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1.
Chemosphere ; 251: 126364, 2020 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-32443231

RESUMO

This study is among the first to systematically study the electrochemical reduction of nitrate on boron-doped diamond (BDD) films with different surface terminations and boron-doping levels. The highest nitrate reduction efficiency was 48% and the highest selectivity in the production of nitrogen gas was 44.5%, which were achieved using a BDD electrode with a hydrogen-terminated surface and a B/C ratio of 1.0%. C-H bonds served as the anchor points for attracting NO3- anions close to the electrode surface, and thus accelerating the formation of NO3-(ads). Compared to oxygen termination, hydrogen-terminated BDD exhibited higher electrochemical reactivity for reducing nitrate, resulting from the formation of shallow acceptor states and small interfacial band bending. The hydrophobicity of the hydrogen-terminated BDD inhibited water electrolysis and the subsequent adsorption of atomic hydrogen, leading to increased selectivity in the production of nitrogen gas. A BDD electrode with a boron-doping level of 1.0% increased the density of acceptor states, thereby enhancing the conductivity and promoting the formation of C-H bonds after the cathodic reduction pretreatment leading to the direct reduction of nitrate.


Assuntos
Boro/química , Técnicas Eletroquímicas , Diamante/química , Doping nos Esportes , Eletrodos , Eletrólise/métodos , Hidrogênio/química , Nitratos , Óxidos de Nitrogênio , Oxirredução , Oxigênio , Água
2.
Chemosphere ; 253: 126599, 2020 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-32278188

RESUMO

It has previously been established during the elimination of organic matter that the addition of sodium dodecyl sulfate in solution is an important condition in the electrochemical oxidation approach that allows to increase the production of persulfate, enhancing the efficacy of the treatment. This outcome was observed when using the anodic oxidation with boron doped diamond (BDD), the extra production of persulfate was achieved after the SDS-sulfate released in solution and it reacts with hydroxyl radicals electrogenerated at BDD surface. However, this effect was not already tested by using active anodes. For this reason, the effect of sodium dodecyl sulfate (SDS) during the electrochemical treatment of caffeine was investigated by comparing non-active and active anodes performances. A significant decrease on the oxidation efficiency of caffeine was observed by using Ti/IrO2-Ta2O5 anode at high current density when SDS was added to the solution. Conversely, at BDD anode, the presence of SDS enhanced the degradation efficiency, depending on the applied current density. This behavior is mainly due to the degradation of SDS molecules, which allows to increase the amount of sulfate in solution, promoting the production of persulfate via the mechanism involving hydroxyl radicals when BDD is used. Meanwhile, no oxidation improvements were observed when Ti/IrO2-Ta2O5 anode was employed, limiting the caffeine oxidation. Results clearly showed that the surfactant concentration had little influence on the degradation efficiency, but this result is satisfactory for the BDD system, since it demonstrates that effluents with complex matrices containing surfactants could be effectively degraded using the electrooxidation technique. Degradation mechanisms were explained by electrochemical measurements (polarization curves) as well as the kinetic analysis. Costs and energy consumption were also evaluated.


Assuntos
Cafeína/química , Eletrodos , Dodecilsulfato de Sódio/química , Poluentes Químicos da Água/química , Boro/química , Diamante/química , Radical Hidroxila/química , Cinética , Oxirredução , Sulfatos/química , Titânio
3.
Chemosphere ; 253: 126701, 2020 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-32302902

RESUMO

In this study, we investigated the impact of a TiO2 nanotube (NT) interlayer on the electrochemical performance and service life of Sb and Bi-doped SnO2-coatings synthesized on a titanium mesh. Ti/SnO2-SbBi electrode was synthetized by a thermal decomposition method using ionic liquid as a precursor solvent. Ti/TiO2-NT/SnO2-SbBi electrode was obtained by a two-step electrochemical anodization, followed by the same process of thermal decomposition. The synthesized electrodes were electrochemically characterized and analyzed by scanning electron microscopy and energy dispersive X-ray spectroscopy. Terephthalic acid (TA) experiments showed that Ti/SnO2-SbBi and Ti/TiO2-NT/SnO2-SbBi electrodes formed somewhat higher amounts of hydroxyl radicals (HO) compared with the mesh boron doped diamond (BDD) anode. Electrochemical oxidation experiments were performed using iodinated contrast media (ICM) as model organic contaminants persistent to oxidation. At current density of 50 A m-2, BDD clearly outperformed the synthesized mixed metal oxide (MMO) electrodes, with 2 to 3-fold higher oxidation rates observed for ICM. However, at 100 and 150 A m-2, Ti/SnO2-SbBi had similar performance to BDD, whereas Ti/TiO2-NT/SnO2-SbBi yielded even higher oxidation rates. Disappearance of the target ICM was followed by up to 80% removal of adsorbable organic iodide (AOI) for all three materials, further demonstrating iodine cleavage and thus oxidative degradation of ICM mediated by HO. The presence of a TiO2 NT interlayer yielded nearly 4-fold increase in anode stability and dislocated the oxygen evolution reaction by +0.2 V. Thus, TiO2 NT interlayer enhanced electrode stability and service life, and the electrocatalytic activity for the degradation of persistent organic contaminants.


