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1.
Environ Sci Pollut Res Int ; 31(32): 45414-45424, 2024 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-38963630

RESUMEN

Solid waste resulting from bauxite ore (red mud) was converted into useful products consisting in hydrogarnet together with zeolite. Red mud (RM) transformation from disposal material into new source was carried out using potassium hydroxide as an activator and hydrothermal process (HY) or vapor phase crystallization (VPC) approach. HY process was performed at 60, 90, and 130 °C whereas during the VPC method, red mud was contacted only with vapor from the distilled water heated at 60 and 90 °C. The results indicate the formation of katoite and zeolite L (LTL topology) with both approaches. All the synthetic products display magnetic properties. In addition, a preliminary investigation on arsenic removal from drinking water (from 59 to 86%), makes the synthetic materials appealing for environmental applications. Finally, the synthesis of a large amount of very useful newly-formed phases using vapor molecules confirms the efficiency of the innovative and green VPC process in waste material transformation.


Asunto(s)
Hidróxidos , Compuestos de Potasio , Purificación del Agua , Zeolitas , Hidróxidos/química , Compuestos de Potasio/química , Purificación del Agua/métodos , Zeolitas/química , Óxido de Aluminio/química , Residuos Sólidos
2.
Nanomaterials (Basel) ; 12(23)2022 Dec 06.
Artículo en Inglés | MEDLINE | ID: mdl-36500953

RESUMEN

The present work aimed at decorating halloysite nanotubes (HNT) with magnetic Fe3O4 nanoparticles through different synthetic routes (co-precipitation, hydrothermal, and sol-gel) to test the efficiency of three magnetic composites (HNT/Fe3O4) to remove the antibiotic ofloxacin (OFL) from waters. The chemical-physical features of the obtained materials were characterized through the application of diverse techniques (XRPD, FT-IR spectroscopy, SEM, EDS, and TEM microscopy, thermogravimetric analysis, and magnetization measurements), while ecotoxicity was assessed through a standard test on the freshwater organism Daphnia magna. Independently of the synthesis procedure, the magnetic composites were successfully obtained. The Fe3O4 is nanometric (about 10 nm) and the weight percentage is sample-dependent. It decorates the HNT's surface and also forms aggregates linking the nanotubes in Fe3O4-rich samples. Thermodynamic and kinetic experiments showed different adsorption capacities of OFL, ranging from 23 to 45 mg g-1. The kinetic process occurred within a few minutes, independently of the composite. The capability of the three HNT/Fe3O4 in removing the OFL was confirmed under realistic conditions, when OFL was added to tap, river, and effluent waters at µg L-1 concentration. No acute toxicity of the composites was observed on freshwater organisms. Despite the good results obtained for all the composites, the sample by co-precipitation is the most performant as it: (i) is easily magnetically separated from the media after the use; (ii) does not undergo any degradation after three adsorption cycles; (iii) is synthetized through a low-cost procedure. These features make this material an excellent candidate for removal of OFL from water.

3.
Angew Chem Int Ed Engl ; 61(32): e202204787, 2022 08 08.
Artículo en Inglés | MEDLINE | ID: mdl-35670285

RESUMEN

Water-soluble melanin-protein-Fe/Cu conjugates derived from norepinephrine and fibrillar ß-lactoglobulin are reliable models for neuromelanin (NM) of human brain locus coeruleus. Both iron and copper promote catecholamine oxidation and exhibit strong tendency to remain coupled in oligonuclear aggregates. The Fe-Cu clusters are EPR silent and affect the 1 H NMR spectra of the conjugates through a specific sequence of signals. Derivatives containing only Fe or Cu exhibit different NMR patterns. The EPR spectra show weak signals of paramagnetic FeIII in conjugates containing Fe or mixed Fe-Cu sites due to small amounts of mononuclear centers. The latter derivatives exhibit EPR signals for isolated CuII centers. These features parallel the EPR behavior of NM from locus coeruleus. The spectral data indicate that FeIII is bound to the melanic fraction, whereas CuII is bound on the protein fibrils, suggesting that the Fe-Cu clusters occur at the interface between the two components of the synthetic NMs.


