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1.
Nanoscale ; 11(39): 18393-18406, 2019 Oct 10.
Artigo em Inglês | MEDLINE | ID: mdl-31573583

RESUMO

Iron oxide nanoparticles (IONPs) are frequently used in biomedical applications due to their magnetic properties and putative chemical stability. Nevertheless, their well-known ability to mimic some features of the peroxidase enzyme activity under specific conditions of pH and temperature could lead to the formation of potentially harmful free radical species. In addition to the intrinsic enzyme-like activity of IONPs, the buffer solution is an important external factor that can alter dramatically the IONP activity because the buffer species can interact with the surface of the particles. In our study, IONP activity was evaluated in different buffering solutions under different experimental conditions and predominant free radical species were measured by electron paramagnetic resonance using the spin-trap 5,5-dimethyl-1-pyrroline N-oxide (DMPO). The formation kinetics of the reactive oxygen species were studied by UV-visible spectroscopy with TMB and DAB peroxidase substrates. We found that the highest catalytic oxidation of peroxidase substrates and free radical generation were achieved in acetate buffer, while phosphate buffer inhibited the peroxidase-like activity of IONPs in a concentration dependent manner. When emulating the physiological conditions, a lower catalytic activity was observed at pH 7.4 when compared to that at pH 5.0. Also, in phosphate buffered saline (PBS), we observed an enhancement in the peroxidase substrate oxidation rate that was not accompanied by an increase in DMPO/adduct formation which could be related to a non-specific oxidation catalyzed by the chloride ion. Similar observations were found after the addition of a bicarbonate to HEPES buffer. TMB oxidation did not occur when the reaction was conducted with free iron ions from metal salts with the same concentration of the IONPs (0.33 Fe2+ and 0.66 Fe3+). However, we observed even higher catalytic activities than those when doubling the IONP concentration when they are combined with the free iron salts. These results indicate that biological buffering solutions need to be carefully considered when evaluating IONP catalytic activity and their potential toxicological effects since under physiological conditions of pH, salinity and buffering species, the peroxidase-like activity of IONPs is dramatically reduced.


Assuntos
Nanopartículas de Magnetita/química , Peroxidase/química , Espécies Reativas de Oxigênio/química , Tampões (Química) , Espectroscopia de Ressonância de Spin Eletrônica , Oxirredução
2.
Exp Parasitol ; 199: 59-66, 2019 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-30825498

RESUMO

Fasciolosis is a zoonotic world widely distributed disease caused by the liver fluke Fasciola hepatica, which affects animals and occasionally humans. On the other hand, natural iron oxide particles like magnetite are commonly found in soils where they participate in a wide range of environmental processes like organic matter decomposition, the adsorption of ions and molecules, and chemical reactions that involve the participation of soil living microorganisms. Since Fasciola eggs become soil components after being released with the infected animal faeces, this study focused on the characterization of the natural interaction between natural sub-micrometric magnetite particles and F. hepatica eggs. Our results indicate that particle binding to the F. hepatica egg depends on the particle size and it is also related to the exposed surface area since any condition that favors particle agglomeration leads to the reduction of the particle-eggshell binding intensity. Interestingly, this binding was avoided when proteins or phosphate were incorporated to the incubation solution, but not after formaldehyde fixation of eggs. Finally, when eggs were exposed to an external magnet after being incubated with magnetite particles, they were attracted to it without particles being detached, indicating a strong type of bonding between them. Therefore, the results presented here give new insights in order to improve the possibility of harvesting F. hepatica eggs by using magnetic materials.


Assuntos
Fasciola hepatica/metabolismo , Óxido Ferroso-Férrico/metabolismo , Animais , Ensaio de Desvio de Mobilidade Eletroforética , Fasciolíase/parasitologia , Fasciolíase/veterinária , Fezes/parasitologia , Fixadores/farmacologia , Formaldeído/farmacologia , Concentração de Íons de Hidrogênio , Nanopartículas de Magnetita/ultraestrutura , Microscopia Eletrônica de Transmissão , Distribuição Normal , Óvulo/metabolismo , Tamanho da Partícula , Peroxidase/análise , Fosfatos/farmacologia , Proteínas/farmacologia , Ovinos , Doenças dos Ovinos/parasitologia , Solo/química , Solo/parasitologia , Espectrometria por Raios X
3.
Nanoscale ; 11(7): 3164-3172, 2019 Feb 14.
Artigo em Inglês | MEDLINE | ID: mdl-30520920

