Abstract: Electron energy loss spectra in conjunction with near-edge fine structures of purely stoichiometric niobium monoxide (NbO) and niobium pentoxide (Nb2O5) reference materials were recorded. The structures of the niobium oxide reference materials were checked by selected area electron diffraction to ensure a proper assignment of the fine structures. NbO and Nb2O5 show clearly different energy loss near-edge fine structures of the Nb-M-4,M-5 and -M-2,M-3 edges and of the O-K edge, reflecting the specific local environments of the ionized atoms. To distinguish the two oxides in a quantitative manner, the intensities under the Nb-M-4,M-5 as well as Nb-M-2,M-3 edges and the O-K edge were measured and their ratios calculated. k-factors were also derived from these measurements.

Abstract: Carbon nanotubes (CNTs) are one of the most promising nanomaterials to be used in biomedicine for drug/gene delivery as well as biomedical imaging. This study develops radio-labeled, iron oxide-decorated multiwalled CNTs (MWNTs) as dual magnetic resonance (MR) and single photon emission computed tomography (SPECT) contrast agents. Hybrids containing different amounts of iron oxide are synthesized by in situ generation. Physicochemical characterisations reveal the presence of superparamagnetic iron oxide nanoparticles (SPION) granted the magnetic properties of the hybrids. Further comprehensive examinations including high resolution transmission electron microscopy (HRTEM), fast Fourier transform simulations, X-ray diffraction, and X-ray photoelectron spectroscopy assure the conformation of prepared SPION as γ-Fe2O3. High r2 relaxivities are obtained in both phantom and in vivo MRI compared to the clinically approved SPION Endorem. The hybrids are successfully radio labeled with technetium-99m through a functionalized bisphosphonate and enable SPECT/CT imaging and γ-scintigraphy to quantitatively analyze the biodistribution in mice. No abnormality is found by histological examination and the presence of SPION and MWNT are identified by Perls stain and Neutral Red stain, respectively. TEM images of liver and spleen tissues show the co-localization of SPION and MWNTs within the same intracellular vesicles, indicating the in vivo stability of the hybrids after intravenous injection. The results demonstrate the capability of the present SPIONMWNT hybrids as dual MRI and SPECT contrast agents for in vivo use.

Abstract: In this work we have investigated the structural and electronic properties of SnO, which is built up from layers kept together by van der Waals (vdW) forces. The combination of a vdW functional within density functional theory (DFT) and quasiparticle band structure calculations within the GW approximation provides accurate values for the lattice parameters, atomic positions, and the electronic band structure including the fundamental (indirect) and the optical (direct) band gap without the need of experimental or empirical input. A systematic comparison is made between different levels of self-consistency within the GW approach {following the scheme of Shishkin et al. [Phys. Rev. B 75, 235102 (2007)]} and the results are compared with DFT and hybrid functional results. Furthermore, the effect of the vdW-corrected functional as a starting point for the GW calculation of the band gap has been investigated. Finally, we studied the effect of the vdW functional on the electron charge density.

Abstract: Recent studies are concisely reviewed, in which X-ray beams of (sub)micrometre to millimetre dimensions have been used for non-destructive analysis and characterization of pigments, minute paint samples, and/or entire paintings from the seventeenth to the early twentieth century painters. The overview presented encompasses the use of laboratory and synchrotron radiation-based instrumentation and deals with the use of several variants of X-ray fluorescence (XRF) as a method of elemental analysis and imaging, as well as with the combined use of X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS). Microscopic XRF is a variant of the method that is well suited to visualize the elemental distribution of key elements, mostly metals, present in paint multi-layers, on the length scale from 1 to 100 μm inside micro-samples taken from paintings. In the context of the characterization of artists pigments subjected to natural degradation, the use of methods limited to elemental analysis or imaging usually is not sufficient to elucidate the chemical transformations that have taken place. However, at synchrotron facilities, combinations of μ-XRF with related methods such as μ-XAS and μ-XRD have proven themselves to be very suitable for such studies. Their use is often combined with microscopic Fourier transform infra-red spectroscopy and/or Raman microscopy since these methods deliver complementary information of high molecular specificity at more or less the same length scale as the X-ray microprobe techniques. Since microscopic investigation of a relatively limited number of minute paint samples, taken from a given work of art, may not yield representative information about the entire artefact, several methods for macroscopic, non-invasive imaging have recently been developed. Those based on XRF scanning and full-field hyperspectral imaging appear very promising; some recent published results are discussed.

