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1.
Chemosphere ; 258: 127371, 2020 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-32554020

RESUMO

Fungal laccase has aroused great concern in rapidly removing estrogens because of its ability to accelerate humification and oligomerization. Here, the effect of two humic acids (HAs) on the reaction kinetics and products distribution of 17α-ethynylestradiol (EE2) in laccase-initiated humification and coupling was systematically elucidated. Laccase from Trametes versicolor exhibited over 98.3% removal rate for EE2 at pH 5.0 within 120 min, while HAs invariably restrained EE2 transformation by competing with target-substrate for the enzymatic catalytic center. EE2 removal followed pseudo-first-order kinetics, and the rate constant was decreased markedly with increasing concentration of two HAs (0-60 mg L-1). Additionally, laccase heightened the aromaticity and humification degrees (A250 nm/A365 nm ratio) of HAs probably due to the formation of new humic polymers such as (HA)m and/or (HA)m-(EE2)n (m and n represent the number of HA and EE2 units, respectively). Three major EE2 oligomers were identified, in accordance with a mechanism involving the phenoxy radical-driven polymerization to yield a wide variety of self-coupling products. Notably, HAs diminished the extent of EE2 self-coupling but aggrandized the cross-coupling between EE2 and HAs, and the inhibition degree of EE2 self-coupling increased with the concentration of HAs. One major reason is EE2 could be covalently incorporated into humic molecules to produce (HA)m-(EE2)n cross-coupling products via radical-caused C-C, C-O-C, and/or C-O-C bonds, thereby reducing EE2 self-oligomerization. These findings highlight that HAs play a vital role in the fungal laccase-induced humification and oligomerization of EE2, which obviously alter the geochemical fate and transport of EE2 in natural aquatic ecosystems.


Assuntos
Etinilestradiol/química , Substâncias Húmicas/análise , Lacase/química , Trametes/enzimologia , Poluentes Químicos da Água/química , Catálise , Ecossistema , Estrogênios , Etinilestradiol/análise , Cinética , Modelos Químicos , Fenóis/química , Poluentes Químicos da Água/análise , Purificação da Água/métodos
2.
J Environ Sci (China) ; 89: 1-8, 2020 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-31892382

RESUMO

Increasing concerns have been raised on endocrine disrupting chemicals like the sex hormone 17α-ethinylestradiol (EE2), the more since traditional wastewater (WW) treatments appear to be ineffective for their removal. The efficacy of the relatively novel disinfectant peracetic acid (PAA) in EE2 removal was evaluated, as well as its potential effects on WW quality parameters. The treatments tested for EE2 removal were also evaluated in terms of toxicity, through the determination of biochemical responses (antioxidant enzymes, lipid peroxidation and vitellogenin induction) using zebrafish (Danio rerio) as a biological model. PAA contact times less than 20 min appeared insufficient regardless of the PAA dose tested, but a 100% EE2 removal was attained at a PAA concentration of 15 mg/L with a contact time of 20 min. Total suspended solids, chemical oxygen demand and pH in PAA treatments remained well within levels set in European legislation for WW discharge. EE2 induced significant increased vitellogenin (VTG) levels in both female and male fish, indicating increased estrogenic activity, especially in males suggesting an endocrine disruption effect. With the addition of PAA (15 mg/L), however, VTG levels in both sexes returned to control values. Although this PAA treatment showed increased levels of the antioxidant enzyme catalase, the lipid peroxidation levels were similar or even lower than in controls. Overall the results suggest that the use of PAA appears a promising way forward as a less toxic alternative to chlorine disinfection with high efficiency in the removal of EDC like EE2.


Assuntos
Etinilestradiol/química , Ácido Peracético/química , Eliminação de Resíduos Líquidos/métodos , Águas Residuárias , Poluentes Químicos da Água/química , Anticoncepcionais , Estradiol , Etinilestradiol/análise , Ácido Peracético/análise , Vitelogeninas , Poluentes Químicos da Água/análise
3.
Environ Pollut ; 254(Pt A): 112959, 2019 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-31377327

RESUMO

Humic acids (HAs) have been shown to dominate the photodegradation of steroid estrogens in natural waters. Nevertheless, how the photosensitizing ability of HAs relates to their structural and optical characteristics remains largely unknown. In this study, 17α-ethynylestradiol (EE2) was selected as a model compound to study to what extent easily-measurable characteristics of HAs might be used to predict their photosensitization potency. HAs were extracted from sediments of two different sources, and then subjected to structural and optical properties characterization using elemental analyzer, UV-vis spectroscopy and fluorescence spectroscopy. Photochemical experiments show that the HAs from the two sources can effectively meditate EE2 photodegradation. Although with drastically different structural and optical properties, the photosensitizing ability of these HAs towards EE2 can be well described by simple linear regressions using a spectroscopic index, the spectral slope ratio (SR). This optical indicator is correlated with various physicochemical properties of HAs, including the molecular weight, lignin content, charge-transfer interaction potential, photobleaching extent and sources. No universal prediction model could be established for predicting EE2 photodegradation kinetics on the basis of SR, but in specific waters SR could be a powerful indictor for predicting the EE2 photodegradation sensitized by HAs.