RESUMO

We report a simple and effective way to control the heat generation of a magnetic colloid under alternate magnetic fields by changing the shell composition of bimagnetic core-shell Fe3O4/ZnxCo1-xFe2O4 nanoparticles. The core-shell structure constitutes a magnetically-coupled biphase system, with an effective anisotropy that can be tuned by the substitution of Co2+ by Zn2+ ions in the shell. Magnetic hyperthermia experiments of nanoparticles dispersed in hexane and butter oil showed that the magnetic relaxation is dominated by Brown relaxation mechanism in samples with higher anisotropy (i.e., larger concentration of Co within the shell) yielding high specific power absorption values in low viscosity media as hexane. Increasing the Zn concentration of the shell, diminishes the magnetic anisotropy, which results in a change to a Néel relaxation that dominates the process when the nanoparticles are dispersed in a high-viscosity medium. We demonstrate that tuning the Zn contents at the shell of these exchange-coupled core/shell nanoparticles provides a way to control the magnetic anisotropy without loss of saturation magnetization. This ability is an essential prerequisite for most biomedical applications, where high viscosities and capturing mechanisms are present.

4.
Small ; 14(15): e1703963, 2018 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-29479814

RESUMO

Although cubic rock salt-CoO has been extensively studied, the magnetic properties of the main nanoscale CoO polymorphs (hexagonal wurtzite and cubic zinc blende structures) are rather poorly understood. Here, a detailed magnetic and neutron diffraction study on zinc blende and wurtzite CoO nanoparticles is presented. The zinc blende-CoO phase is antiferromagnetic with a 3rd type structure in a face-centered cubic lattice and a Néel temperature of TN (zinc-blende) ≈225 K. Wurtzite-CoO also presents an antiferromagnetic order, TN (wurtzite) ≈109 K, although much more complex, with a 2nd type order along the c-axis but an incommensurate order along the y-axis. Importantly, the overall magnetic properties are overwhelmed by the uncompensated spins, which confer the system a ferromagnetic-like behavior even at room temperature.

5.
Nanoscale ; 9(29): 10240-10247, 2017 Jul 27.
Artigo em Inglês | MEDLINE | ID: mdl-28696450

RESUMO

In order to explore an alternative strategy to design exchange-biased magnetic nanostructures, bimagnetic core/shell nanoparticles have been fabricated by a thermal decomposition method and systematically studied as a function of the interface exchange coupling. The nanoparticles are constituted by a ∼3 nm antiferromagnetic (AFM) CoO core encapsulated in a ∼4 nm-thick Co1-xZnxFe2O4 (x = 0-1) ferrimagnetic (FiM) shell. The system presents an enhancement of the coercivity (HC) as compared to its FiM single-phase counterpart and exchange bias fields (HEB). While HC decreases monotonically with the Zn concentration from ∼21.5 kOe for x = 0, to ∼7.1 kOe for x = 1, HEB exhibits a non-monotonous behavior being maximum, HEB ∼ 1.4 kOe, for intermediate concentrations. We found that the relationship between the AFM anisotropy energy and the exchange coupling energy can be tuned by replacing Co2+ with Zn2+ ions in the shell. As a consequence, the magnetization reversal mechanism of the system is changed from an AFM/FiM rigid-coupling regime to an exchange-biased regime, providing a new approach to tune the magnetic properties and to design novel hybrid nanostructures.