Asunto(s)
Melaninas , Agua , Cobre/química , Espectroscopía de Resonancia por Spin del Electrón , Compuestos Férricos/química , Humanos , Locus Coeruleus/metabolismo , Melaninas/química , Norepinefrina
4.
Photochem Photobiol Sci ; 21(5): 899-912, 2022 May.
Artículo en Inglés | MEDLINE | ID: mdl-35416639

RESUMEN

Heterogeneous photocatalysis is one of the most studied and promising techniques for degradation of contaminants of emerging concern, especially pharmaceuticals, and it represents a potential application in wastewater treatment of recalcitrant pollutants, such as fluoroquinolones, which are almost not abated by standard WWTPs. Although photodegradation partially contributes to alleviate their accumulation into the aquatic systems, heterogeneous photocatalysis assures complete sequestration and mineralization of FQs and their photoproducts and offers many advantages with respect to the other advanced oxidation processes (AOPs). The present brief review summarizes the most recent studies regarding the development and application of novel photocatalytic materials to the removal of FQs from contaminated waters. The collected data are arranged relating the mechanistic aspects to specific catalysts' properties, such as adsorption capacity, easy recovery, and reusability, especially under actual conditions.


Asunto(s)
Contaminantes Químicos del Agua , Purificación del Agua , Catálisis , Fluoroquinolonas , Oxidación-Reducción , Fotólisis , Aguas Residuales , Contaminantes Químicos del Agua/análisis , Purificación del Agua/métodos
5.
Nanomaterials (Basel) ; 11(12)2021 Dec 02.
Artículo en Inglés | MEDLINE | ID: mdl-34947624

RESUMEN

A simple not solvent and time consuming Fe3O4@MIL-100(Fe), synthesized in the presence of a small amount of magnetite (Fe3O4) nanoparticles (27.3 wt%), is here presented and discussed. Layer-by-layer alone (20 shell), and combined layer-by-layer (5 shell)/reflux or /hydrothermal synthetic procedures were compared. The last approach (Fe3O4@MIL-100_H sample) is suitable (i) to obtain rounded-shaped nanoparticles (200-400 nm diameter) of magnetite core and MIL-100(Fe) shell; (ii) to reduce the solvent and time consumption (the layer-by-layer procedure is applied only 5 times); (iii) to give the highest MIL-100(Fe) amount in the composite (72.7 vs. 18.5 wt% in the layer-by-layer alone); (iv) to obtain a high surface area of 3546 m2 g-1. The MIL-100(Fe) sample was also synthesized and both materials were tested for the absorption of Ofloxacin antibiotic (OFL). Langmuir model well describes OFL adsorption on Fe3O4@MIL-100_H, indicating an even higher adsorption capacity (218 ± 7 mg g-1) with respect to MIL-100 (123 ± 5 mg g-1). Chemisorption regulates the kinetic process on both the composite materials. Fe3O4@MIL-100_H performance was then verified for OFL removal at µg per liter in tap and river waters, and compared with MIL-100. Its relevant and higher adsorption efficiency and the magnetic behavior make it an excellent candidate for environmental depollution.

6.
Materials (Basel) ; 14(23)2021 Dec 01.
Artículo en Inglés | MEDLINE | ID: mdl-34885523

RESUMEN

Photocatalysis is an attractive strategy for emerging pollutants remediation. Research towards the development of new, efficient and effective catalytic materials with high activity under wide irradiation spectra is a highly active sector in material science. Various semiconductor materials have been employed as photocatalysts, including TiO2, SrTiO3, CdS, BiVO4, Ta3N5, TaON, Ag3PO4, and g-C3N4. The latter is a metal-free, low cost polymer, providing high adsorption and catalytic properties, shown to be promising for photocatalysis applications under visible light. Furthermore, g-C3N4 composites are among the most promising advanced photocatalytical materials that can be produced by green synthesis processes. In this paper, the state-of-the-art of g-C3N4 applications is reviewed, and application perspectives are discussed. Photocatalysis tests with g-C3N4 under Xenon irradiation were performed to gather first-hand information to improve photoreactor design. Xenon light spectrum appears to be a suitable radiation source to replace direct sunlight in engineered pollutants removal processes catalyzed by g-C3N4, in lieu of other currently used heterogeneous photocatalysis processes (e.g., TiO2-UV). LED sources are also very promising due to higher energy efficiency and customizable, catalyzer-specific irradiation spectra.