Assuntos
Etinilestradiol/química , Substâncias Húmicas/análise , Poluentes Químicos da Água/química , Estrogênios , Etinilestradiol/análise , Cinética , Modelos Químicos , Peso Molecular , Fotodegradação , Processos Fotoquímicos , Fotólise , Espectrometria de Fluorescência , Poluentes Químicos da Água/análise
4.
Sci Total Environ ; 686: 959-967, 2019 Oct 10.
Artigo em Inglês | MEDLINE | ID: mdl-31200312

RESUMO

Animal manure application in agricultural land has caused the release of steroid estrogens in the soil environment and further movement to aquatic systems. The objective of this study was to investigate the effects of biochar addition on sorption-desorption and dissipation behaviors of 17α­ethinylestradiol (EE2) in two different textured soils. A Commerce sandy loam and a Shakey clay were selected and subjected to sterilization. Soil samples with and without sterilization were reacted with a series of EE2 solutions of different concentrations for sorption followed by desorption and quantification using HPLC-MS/MS. Long-term dissipation of EE2 in the same soils was also evaluated over a 30-d incubation. Biochar amendment increased the maximum EE2 sorption capacity but decreased its water desorption in both sandy loam and clay soils. On other hand, biochar addition increased the Koc in the clay soil which had low EE2 sorption efficiency but decreased Koc in the sandy loam which had high EE2 sorption efficiency. Biochar did significantly increase both desorbable and non-extractable fractions of EE2, while it reduced the bioavailability of EE2 to microbial degradation. The dissipation of EE2 in non-sterilized soils fit to the first-order kinetic model, whereas it was better described by zero-order kinetic for sterilized soil. Biochar increased the half-life of EE2 dissipation in non-sterilized Commerce sandy loam soil by 48% (from 3.63 to 5.37 d) and in non-sterilized Sharkey clay soil by 67% (from 2.28 to 3.81 d). Overall, this study demonstrated positive impacts of biochar on the retention of estrogen hormones in soils.


Assuntos
Carvão Vegetal/química , Recuperação e Remediação Ambiental/métodos , Etinilestradiol/química , Poluentes do Solo/química , Argila/química , Solo/química , Poluentes do Solo/análise
5.
Environ Sci Pollut Res Int ; 26(28): 28419-28428, 2019 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-31028620

RESUMO

Yeast biomass from ethanol industry (YB) was evaluated as a biosorbent to 17α-ethinylestradiol (EE) alone and along with estrone (EST). This material is rich in sorption sites and has a good cost-benefit ratio, since it is an industrial residue largely produced (around 30 g for each liter of ethanol). A 2k-factorial design was carried out to evaluate the sorption capacity of YB for EE considering the variables pH, biosorbent dose (BD), and ionic strength (IS), at two hormone concentration (HC) levels. The best conditions assessed for individual EE adsorption (pH = 10, IS = 0.1 mol/L, and BD = 0.5 mg/L) were also established for adsorption carried out in the presence of EST. Individuals EE and EST experimental sorption capacities (SCexp) were, respectively, 24.50 ± 0.07 and 0.80 ± 0.07 mg/g, fairly similar to Qmax (EE, 21.41 ± 1.27 mg/g; EST, 0.93 ± 0.075 mg/g) from Langmuir model. The Freundlich model best fitted the experimental data for EE adsorption (r2 = 0.9925; χ2 = 0.5575). The study carried out in the presence of EST showed an associative/competitive sorption process between EE and EST, which may be explained by their similar chemical structures and organic carbon-water partition coefficients Koc.