Assuntos
Meios de Contraste/química , Poluentes Químicos da Água/química , Purificação da Água/métodos , Boro/química , Diamante/química , Eletrodos , Nanotubos/química , Oxirredução , Óxidos/química , Titânio/química
4.
Chemosphere ; 252: 126496, 2020 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-32203782

RESUMO

The surface products have a significant influence on the reactivity of zero-valent iron-based materials. Although the enhancing effect of graphene on the reactivity of nanoscale zero-valent iron (NZVI)/graphene composites have been confirmed, the effect of graphene on the formation of surface products of NZVI is not well understood. In order to assess the effect of graphene on the structural of the outer iron oxide layers of NZVI, the NZVI was pre-oxidized by graphene oxide (ONZVI-GO). Compared with the NZVI oxidized by O2 (ONZVI-O2), ONZVI-GO was shown to be effective at NO3- removal with a high efficiency over a wide range of initial pH values. The results from characterization showed that GO could induce the formation of a tight iron oxide shell with dense spinel structures. The boron introduced during the preparation of NZVI was doped into iron oxides on the surface of ONZVI-GO. The B-O in adsorbed borate was transformed to B-B/B-Fe in the lattice structure of iron oxides, causing the formation of highly electron-deficient Lewis acid sites on the surface of ONZVI-GO, which could effectively gather NO3- and OH-, leading to the higher efficiency removal of NO3- than ONZVI-O2 over a wide range of initial pH values. This study provides new insight into the interaction between graphene and the surface species of NZVI.


Assuntos
Grafite/química , Poluentes Químicos da Água/química , Adsorção , Boro/química , Compostos Férricos , Ferro/química , Nitratos , Óxidos de Nitrogênio , Oxirredução , Poluentes Químicos da Água/análise
5.
Chemosphere ; 248: 126033, 2020 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-32004882

RESUMO

Degradation of phenols with different substituent groups (including -OCH3, -CHO, -NHCOCH3, -NO2, and -Cl) at boron-doped diamond (BDD) anodes has been studied previously based on the removal efficiency and •OH detection. Innovatively, formations of CO2 gas and various inorganic ions were examined to probe the mineralization process combined with quantitative structure-activity relationship (QSAR) analysis. As results, all phenols were efficiently degraded within 8 h with high COD removal efficiency. Three primary intermediates (hydroquinone, 1,4-benzoquinone and catechol) were identified during electrochemical oxidation and degradation pathway was proposed. More importantly, CO2 transformation efficiency ranked as: no N or Cl contained phenols (p-CHO, p-OCH3 and Ph) > N-contained phenols (p-NHCOCH3 and p-NO2) > Cl-contained phenols (p-Cl and o,p-Cl). Carbon mass balance study suggested formation of inorganic carbon (H2CO3, CO32- and HCO3-) and CO2 after organic carbon elimination. Inorganic nitrogen species (NH4+, NO3- and NO2-) and chlorine species (Cl-, ClO3- and ClO4-) were also formed after N- and Cl-contained phenols mineralization, while no volatile nitrogen species were detected. The phenols with electron-withdrawing substituents were easier to be oxidized than those with electron-donating substituents. QSAR analysis indicated that the reaction rate constant (k1) for phenols degradation was highly related to Hammett constant (∑σo,m,p) and energy gap (ELUMO - EHOMO) of the compound (R2 = 0.908), which were key parameters on evaluating the effect of structural moieties on electronic character and the chemical stability upon radical attack for a specific compound. This study presents clear evidence on mineralization mechanisms of phenols degradation at BDD anodes.


