE | ID: mdl-30585484

RESUMO

The effects measured with in vitro cell-based bioassays are typically reported as nominal effect concentrations ( Cnom), but the freely dissolved concentration in the exposure medium ( Cw) and the total cellular concentration ( Ccell) are considered more quantitative dose metrics that allow extrapolation to the whole-organism level. To predict Cw and Ccell, the partitioning of the test chemicals to medium proteins and lipids and cells has to be known. In this study, we developed a solid-phase microextraction (SPME) method based on C18-coated fibers to quantify the partitioning of diclofenac, 2,4-dichlorophenoxyacetic acid (2,4-D), ibuprofen, naproxen, torasemide, warfarin, and genistein to bovine serum albumin (BSA), phospholipid liposomes, fetal bovine serum (FBS), and cells. For ibuprofen, 2,4-D, naproxen, and warfarin, the partitioning to the SPME fibers was found to be concentration dependent, which had to be considered for the calculation of distribution ratios to biological materials. The sorption isotherms to FBS were nonlinear for diclofenac, 2,4-D, ibuprofen, naproxen, and warfarin. The FBS isotherms could be described by assuming that the total amount of chemical bound to FBS is the sum of the amount specifically bound to the binding sites of albumin and nonspecifically bound to all medium proteins and lipids. The determined cell-water distribution ratios ( Dcell/w) differed considerably between four different cell lines (up to 1.83 log-units) and also between different batches of the same cell line (up to 0.48 log-units). The relative importance of protein and lipid content for Dcell/w was evaluated with a mass balance model and different types of cellular proteins and lipids as input parameters. Existing in vitro mass balance models may underestimate Cw because they do not account for saturable protein binding and overestimate Ccell for organic acids, if BSA is used as surrogate for cellular proteins.


Assuntos
Fosfolipídeos/química , Soroalbumina Bovina/química , Microextração em Fase Sólida , Ácido 2,4-Diclorofenoxiacético/análise , Animais , Bovinos , Células Cultivadas , Diclofenaco/análise , Genisteína/análise , Células HEK293 , Humanos , Ibuprofeno/análise , Cinética , Lipossomos/química , Naproxeno/análise , Torasemida/análise , Varfarina/análise
12.
Artigo em Inglês | MEDLINE | ID: mdl-29518680

RESUMO

In this paper, novel univariate and multivariate regression methods along with model-updating technique were developed and validated for the simultaneous determination of quaternary mixture of imatinib (IMB), gemifloxacin (GMI), nalbuphine (NLP) and naproxen (NAP). The univariate method is extended derivative ratio (EDR) which depends on measuring every drug in the quaternary mixture by using a ternary mixture of the other three drugs as divisor. Peak amplitudes were measured at 294nm, 250nm, 283nm and 239nm within linear concentration ranges of 4.0-17.0, 3.0-15.0, 4.0-80.0 and 1.0-6.0µgmL-1 for IMB, GMI, NLP and NAB, respectively. Multivariate methods adopted are partial least squares (PLS) in original and derivative mode. These models were constructed for simultaneous determination of the studied drugs in the ranges of 4.0-8.0, 3.0-11.0, 10.0-18.0 and 1.0-3.0µgmL-1 for IMB, GMI, NLP and NAB, respectively, by using eighteen mixtures as a calibration set and seven mixtures as a validation set. The root mean square error of predication (RMSEP) were 0.09 and 0.06 for IMB, 0.14 and 0.13 for GMI, 0.07 and 0.02 for NLP and 0.64 and 0.27 for NAP by PLS in original and derivative mode, respectively. Both models were successfully applied for analysis of IMB, GMI, NLP and NAP in their dosage forms. Updated PLS in derivative mode and EDR were applied for determination of the studied drugs in spiked human urine. The obtained results were statistically compared with those obtained by the reported methods giving a conclusion that there is no significant difference regarding accuracy and precision.