Assuntos
Estrona/química , Etinilestradiol/metabolismo , Saccharomyces cerevisiae/química , Adsorção , Biomassa , Estrona/metabolismo , Etanol/química , Etinilestradiol/química , Concentração de Íons de Hidrogênio , Cinética , Concentração Osmolar , Termodinâmica
6.
Prep Biochem Biotechnol ; 49(4): 375-383, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-30777480

RESUMO

Laccase extract (LE) from Pycnoporus sanguineus was immobilized on calcium and copper alginate-chitosan beads and applied for the removal of 17α-ethinylestradiol (EE2). Effects of immobilization conditions such as: sodium alginate (SA) concentration; LE/SA ratio and chitosan/ion (Ca+2 or Cu+2) ratio on the immobilization yield were investigated. Immobilized LE on Ca-beads and Cu-beads was then used to degrade an EE2 solution. The optimal conditions for LE immobilization on Ca-beads were: 1.5% (w/v) SA, 1:5 (v/v) LE/SA and 3:7 (v/v) chitosan/ion (Ca+2). The optimal conditions for immobilization on Cu-beads were 2.0% (w/v) SA, 0.5:5 (v/v) LE/SA and 3:7 (v/v) chitosan/ion (Cu+2). The best result was obtained for immobilized LE on Ca-beads in buffer-absent medium. Furthermore, the immobilized enzyme was reused in five cycles for EE2 removal. The formation of EE2 dimers by LE treatment has been demonstrated by electrospray ionization coupled to time of flight mass spectrometer (ESI-TOF-MS). The results evidenced that immobilized LE in alginate-chitosan-divalent cation bead is an effective alternative for EE2 removal.


Assuntos
Alginatos/química , Quitosana/química , Recuperação e Remediação Ambiental/métodos , Etinilestradiol/isolamento & purificação , Lacase/química , Gerenciamento de Resíduos/métodos , Enzimas Imobilizadas/química , Etinilestradiol/química , Porosidade , Pycnoporus/enzimologia , Estereoisomerismo
7.
Ecotoxicol Environ Saf ; 171: 313-320, 2019 Apr 30.
Artigo em Inglês | MEDLINE | ID: mdl-30612019

RESUMO

Photolysis and microbial activity are relatively obvious in shallow, eutrophic waters with low dissolved oxygen content. Ubiquitous humic acid (HA) can act as electron acceptor and be reduced by bacterial under such conditions, and the reduced form of humic acid (RHA) plays an important role in the photolysis contaminants. In this study, anaerobic 17α-ethinylestradiol (EE2) photodegradation was performed along with biodegradation by Shewanella putrefaciens mediated by HA. The mechanism of such coupled photolysis and biodegradation of EE2 was thus elucidated. The removal rate in such coupled degradation in the presence of 10 mgC L-1 of HA at pH 8.0 was greater than that of either photolysis or biodegradation alone. HA which had been reduced in a double-chamber microbial fuel cell showed better promotion to EE2 photodegradation than fresh HA. Reactive species scavenging experiments indicated that hydroxyl radical and excited triplet states of HA were primary contributors to EE2 photodegradation in anaerobic conditions. More of them were produced from RHA than from pristine HA. Besides, the degraded EE2 solutions inhibited the proliferation of MCF-7 human cancer Cells. These findings improve our understanding of the environmental transformation of EE2 in the shallow, anoxic waters.


Assuntos
Biodegradação Ambiental , Etinilestradiol/química , Substâncias Húmicas/microbiologia , Fotólise , Shewanella putrefaciens , Poluentes Químicos da Água/química , Proliferação de Células/efeitos dos fármacos , Etinilestradiol/análise , Humanos , Concentração de Íons de Hidrogênio , Células MCF-7/fisiologia , Oxirredução , Poluentes Químicos da Água/análise
8.
Environ Sci Pollut Res Int ; 26(33): 34018-34026, 2019 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-30225689

RESUMO

In this work, TiO2 (B) nano-belts were synthesized by hydrothermal method under stirring, and static conditions and preparation conditions were optimized. The prepared materials were characterized by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), photoluminescence spectroscopy (PL), and N2 adsorption/desorption measurement. The photocatalytic performance was evaluated by removing synthetic estrogen 17α-ethynylestradiol (EE2), which is the most potent endocrine-disrupting chemical. The results show that the TiO2 nano-belt possesses pure metastable monoclinic TiO2 (B) and has uniform nano-belt shape with 80~120-nm diameters and 62.904 m2 g-1 of specific surface area. Under the best optimal preparation conditions (0.5 g P25, 20 mL 10 mol L-1 NaOH, hydrothermal temperature 180 °C for 18 h under stirring, 400 °C calcination for 2 h), the TiO2 (B) has better catalytic activity with 100.00% removal rate towards 3 mg L-1 EE2 in 120 min. The removal rates of EE2 over catalyst which was prepared under static condition and P25 are 74.66% and 70.71%, respectively. The photocatalytic degradation rate constant of TiO2 (B) prepared under stirring condition (0.0379 min-1) is 4.51 times and 8.42 times than those of TiO2 prepared under static condition (0.0084 min-1) and P25 (0.0045 min-1). The excellent photocatalytic activity is mainly ascribed to longer one-dimensional nano-belt structure and effective suppression of photo-produced electron-hole.