Assuntos
Técnicas Eletroquímicas/instrumentação , Eletrodos , Fenóis/química , Relação Quantitativa Estrutura-Atividade , Poluentes Químicos da Água/química , Análise da Demanda Biológica de Oxigênio , Boro/química , Carbono/química , Dióxido de Carbono/química , Cloro/química , Diamante/química , Nitrogênio/química , Oxirredução
6.
Chemosphere ; 249: 126176, 2020 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-32087453

RESUMO

Sequential soil washing and electrochemical advanced oxidation processes (EAOPs) were applied for the remediation of synthetic soil contaminated with diesel. The surfactant Tween 80 was used to enhance the extraction of diesel from synthetic soil, and diesel extraction efficiency was improved with the increase of Tween 80 concentration. Under conditions of 180 min washing time, 10 g synthetic soil with 100 mL surfactant solution and two times of soil washing, about 75.2%, 80.0% and 87.9% of diesel was extracted from synthetic soil with 5.0, 7.5 and 10.0 g L-1 Tween 80. The degradation of diesel in soil washing effluent was carried out by two EAOPs, electro-oxidation (EO) and electro-Fenton (EF) using boron-doped diamond (BDD) anode and carbon felt cathode cell. After 360 min EO treatment, 72.7-83.0% of diesel was removed from the effluent after soil washing with 5.0-10.0 g L-1 Tween 80 while higher removal efficiencies (77.7-87.2%) were attained with EF process. Parallel factor analysis (PARAFAC) of excitation emission matrix (EEM) fluorescence spectroscopy was conducted to analysis the transformation of fluorescent components in diesel during the treatment by two EAOPs.


Assuntos
Recuperação e Remediação Ambiental/métodos , Gasolina/análise , Poluentes do Solo/química , Solo/química , Boro/química , Diamante/química , Técnicas Eletroquímicas/métodos , Eletrodos , Oxirredução , Polissorbatos/química , Tensoativos/química
7.
Chemosphere ; 248: 126062, 2020 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-32032880

RESUMO

Glucocorticoids are widely used to treat a variety of diseases. Consequently, these compounds have been found in water and wastewater matrix. Despite studies have proven its toxicity, just a few works investigate techniques to degrade and mineralize them. To solve this issue, this work presents the degradation and mineralization of prednisone (PRED) by electrochemical advanced oxidation (EAO) using a boron-doped diamond supported on niobium (Nb/BDD) anode in synthetic and real wastewater. Cyclic voltammetry (CV) was performed to investigate the PRED oxidation mechanisms. CV suggest that PRED will be oxidized via HO• and other oxidants generated from the ions present in the liquid matrix (S2O82-, SO4•-, HClO, ClO- etc.). Different EAO conditions as initial pH (3, 7 and 11) and applied current densities (5, 10 and 20 mA cm-2) were evaluated. The best result was obtained at alkaline pH (11) and a current density of 20 mA cm-2, achieving 78% of degradation and 42% of mineralization. Using the best conditions, the EAO was applied as a polishing treatment stage to remove PRED from a biological pre-treated municipal wastewater spiked with PRED. The results indicate that EAO applied in the real matrix provides better results than the synthetic solution, probably associated with the presence of ions that can be electrochemically converted into oxidant species, resulting in higher kinetic constant, mineralization current efficiency and lower energetic consumption. Therefore, the EAO process without the addition of chemicals has proven to be an effective alternative as a tertiary treatment of municipal wastewater contaminated with PRED.


Assuntos
Nióbio/química , Prednisona/química , Poluentes Químicos da Água/química , Boro/química , Diamante/química , Dioxóis , Eletrodos , Cinética , Modelos Químicos , Oxidantes , Oxirredução , Águas Residuárias/química , Água/química
8.
Chemistry ; 26(24): 5388-5399, 2020 Apr 24.
Artigo em Inglês | MEDLINE | ID: mdl-31999023

RESUMO

A series of fluorescent boron-dipyrromethene (BODIPY, 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) dyes have been designed to participate, as aglycons, in synthetic oligosaccharide protocols. As such, they served a dual purpose: first, by being incorporated at the beginning of the process (at the reducing-end of the growing saccharide moiety), they can function as fluorescent glycosyl tags, facilitating the detection and purification of the desired glycosidic intermediates, and secondly, the presence of these chromophores on the ensuing compounds grants access to fluorescently labeled saccharides. In this context, a sought-after feature of the fluorescent dyes has been their chemical robustness. Accordingly, some BODIPY derivatives described in this work can withstand the reaction conditions commonly employed in the chemical synthesis of saccharides; namely, glycosylation and protecting-group manipulations. Regarding their photophysical properties, the BODIPY-labeled saccharides obtained in this work display remarkable fluorescence efficiency in water, reaching quantum yield values up to 82 %, as well as notable lasing efficiencies and photostabilities.