Abstract: We calculated the temperature dependence of the Debye-Waller factors for a variety of group IV, III-V and II-VI semiconductors from 0.1 to 1000 K. The approach used to fit the temperature dependence is described and resulting fit parameters are tabulated for each material. The Debye-Waller factors are deduced from generalized phonon densities of states which were derived from first principles using the WIEN2k and the ABINIT codes.

Abstract: In order to take advantage of both grain refinement and precipitation hardening effects, nanoscaled Ni4Ti3 precipitates are introduced in a Ti50.8 at.% Ni alloy with micron-sized grains (average grain size of 1.7 μm). Calorimetry, electrical resistance studies and thermomechanical tests were employed to study the transformation behavior and functional properties in relation to the obtained microstructure. A significant suppression of martensite transformation by the obtained microstructure is observed. The thermomechanical tests show that the advantageous properties of both grain refinement and precipitation hardening are combined in the developed materials, resulting in superior shape memory characteristics and stability of pseudoelasticity. It is concluded that introducing nanoscaled Ni4Ti3 precipitates into small grains is a new approach to improve the functional properties of NiTi shape memory alloys.

Abstract: We present a simple method for the co-encapsulation of gold nanostars and iron-oxide nanoparticles into hybrid colloidal composites that are highly responsive to both light and external magnetic fields. Self-assembly was driven by hydrophobic interactions between polystyrene capped gold nanostars and iron oxide nanocrystals stabilized with oleic acid, upon addition of water. A block copolymer was then used to encapsulate the resulting spherical colloidal particle clusters, which thereby became hydrophilic. Electron microscopy analysis unequivocally shows that each composite particle comprises a single Au nanostar surrounded by a few hundreds of iron oxide nanocrystals. We demonstrate that this hybrid colloidal system can be used as an efficient substrate for surface enhanced Raman scattering, using common dyes as model molecular probes. The co-encapsulation of iron oxide nanoparticles renders the system magnetically responsive, so that application of an external magnetic field leads to particle accumulation and limits of detection are in the nM range.

Abstract: Characterization methods for the structural investigation of biotemplates for nanodevices remain widely unexplored, despite the fact that biotemplating methods for nanodevice fabrication are becoming more widespread. In this study several techniques are used to characterize the morphology and 3D distribution of silver nanoparticles deposited on insulin fibrils.

Abstract: In this study, the uptake and elimination of ZnO and CuO nanoparticles in Daphnia magna was tested. Daphnids were exposed during 10 days to sublethal concentrations of ZnO and CuO nanoparticles and corresponding metal salts (ZnCl2 and CuCl2.2H2O), after which they were transferred to unexposed medium for another 10 days. At different times during the exposure and none-exposure, the total and internal zinc or copper concentration of the daphnids was determined and the nanoparticles were localized in the organism using electron microscopy. The exposure concentrations were characterized by measuring the dissolved, nanoparticle and aggregated fraction in the medium. The results showed that the ZnO nanoparticles quickly dissolved after addition to the medium. Contrarily, only a small fraction (corresponding to the dissolved metal salt) of the CuO nanoparticles dissolved, while most of these nanoparticles formed large aggregates. Despite an initial increase in zinc and copper concentration during the first 48 hour to 5 day exposure, the body concentration reached a plateau level that was comparable for the ZnO nanoparticles and ZnCl2, but much higher for the CuO nanoparticles (with visible aggregates accumulating in the gut) than CuCl2.2H2O. During the remaining exposure and subsequent none-exposure phase, the zinc and copper concentration decreased fast to concentrations comparable with the unexposed daphnids. The results indicate that D. magna can regulate its internal zinc and copper concentration after exposure to ZnO and CuO nanoparticles, similar as after exposure to metal salts. The combined dissolution, accumulation and toxicity results confirm that the toxicity of ZnO and CuO nanoparticles is caused by the dissolved fraction. Keywords nano; zinc; copper; dissolution; aggregation; electron microscopy