6.
Biomater Sci ; 5(4): 772-783, 2017 Mar 28.
Artigo em Inglês | MEDLINE | ID: mdl-28256646

RESUMO

A simple two-step drug encapsulation method was developed to obtain biocompatible magnetic nanocarriers for the potential targeted treatment of diverse diseases. The nanodevice consists of a magnetite core coated with chitosan (Chit@MNPs) as a platform for diclofenac (Dic) loading as a model drug (Dic-Chit@MNPs). Mechanistic and experimental conditions related to drug incorporation and quantification are further addressed. This multi-disciplinary study aims to elucidate the toxicological impact of the MNPs at hematological, vascular, neurological and behavioral levels. Blood compatibility assays revealed that MNPs did not affect either erythrosedimentation rates or erythrocyte integrity at the evaluated doses (1, 10 and 100 µg mL-1). A microscopic evaluation of blood smears indicated that MNPs did not induce morphological changes in blood cells. Platelet aggregation was not affected by MNPs either and just a slight diminution was observed with Dic-Chit@MNPs, an effect possibly due to diclofenac. The examined formulations did not exert cytotoxicity on rat aortic endothelial cells and no changes in cell viability or their capacity to synthesize NO were observed. Behavioral and functional nervous system parameters in a functional observational battery were assessed after a subacute treatment of mice with Chit@MNPs. The urine pools of the exposed group were decreased. Nephritis and an increased number of megakaryocytes in the spleen were observed in the histopathological studies. Sub-acute exposure to Chit@MNPs did not produce significant changes in the parameters used to evaluate neurobehavioral toxicity. The aspects focused on within this manuscript are relevant at the pre-clinical level providing new and novel knowledge concerning the biocompatibility of magnetic nanodevices for biomedical applications.


Assuntos
Anti-Inflamatórios não Esteroides/administração & dosagem , Quitosana/toxicidade , Diclofenaco/administração & dosagem , Portadores de Fármacos/toxicidade , Sistemas de Liberação de Medicamentos/métodos , Nanopartículas de Magnetita/toxicidade , Animais , Sobrevivência Celular/efeitos dos fármacos , Células Cultivadas , Quitosana/química , Portadores de Fármacos/química , Células Endoteliais/citologia , Células Endoteliais/efeitos dos fármacos , Células Endoteliais/metabolismo , Eritrócitos/citologia , Eritrócitos/efeitos dos fármacos , Eritrócitos/metabolismo , Feminino , Nanopartículas de Magnetita/química , Nanopartículas de Magnetita/ultraestrutura , Camundongos , Óxido Nítrico/metabolismo , Agregação Plaquetária/efeitos dos fármacos , Ratos Wistar
7.
Sci Rep ; 6: 38733, 2016 12 07.
Artigo em Inglês | MEDLINE | ID: mdl-27924942

RESUMO

This work aims to demonstrate the need for in silico design via numerical simulation to produce optimal Fe3O4-based magnetic nanoparticles (MNPs) for magnetic hyperthermia by minimizing the impact of intracellular environments on heating efficiency. By including the relevant magnetic parameters, such as magnetic anisotropy and dipolar interactions, into a numerical model, the heating efficiency of as prepared colloids was preserved in the intracellular environment, providing the largest in vitro specific power absorption (SPA) values yet reported. Dipolar interactions due to intracellular agglomeration, which are included in the simulated SPA, were found to be the main cause of changes in the magnetic relaxation dynamics of MNPs under in vitro conditions. These results pave the way for the magnetism-based design of MNPs that can retain their heating efficiency in vivo, thereby improving the outcome of clinical hyperthermia experiments.

8.
Nanomedicine ; 12(4): 909-919, 2016 May.
Artigo em Inglês | MEDLINE | ID: mdl-26767515

RESUMO

UNLABELLED: Superparamagnetic iron oxide nanoparticles (SPIONS) were synthesized by thermal decomposition of an organometallic precursor at high temperature and coated with a bi-layer composed of oleic acid and methoxy-polyethylene glycol-phospholipid. The formulations were named SPION-PEG350 and SPION-PEG2000. Transmission electron microscopy, X-ray diffraction and magnetic measurements show that the SPIONs are near-spherical, well-crystalline, and have high saturation magnetization and susceptibility. FTIR spectroscopy identifies the presence of oleic acid and of the conjugates mPEG for each sample. In vitro biocompatibility of SPIONS was investigated using three cell lines; up to 100µg/ml SPION-PEG350 showed non-toxicity, while SPION-PEG2000 showed no signal of toxicity even up to 200µg/ml. The uptake of SPIONS was detected using magnetization measurement, confocal and atomic force microscopy. SPION-PEG2000 presented the highest internalization capacity, which should be correlated with the mPEG chain size. The in vivo results suggested that SPION-PEG2000 administration in mice triggered liver and kidney injury. FROM THE CLINICAL EDITOR: The potential use of superparamagnetic iron oxide nanoparticles (SPIONS) in the clinical setting have been studied by many researchers. The authors synthesized two types of SPIONS here and investigated the physical properties and biological compatibility. The findings should provide more data on the design of SPIONS for clinical application in the future.