Assuntos
Compostos de Boro/química , Boro/química , Corantes Fluorescentes/química , Porfobilinogênio/análogos & derivados , Fluorescência , Glicosilação , Luz , Porfobilinogênio/química
9.
Talanta ; 209: 120574, 2020 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-31892056

RESUMO

The paper outlines the first report of application of a differential pulse voltammetry for simultaneous quantification of clinically important molecular markers - tryptophan and its metabolite - kynurenine. The analytes were determined in less than 60 s at the boron-doped diamond electrode modified in situ with bismuth film (BiF/BDDE). Proper adjustment of a supporting electrolyte composition allowed to obtain good separation of tryptophan and kynurenine oxidation peaks that appeared at potential of 0.88 and 1.05 V (vs. Ag/AgCl), respectively. Studies using an optical profilometer have confirmed an increase in electrode surface area after deposition of Bi film. At the optimized conditions, the obtained detection limits of tryptophan and kynurenine were at 30 nM concentrations. The method was validated for linearity, precision, accuracy, selectivity and recovery. We have investigated an impact of numerous relevant interfering organic compounds (including amino acids and different tryptophan metabolites of kynurenine pathway) on voltammetric signals of the measured analytes. Finally, for proof-of-technology, the sensor was used for tryptophan and kynurenine quantification in culture medium collected from human cancer cell lines (breast MDA-MB-231 and ovary SK-OV-3). The target molecules were analyzed directly, without any sample preparation step. The sensor showed good accuracy in presence of the sample matrix components that was confirmed by high performance liquid chromatography measurements. Our work emphasizes the advantages of application of the herein proposed, easy to fabricate voltammetric sensor, instead of popular chromatographic assays or previously proposed potentiometric immunosensor. The method might serve for rapid assessment of kynurenine pathway activity in cancer cells.


Assuntos
Meios de Cultura/metabolismo , Cinurenina/metabolismo , Neoplasias/metabolismo , Triptofano/metabolismo , Técnicas Biossensoriais , Boro/química , Técnicas de Cultura de Células , Linhagem Celular Tumoral , Cromatografia Líquida de Alta Pressão , Meios de Cultura/química , Diamante/química , Técnicas Eletroquímicas , Eletrodos , Humanos , Cinurenina/análise , Neoplasias/química , Triptofano/análise
10.
Chemosphere ; 246: 125786, 2020 May.
Artigo em Inglês | MEDLINE | ID: mdl-31918097

RESUMO

The choice of anode materials has a significant influence on the electrocatalytic degradation of organics. Accordingly, the electrocatalytic activity of several active anodes (Ti/Ru-Ir, Ti/Ir-Ta, Ti/Pt) and non-active anodes (Ti/PbO2, Ti/SnO2, Si/BDD (boron-doped diamond)) was compared by electrocatalytic degradation of m-cresol. The results indicated Si/BDD electrode had the strongest mineralization ability and the lowest energy consumption. And the order of the activity of m-cresol degradation was as follows: Si/BDD > Ti/SnO2>Ti/PbO2>Ti/Pt > Ti/Ir-Ta > Ti/Ru-Ir. Also their intermediate products were compared. The effects of experimental parameters on electrocatalytic degradation of m-cresol with Si/BDD electrode showed m-cresol conversion was affected slightly by the electrode spacing and electrolyte concentration, but affected greatly by the temperature and current density. And smaller electrode spacing and current density, higher electrolyte concentration and temperature were beneficial to reduce energy consumption. Their degradation processes were all accord with the pseudo-first-order reaction kinetics completely. In addition, the results of electrocatalytic degradation of m, o, p-cresol indicated there was almost no significant difference on conversion rate between cresols isomers with the current density of 30 mA cm-2. However, the influence of group position was shown when the current density was reduced to 10 mA cm-2 and cresols conversion followed the sequence of m-cresol ≈ o-cresol > p-cresol.