Assuntos
Etinilestradiol/química , Poluentes Químicos da Água/química , Purificação da Água/métodos , Adsorção , Catálise , Etinilestradiol/análise , Microscopia Eletrônica de Varredura , Microscopia Eletrônica de Transmissão , Titânio/química , Poluentes Químicos da Água/análise , Difração de Raios X
9.
Org Biomol Chem ; 17(3): 509-518, 2019 01 16.
Artigo em Inglês | MEDLINE | ID: mdl-30569048

RESUMO

Three new luminescent conjugates between dinuclear rhenium complexes and an estradiol, namely E2-Re, are described. The derivatives have the general formula [Re2(µ-Cl)2(CO)6(µ-R-pydz-17α-ethynylestradiol)] (R-pydz = functionalized 1,2-pyridazine), where the estradiol moiety is covalently bound to the ß position of the pyridazine ligand. Different synthetic pathways are investigated, including the inverse-type [4 + 2] Diels Alder cycloaddition reaction between the electron poor 1,2,4,5-tetrazine and 17α-ethynylestradiol for the synthesis of E2-Re1. The three E2-Re conjugates are purified on silica gel and isolated in a spectroscopically pure form in moderate to good yields (28-50%). All the E2-Re conjugates are comprehensively characterized from the spectroscopic and photophysical points of view. Cellular internalization experiments on human MCF-7 and 231 cells are also reported, displaying interesting staining differences depending on the nature of the spacer linking the estradiol unit to the organometallic fragment. Furthermore, the suitability of these conjugates to also stain simple multicellular organisms, i.e. Ciona intestinalis embryos and larvae at different stages of development, is reported here for the first time.


Assuntos
Complexos de Coordenação/química , Etinilestradiol/química , Substâncias Luminescentes/química , Imagem Óptica , Rênio/química , Animais , Linhagem Celular Tumoral , Ciona intestinalis/embriologia , Complexos de Coordenação/síntese química , Reação de Cicloadição , Relação Dose-Resposta a Droga , Humanos , Substâncias Luminescentes/síntese química , Células MCF-7 , Estrutura Molecular , Relação Estrutura-Atividade
10.
Chemosphere ; 216: 59-68, 2019 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-30359917

RESUMO

17α-Ethinylestradiol (EE2) and bisphenol A (BPA) are highly toxic and widely detected endocrine-disrupting compounds (EDCs) throughout the world in surface waters. Adsorption is an effective way to remove EE2 and BPA from water. However, it is difficult to clearly explain the mechanism of adsorption theoretically only through classic adsorption models. In order to insight into the adsorption of EE2 and BPA, site energy distribution (SED) theory was introduced to investigate the adsorption of EE2 and BPA on heterogeneous surfaces. EE2 and BPA were adsorbed on un-anthracite (unmodified anthracite) and 4K anthracite (4 mol L-1 KOH-modified anthracite) in single- and bi-component systems under various temperatures and pHs. The results suggested that EE2 and BPA molecules first occupied the high-energy adsorption sites and then spread to low-energy adsorption sites. There were more high-energy sites on 4K anthracite, resulting in a higher adsorption capability for EE2 and BPA. Besides, increasing temperature and acidic environment were conducive to the EE2 and BPA adsorption. SED analyses indicated that, in neutral solutions, π-π electron donor-acceptor (EDA) interaction might be the primary mechanism for BPA adsorption, while ligand exchange, hydrogen bonds, and π-π EDA interaction might simultaneously work in the adsorption of EE2. It was possible that EE2 molecule was near perpendicular to surface, while BPA molecule was parallel to surface, resulting in the higher adsorption capacities of EE2. However, compared with EE2, BPA had outstanding competitive advantages in bi-component system because of the stronger π-π EDA interaction between BPA and anthracite.


