Superparamagnetic iron oxide nanoparticles induce persistent large foci of DNA damage in human melanoma cells post-irradiation.

The synergy of superparamagnetic iron oxide nanoparticles (SPIONs) and ionizing radiation (IR), attributed to reactive oxygen species (ROS) and DNA double-strand breaks (DSBs) increase, was widely investigated in different cancers, but scarcely in melanoma. Herein, SPIONs were evaluated as radiosensitizers in A-375 human melanoma cells. Moreover, the effect of the combined treatment of SPIONs and gamma irradiation (SPIONs-IR) was assessed at the DNA level, where DSBs induction and their repair capacity were studied. SPIONs were synthesized, stabilized by poly(ethylene glycol) methyl ether and physicochemically characterized by high resolution-transmission electron microscopy (HR-TEM), X-ray diffraction and magnetometry and dynamic light scattering. The obtained nanoparticles showing superparamagnetic behavior and low dispersion in shape and sizes were tested in A-375 cells. The intracellular internalization of SPIONs was verified by HR-TEM and quantified by inductively coupled plasma atomic emission spectroscopy. Cells treated with SPIONs exhibited high ROS levels without associated cytotoxicity. Next, a significant radiosensitization in SPIONs-IR vs. control (IR) cells was demonstrated at 1 Gy of gamma radiation. Furthermore, a decreased DSBs repair capacity in SPIONs-IR vs. IR-treated cells was evidenced by the size increase of persistent phosphorylated H2AX foci at 24 h post-irradiation. In conclusion, these nanoparticles show the potential to radiosensitize melanoma cells by the induction of unrepairable DNA damage.

Synthesis and evaluation of thermal neutron attenuation properties of lithium orthosilicate for its application as a beam shaping material on BNCT facilities.

Thermal neutron attenuation capacity of Li4SiO4 was evaluated to assess its potential capabilities as a beam shaping material for boron neutron capture therapy (BNCT) facilities. Samples of Li4SiO4 were prepared by two different synthesis methods, using different raw materials and were characterized using x-ray, electron diffraction and transmission electron microscopy. Neutron measurements were performed at the BNCT and the neutron radiography facilities of Centro Atómico Bariloche. Considering its natural isotopic abundance, Li4SiO4 proved to be remarkably effective in comparison with other neutron-absorbing materials. Given the availability of natural Lithium in local salt mines and the scalable feasibility, Li4SiO4 qualifies as a potential material for BNCT beam shaping applications.

Elastic distortion determining conduction in BiFeO3 phase boundaries.

It is now well-established that boundaries separating tetragonal-like (T) and rhombohedral-like (R) phases in BiFeO3 thin films can show enhanced electrical conductivity. However, the origin of this conductivity remains elusive. Here, we study mixed-phase BiFeO3 thin films, where local populations of T and R can be readily altered using stress and electric fields. We observe that phase boundary electrical conductivity in regions which have undergone stress-writing is significantly greater than in the virgin microstructure. We use high-end electron microscopy techniques to identify key differences between the R-T boundaries present in stress-written and as-grown microstructures, to gain a better understanding of the mechanism responsible for electrical conduction. We find that point defects (and associated mixed valence states) are present in both electrically conducting and non-conducting regions; crucially, in both cases, the spatial distribution of defects is relatively homogeneous: there is no evidence of phase boundary defect aggregation. Atomic resolution imaging reveals that the only significant difference between non-conducting and conducting boundaries is the elastic distortion evident - detailed analysis of localised crystallography shows that the strain accommodation across the R-T boundaries is much more extensive in stress-written than in as-grown microstructures; this has a substantial effect on the straightening of local bonds within regions seen to electrically conduct. This work therefore offers distinct evidence that the elastic distortion is more important than point defect accumulation in determining the phase boundary conduction properties in mixed-phase BiFeO3.

Interaction between natural magnetite sub-micrometric particles and the Fasciola hepatica egg: The role of the exposed surface area.

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.

Physicochemical characterization of 2-hydroxybenzophenone with ß-cyclodextrin in solution and solid state.

The characterization of the inclusion complex between 2-hydroxybenzophenone (2OHBP) and ß-cyclodextrin (ßCD) in the solid state was performed using Fourier transform infrared spectroscopy (FTIR), powder X-ray diffractometry (PXRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and transmission electron microscopy (TEM). The apparent formation constant of the complex was determined by phase solubility diagrams and liquid chromatography (HPLC) at different temperatures. The formation of the inclusion complex induced slight shifts in the FTIR spectrum while by PXRD a new crystalline phase was observed. TEM studies revealed that the complex forms aggregates of nanometric size. The inclusion complex showed a higher solubility in the tested dissolution media than free 2OHBP. Moreover, the freeze-dried solid complex exhibits a higher thermal stability than the solid free drug. The thermodynamic analysis allowed us to conclude that the encapsulation process is endothermic in water and exothermic in methanol-water.