Assuntos
Cresóis/química , Eletrodos , Poluentes Ambientais/química , Modelos Químicos , Boro/química , Diamante , Cinética , Oxirredução , Titânio
11.
J Chromatogr A ; 1612: 460649, 2020 Feb 08.
Artigo em Inglês | MEDLINE | ID: mdl-31708221

RESUMO

A high-performance liquid chromatography (HPLC) method equipped with a boron-doped diamond (BDD) electrode was established for the simultaneous determination of phenol, 4-ethylphenol (4-EP), guaiacol, 4-ethylguaiacol (4-EG), 4-vinylguaiacol (4-VG), eugenol, and o-, m- and p-cresol. The separation was performed on a reversed-phase HALO C18 core-shell column (3.0 × 50 mm, 2.7 µm) with a mobile phase comprising 10 mM formate, pH 3, and 15% acetonitrile (ACN) (v/v), a flow rate of 1.5 mL/min, corresponding to a total run time of 9 min. The electrochemical detection (ECD) was set at +1.5 V vs. Pd/H2 in oxidative mode. Under optimized operating conditions, good linearity was obtained for the nine phenolics with corresponding coefficients of determination (R2) above 0.998. The limits of detection (LODs, S/N = 3) were 10 nM-1 µM, with an 80-fold increase in sensitivity for guaiacol achieved with ECD over ultraviolet (UV) detection. The sensitive and selective HPLC-ECD method was successfully applied for the identification and quantification of the nine phenolics in Islay, Irish, Scotch, and Highland whiskey samples, with significantly higher concentrations of the flavorings determined in Islay whiskey.


Assuntos
Boro/química , Técnicas Eletroquímicas/métodos , Aromatizantes/análise , Fenóis/química , Bebidas Alcoólicas/análise , Cromatografia Líquida de Alta Pressão , Cromatografia de Fase Reversa , Cresóis/química , Diamante/química , Eletrodos , Limite de Detecção
12.
Inorg Chem ; 59(1): 913-924, 2020 Jan 06.
Artigo em Inglês | MEDLINE | ID: mdl-31825210

RESUMO

The ruthenium(II) complexes [RuCl(L1)(L3)]Cl (1), [RuCl(L1)(L4)]Cl (2), [RuCl(L2)(L4)]Cl (3), [RuCl(L1)(L5)]Cl (4), and [RuCl(L2)(L5)]Cl (5) of NNN-donor dipicolylamine (dpa) bases (L4, L5) having BODIPY (boron-dipyrromethene) moieties, NN-donor phenanthroline derivatives (L1, L2), and benzyldipicolylamine (bzdpa, L3) were prepared and characterized by spectroscopic techniques and their cellular localization/uptake and photocytotoxicity studied. Complex 1, as its PF6 salt (1a), has been structurally characterized with help of a single-crystal X-ray diffraction technique. It has a RuN5Cl core with the Cl bonded trans to the amine nitrogen atom of bzdpa. The complexes showed intense absorption spectral bands near 500 nm (ε ≈ 58000 M-1 cm-1) in 2 and 3 and 654 nm (ε ≈ 80000 M-1 cm-1) in 4 and 5 in 1/1 DMSO/DPBS (v/v). Complex 5 having biotin and PEGylated-disteryl BODIPY gave a singlet oxygen quantum yield (ΦΔ) of ∼0.65 in DMSO. Complex 5 exhibited remarkable PDT (photodynamic therapy) activity (IC50 ≈ 0.02 µM) with a photocytotoxicity index (PI) value of >5000 in red light of 600-720 nm in A549 cancer cells. The biotin-conjugated complexes showed better photocytotoxicity in comparison to nonbiotinylated analogues in A549 cells. The complexes displayed less toxicity in HPL1D normal cells in comparison to A549 cancer cells. The emissive BODIPY complexes 3 and 5 (ΦF ≈ 0.07 in DMSO) showed significant mitochondrial localization.


Assuntos
Antineoplásicos/farmacologia , Complexos de Coordenação/farmacologia , Luz , Fotoquimioterapia , Fármacos Fotossensibilizantes/farmacologia , Células A549 , Antineoplásicos/síntese química , Antineoplásicos/química , Biotina/química , Biotina/farmacologia , Boro/química , Boro/farmacologia , Linhagem Celular , Proliferação de Células/efeitos dos fármacos , Sobrevivência Celular/efeitos dos fármacos , Complexos de Coordenação/síntese química , Complexos de Coordenação/química , Clivagem do DNA/efeitos dos fármacos , Teoria da Densidade Funcional , Ensaios de Seleção de Medicamentos Antitumorais , Humanos , Modelos Moleculares , Imagem Óptica , Fármacos Fotossensibilizantes/síntese química , Fármacos Fotossensibilizantes/química , Porfobilinogênio/análogos & derivados , Porfobilinogênio/química , Porfobilinogênio/farmacologia , Rutênio/química , Rutênio/farmacologia
13.
Chemistry ; 26(19): 4261-4268, 2020 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-31793681

