RESUMO

There is increasing interest in the development of new magnetic polymeric carriers for biomedical applications such as trigger-controlled drug release, magnetic hyperthermia (MH) for the treatment of cancer, and as contrast agents in magnetic resonance imaging (MRI). This work describes the synthesis of sub-micrometer and magnetic polymer nanocomposite capsules (MPNCs) by combining in one single platform the biodegradable polymer poly-ε-caprolactone (PCL) and different concentrations of ∼8 nm oleic acid (OA)-functionalized magnetite nanoparticles (Fe3O4@OA), employing the oil-in-water emulsion/solvent evaporation method. The MPNCs showed a significant increase in particle size from ∼400 to ∼800 nm as the magnetic loading in the organic-inorganic hybrids increases from 1.0% to 10%. The MPNCs presented high incorporation efficiency of Fe3O4@OA nanoparticles, good colloidal stability, and super-paramagnetic properties. Interestingly, electron microscopy results showed that the Fe3O4@OA nanoparticles were preferentially located at the surface of the capsules. Evaluation of the magnetic properties showed that the saturation magnetization and the blocking temperature of the MPNCs samples increased as a function of the Fe3O4@OA loading. All the MPNCs exhibited heating when subjected to MH, and showed good specific absorption rates. Use of the formulations decreased the longitudinal (T1) and transverse (T2) relaxation times of water protons' nuclei, with excellent transverse relaxivity (r2) values, especially in the case of the formulation with lowest Fe3O4@OA loading. Furthermore, the MPNCs-cell interaction was studied, and MPNCs showed lower cellular toxicity to normal cells compared to cancer cells. These findings help in understanding the relationships between magnetic nanoparticles and polymeric capsules, opening perspectives for their potential clinical uses as simultaneous heating sources and imaging probes in MH and MRI, respectively.

RESUMO

A theoretical approach aiming at the prediction of segregation of dopant atoms on nanocrystalline systems is discussed here. It considers the free energy minimization argument in order to provide the most likely dopant distribution as a function of the total doping level. For this, it requires as input (i) a fixed polyhedral geometry with defined facets, and (ii) a set of functions that describe the surface energy as a function of dopant content for different crystallographic planes. Two Sb-doped SnO2 nanocrystalline systems with different morphology and dopant content were selected as a case study, and the calculation of the dopant distributions expected for them is presented in detail. The obtained results were compared to previously reported characterization of this system by a combination of HRTEM and surface energy calculations, and both methods are shown to be equivalent. Considering its application pre-requisites, the present theoretical approach can provide a first estimation of doping atom distribution for a wide range of nanocrystalline systems. We expect that its use will support the reduction of experimental effort for the characterization of doped nanocrystals, and also provide a solution to the characterization of systems where even state-of-art analytical techniques are limited.

RESUMO

This work presents the morphological characterization of CeO2 nanocrystals by the analysis of single unfiltered high-angle annular dark-field (HAADF)-high-resolution scanning transmission electron microscopy (HRSTEM) images. The thickness of each individual atomic column is estimated by the classification of its HAADF integrated intensity using a Gaussian mixture model. The resulting thickness maps obtained from two example nanocrystals with distinct morphology were analyzed with aid of the symmetry from the CeO2 crystallographic structure, providing an approximation for their 3-D morphology with high spatial resolution. A confidence level of ±1 atom per atomic column along the viewing direction on the thickness estimation is indicated by the use of multislice image simulation. The described characterization procedure stands out as a simple approach for retrieving morphological parameters of individual nanocrystals, such as volume and specific surface areas for different crystalline planes. The procedure is an alternative to the tilt-series tomography technique for a number of nanocrystalline systems, since its application does not require the acquisition of multiple images from the same nanocrystal along different zone axes.

RESUMO

This work presents an overview of high-resolution scanning transmission electron microscopy (HRSTEM) techniques and exemplifies the novel quantitative characterization possibilities that have emerged from recent advances in these methods. The synergistic combination of atomic resolution imaging and spectroscopy provided by HRSTEM is highlighted as a unique feature that can provide a comprehensive analytical description of material properties at the nanoscale. State-of-the-art high-angle annular dark field and annular bright field examples are depicted as well as the use of X-ray energy-dispersive spectroscopy and electron energy-loss spectroscopy for probing samples properties at the atomic scale. In addition, promising techniques such as cathodoluminescence, confocal HRSTEM, and diffraction mapping are introduced. The presented examples and results indicate that HRSTEM-related techniques are fundamental tools for comprehensive assessment of properties at the atomic scale.