7.
Artículo en Inglés | MEDLINE | ID: mdl-33546512

RESUMEN

Two different zinc-based metal-organic frameworks (MOFs) were investigated to remove one of the most used fluoroquinolone antibiotic, Ofloxacin (OFL), from polluted water. The most common zeolitic imidazolate framework-8 (ZIF-8) and the green Zn(II) and benzene-1,3,5-tri-carboxylate (Zn3(BTC)2) were prepared through a facile synthetic route and characterized by means of Fourier-Transform Infrared (FT-IR) Spectroscopy, X-ray Powder Diffraction (XRPD), and Scanning Electron Microscopy (SEM) analyses. The two MOFs were compared in terms of both adsorption and kinetic aspects under real conditions (tap water, natural pH). Results showed that OFL was adsorbed in remarkable amounts, 95 ± 10 and 25.3 ± 0.8 mg g-1 on ZIF-8 and Zn3(BTC)2, respectively, following different mechanisms. Specifically, a Langmuir model well described the ZIF-8 profile, while for Zn3(BTC)2, cooperative adsorption occurred. Moreover the kinetic results were quite different, pseudo-second-order and sigmoidal, respectively. The suitability of ZIF-8 and Zn3(BTC)2 as adsorbent phases for water depollution was tested on tap water samples spiked with OFL 10 µg L-1. The obtained removal efficiencies, of 88% for ZIF-8 and 72% for Zn3(BTC)2, make these materials promising candidates for removing fluoroquinolone antibiotics (FQs) from polluted waters, notwithstanding their limited reusability in tap water, as demonstrated by in-depth characterization of the two MOFs after usage.


Asunto(s)
Estructuras Metalorgánicas , Contaminantes Químicos del Agua , Zeolitas , Adsorción , Ofloxacino , Espectroscopía Infrarroja por Transformada de Fourier , Contaminantes Químicos del Agua/análisis , Zinc
8.
Environ Sci Pollut Res Int ; 28(13): 15828-15837, 2021 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-33244688

RESUMEN

Trace elements are widespread contaminants that can potentially threaten ecosystems and human health. Considering their distribution and toxicity, monitoring their presence in animals represents a priority in environmental risk assessment. Migratory birds have been suggested to be useful biomonitors for trace elements because they can provide information on contaminants even from remote areas that they may exploit during their life cycle. The aim of this study was to analyse the contamination fingerprint of trace elements of African non-breeding staging grounds and European breeding areas in a long-distance migratory passerine bird, the barn swallow (Hirundo rustica). We collected feathers grown in the African non-breeding grounds and those grown in the breeding areas of Northern Italy and measured the levels of 12 trace elements (Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Se and Zn) by DRC-ICP-MS. Multivariate analysis showed that elemental profiles of feathers grown in African non-breeding areas and in the Italian breeding ones clearly differed, with feathers grown in Africa showing higher concentrations of Al, Cu, Fe, Mn and Ni, but lower concentrations of As, Se and Zn, compared to those grown in Italy. In addition, levels of trace elements were age-dependent, with higher levels in older individuals than in younger ones. Our results add to the growing evidence that feathers of long-distance migratory birds are useful tools to monitor trace elements contamination profiles across continents.