RESUMO

A series of carbazole-based boron dipyrromethenes (BODIPYs) 2 a-g bearing binaphthyl units have been synthesized by the Et2 AlCl-mediated reaction of the corresponding BODIPY difluorides 1 a-g with 1,1'-binaphthalene-2,2'-diol. Substituents such as halogen, nitrile, and amino groups were tolerated under the reaction conditions, and the reaction of the phenylethynyl-substituted 1 h gave (R,R)-3 h bearing two binaphthyl units. The chiroptical properties of these dyes with different substituents were investigated by UV/Vis, CD, fluorescence, and circularly polarized luminescence (CPL) spectroscopy. The CD spectra showed Cotton effects in the absorption region of the BODIPY moieties. In addition, they showed CPL both in solution and in the solid state. Interestingly, several dyes recorded higher glum values in the solid state, probably due to intermolecular interactions. Because (R,R)-3 h recorded relatively low glum values, the diastereomer (R,S)-3 h was prepared. The (R,S) diastereomer showed intense CPL, which suggests a synergetic effect of the two binaphthyl groups. Finally, chiral carbazole-based BODIPY dimers have been synthesized for the first time and their chiroptical properties were investigated. They showed redshifted fluorescence and CPL, which reached the near-IR (NIR) region in the solid state.


Assuntos
Compostos de Boro/síntese química , Carbazóis/síntese química , Corantes/química , Boro/química , Compostos de Boro/química , Carbazóis/química , Fluorescência , Luminescência , Estrutura Molecular , Análise Espectral
14.
Chemosphere ; 243: 125349, 2020 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-31756655

RESUMO

This study investigates electrooxidation of short (C3-C6) and long (C7-C-18) chain perfluorocarboxylic acids (PFCAs) including perfluorooctane sulfonate (PFOA) using Si/BDD electrode. The effect of operational parameters (supporting electrolyte type, applied current density, and initial pH) were explored for PFOA removal. At the optimized conditions, 74% TOC removal and 37% defluorination ratio were gained for 10 mg L-1 of PFOA solution which evidences that the shorter chain PFCAs were formed. The PFOA degradation pathway followed one direct electron transfer from PFOA molecule to anode surface. Then two different degradation pathways were proposed. The first proposed degradation mechanism involved the reaction of perfluoroheptyl radical and hydroxyl radical, the release of HF and hydrolysis. The second mechanism involved the reaction between perfluoroheptyl radical and O2, formation of C7F15O and perfluorohexyl radical with releasing COF2. The removal of short- (C3-C6) and long-chain PFCAs (C7-C18) was also characterized. More than 95% of removal efficiency was gained for all long-chain PFCAs, excluding C7. The removal ratios of short-chain PFCAs (C3-C6) were 39%, 41%, 66% and 70% for C3, C4, C5 and C6, respectively. Contrary to long-chain PFCAs, chain-length dependence for short-chain PFCAs were observed. Defluorination ratio of short-chain PFCAs was only 45% signifying that defluorination partially occurred. Water matrix did not significantly affect the degradation of short-chain PFCAs in deionized water (DI), river water and secondary effluent of a wastewater treatment plant (WWTP). In contrast, defluorination ratio of long-chain PFCAs was noticeably affected by water matrix with the order of DI water > WWTP effluent > river water.


Assuntos
Ácidos Alcanossulfônicos/química , Boro/química , Eletrodos , Fluorcarbonetos/química , Eliminação de Resíduos Líquidos/métodos , Poluentes Químicos da Água/química , Diamante/química , Radical Hidroxila/química , Águas Residuárias/química , Poluentes Químicos da Água/análise
15.
Chemosphere ; 238: 124550, 2020 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-31425868

RESUMO

Large volumes of contaminated water are produced via intentional and unintentional incidents, including terrorist attacks, natural disasters and accidental spills. Contaminated waters could contain harmful chemicals, which present management and disposal challenges. This study investigates three Advanced Oxidation Processes (AOPs) - UV/H2O2, O3/H2O2, and electrochemical oxidation using a boron-doped diamond (BDD) anode - to treat eleven contaminants including herbicides, pesticides, pharmaceuticals, and flame retardant compounds. To address treatment and toxicity concerns, this study focuses on the resulting microbial toxicity via Microtox® toxicity and Nitrification Inhibition tests. The results suggest four functional Microtox® toxicity categories upon AOP treatment, which are useful for streamlining AOP selection for specific applications. Except for one compound, the O3/H2O2 and UV/H2O2 AOPs achieved, within experimental error, 100% parent compound degradation during 2 h of treatment for all contaminants, as well as Microtox® toxicities that declined below 10% by the end of the treatment. In addition, anodic oxidation with a BDD electrode exhibited slower degradation and some increases in Microtox® toxicity. Only one compound exhibited above 50% Nitrification Inhibition, indicating the robustness of activated sludge to many contaminated and AOP-treated waters. These results indicate that AOP pre-treatment can be a viable strategy to facilitate drain disposal of contaminated waters, but that eco-toxicity may remain a concern.