Assuntos
Fluoroquinolonas/análise , Mesilato de Imatinib/análise , Nalbufina/análise , Naftiridinas/análise , Naproxeno/análise , Calibragem , Fluoroquinolonas/urina , Gemifloxacina , Humanos , Mesilato de Imatinib/urina , Análise dos Mínimos Quadrados , Nalbufina/urina , Naftiridinas/urina , Naproxeno/urina , Espectrofotometria/métodos , Espectrofotometria/estatística & dados numéricos
13.
Anal Chem ; 90(6): 4089-4097, 2018 03 20.
Artigo em Inglês | MEDLINE | ID: mdl-29455521

RESUMO

Naproxen is one of the most consumed nonsteroidal anti-inflammatory drugs and marketed as S-naproxen since R-naproxen is hepatotoxic. In this study, chiral recognition of naproxen has been investigated by tandem mass spectrometry (MS/MS). Among all diastereomeric complexes formed between naproxen and the examined chiral selectors, including cyclodextrins (α/ß/γ-CD), modified phenylalanines ( N-acetyl-phenylalanine, N-t-butoxycarbonyl-phenylalanine, N-9-fluorenylmethyloxycarbonyl-phenylalanine), amino acids (Trp, Phe, Tyr, His), glucose, tartaric acid, and vancomycin, a novel binuclear metal bound diastereomeric complexes [(M(II))2( S/ R-naproxen)(l-His)2-3H]+ (M = Cu, Ni, or Co with Cu being the best) could allow effective identification of the absolute configuration of naproxen and determination of its enantiomeric excess ( ee) through MS/MS analysis. The key candidate structure of [(Cu(II))2( S/ R-naproxen)(l-His)2-3H]+ has been revealed by means of collision-induced dissociation, ion mobility mass spectrometry and density functional theory calculations, indicating an interesting and unusual self-assembled compact geometry with the two Cu(II) ions bridged closely together (Cu-Cu distance is 3.04 Å) by the carboxylate groups of the two histidines. It was shown that the difference in dissociation efficiency between the two diastereomers was attributed to the interaction between the NH2 bond of the amino group of one histidine and the naphthyl ring of naproxen. The present report is the first to observe and characterize the complex of (Cu(II))2(His)2 with aromatic acid, which could contribute to the chiral recognition of other chiral aromatic acids, design of catalysts based on binuclear copper bound complex, as well as the better understanding of metal ion complexation by His or His-containing ligands.


Assuntos
Anti-Inflamatórios não Esteroides/análise , Complexos de Coordenação/química , Cobre/química , Histidina/química , Naproxeno/análise , Espectrometria de Massas em Tandem/métodos , Anti-Inflamatórios não Esteroides/química , Modelos Moleculares , Naproxeno/química , Estereoisomerismo , Termodinâmica
14.
Water Res ; 135: 278-287, 2018 05 15.
Artigo em Inglês | MEDLINE | ID: mdl-29482095

RESUMO

Emerging pollutants, including pharmaceutical compounds, are producing water pollution problems around the world. Some pharmaceutical pollutants, which mainly reach ecosystems within wastewater discharges, are persistent in the water cycle and can also reach the food chain. This work addresses this issue, accounting the grey component of the water footprint (GWFP) for four of the most common pharmaceutical compounds (carbamazepine (CBZ), diclofenac (DCF), ketoprofen (KTP) and naproxen (NPX)). In addition, the GWFC for the main conventional pollutants is also accounted (nitrate, phosphates and organic matter). The case study is the Murcia Region of southeastern Spain, where wastewater treatment plants (WWTPs) purify 99.1% of the wastewater discharges and there is an important direct reuse of the treated wastewater in irrigation. Thus, the influence of WWTPs and reuse on the GWF is analysed. The results reveal that GWFP, only taking into account pharmaceutical pollutants, has a value of 301 m3 inhabitant-1 year-1; considering only conventional pollutants (GWFC), this value increases to 4718 m3 inhabitant-1 year-1. So, the difference between these values is such that in other areas with consumption habits similar to those of the Murcia Region, and without wastewater purification, conventional pollutants may well establish the value of the GWF. On average, the WWTPs reduce the GWFC by 90% and the GWFP by 26%. These different reductions of the pollutant concentrations in the treated effluents show that the GWF is not only due to conventional pollutants, and other contaminants can became critical, such as the pharmaceutical pollutants. The reuse further reduces the value of the GWF for the Murcia Region, by around 43.6%. However, the reuse of treated wastewater is controversial, considering the pharmaceutical contaminants and their possible consequences in the food chain. In these cases, the GWF of pharmaceutical pollutants can be used to provide a first approximation of the dilution that should be applied to the treated wastewater discharges when they are reused for another economic activity that imposes quality restrictions. For the case of agriculture in the Murcia Region, the dilution required is 2 (fresh water) to 1 (treated wastewater), taking into account the pollution thresholds established in this work.