Assuntos
Compostos Benzidrílicos/análise , Carvão Mineral , Disruptores Endócrinos/análise , Etinilestradiol/análise , Fenóis/análise , Adsorção , Compostos Benzidrílicos/isolamento & purificação , Sítios de Ligação , Disruptores Endócrinos/química , Disruptores Endócrinos/isolamento & purificação , Etinilestradiol/química , Etinilestradiol/isolamento & purificação , Concentração de Íons de Hidrogênio , Fenóis/isolamento & purificação , Temperatura , Poluentes Químicos da Água/química
11.
AAPS PharmSciTech ; 19(8): 3850-3858, 2018 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-30280353

RESUMO

Chlormadinone acetate (CMA) is a derivative of the naturally secreted hormone progesterone and exhibits reliable contraceptive and non-contraceptive benefits. Although the marketed product of CMA as oral tablets under the trade name Belara® has been highly successful, there is still room for further improvements in oral bioavailability and a reduction in the clinical dose to decrease related adverse effects. In the current study, a CMA-based self-microemulsifying drug delivery system (SMEDDS) was developed using 32% ethyl oleate as an oil phase, 40% Tween-80 as a surfactant, and 12% Transcutol P combined with 16% PEG400 as a cosurfactant, resulting in spherical droplets with a z-average particle size of 38.92 nm and an average zeta potential of - 3.18 mv. The in vitro release rate of CMA from CMA-SMEDDS in different media (distilled water, HCl solution at pH 1.2, phosphate buffers at pH 4.5 and pH 6.8) was significantly faster than that from Belara® in the first 15 min. A pharmacokinetic study in rats showed that the Cmax and AUC of CMA-SMEDDS were significantly higher (P < 0.01) than those of Belara®, with a 1.98-fold increase in oral bioavailability. In comparison with Belara®, the developed CMA-SMEDDS showed promising release profiles both in vitro and in vivo, which could potentially be useful in enhancing oral bioavailability and reducing the clinical dose of CMA.


Assuntos
Acetato de Clormadinona/administração & dosagem , Sistemas de Liberação de Medicamentos/métodos , Emulsificantes/administração & dosagem , Administração Oral , Animais , Disponibilidade Biológica , Acetato de Clormadinona/química , Acetato de Clormadinona/metabolismo , Relação Dose-Resposta a Droga , Emulsificantes/química , Emulsificantes/metabolismo , Etinilestradiol/administração & dosagem , Etinilestradiol/química , Etinilestradiol/metabolismo , Feminino , Tamanho da Partícula , Ratos , Ratos Sprague-Dawley , Solubilidade , Tensoativos/administração & dosagem , Tensoativos/química , Tensoativos/metabolismo
12.
Int J Pharm ; 548(1): 689-697, 2018 Sep 05.
Artigo em Inglês | MEDLINE | ID: mdl-30016672

RESUMO

Steroid molecules have a long history of incorporation into silicone elastomer materials for controlled release drug delivery applications. Previously, based on in vitro release testing and drug content analysis, we demonstrated indirectly that the contraceptive progestin levonorgestrel (LNG) chemically and irreversibly binds to addition cure silicone elastomers, presumably via a hydrosilylation reaction between the levonorgestrel ethynyl group and the hydrosilane groups in the poly(dimethylsiloxane-co-methylhydrosiloxane) crosslinker of the silicone elastomer. Here, for the first time, we report that solid state 13C nuclear magnetic resonance (NMR) spectroscopy provides direct evidence for the irreversible binding of ethinyl estradiol (EE) - an estrogenic steroid molecule also containing an ethynyl functional group - to an addition cure silicone elastomer. By preparing silicone elastomer samples containing 13C-labelled EE, signals in the NMR spectra could readily be assigned to both the free and bound EE. Additional depolymerisation studies, performed on an addition cure silicone elastomer system from which the unbound EE fraction was completely extracted, further confirmed the presence of bound EE through the formation of coloured reaction mixtures resulting from the reaction of bound EE and trifluoroacetic acid (TFA). These methods will be particularly useful in the ongoing development of new steroid-releasing silicone drug delivery devices, including various vaginal ring devices for contraception, HIV prevention and multipurpose prevention technology applications.