Assuntos
Materiais Revestidos Biocompatíveis/administração & dosagem , Nanopartículas de Magnetita/administração & dosagem , Polietilenoglicóis/administração & dosagem , Animais , Linhagem Celular , Sobrevivência Celular/efeitos dos fármacos , Materiais Revestidos Biocompatíveis/química , Compostos Férricos/administração & dosagem , Compostos Férricos/química , Humanos , Rim/efeitos dos fármacos , Fígado/efeitos dos fármacos , Nanopartículas de Magnetita/química , Camundongos , Ácido Oleico/química , Polietilenoglicóis/química , Difração de Raios X
9.
Nanoscale ; 7(7): 3002-15, 2015 Feb 21.
Artigo em Inglês | MEDLINE | ID: mdl-25600147

RESUMO

The intimate relationship between stoichiometry and physicochemical properties in transition-metal oxides makes them appealing as tunable materials. These features become exacerbated when dealing with nanostructures. However, due to the complexity of nanoscale materials, establishing a distinct relationship between structure-morphology and functionalities is often complicated. In this regard, in the FexO/Fe3O4 system a largely unexplained broad dispersion of magnetic properties has been observed. Here we show, thanks to a comprehensive multi-technique approach, a clear correlation between the magneto-structural properties in large (45 nm) and small (9 nm) FexO/Fe3O4 core/shell nanoparticles that can explain the spread of magnetic behaviors. The results reveal that while the FexO core in the large nanoparticles is antiferromagnetic and has bulk-like stoichiometry and unit-cell parameters, the FexO core in the small particles is highly non-stoichiometric and strained, displaying no significant antiferromagnetism. These results highlight the importance of ample characterization to fully understand the properties of nanostructured metal oxides.

10.
Nanotechnology ; 25(35): 355704, 2014 Sep 05.
Artigo em Inglês | MEDLINE | ID: mdl-25120018

RESUMO

The control of the size of bimagnetic nanoparticles represents an important step toward the study of fundamental properties and the design of new nanostructured magnetic materials. We report the synthesis and the structural and magnetic characterization of bimagnetic CoO/CoFe2O4 core/shell nanoparticles. The material was fabricated by a seed-mediated growth high-temperature decomposition method with sizes in the range of 5-11 nm. We show that the core/shell morphology favours the crystallinity of the shell phase, and the reduction of the particle size leads to a remarkable increase of the magnetic hardening. When the size is reduced, the coercive field at 5 K increases from 21.5 kOe to 30.8 kOe, while the blocking temperature decreases from 388 K to 167 K. The size effects on the magnetic behaviour are described through a phenomenological model for strongly ferri-/antiferromagnetic coupled phases.

11.
J Am Chem Soc ; 132(27): 9398-407, 2010 Jul 14.
Artigo em Inglês | MEDLINE | ID: mdl-20568759

RESUMO

The magnetic properties of bimagnetic core/shell nanoparticles consisting of an antiferromagnetic MnO core and a ferrimagnetic passivation shell have been investigated. It is found that the phase of the passivation shell (gamma-Mn(2)O(3) or Mn(3)O(4)) depends on the size of the nanoparticles. Structural and magnetic characterizations concur that while the smallest nanoparticles have a predominantly gamma-Mn(2)O(3) shell, larger ones have increasing amounts of Mn(3)O(4). A considerable enhancement of the Néel temperature, T(N), and the magnetic anisotropy of the MnO core for decreasing core sizes has been observed. The size reduction also leads to other phenomena such as persistent magnetic moment in MnO up to high temperatures and an unusual temperature behavior of the magnetic domains.

12.
Nanotechnology ; 20(4): 045606, 2009 Jan 28.
Artigo em Inglês | MEDLINE | ID: mdl-19417326

RESUMO

We report a single-step chemical synthesis of iron oxide hollow nanospheres with 9.3 nm in diameter. The sample presents a narrow particle diameter distribution and chemical homogeneity. The hollow nature of the particles is confirmed by HRTEM and HAADF STEM analysis. Electron and x-ray diffraction show that the outer material component is constituted by 2 nm ferrite crystals. Mössbauer data provide further evidence for the formation of iron oxide with high structural disorder, magnetically ordered at 4.2 K and superparamagnetism at room temperature. An unusual magnetic behavior under an applied field is reported, which can be explained by the large fraction of atoms existing at both inner and outer surfaces.

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