RESUMO

The development of reliable nanostructured devices is intrinsically dependent on the description and manipulation of materials' properties at the atomic scale. Consequently, several technological advances are dependent on improvements in the characterization techniques and in the models used to describe the properties of nanosized materials as a function of the synthesis parameters. The evaluation of doping element distributions in nanocrystals is directly linked to fundamental aspects that define the properties of the material, such as surface-energy distribution, nanoparticle shape, and crystal growth mechanism. However, this is still one of the most challenging tasks in the characterization of materials because of the required spatial resolution and other various restrictions from quantitative characterization techniques, such as sample degradation and signal-to-noise ratio. This paper addresses the dopant segregation characterization for two antimony-doped tin oxide (Sb:SnO(2)) systems, with different Sb doping levels, by the combined use of experimental and simulated high-resolution transmission electron microscopy (HRTEM) images and surface-energy ab initio calculations. The applied methodology provided three-dimensional models with geometrical and compositional information that were demonstrated to be self-consistent and correspond to the systems' mean properties. The results evidence that the dopant distribution configuration is dependent on the system composition and that dopant atom redistribution may be an active mechanism for the overall surface-energy minimization.

RESUMO

Image simulation has an invaluable importance for the accurate analysis of High Resolution Transmission Electron Microscope (HRTEM) results, especially due to its non-linear image formation mechanism. Because the as-obtained images cannot be interpreted in a straightforward fashion, the retrieval of both qualitative and quantitative information from HRTEM micrographs requires an iterative process including the simulation of a nanocrystal model and its comparison with experimental images. However most of the available image simulation software requires atom-by-atom coordinates as input for the calculations, which can be prohibitive for large finite crystals and/or low-symmetry systems and zone axis orientations. This paper presents an open source citation-ware tool named MEGACELL, which was developed to assist on the construction of nanocrystals models. It allows the user to build nanocrystals with virtually any convex polyhedral geometry and to retrieve its atomic positions either as a plain text file or as an output compatible with EMS (Electron Microscopy Software) input protocol. In addition to the description of this tool features, some construction examples and its application for scientific studies are presented. These studies show MEGACELL as a handy tool, which allows an easier construction of complex nanocrystal models and improves the quantitative information extraction from HRTEM images.

RESUMO

In this work, we describe a kinetically controlled crystallization process assisted by an oriented attachment (OA) mechanism based on a nonaqueous sol-gel synthetic method (specifically, the reaction of titanium(IV) chloride (TiCl(4)) with n-octanol) to prepare re-crystallized anatase TiO(2) mesocrystals (single crystal). The kinetics study revealed a multi-step and hierarchical process controlled by OA, and a high resolution transmission electron microscopy (HRTEM) analysis clearly shows that the synthesized mesocrystal presents a truncated bipyramidal Wulff shape, indicating that its surface is dominated by {101} facets. This shape is developed during the recrystallization step. The material developed here displayed superior photocatalytic activity under visible light irradiation compared to TiO(2)-P25 as a benchmarking.

Assuntos

Cristalização/métodos , Nanoestruturas/química , Nanoestruturas/ultraestrutura , Titânio/química , Substâncias Macromoleculares/química , Teste de Materiais , Conformação Molecular , Tamanho da Partícula , Propriedades de Superfície

RESUMO

This work reports a detailed characterization of an anomalous oriented attachment behaviour for SnO(2) nanocrystals. Our results evidenced an anisotropic growth for two identical <110> directions, which are equivalent according to the SnO(2) crystallographic structure symmetry. A hypothesis is proposed to describe this behaviour.

RESUMO

Modeling of nanocrystals supported by advanced morphological and chemical characterization is a unique tool for the development of reliable nanostructured devices, which depends on the ability to synthesize and characterize materials on the atomic scale. Among the most significant challenges in nanostructural characterization is the evaluation of crystal growth mechanisms and their dependence on the shape of nanoparticles and the distribution of doping elements. This paper presents a new strategy to characterize nanocrystals, applied here to antimony-doped tin oxide (Sb-SnO(2)) (ATO) by the combined use of experimental and simulated high-resolution transmission electron microscopy (HRTEM) images and surface energy ab initio calculations. The results show that the Wulff construction can not only describe the shape of nanocrystals as a function of surface energy distribution but also retrieve quantitative information on dopant distribution by the dimensional analysis of nanoparticle shapes. In addition, a novel three-dimensional evaluation of an oriented attachment growth mechanism is provided in the proposed methodology. This procedure is a useful approach for faceted nanocrystal shape modeling and indirect quantitative evaluation of dopant spatial distribution, which are difficult to evaluate by other techniques.

RESUMO

This work focuses on the nonaqueous synthesis of antimony-doped tin oxide nanocrystals in the size range of 2-6 nm and the investigation of their solubility in organic solvents (CHCl(3) and THF) in the presence of amphiphilic molecules (oleic acid and oleylamine). To unravel the underlying processes, a set of molecular dynamics simulations is performed involving the compatibility of oleic acid and oleylamine in mixtures with both CHCl(3) and THF. The results show that the method is useful for obtaining the desired oxide, and that the interaction between amphiphilic molecules and solvents can be predicted by molecular dynamics simulations with very good qualitative agreement.