Assuntos
Reatores Biológicos , Diamante/química , Eletrodos , Eliminação de Resíduos Líquidos/métodos , Poluentes Químicos da Água/química , Poluentes Químicos da Água/toxicidade , Poluição da Água/análise , Boro/química , Herbicidas/análise , Herbicidas/química , Herbicidas/toxicidade , Peróxido de Hidrogênio/química , Oxirredução , Praguicidas/análise , Praguicidas/química , Praguicidas/toxicidade , Microbiologia da Água , Poluentes Químicos da Água/análise , Purificação da Água/métodos
16.
Chemosphere ; 238: 124854, 2020 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-31549676

RESUMO

This work focusses on the production of hydrogen peroxide and in the removal of bromacil by the electro-Fenton process using two different electrochemical cells: mixed tank cell (MTC) and flow-through cell (FTC). Both cells use boron doped diamond (BDD) as anode and carbon felt as cathode to promote the formation of hydrogen peroxide. In the case of the MTC, two surface area ratios, Acathode/Aanode, have been used. Results show that the H2O2 produced by MTC and FTCPSC increases with the time until a stabilization state. For the FTCPSC, the average hydrogen peroxide concentration produced increases progressively with the current, while for MTC the maximum values are found in applying very low current densities. In addition, the FTCPSC provides higher concentrations of hydrogen peroxide for the same current density applied. Regarding the MTC, it can be stated that the higher the area of the cathode, the higher is the amount of H2O2 produced and the lower is the cell voltage (because of a more efficient current lines distribution). The initial oxidation of bromacil is very efficiently attained being rapidly depleted from wastewater. However, the higher production of hydrogen peroxide obtained by the FTCPSC cell does not reflect on a better performance of the electro-Fenton process. Thus, bromacil is better mineralized using the MTC cell with the lowest cathode area. This observation has been explained because larger concentrations of produced hydrogen peroxide seems to benefit the oxidation of intermediates and not the mineralization.


Assuntos
Bromouracila/análogos & derivados , Diamante/química , Peróxido de Hidrogênio/síntese química , Águas Residuárias/química , Poluentes Químicos da Água/análise , Boro/química , Bromouracila/análise , Carbono/química , Condutividade Elétrica , Ferro/química , Oxirredução
17.
Ecotoxicol Environ Saf ; 188: 109923, 2020 Jan 30.
Artigo em Inglês | MEDLINE | ID: mdl-31711779

RESUMO

In this work, ecotoxicological bioassays based on Lactuca sativa seeds and bioluminescent bacterium (Vibrio fischeri) have been carried out in order to quantify the toxicity of Norfloxacin (NOR) and sodium sulfate solutions, before and after treating them using electrochemical advanced oxidation. The effect of some process variables (anode material, reactor configuration and applied current) on the toxicity evolution of the treated solution has been studied. A NOR solution shows an EC50(5 days) of 336 mg L-1towards Lactuca sativa. This threshold NOR concentration decreases with sodium sulfate concentration, in solutions that contain simultaneously Norfloxacin and sodium sulfate. In every case considered in this work, the electrochemical advanced oxidation process increased the toxicity (towards both Lactuca sativa and Vibrio fischeri) of the solution. This toxicity increase is mainly due to the persulfate formation during the electrochemical treatment. From a final solution toxicity point of view, the best results were obtained using a BDD anode in a divided reactor applying the lowest current intensity.