Asunto(s)
Golondrinas , Oligoelementos , África , Anciano , Animales , Ecosistema , Monitoreo del Ambiente , Plumas/química , Humanos , Italia , Oligoelementos/análisis
9.
Artículo en Inglés | MEDLINE | ID: mdl-33255235

RESUMEN

The photodegradation process of seven glucocorticoids (GCs), cortisone (CORT), hydrocortisone (HCORT), betamethasone (BETA), dexamethasone (DEXA), prednisone (PRED), prednisolone (PREDLO) and triamcinolone (TRIAM) was studied in tap and river water at a concentration close to the environmental ones. All drugs underwent sunlight degradation according to a pseudo-first-order decay. The kinetic constants ranged from 0.00082 min-1 for CORT to 0.024 min-1 for PRED and PREDLO. The photo-generated products were identified by high-pressure liquid chromatography coupled to electrospray ionization tandem mass spectrometry (HPLC-ESI-MS/MS). The main steps of the degradation pathways were the oxidative cleavage of the chain 17 for CORT, HCORT and the rearrangement of the cyclohexadiene moiety for the other GCs. The acute and chronic toxicity of GCs and of their photoproducts was assessed by the V. fischeri and P.subcapitata inhibition assays. The bioassays revealed no significant differences in toxicity between the parent compounds and their photoproducts, but the two organisms showed different responses. All samples produced a moderate acute toxic effect on V. fisheri and no one in the chronic tests. On the contrary, evident hormesis or eutrophic effect was produced on the algae, especially for long-term contact.


Asunto(s)
Agua Dulce , Glucocorticoides , Luz Solar , Aliivibrio fischeri/efectos de los fármacos , Chlorophyceae/efectos de los fármacos , Cromatografía Líquida de Alta Presión , Agua Dulce/química , Glucocorticoides/análisis , Glucocorticoides/química , Glucocorticoides/efectos de la radiación , Glucocorticoides/toxicidad , Fotólisis/efectos de la radiación , Espectrometría de Masas en Tándem
10.
Artículo en Inglés | MEDLINE | ID: mdl-33114248

RESUMEN

The concentration of 12 elements (As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Se, and Zn) has been investigated in the feathers of three species of Ardeidae, namely the Grey Heron Ardea cinerea, the Little Egret Egretta garzetta, and the Cattle Egret Bubulcus ibis, all breeding at a colony located in the southern Padana Plain (NW Italy). This study is a first step for an evaluation of possible direct effects of these elements on chicks' survival and growth rate. Fe, Zn, Cu, and Mn were in the range 7-69 mg Kg-1, while lower levels of Pb, Ni, As, and Se (0.27-1.45 mg Kg-1) were measured. Co, Cd, and Cr were close to the method detection limits (MDLs) in all the species. The measured concentrations of the most abundant trace elements, such as Zn and Cu, seem to reflect the geochemical pattern of the background (running water and soil), while Hg concentration is lower and it appears to be biomagnified, particularly in Grey Heron feathers. Its concentration is higher in adults than in chicks, and it differs among the three species, as it is closely related to the fish-based dietary pattern. The measured trace elements' concentrations are below the threshold levels in all the heron species, and consequently, harmful and acute effects on the local population are unlikely; the conservation status of herons populations in northern Italy is probably more affected by other factors, such as climate changes, altered aquatic environment, and, consequently, food quality.


Asunto(s)
Monitoreo del Ambiente , Plumas , Metales Pesados , Animales , Aves , Ecosistema , Plumas/química , Italia , Metales Pesados/análisis
11.
Materials (Basel) ; 13(3)2020 Jan 23.
Artículo en Inglés | MEDLINE | ID: mdl-31979204

RESUMEN

TiO2 sepiolite and zeolite composites, as well the corresponding N-doped composites, synthesized through a sol-gel method, were tested for the photocatalytic degradation of a widespread fluoroquinolone antibiotic (ofloxacin) under environmental conditions. The catalysts were characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), scanning electron microscopy (SEM), and diffuse reflectance spectroscopy (DRS) analyses. A complete drug degradation occurred in 10-15 min in the presence of both TiO2 sepiolite and zeolite catalysts, and in 20-30 min with the N-doped ones. Sepiolite proved to be a better TiO2 support compared to the most common zeolite both in terms of adsorption capacity and photocatalytic efficiency in pollutants degradation. The influence of nitrogen doping (red shift from 3.2 to 3.0 eV) was also investigated. Although it was blurred by a marked increase of the particle dimension and thus a decrease of the specific surface area of the doped catalysts, it allowed a faster drug removal than direct photolysis. The photochemical paths and photoproducts were investigated, too.

