Structural Characterization of La0.6Sr0.4CoO3-δ Thin Films Grown on (100)-, (110)-, and (111)-Oriented La0.95Sr0.05Ga0.95Mg0.05O3-δ.

In this study, a detailed structural characterization of epitaxial La0.6Sr0.4CoO3-δ (LSC) films grown in (100), (110), and (111) orientations was conducted. LSC is a model air electrode material in solid oxide fuel and electrolysis cells and understanding the correlation of bulk structure and catalytic activity is essential for the design of future electrode materials. Thin films were grown on single crystals of the perovskite material La0.95Sr0.05Ga0.95Mg0.05O3-δ cut in three different directions. This enabled an examination of structural details at the atomic scale for a realistic material combination in solid oxide cells. The investigation involved the application of atomic force microscopy, X-ray diffraction, and high-resolution transmission electron microscopy to explore the distinct properties of these thin films. Interestingly, ordering phenomena in both cationic as well as anionic sublattices were found, despite the fact that the thin films were never at higher temperatures than 600 °C. Cationic ordering was found in spherical precipitates, whereas the ordering of oxygen vacancies led to the partial transition to brownmillerite in all three orientations. Our results indicate a very high oxygen vacancy concentration in all three thin films. Lattice strains in-plane and out-of-plane was measured, and its implications for the structural modifications are discussed.

Surface Morphology of Textured Transparent Conductive Oxide Thin Film Seen by Various Probes: Visible Light, X-rays, Electron Scattering and Contact Probe.

Fluorine-doped tin oxide thin films (SnO2:F) are widely used as transparent conductive oxide electrodes in thin-film solar cells because of their appropriate electrical and optical properties. The surface morphology of these films influences their optical properties and therefore plays an important role in the overall efficiencies of the solar cells in which they are implemented. At rough surfaces light is diffusely scattered, extending the optical path of light inside the active layer of the solar cell, which in term improves light absorption and solar cell conversion efficiency. In this work, we investigated the surface morphology of undoped and doped SnO2 thin films and their influence on the optical properties of the films. We have compared and analysed the results obtained by several complementary methods for thin-film surface morphology investigation: atomic force microscopy (AFM), transmission electron microscopy (TEM), and grazing-incidence small-angle X-ray scattering (GISAXS). Based on the AFM and TEM results we propose a theoretical model that reproduces well the GISAXS scattering patterns.

Modification of bacterial cells for in vivo remotely guided systems.

It was shown recently that bacterial strains, which can act specifically against malignant cells, can be used efficiently in cancer therapy. Many appropriate bacterial strains are either pathogenic or invasive and there is a substantial shortage of methods with which to monitor in vivo the distribution of bacteria used in this way. Here, it is proposed to use a Layer-by-Layer (LbL) approach that can encapsulate individual bacterial cells with fluorescently labeled polyelectrolytes (PE)s and magnetite nanoparticles (NP)s. The NP enable remote direction in vivo to the site in question and the labeled shells in the far-red emission spectra allow non-invasive monitoring of the distribution of bacteria in the body. The magnetic entrapment of the modified bacteria causes the local concentration of the bacteria to increase by a factor of at least 5. The PEs create a strong barrier, and it has been shown in vitro experiments that the division time of bacterial cells coated in this way can be regulated, resulting in control of their invasion into tissues. That animals used in the study survived and did not suffer septic shock, which can be attributed to PE capsules that prevent release of endotoxins from bacterial cells.

Toward a Flexible and Efficient TiO2 Photocatalyst Immobilized on a Titanium Foil.

Titanium foils of different thicknesses were anodized, and the photocatalytic activity of the resulting TiO2 nanotube (NT) layers was determined. All of the titanium foils were anodized simultaneously under identical experimental conditions to avoid the influence of the aging of the anodizing electrolyte and other anodization parameters, such as voltage, time, and temperature. To characterize the microstructures of the titanium foils, we used electron backscatter diffraction (EBSD), scanning electron microscopy (SEM), and stylus profilometry analyses. The adhesion was tested with a Scotch tape test and the morphology of the TiO2 NTs was studied in detail using the SEM technique, while the surface areas of the TiO2 NTs were determined using a three-dimensional (3D) optical interference profilometer. With X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), the chemical composition and structure of TiO2 oxide were established. The degradation of caffeine under UV irradiation was measured with a high-precision UV-vis-IR spectrophotometer, and the photoluminescence method was used to confirm the photocatalytic behavior of the TiO2 NT layers. The influence of the intrinsic properties, including twinning and the grain boundaries of the starting titanium foils with similar chemical compositions, was determined and explained. Finally, we identified the main characteristics that define a highly effective and flexible photocatalyst.

Influence of Anodization-Electrolyte Aging on the Photocatalytic Activity of TiO2 Nanotube Arrays.