Assuntos
Técnicas Eletroquímicas/métodos , Norfloxacino/toxicidade , Poluentes Químicos da Água/toxicidade , Purificação da Água/métodos , Aliivibrio fischeri/efeitos dos fármacos , Boro/química , Cerâmica/química , Diamante/química , Ecotoxicologia , Técnicas Eletroquímicas/instrumentação , Eletrodos , Alface/efeitos dos fármacos , Norfloxacino/análise , Oxirredução , Sulfatos/química , Poluentes Químicos da Água/análise
18.
Mikrochim Acta ; 187(1): 14, 2019 12 04.
Artigo em Inglês | MEDLINE | ID: mdl-31802283

RESUMO

Boronic acid-doped carbon nanoparticles were prepared and are shown to undergo aggregation induced emission (AIE). The nanoparticle composite is a viable fluorescent probe for glucose determination by using the RGB technique and a smartphone. The structure and the chemical composition of the doped carbon nanoparticles were confirmed by SEM, TEM, FTIR and UV-vis spectroscopy. The combination of 4-carboxyphenylboronic acid with o-phenylenediamine and rhodamine B endowed the hybrid with high fluorescence intensity (quantum yield 46%). Compared with conventional two-step preparation of boronic acid-based fluorescent probes for glucose, the present one step synthesis strategy is simpler and more effective. The addition of glucose causes the formation of covalent bonds between the cis-diols group of glucose molecules and boronic acid moiety. Fluorescent intensity can be quantified using dual wavelengths simultaneously, where both increases, as the target analytes bind to the bronic acid. These variations was monitored by the smartphone camera, and the green channel intensities of the colored images were processed by using the RGB option of a smartphone. The assay works in the 32 µM to 2 mM glucose concentration range and has an 8 µM detection limit. The method was successfully used for the assay of glucose in diluted human serum. Graphical abstractThe fluorometric method was developed for determination of glucose using boron doped carbon nanoparticles (BCNBs). The BCNPs aggregate after covalent binding between the cis-diols of glucose and boronic acid. The green channel of the images is recorded by a smartphone camera.


Assuntos
Boro/química , Carbono/química , Corantes Fluorescentes/química , Glucose/análise , Nanopartículas/química , Fenômenos Ópticos , Smartphone , Glucose/química , Humanos
19.
J Chem Phys ; 151(21): 211103, 2019 Dec 07.
Artigo em Inglês | MEDLINE | ID: mdl-31822090

RESUMO

Silicon nanocrystals are intriguing materials for biomedical imaging applications because of their unique optical properties and biological compatibility. We report a new surface functionalization route to synthesize biological buffer soluble and colloidally stable silicon nanocrystals, which is enabled by surface boron doping. Harnessing the distinctive Lewis acidic boron surface sites, postsynthetic modifications of plasma synthesized boron doped nanocrystals were carried out with polyethylene glycol (PEG-OH) ligands in dimethyl sulfoxide under photochemical conditions. The influence of PEG concentration, PEG molecular weight, and boron doping percentage on the nanocrystal solubility in a biological buffer has been investigated. The boron doping facilitates the surface functionalization via two probable pathways, by providing excellent initial dispersiblity in polar solvents and providing available acidic boron surface sites for bonding. These boron doped silicon nanocrystals have nearly identical absorption features as intrinsic silicon nanocrystals, indicating that they are promising candidates for biological imaging applications.


Assuntos
Boro/química , Nanopartículas/química , Polietilenoglicóis/química , Silício/química , Tamanho da Partícula , Propriedades de Superfície
20.
Chem Pharm Bull (Tokyo) ; 67(12): 1278-1283, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-31787654

RESUMO

The progesterone receptor (PR) plays an important role in various physiological processes, especially in the female reproductive system, and abnormalities of PR function are associated with several diseases, including some types of cancer. Non-steroidal PR ligands are of interest as candidate drugs for treatment of PR-related diseases without the serious adverse effects that may be caused by steroidal ligands. For the development of non-steroidal PR ligands, both a hydrophobic backbone and a polar functional group corresponding to the 3-carbonyl group of progesterone, which interacts with Gln725 and Arg766 of the PR-ligand binding domain, are critically important. We previously showed that carborane is a useful hydrophobic pharmacophore for PR antagonists, and in this work, we introduced the pentafluorosulfanyl (SF5) group as a novel polar functional group of carborane-based non-steroidal PR antagonists. All the synthesized SF5-containing carborane derivatives exhibited PR-antagonistic activity at micromolar or submicromolar concentration. Among them, compounds 11 are potent progesterone antagonists with submicromolar IC50 values.


Assuntos
Boro/farmacologia , Fluoretos/farmacologia , Receptores de Progesterona/antagonistas & inibidores , Compostos de Enxofre/farmacologia , Boro/química , Fluoretos/química , Humanos , Interações Hidrofóbicas e Hidrofílicas , Estrutura Molecular , Relação Estrutura-Atividade , Compostos de Enxofre/química
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