Assuntos
Irrigação Agrícola/métodos , Preparações Farmacêuticas/análise , Eliminação de Resíduos Líquidos/métodos , Poluentes Químicos da Água/análise , Carbamazepina/análise , Diclofenaco/análise , Naproxeno/análise , Nitratos/análise , Fosfatos/análise , Reciclagem , Espanha , Águas Residuárias/análise
15.
J Pharm Biomed Anal ; 151: 209-218, 2018 Mar 20.
Artigo em Inglês | MEDLINE | ID: mdl-29353809

RESUMO

Near-infrared spectroscopy is frequently used by the pharmaceutical industry to monitor and optimize several production processes. In combination with chemometrics, a mathematical-statistical technique, the following advantages of near-infrared spectroscopy can be applied: It is a fast, non-destructive, non-invasive, and economical analytical method. One of the most advanced and popular chemometric technique is the partial least square algorithm with its best applicability in routine and its results. The required reference analytic enables the analysis of various parameters of interest, for example, moisture content, particle size, and many others. Parameters like the correlation coefficient, root mean square error of prediction, root mean square error of calibration, and root mean square error of validation have been used for evaluating the applicability and robustness of these analytical methods developed. This study deals with investigating a Naproxen Sodium granulation process using near-infrared spectroscopy and the development of water content and particle-size methods. For the water content method, one should consider a maximum water content of about 21% in the granulation process, which must be confirmed by the loss on drying. Further influences to be considered are the constantly changing product temperature, rising to about 54 °C, the creation of hydrated states of Naproxen Sodium when using a maximum of about 21% water content, and the large quantity of about 87% Naproxen Sodium in the formulation. It was considered to use a combination of these influences in developing the near-infrared spectroscopy method for the water content of Naproxen Sodium granules. The "Root Mean Square Error" was 0.25% for calibration dataset and 0.30% for the validation dataset, which was obtained after different stages of optimization by multiplicative scatter correction and the first derivative. Using laser diffraction, the granules have been analyzed for particle sizes and obtaining the summary sieve sizes of >63 µm and >100 µm. The following influences should be considered for application in routine production: constant changes in water content up to 21% and a product temperature up to 54 °C. The different stages of optimization result in a "Root Mean Square Error" of 2.54% for the calibration data set and 3.53% for the validation set by using the Kubelka-Munk conversion and first derivative for the near-infrared spectroscopy method for a particle size >63 µm. For the near-infrared spectroscopy method using a particle size >100 µm, the "Root Mean Square Error" was 3.47% for the calibration data set and 4.51% for the validation set, while using the same pre-treatments. - The robustness and suitability of this methodology has already been demonstrated by its recent successful implementation in a routine granulate production process.


Assuntos
Anti-Inflamatórios não Esteroides/análise , Naproxeno/análise , Tamanho da Partícula , Tecnologia Farmacêutica/métodos , Anti-Inflamatórios não Esteroides/química , Calibragem , Química Farmacêutica/métodos , Dessecação/métodos , Interações Hidrofóbicas e Hidrofílicas , Análise dos Mínimos Quadrados , Naproxeno/química , Espectroscopia de Luz Próxima ao Infravermelho/métodos , Temperatura Ambiente , Água/química
16.
J Chromatogr A ; 1527: 10-17, 2017 Dec 08.
Artigo em Inglês | MEDLINE | ID: mdl-29102060

RESUMO

A mesoporous silica Santa Barbara Amorphous-15 (SBA-15) has been first functionalized with 3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane (a silane with three amines) and then reacted with an excess of phenyl glycidyl ether to generate a mixed-mode anion-exchanger containing both anion-exchange (three amines) and reversed-phase (multiple ether-linked phenyls) functionalities in a single branched ligand. The resulting material has been characterized by scanning electron microscopy, transmission electron microscopy, nitrogen adsorption-desorption measurements, Fourier-transform infrared spectroscopy, and elemental analysis. The results obtained indicated a BET specific surface area (SBET) of 362.5m2g-1, a pore volume of 0.70cm3g-1 with a narrow pore size distribution centered at 6.6nm, and carbon and nitrogen contents of 28.30% and 2.84%, respectively. The dimensions of these particles (∼5µm diameter, ∼60µm length), their large surface areas, their high-density functionalities and anion-exchange mixed-mode characteristics make them very attractive for highly effective solid phase extraction (SPE) of acidic nonsteroidal anti-inflammatory drugs (NSAIDs). The important parameters on extraction efficiency including sample pH, breakthrough volume, type and volume of eluent were optimized. A simple and sensitive analytical method based on mixed-mode SPE coupled to high-performance liquid chromatography with ultraviolet detection (HPLC-UV) was developed and successfully applied to the analysis of four NSAIDs (ketoprofen, naproxen, diclofenac, and ibuprofen) in spiked real water samples with satisfactory recoveries (80.6-110.9%) and repeatability (relative standard deviation <11.3%, n=3). The limit of detections of four NSAIDs were 0.006-0.070µgL-1 for tap water, and 0.014-0.16µgL-1 for river water and wastewater, with the enrichment factors of 806-1109-fold.