The optoelectronic behaviour of carbon nanoparticles: evidence of the importance of the outer carbon shell.

The particular properties of carbon nanoparticles (CNPs) have generated great interest in biomedicine, bioanalysis and optoelectronics. However, an association between the CNPs' physicochemical properties with their molecular and morphological characteristics is, even today, a topic of discussion. In this work, we use a simple method of synthesis with the ultimate aim of elucidating the structural nature of the obtained CNPs and its relationship with their well-known fluorescent properties. The sample is studied by high-resolution transmission electron microscopy (HRTEM), electron energy-loss spectroscopy (EELS), nuclear magnetic resonance (NMR), UV-visible and IR spectroscopy, electrochemistry and electrogenerated chemiluminescence (ECL). The results showed that the nanoparticles are constituted by a graphitic core surrounded by an amorphous layer, which seems to be significant in the determination of the optical and electronic properties observed in the system under study.

Chemical distribution and bonding of lithium in intercalated graphite: identification with optimized electron energy loss spectroscopy.

Direct mapping of the lithium spatial distribution and the chemical state provides critical information on structure-correlated lithium transport in electrode materials for lithium batteries. Nevertheless, probing lithium, the lightest solid element in the periodic table, poses an extreme challenge with traditional X-ray or electron scattering techniques due to its weak scattering power and vulnerability to radiation damage. Here, we report nanoscale maps of the lithium spatial distribution in electrochemically lithiated graphite using electron energy loss spectroscopy in the transmission electron microscope under optimized experimental conditions. The electronic structure of the discharged graphite was obtained from the near-edge fine structure of the Li and C K-edges and ab initio calculations. A 2.7 eV chemical shift of the Li K-edge, along with changes in the density of states, reveals the ionic nature of the intercalated lithium with significant charge transfer to the graphene sheets. Direct mapping of lithium in graphite revealed nanoscale inhomogeneities (nonstoichiometric regions), which are correlated with local phase separation and structural disorder (i.e., lattice distortion and dislocations) as observed by high-resolution transmission electron microscopy. The surface solid-electrolyte interphase (SEI) layer was also imaged and determined to have a thickness of 10-50 nm, covering both edge and basal planes with LiF as its primary inorganic component. The Li K-edge spectroscopy and mapping, combined with electron microscopy-based structural analysis provide a comprehensive view of the structure-correlated lithium intercalation in graphite and of the formation of the SEI layer.

Using highly accurate 3D nanometrology to model the optical properties of highly irregular nanoparticles: a powerful tool for rational design of plasmonic devices.

The realization of materials at the nanometer scale creates new challenges for quantitative characterization and modeling as many physical and chemical properties at the nanoscale are highly size and shape-dependent. In particular, the accurate nanometrological characterization of noble metal nanoparticles (NPs) is crucial for understanding their optical response that is determined by the collective excitation of conduction electrons, known as localized surface plasmons. Its manipulation gives place to a variety of applications in ultrasensitive spectroscopies, photonics, improved photovoltaics, imaging, and cancer therapy. Here we show that by combining electron tomography with electrodynamic simulations an accurate optical model of a highly irregular gold NP synthesized by chemical methods could be achieved. This constitutes a novel and rigorous tool for understanding the plasmonic properties of real three-dimensional nano-objects.

Electrochemical preparation and delivery of melanin-iron covered gold nanoparticles.

Attractive combination: Biopolymer-modified nanoparticles which combine magnetic properties with biocompatibility are prepared and delivered following a three-step strategy (see figure): i) Adsorption of thiol-capped metal nanoparticles on graphite, ii) electrochemical modification, iii) potential-induced delivery of the modified nanoparticles to the electrolyte. Thiol-capped gold nanoparticles modified with iron-melanin are attractive because they combine magnetic properties and biocompatibility. The biopolymer modified nanoparticles are prepared and delivered following a three step strategy: i) adsorption of thiol-capped metal nanoparticles on graphite, ii) electrochemical deposition of melanin-iron, iii) potential-induced delivery of the modified nanoparticles to the electrolyte.

Highly anisotropic distribution of iron nanoparticles within MCM-41 Mesoporous Silica.

Electron microscopy techniques are used to visualize the spatial distribution of iron nanoparticles inside a mesoporous MCM-41 molecular sieve. Direct observation of the iron oxide nanoparticles by STEM-HAADF imaging reveals a highly non-uniform spatial distribution inside the mesopores. These particles are retained in the pores after a reduction treatment unlike the behavior found in other similar systems. It is found that thermal treatments induce changes in its morphology, creating nanowires from particle strings.