Assuntos
Dispositivos Anticoncepcionais Femininos , Sistemas de Liberação de Medicamentos , Estrogênios/química , Etinilestradiol/química , Elastômeros de Silicone/química , Espectroscopia de Ressonância Magnética Nuclear de Carbono-13 , Ácido Trifluoracético/química
13.
J Proteome Res ; 17(8): 2590-2599, 2018 08 03.
Artigo em Inglês | MEDLINE | ID: mdl-29897771

RESUMO

Catechol estrogens (CEs) are metabolic electrophiles that actively undergo covalent interaction with cellular proteins, influencing molecular function. There is no feasible method to identify their binders in a living system. Herein, we developed a click chemistry-based approach using ethinylestradiol (EE2) as the precursor probe coupled with quantitative proteomics to identify protein targets of CEs and classify their binding strengths. Using in situ metabolic conversion and click reaction in liver microsomes, CEs-protein complex was captured by the probe, digested by trypsin, stable isotope labeled via reductive amination, and analyzed by liquid chromatography-mass spectrometry (LC-MS). A total of 334 liver proteins were repeatedly identified ( n ≥ 2); 274 identified proteins were classified as strong binders based on precursor mass mapping. The binding strength was further scaled by D/H ratio (activity probe/solvent): 259 strong binders had D/H > 5.25; 46 weak binders had 5.25 > D/H > 1; 5 nonspecific binders (keratins) had D/H < 1. These results were confirmed using spiked covalent control (strong binder) and noncovalent control (weak binder), as well as in vitro testing of cytochrome c (D/H = 5.9), which showed covalent conjugation with CEs. Many identified strong binders, such as glutathione transferase, catechol-O-methyl transferase, superoxide dismutase, catalase, glutathione peroxidase, and cytochrome c, are involved in cellular redox processes or detoxification activities. CE conjugation was shown to suppress the superoxide oxidase activity of cytochrome c, suggesting that CEs modification may alter the redox action of cellular proteins. Due to structural similarity and inert alkyne group, EE2 probe is very likely to capture protein targets of CEs in general. Thus, this strategy can be adopted to explore the biological impact of CEs modification in living systems.


Assuntos
Estrogênios de Catecol/antagonistas & inibidores , Proteínas/farmacologia , Proteômica/métodos , Animais , Cromatografia Líquida , Química Click/métodos , Etinilestradiol/química , Espectrometria de Massas , Microssomos Hepáticos/química , Sondas Moleculares , Ligação Proteica , Ratos
14.
J Hazard Mater ; 356: 9-16, 2018 08 15.
Artigo em Inglês | MEDLINE | ID: mdl-29803032

RESUMO

Ubiquitous natural organic matter (NOM) plays a crucial role in the peroxidase-mediated transformation of phenolic pollutants in aquatic environment. As a poorly defined polydispersed mixture of assorted organic substances with wide molecular weight (MW) distribution, NOM has far prevented researchers from finding out the primarily responsible components for the specific effect. In this work, MW fractionated NOMs (Mf-NOMs) were used to investigate their roles on horseradish peroxidase (HRP)-mediated transformation of 17α-ethinylestradiol (EE2). The removal rate of EE2 was restrained in the presence of pristine or Mf-NOMs, and the inhibitory mechanism was MW-dependent. Low Mf-NOMs restrained the enzymatic reaction by acting as competitive substrates, while high Mf-NOMs retained freely dissolved EE2 which reduced its availability for enzymatic reaction. The contribution of these two processes to the inhibition induced by pristine NOM was further quantified and found to be relevant to the reaction conditions, especially EE2 concentration. The findings of this work reveal more complex influences of NOM on the enzymatic reaction than ever demonstrated, which aids in understanding the fate of EE2 and other congener contaminants in natural and municipal water.


Assuntos
Etinilestradiol/química , Peroxidase do Rábano Silvestre/química , Substâncias Húmicas , Poluentes Químicos da Água/química , Adsorção , Peso Molecular , Purificação da Água/métodos
15.
An Acad Bras Cienc ; 90(2): 1327-1336, 2018.
Artigo em Inglês | MEDLINE | ID: mdl-29768570

RESUMO

One of the most prominent fields of environmental chemistry is the study and the removal of micro-pollutants from aqueous matrices. Analytical techniques for their identification and quantification are becoming more sensitive and comprehensive and, as a result, an increasing number of drugs have been detected in environmental samples. However, the literature shows that conventional treatments for drinking water and wastewater are not sufficient for remove these compounds. This study aims to check whether the process of hydrothermal carbonization (CHT) is effective in removing the synthetic sex hormones: ethinyl estradiol, gestodene and cyproterone acetate from aqueous samples. The system used in CHT basically consists of a pressurized reactor made of stainless steel and solutions of compounds of interest, both individual and mixed, with a concentration of 1.0 µg.L-1 and a pH range of 2.0 to 3.0. The maximum surface temperature in the reactor was about 180 °C, the internal pressure was 20 bar with 90 minutes for the reaction. Four experiments were conducted, one for each hormone and one with the three hormones together. In individual tests removal of the compounds was found to be 99.8% for ethinyl estradiol, 99.3% for gestodene and 100% for cyproterone acetate. For a mixture of the hormones treated under the same conditions, the mean values of CHT-removal of Ethinylestradiol, Gestodene and Cyproterone Acetate were 99.60%, 96.80% and 68.90%, respectively. The impact of the matrix effect may have affected the efficiency of the hormone removal process by CHT.