12.
Anal Bioanal Chem ; 410(29): 7635-7643, 2018 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-30255326

RESUMEN

Silica-supported pyrolyzed lignin (pLG@silica) was investigated as a solid sorbent for the pre-concentration of rare earth elements (REE) from natural waters followed by inductively coupled plasma mass spectrometry (ICP-MS) analysis. The carbon-based material was easily prepared by pyrolytic treatment of lignin at 600 °C after its adsorption onto silica micro-particles. pLG@silica was characterized by scanning electron microscopy (SEM), surface area measurements (BET method), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), point of zero charge measurement, and X-ray photoelectron spectroscopy (XPS). The as-prepared material (50 mg) was tested as fixed-bed sorbent for the solid-phase extraction (SPE) of tap, river, and sea water samples spiked with REE in the 10-150 ng L-1 range, followed by ICP-MS analysis. A quantitative adsorption was observed for all REE with recoveries in the range of 72-118%. A suitable inter-day precision (RSDs 5-12%, n = 3) was obtained. Sample volumes up to 250 mL provided enrichment factors up to 100. The method detection and quantification limits (MDLs and MQLs) were in the range of 0.4-0.6 ng L-1 and 1-2 ng L-1, respectively. The batch-to-batch reproducibility was verified on four pLG@silica independent preparations. As remarkable advantages, pLG@silica proved to be of easy preparation using a waste material, inexpensive, and reusable for at least 20 SPE cycles.

13.
J Chromatogr A ; 1540: 38-46, 2018 Mar 09.
Artículo en Inglés | MEDLINE | ID: mdl-29429744

RESUMEN

Pristine humic acids (HAs) were thermally condensed onto silica microparticles by a one-pot, inexpensive and green preparation route obtaining a mixed-mode sorbent (HA-C@silica) with good sorption affinity for glucocorticoids (GCs). The carbon-based material, characterized by various techniques, was indeed applied as the sorbent for fixed-bed solid-phase extraction of eight GCs from river water and wastewater treatment plant effluent, spiked at different concentration levels in the range 1-400 ng L-1. After sample extraction, the target analytes were simultaneously and quantitatively eluted in a single fraction of methanol, achieving enrichment factor 4000 and 1000 in river water and wastewater effluent, respectively. Full recovery for all compounds, was gained in the real matrices studied (80-125% in river water, 79-126% in wastewater effluent), with inter-day precision showing relative standard deviations (RSD) below 15% and 18% (n = 3), for river and wastewater effluent, correspondingly. The high enrichment factors coupled with high-performance liquid chromatography tandem mass spectrometry quantification (MRM mode) provided method quantification limits of 0.009-0.48 ng L-1 in river water and 0.06-3 ng L-1 in wastewater effluent and, at the same time, secure identification of the selected drugs. As also evidenced by comparison with literature, HA-C@silica proved to be a valid alternative to the current commercial sorbents, in terms of extraction capability, enrichment factor, ease of preparation and cost. The batch-to-batch reproducibility was assessed by recovery tests on three independently prepared HA-C@silica powders (RSD lower than 7%).


Asunto(s)
Cromatografía Líquida de Alta Presión , Monitoreo del Ambiente/métodos , Glucocorticoides/aislamiento & purificación , Sustancias Húmicas , Dióxido de Silicio/química , Extracción en Fase Sólida , Espectrometría de Masas en Tándem , Agua Dulce/química , Glucocorticoides/análisis , Límite de Detección , Reproducibilidad de los Resultados , Contaminantes Químicos del Agua/análisis
14.
Anal Bioanal Chem ; 409(28): 6709-6718, 2017 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-29071365