Assuntos
Anti-Inflamatórios não Esteroides/isolamento & purificação , Monitoramento Ambiental/métodos , Água Doce/química , Dióxido de Silício/química , Extração em Fase Sólida/métodos , Adsorção , Anti-Inflamatórios não Esteroides/análise , Cromatografia Líquida de Alta Pressão , Ibuprofeno/análise , Cetoprofeno/análise , Microscopia Eletrônica de Varredura , Microscopia Eletrônica de Transmissão , Naproxeno/análise , Silanos/análise , Espectroscopia de Infravermelho com Transformada de Fourier , Águas Residuárias/química , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/isolamento & purificação
17.
J Chromatogr A ; 1521: 1-9, 2017 Oct 27.
Artigo em Inglês | MEDLINE | ID: mdl-28947204

RESUMO

The present work represents a simple and effective preparation of a novel mixed-mode anion-exchange (MAX) sorbent based on porous poly[2-(diethylamino)ethyl methacrylate-divinylbenzene] (poly(DEAEMA-DVB)) spherical particles synthesized by one-step Pickering emulsion polymerization. The poly(DEAEMA-DVB) particles were quaternized with 1,4-butanediol diglycidyl ether (BDDE) followed by triethylamine (TEA) via epoxy-amine reaction to offer strong anion exchange properties. The synthesized MAX sorbent was characterized by scanning electron microscopy, Fourier-transform infrared spectroscopy, nitrogen adsorption-desorption measurements and elemental analysis. The MAX sorbent possessed regular spherical shape and narrow diameter distribution (15-35µm), a high IEC of 0.54meq/g, with carbon and nitrogen contents of 80.3% and 1.62%, respectively. Compared to poly(DEAEMA-DVB), the MAX sorbent exhibited decreased SBET (390.5 vs. 515.3m2g-1), pore volume (0.74 vs. 0.85cm3g-1) and pore size (16.8 vs. 17.3nm). Moreover, changes of N content for producing the MAX sorbent reveal a successful two-step quaternization, which can be highly related to such a high IEC. Finally, the MAX sorbent was successfully evaluated for selective isolation and purification of some selected acidic pharmaceuticals (ketoprofen, KEP; naproxen, NAP; and ibuprofen, IBP) from neutral (hydrocortisone, HYC), basic (carbamazepine, CAZ; amitriptyline, AMT) pharmaceuticals and other interferences in water samples using solid phase extraction (SPE). An efficient analytical method based on the MAX-based mixed-mode SPE coupled with HPLC-UV was developed for highly selective extraction and cleanup of acidic KEP, NAP and IBP in spiked wastewater samples. The developed method exhibited good sensitivity (0.009-0.085µgL-1 limit of detection), satisfactory recoveries (82.1%-105.5%) and repeatabilities (relative standard deviation < 7.9%, n=3).


Assuntos
Monitoramento Ambiental/métodos , Preparações Farmacêuticas/isolamento & purificação , Extração em Fase Sólida , Águas Residuárias/química , Butileno Glicóis , Emulsões , Monitoramento Ambiental/instrumentação , Ibuprofeno/análise , Ibuprofeno/isolamento & purificação , Cetoprofeno/análise , Cetoprofeno/isolamento & purificação , Limite de Detecção , Naproxeno/análise , Naproxeno/isolamento & purificação , Preparações Farmacêuticas/análise , Polimerização , Reprodutibilidade dos Testes , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/isolamento & purificação
18.
Chemosphere ; 187: 261-267, 2017 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-28850910