Assuntos
Carbono , Acetato de Ciproterona/química , Recuperação e Remediação Ambiental/métodos , Etinilestradiol/química , Temperatura Alta , Norpregnenos/química , Cromatografia Líquida
16.
Water Res ; 137: 251-261, 2018 06 15.
Artigo em Inglês | MEDLINE | ID: mdl-29550728

RESUMO

The photochemical conversion and microbial transformation of pollutants mediated by dissolved organic matter (DOM), including 17α-ethinylestradiol (EE2), are often accompanied in natural water. However, there are few studies to explore the connection and mechanism between the two processes. This research aims to investigate the mechanism of DOM after electrochemically modification mediated EE2 combining photodegradation and biodegradation in the environment and it want to explain the natural phenomena of DOM after electrochemical advanced treatment entering the water environment mediated EE2 natural degradation. The results showed that combining photodegradation with biodegradation rates of EE2 mediated by DOM and electrochemically modified DOM (E-DOM) were promoted obviously. The efficiency of EE2 biodegradation was shown to be strongly correlated with electron accepting capacity (EAC) of DOM. Electrochemical modification can increase the EAC of DOM leading to EE2 biodegradation accelerated, and it also can form more triplet-state DOM moieties to promote the EE2 photodegradation in irradiation conditions, due to the increasing of quinone-type structures in DOM. Moreover, cell polymeric secretion (CPS) secreted from the microorganism could be stimulated to an excited state by irradiation, and that also accelerated EE2 degradation. Photolysis combined with biochemical degradation yielded less toxic degradation products. This study shows that the emission of DOM in wastewater after electrochemical treatment could accelerate estrogen degradation and play a positive role on the pollutant transformation in the environment.


Assuntos
Etinilestradiol , Poluentes Químicos da Água , Biodegradação Ambiental , Técnicas Eletroquímicas , Etinilestradiol/química , Etinilestradiol/metabolismo , Etinilestradiol/efeitos da radiação , Fotólise , Poluentes Químicos da Água/química , Poluentes Químicos da Água/metabolismo , Poluentes Químicos da Água/efeitos da radiação
17.
Biomacromolecules ; 19(2): 652-661, 2018 02 12.
Artigo em Inglês | MEDLINE | ID: mdl-29366320

RESUMO

A wood based yarn platform for capturing pharmaceutical molecules from water was developed. Cellulose fiber yarns were modified with cyclodextrins, and the capture of 17α-ethinyl estradiol (EE2), a synthetic estrogen hormone used as contraceptive, from water was tested. The yarns were prepared by spinning a deep eutectic solution (DES) of cellulose in choline chloride-urea. Despite their high porosity and water sorption capacity (5 g/g), the spun fiber yarns displayed high wet strength, up to 60% of that recorded in dry condition (128 MPa with 17% strain at break). Cyclodextrin irreversible attachment on the yarns was achieved with adsorbed chitosan and the conjugation reactions and capture of EE2 by the cyclodextrin-modified cellulose were confirmed via online detection with Surface Plasmon Resonance (SPR). The facile synthesis of the bioactive yarns and EE2 binding capacity from aqueous matrices (as high as 2.5 mg/g) indicate excellent prospects for inexpensive platforms in disposable affinity filtration. The study presents a strategy to produce a wood fiber based yarn to be used as a platform for human and veterinary pharmaceutical hormone capture.


Assuntos
Etinilestradiol/química , Ressonância de Plasmônio de Superfície , Madeira/química , beta-Ciclodextrinas/química , Animais , Humanos
18.
Bioresour Technol ; 249: 284-289, 2018 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-29054057