RESUMEN

This work shows a novel analytical method for the simultaneous extraction of environmental emerging contaminants as benzenesulfonamides (BSAs), benzotriazoles (BTRs), and benzothiazoles (BTs) from water samples. Pristine multi-walled carbon nanotubes (MWCNTs), not yet tested for such analytes, are here employed as the sorbent phase for dispersive solid-phase extraction (d-SPE) followed by high-performance liquid chromatography/electrospray ionization tandem mass spectrometry (HPLC-HESI-MS/MS). Quantitative sorption is gained by treating 50 mL sample with 100 mg MWCNTs (2 g L-1) in 10 min contact, both in tap and raw river water. After sorption, the analytes are quantitatively desorbed by microwaves (20 min, 160 °C, 250 W) by using 5 mL methanol-ethylacetate-acetic acid (10:70:20, v/v), according to the indications obtained by a chemometric study. The extract is reduced to small volume before analysis, thus reaching overall enrichment factors up to 400. Recovery of the entire procedure, evaluated on tap and surface water samples spiked with 0.1/0.5-50 µg L-1 of each analyte, was in the range 70-116%, with excellent inter-day precision (RSD < 7%). Selectivity and firm analyte identification were assured by MRM detection, and suitable sensitivity was obtained for determination of these pollutants in actual matrices (experimental MDLs 30-170 ng L-1). The proposed analytical method was applied to the analysis of surface water samples, containing concentrations of these contaminants ranging from 100 ng L-1 to 2 µg L-1. Pristine MWCNTs proved to be a valid alternative to other commercial sorbents, both in terms of cost and sorption capacity. Graphical abstract Determination of benzenesulfonamides, benzotriazoles, and benzothiazoles in environmental waters by dispersive multi-walled carbon nanotube extraction prior HPLC-MS.

15.
Anal Chim Acta ; 974: 1-26, 2017 06 29.
Artículo en Inglés | MEDLINE | ID: mdl-28535878

RESUMEN

This paper presents an overview of the recent applications of molecularly imprinted polymers (MIPs) to sample preparation. The review is thought to cover analytical procedures for extraction of contaminants (mainly illegal/noxious organic compounds) from food and environmental matrices, with a particular focus on the various pre-concentration/cleanup techniques, that is offline and online solid-phase extraction (SPE), dispersive SPE (d-SPE), magnetic SPE (MSPE), solid-phase microextraction (SPME) and stir-bar sorptive extraction (SBSE), applied before instrumental quantification. The selectivity and extraction efficiency of MIP-based sorbent phases are critically discussed, also in relation to the physical-chemical properties resulting from the synthetic procedures. A variety of molecularly imprinted sorbents is presented, including hybrid composites embedding carbon nanomaterials and ionic liquids. The analytical performance of MIP materials in sample preparation is commented as function of the complexity of the matrix, and it is compared to that exhibited by (commercial) aspecific and/or immunosorbent phases.


Asunto(s)
Contaminantes Ambientales/análisis , Análisis de los Alimentos , Contaminación de Alimentos/análisis , Impresión Molecular , Polímeros , Compuestos Orgánicos/análisis , Extracción en Fase Sólida , Microextracción en Fase Sólida
16.
ACS Chem Neurosci ; 8(3): 501-512, 2017 03 15.
Artículo en Inglés | MEDLINE | ID: mdl-28292181

RESUMEN

In the substantia nigra of human brain, neuromelanin (NM) released by degenerating neurons can activate microglia with consequent neurodegeneration, typical of Parkinson's disease (PD). Synthetic analogues of NM were prepared to develop a PD model reproducing the neuropathological conditions of the disease. Soluble melanin-protein conjugates were obtained by melanization of fibrillated ß-lactoglobulin (fLG). The melanic portion of the conjugates contains either eumelanic (EufLG) or mixed eumelanic/pheomelanic composition (PheofLG), the latter better simulating natural NMs. In addition, the conjugates can be loaded with controlled amounts of iron. Upon melanization, PheofLG-Fe conjugates maintain the amyloid cross-ß protein core as the only structurally organized element, similarly to human NMs. The similarity in composition and structural organization with the natural pigment is reflected by the ability of synthetic NMs to activate microglia, showing potential of the novel conjugates to model NM induced neuroinflammation. Thus, synthetic NM/microglia constitute a new model to develop anti-Parkinson drugs.