RESUMO

Humic substances (HS) including humic acid (HA) and fulvic acid (FA) are ubiquitous in the natural waters. Although numerous studies documented their role in photodegradation of organic pollutants, the competitive effects of photosensitization and light-screening of HS on the photodegradation of pollutants are not yet clear. In this work, the role of HS in the photodegradation of the pharmaceutical naproxen (NP) was studied under simulated sunlight. The direct photodegradation quantum yield of NP in deionized water was 2.1 × 10-2, and the apparent quantum yields for photosensitized degradation of NP in the presence of FA and HA were 2.3 × 10-4 and 2.6 × 10-5, respectively. Both direct and photosensitized photodegradation decreased with increasing pH, consistent with the trend of singlet oxygen (1O2) reaction rate constants of NP. HA inhibited the photodegradation of naproxen thoroughly. In contrast, FA accelerated the photodegradation of NP at lower substrate concentration and light intensity, and vice versa. Direct photodegradation of NP declined sharply with spectral radiation attenuation of UV region, when HS-mediated photosensitization predominantly accounted for the photodegradation. The direct photodegradation was ascribed to decomposition of excited triplet state of naproxen (3NP∗) and self-sensitization effect involving 1O2. The FA-mediated photodegradation was mainly attributed to 1O2 oxidation in aerated solution. These findings are important for assessing the competitive effects of humic substances on the photodegradation of pollutants under various conditions in natural waters.


Assuntos
Naproxeno/química , Luz Solar , Poluentes Químicos da Água/química , Benzopiranos/química , Substâncias Húmicas/análise , Luz , Modelos Químicos , Naproxeno/análise , Fotólise , Oxigênio Singlete , Poluentes Químicos da Água/análise
19.
Artigo em Inglês | MEDLINE | ID: mdl-28686186

RESUMO

A new analytical method coupling a (off-line) solid-phase microextraction with an on-line capillary electrophoresis (CE) sample enrichment technique was developed for the analysis of ketoprofen, naproxen and clofibric acid from water samples, which are known as contaminants of emerging concern in aquatic environments. New solid-phase microextraction fibers based on physical coupling of chromatographic supports onto epoxy glue coated needle were studied for the off-line preconcentration of these micropollutants. Identification and quantification of such acidic drugs were done by capillary zone electrophoresis (CZE) using ultraviolet diode array detection (DAD). Further enhancement of concentration sensitivity detection was achieved by on-line CE "acetonitrile stacking" preconcentration technique. Among the eight chromatographic supports investigated, Porapak Q sorbent showed higher extraction and preconcentration capacities. The screening of parameters that influence the microextraction process was carried out using a two-level fractional factorial. Optimization of the most relevant parameters was then done through a surface response three-factor Box-Behnken design. The limits of detection and limits of quantification for the three drugs ranged between 0.96 and 1.27 µg∙L-1 and 2.91 and 3.86 µg∙L-1, respectively. Recovery yields of approximately 95 to 104% were measured. The developed method is simple, precise, accurate, and allows quantification of residues of these micropollutants in Genil River water samples using inexpensive fibers.


Assuntos
Ácido Clofíbrico/análise , Cetoprofeno/análise , Naproxeno/análise , Microextração em Fase Sólida/instrumentação , Poluentes Químicos da Água/análise , Eletroforese Capilar/instrumentação , Eletroforese Capilar/métodos , Microextração em Fase Sólida/métodos
20.
Environ Monit Assess ; 189(7): 348, 2017 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-28639109

RESUMO

The present paper reports a detailed study that is based on the monitoring of naproxen, ibuprofen, and diclofenac in Mbokodweni River and wastewater treatment plants (WWTPs) located around the city of Durban in KwaZulu-Natal Province of South Africa. Target compounds were extracted from water samples using a multi-template molecularly imprinted solid-phase extraction prior to separation and quantification on a high-performance liquid chromatography equipped with photo diode array detector. The analytical method yielded the detection limits of 0.15, 1.00, and 0.63 µg/L for naproxen, ibuprofen, and diclofenac, respectively. Solid-phase extraction method was evaluated for its performance using deionized water samples that were spiked with 5 and 50 µg/L of target compounds. Recoveries were greater than 80% for all target compounds with RSD values in the range of 4.1 to 10%. Target compounds were detected in most wastewater and river water samples with ibuprofen being the most frequently detected pharmaceutical. Maximum concentrations detected in river water for naproxen, ibuprofen, and diclofenac were 6.84, 19.2, and 9.69 µg/L, respectively. The concentrations of target compounds found in effluent and river water samples compared well with some studies. The analytical method employed in this work is fast, selective, sensitive, and affordable; therefore, it can be used routinely to evaluate the occurrence of acidic pharmaceuticals in South African water resources.


Assuntos
Diclofenaco/análise , Ibuprofeno/análise , Naproxeno/análise , Rios/química , Águas Residuárias/química , Poluentes Químicos da Água/análise , Cromatografia Líquida de Alta Pressão , Cidades , Relação Dose-Resposta a Droga , Monitoramento Ambiental/métodos , Extração em Fase Sólida/métodos , África do Sul
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