RESUMO

Removal of endocrine-disrupting chemical ethinylestradiol (EE2) from wastewater by microalgal mutant Chlorella PY-ZU1 under 15% CO2 were investigated. Moreover, the effects of EE2 on microscopic structure and antioxidation ability of microalgal cells were determined. EE2 concentrations in range of 0.01-5 mg L-1 stimulated microalgal growth. Increasing the original EE2 concentration from 0 to 5 mg L-1 increased the cell fractal dimension from 1.38 to 1.59 and reduced the cell size from 5.18 to 3.41 µm. Meanwhile, superoxide dismutase and catalase activities, which represented cellular antioxidant capacity, first increased from 44.59 and 0.54 U mL-1 to peak values of 65.57 and 1.49 U mL-1, respectively, and then correspondingly decreased to 34.36 and 0.36 U mL-1. Malondialdehyde content that indicated the cell oxidation damage degree first decreased from 2.57 to 2.03 nmol mL-1, then increased to 2.59 nmol mL-1. The highest EE2 removal efficiency of 94% by Chlorella PY-ZU1 was achieved at the original EE2 concentration of 5 mg L-1.


Assuntos
Chlorella , Etinilestradiol/química , Águas Residuárias , Dióxido de Carbono , Microalgas , Purificação da Água
19.
J Hazard Mater ; 344: 707-715, 2018 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-29154096

RESUMO

Many studies have addressed the desorption and mobilization performances of sorbed contaminants affected by different rhamnolipidic biosurfactants. Study results have been mixed and complicated. Rhamnolipids are always microbial produced with variable homologues. In this study, two representative rhamnolipidic fractions (i.e., RL-F1 and RL-F2, which are mono- and di-rhamnolipids, respectively) were investigated and compared to determine their influence on 17α-ethynylestradiol (EE2) distribution within sediment-water sorption and desorption systems. In general, the coexistence of RL-F1 and EE2 enhanced EE2 sorption in a wider monorhamnolipidic dosage range when freshly treated sorbate was used. The sorbed EE2 concentration decreased as the RL-F1 dosage increased in the aged sorbate desorption systems. However, RL-F2 facilitated EE2 mobilization in both sorption and desorption processes. Experimental data were estimated using a conceptual model that considered the sorbed rhamnolipids and aqueous micelles for organic partitioning. The model results indicated that the rhamnolipid type is an important factor influencing organic distribution, in addition to sorbate aging process and sediment characteristics. The use of a rhamnolipidic mixture containing both mono- and di-rhamnosyl components may not achieve the desired effect when the biosurfactant-enhanced mobilization or immobilization approach is selected. These results are significant for selecting and applying rhamnolipids to remediate contaminants.


Assuntos
Etinilestradiol/química , Sedimentos Geológicos/química , Glicolipídeos/química , Tensoativos/química , Poluentes Químicos da Água/química , Adsorção
20.
Biomed Chromatogr ; 32(5): e4165, 2018 May.
Artigo em Inglês | MEDLINE | ID: mdl-29228469

RESUMO

A selective, sensitive and rapid ultra-performance liquid chromatography tandem mass spectrometry method was developed and validated for the simultaneous determination of etonogestrel (ENG) and ethinyl estradiol (EE) in human plasma. The analytes and their deuterated internal standards, ENG-d7 and EE-d4, were extracted from plasma samples by solid-phase extraction on HyperSep™ Retain PEP cartridges. The chromatographic analysis was performed on an Acquity UPLC HSS Cyano column, 100 Å (50 × 2.1 mm, 1.8 µm), column using gradient mobile phase, acetonitrile and 2.0 mm ammonium trifluoroacetate at 0-1.7 min (65:35, v/v) and 1.8-2.7 min (95:5, v/v) with 0.250 mL/min flow rate. Analytes and IS protonated precursor → product ion transitions (ENG, m/z 325.2 → 257.2; EE, m/z 530.2 → 171.2; ENG-d7, m/z 332.2 → 263.2; EE-d4, m/z 534.2 → 171.2) were monitored on a Triple Quadrupole Mass spectrometer (TQMS), operating in multiple reaction monitoring and positive ionization mode. The calibration curves were established at 10.00-2500 pg/mL for ENG and 1.500-150.0 pg/mL for EE with a correlation coefficient (r2 ) ≥0.9996 for both. The validated method was successfully applied to support a bioequivalence study of 0.15 mg ENG and EE 0.03 mg tablet formulation, administered in 24 healthy Indian females. Method reliability was assessed by reanalysis of 94 incurred study samples.


Assuntos
Cromatografia Líquida de Alta Pressão/métodos , Desogestrel/sangue , Desogestrel/farmacocinética , Etinilestradiol/sangue , Etinilestradiol/farmacocinética , Espectrometria de Massas em Tandem/métodos , Desogestrel/química , Etinilestradiol/química , Feminino , Humanos , Limite de Detecção , Modelos Lineares , Reprodutibilidade dos Testes
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