Asunto(s)
Melaninas/análisis , Melaninas/síntesis química , Melaninas/farmacología , Microglía/efectos de los fármacos , Enfermedad de Parkinson/patología , Amiloide/farmacocinética , Animales , Animales Recién Nacidos , Arginasa/genética , Arginasa/metabolismo , Células Cultivadas , Ciclooxigenasa 2/genética , Ciclooxigenasa 2/metabolismo , Dopamina/metabolismo , Proteínas Filagrina , Humanos , Interleucina-1beta/genética , Interleucina-1beta/metabolismo , Hierro/metabolismo , Lactoglobulinas/farmacocinética , Lectinas Tipo C/genética , Lectinas Tipo C/metabolismo , Receptor de Manosa , Lectinas de Unión a Manosa/genética , Lectinas de Unión a Manosa/metabolismo , Melaninas/química , Microglía/ultraestructura , Modelos Biológicos , Óxido Nítrico Sintasa de Tipo II/genética , Óxido Nítrico Sintasa de Tipo II/metabolismo , Ratas , Ratas Sprague-Dawley , Receptores de Superficie Celular/genética , Receptores de Superficie Celular/metabolismo , Sustancia Negra/efectos de los fármacos , Sustancia Negra/metabolismo
17.
J Chromatogr A ; 1489: 9-17, 2017 Mar 17.
Artículo en Inglés | MEDLINE | ID: mdl-28190596

RESUMEN

The analytical application of silica-supported graphitic carbon nitride (g-C3N4@silica) for solid-phase extraction (SPE) of fluoroquinolone (FQ) pollutants from water is presented for the first time. g-C3N4@silica was easily and quickly prepared by one-pot thermal condensation of dicyandiamide and characterized by powder X-ray diffraction, thermogravimetric analysis, scanning electron microscopy, Fourier transform infrared spectroscopy and surface area measurements. The novel composite was applied as sorbent for SPE of FQs from water prior high-performance liquid chromatography with fluorescence detection. The extraction efficiency of g-C3N4 was tested in tap and surface waters at actual concentrations (10-100ngL-1). Quantitative adsorption was achieved using 100mg sorbent (20wt% g-C3N4) for pre-concentration of 50-500mL sample, at the native pH (∼7.5-8). Elution was performed with 25mM H3PO4 aqueous solution-acetonitrile (80:20), obtaining recoveries in the range 70-114%, enrichment factors up to 500 and inter-day RSDs≤12%. The batch-to-batch reproducibility was assessed on three independently synthesized g-C3N4@silica preparations (RSD 6-12%). g-C3N4 supported on silica microparticles proved to be of easy preparation, inexpensive, reusable for at least 4 extractions of raw surface waters, and suitable for determination in real matrices.


Asunto(s)
Antibacterianos/análisis , Fluoroquinolonas/análisis , Grafito/química , Nitrilos/química , Extracción en Fase Sólida/métodos , Contaminantes Químicos del Agua/análisis , Antibacterianos/aislamiento & purificación , Cromatografía Líquida de Alta Presión , Fluoroquinolonas/aislamiento & purificación , Reproducibilidad de los Resultados , Dióxido de Silicio/química , Extracción en Fase Sólida/economía , Contaminantes Químicos del Agua/aislamiento & purificación
18.
Magn Reson Med ; 78(5): 1790-1800, 2017 11.
Artículo en Inglés | MEDLINE | ID: mdl-28019018