Abstract: Phase transitions that occur in materials, driven, for instance, by changes in temperature or pressure, can dramatically change the materials' properties. Discovering new types of transitions and understanding their mechanisms is important not only from a fundamental perspective, but also for practical applications. Here we investigate a recently discovered Fe4O5 that adopts an orthorhombic CaFe3O5-type crystal structure that features linear chains of Fe ions. On cooling below approximately 150 K, Fe4O5 undergoes an unusual charge-ordering transition that involves competing dimeric and trimeric ordering within the chains of Fe ions. This transition is concurrent with a significant increase in electrical resistivity. Magnetic-susceptibility measurements and neutron diffraction establish the formation of a collinear antiferromagnetic order above room temperature and a spin canting at 85 K that gives rise to spontaneous magnetization. We discuss possible mechanisms of this transition and compare it with the trimeronic charge ordering observed in magnetite below the Verwey transition temperature.

Abstract: Herein, by studying a stepwise phase transformation of 23 nm FeO-Fe3O4 core-shell nanocubes into Fe3O4, we identify a composition at which the magnetic heating performance of the nanocubes is not affected by the medium viscosity and aggregation. Structural and magnetic characterizations reveal the transformation of the FeO-Fe3O4 nanocubes from having stoichiometric phase compositions into Fe2+ deficient Fe3O4 phases. The resultant nanocubes contain tiny compressed and randomly distributed FeO sub-domains as well as structural defects. This phase transformation causes a tenfold increase in the magnetic losses of the nanocubes, which remains exceptionally insensitive to the medium viscosity as well as aggregation unlike similarly sized single-phase magnetite nanocubes. We observe that the dominant relaxation mechanism switches from Néel in fresh core-shell nanocubes to Brownian in partially oxidized nanocubes and once again to Néel in completely treated nanocubes. The Fe2+ deficiencies and structural defects appear to reduce the magnetic energy barrier and anisotropy field, thereby driving the overall relaxation into Néel process. The magnetic losses of the particles remain unchanged through a progressive internalization/association to ovarian cancer cells. Moreover, the particles induce a significant cell death after being exposed to hyperthermia treatment. Here, we present the largest heating performance that has been reported to date for 23 nm iron oxide nanoparticles under cellular and intracellular conditions. Our findings clearly demonstrate the positive impacts of the Fe2+ deficiencies and structural defects in the Fe3O4 structure on the heating performance under cellular and intracellular conditions.

Abstract: An innovative experimental approach to study the electrodeposition of small nanoparticles and the early stages of electrochemical nucleation and growth is presented. Carbon coated gold TEM grids are used as substrates for the electrodeposition of silver nanoparticles so that electrochemical data, FESEM, HAADFSTEM and HRTEM data can be acquired from the same sample without the need to remove the particles from the substrate. It is shown that the real distribution of nanoparticles cannot be resolved by FESEM whereas HAADFSTEM analysis confirms that a distribution of small nanoparticles (d ≈ 12 nm) coexist with large nanoparticles corresponding to a bimodal size distribution. Besides, particles grown under the same conditions have been found to present different structures such as monocrystals, polycrystals or aggregates of smaller particles.

Abstract: We have prepared tungsten oxide films decorated with gold particles on Si substrates by aerosol assisted chemical vapor deposition (AACVD) and characterized them using scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). SEM shows that the films are composed of needle-like structures and TEM shows that both the needles and the gold particles are crystalline. XPS indicates the presence of oxygen vacancies, i.e. the films are WO3−x, and hence the deposited material is composed of semiconducting nanostructures and that the interaction between the gold particles and the WO3 needles surface is weak. The synthesis of semiconducting tungsten oxide nanostructures decorated with metal particles represents an important step towards the development of sensing devices with optimal properties.