RESUMEN

PURPOSE: To investigate the physical mechanisms associated with the contrast observed in neuromelanin MRI. METHODS: Phantoms having different concentrations of synthetic melanins with different degrees of iron loading were examined on a 3 Tesla scanner using relaxometry and quantitative magnetization transfer (MT). RESULTS: Concentration-dependent T1 and T2 shortening was most pronounced for the melanin pigment when combined with iron. Metal-free melanin had a negligible effect on the magnetization transfer spectra. On the contrary, the presence of iron-laden melanins resulted in a decreased magnetization transfer ratio. The presence of melanin or iron (or both) did not have a significant effect on the macromolecular content, represented by the pool size ratio. CONCLUSION: The primary mechanism underlying contrast in neuromelanin-MRI appears to be the T1 reduction associated with melanin-iron complexes. The macromolecular content is not significantly influenced by the presence of melanin with or without iron, and thus the MT is not directly affected. However, as T1 plays a role in determining the MT-weighted signal, the magnetization transfer ratio is reduced in the presence of melanin-iron complexes. Magn Reson Med 78:1790-1800, 2017. © 2016 International Society for Magnetic Resonance in Medicine.


Asunto(s)
Imagen por Resonancia Magnética/métodos , Melaninas/análisis , Melaninas/química , Humanos , Hierro/química , Imagen por Resonancia Magnética/instrumentación , Modelos Biológicos , Fantasmas de Imagen , Sustancia Negra/química
19.
Environ Sci Pollut Res Int ; 24(4): 4153-4161, 2017 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-27943136

RESUMEN

This is the first report on the photodegradation of ofloxacin under simulated solar light and in actual environmental matrices in the presence of a g-C3N4 suspension. The catalyst, prepared from the polymerization of dicyandiamide (650 °C, reaction yield 60%), was characterized by means of powder X-ray diffraction (PXRD), UV-vis diffuse reflectance spectroscopy (DRS), scanning electron microscopy (SEM), and BET surface area measurements. The experiments were carried out in a lab-scale batch reactor at concentrations in the range of micrograms/milligrams per liter. The course of the reaction was monitored by high-pressure liquid chromatography with UV-vis and fluorescence detectors. The g-C3N4-promoted photodegradation occurred at a rate 10 times faster than the direct photolysis and obeyed a first-order kinetics; in addition, the photodegradation kinetics of sonicated g-C3N4 resulted to be of the same order of that caused by P25 TiO2. Finally, the photochemical paths and the photoproducts have been identified and compared to those obtained by using P25 TiO2. From the results of this study, it can be concluded that g-C3N4 is a very attractive photocatalyst compared to P25 TiO2 in view of its ease of preparation, low cost, excellent oxidizing properties, large fraction of solar radiation absorbed, and intrinsically layered structure.


Asunto(s)
Antibacterianos/química , Nitrilos/química , Ofloxacino/química , Fotólisis , Luz Solar , Catálisis , Cinética , Luz , Agua/química
20.
J Forensic Leg Med ; 39: 22-6, 2016 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-26807996

RESUMEN

The aim of this paper was to evaluate silicon (Si) concentration in human whole ventricular blood as a further potential chemical marker in the diagnosis of drowning. We employed an acidic digestion for the extraction of soluble Si, and an alkaline digestion for the determination of total Si, including particulate matter, both arising from drowning medium. 29 suspected drowning situations, 24 in fresh water (Fw) and 5 in seawater (Sw), were examined. The difference in Si concentration between the left and right ventricular blood (Si ΔL-R) was measured and alkaline Si ΔL-R seems, indeed, a potentially significant complementary tool in the diagnosis of Fw drowning, because insoluble silicon fraction does not undergo hemo-dilution or hemo-concentration, and the ΔL-R is not affected by exogenous factors. In spite of the limited number of cases investigated, a good correlation was observed between the analytical results and the macro-microscopic autoptic findings.


Asunto(s)
Ahogamiento/diagnóstico , Silicio/sangre , Adolescente , Adulto , Anciano , Anciano de 80 o más Años , Biomarcadores/sangre , Estudios de Casos y Controles , Niño , Preescolar , Método Doble Ciego , Femenino , Patologia Forense , Agua Dulce , Ventrículos Cardíacos , Humanos , Masculino , Persona de Mediana Edad , Agua de Mar , Adulto Joven
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