TiO2 nanotubular films prepared using the anodic oxidation process applied to various forms of metal titanium are promising materials for photocatalytic applications. However, during successive anodizations in batch-anodization cells, the chemical composition of the NH4F- and water-based ethylene glycol electrolyte changes with each subsequent anodization, which greatly affects the final photocatalytic properties of the annealed TiO2 nanotubular films. In the present study, 20 titanium discs (Φ 90 mm) were sequentially anodized in the same anodization electrolyte. The chemical composition of the electrolyte was measured after each anodization and correlated with the anodization current density, temperature, electrical conductivity, and pH of the electrolyte and with the morphology, structure, composition, and photocatalytic activity of the resulting TiO2 nanotube films. It was found that the length of the TiO2 nanotubes decreased with the age of the electrolyte due to its lower conductivity. The subsurface chemical composition was evaluated by time of flight secondary ion mass spectrometry (ToF SIMS) analyses, and the integrated ToF SIMS signals over a depth of 250 nm for the TiO2 nanotube films showed that the concentration of F- in the annealed TiO2 film increased with each subsequent anodization due to the increased pH value of the electrolyte. As a consequence, the concentration of the OH- and O2 - species decreased, which is a major reason for the reduced photocatalytic activity of the TiO2 films. It is proposed that the length of the TiO2 nanotubes does not play a decisive role in determining the photocatalytic activity of the TiO2 nanotube films. Finally, the best measured degradation results of 60% for caffeine were thus achieved for the first anodized titanium discs. After that the efficiency gradually decreased for each subsequent anodized disc.

Mechanical properties of zirconia ceramics biomimetically coated with calcium deficient hydroxyapatite.

Mechanical properties and stability of porous tetragonal yttria-stabilised zirconia (Y-TZ) ceramics, biomimetically coated with calcium deficient hydroxyapatite (CaDHA) to obtain a bioactive material, were investigated. The 5.7 mol% yttria-stabilised tetragonal zirconia was obtained by sol-gel process and sintered at different temperatures to obtain a homogeneous and porous structure whose strength would match that of human bone. Sufficient strength was achieved by sintering at 1400 °C. The CaDHA coating was obtained at room temperature by a simplified preparation method consisting of immersion of the Y-TZ ceramics into a calcifying solution, after a short surface pretreatment in HCl. Although HAP or ß-TCP are more frequently used, CaDHA was chosen due to its structural similarity to the bone mineral and ability to support bone ingrowth to a greater extent than biphasic calcium phosphates. To verify the applicability CaDHA coatings, we tested their adherence to Y-TZ ceramics for the first time to the best of our knowledge. Vickers hardness (3.8 ± 0.2 GPa) reflected the hardness of underlying ceramic. The tensile strength (269 ± 52 MPa) and Weibull modulus (5) of the obtained biomaterials matched or exceeded those of bone. There was no statistical difference in the tensile strength between the coated (269 ± 52 MPa) and the uncoated (239 ± 46 MPa) ceramics. The Y-TZ-CaDHA coating system presented adequate structural integrity under scratch test with critical load for coating cracking of 18 ± 2 N. These results indicate the potential of the prepared bioceramic to be used as bone implants.

99mTc-, 90Y-, and 177Lu-Labeled Iron Oxide Nanoflowers Designed for Potential Use in Dual Magnetic Hyperthermia/Radionuclide Cancer Therapy and Diagnosis.

Development of a complex based on iron oxide nanoparticles (IONPs) for diagnosis and dual magnetic hyperthermia/radionuclide cancer therapy accomplishing high yields of radiolabeling and great magnetic heat induction is still a challenge. We report here the synthesis of citric acid, poly(acrylic acid) (PAA) and poly(ethylene glycol) coated IONPs and their labeling with three radionuclides, namely, technetium (99mTc), yttrium (90Y), and lutetium (177Lu), aiming at potential use in cancer diagnosis and therapy. Polyol-synthesized IONPs are a flowerlike structure with 13.5 nm spherically shaped cores and 24.8 nm diameter. PAA-coated nanoparticles (PAA@IONP) showed the best characteristics such as easy radiolabeling with very high yields (>97.5%) with all three radionuclides, and excellent in vitro stabilities with less than 10% of radionuclides detaching after 24 h. Heating ability of PAA@IONP in an alternating external magnetic field showed intrinsic loss power value of 7.3 nH m2/kg, which is one of higher reported values. Additionally, PAA@IONP itself presented no significant cytotoxicity to the CT-26 cancer cells, reaching IC50 at 60 µg/mL. However, under the external magnetic field, they show hyperthermia-mediated cells killing, which correlated with the magnetic field strength and time of exposure. Since PAA@IONP are easy to prepare, biocompatible, and with excellent magnetic heat induction, these nanoparticles radiolabeled with high-energy beta emitters 90Y and 177Lu have valuable potential as agent for dual magnetic hyperthermia/radionuclide therapy, while radiolabeled with 99mTc could be used in diagnostic imaging.

Nanoparticles Can Wrap Epithelial Cell Membranes and Relocate Them Across the Epithelial Cell Layer.

Although the link between the inhalation of nanoparticles and cardiovascular disease is well established, the causal pathway between nanoparticle exposure and increased activity of blood coagulation factors remains unexplained. To initiate coagulation tissue factor bearing epithelial cell membranes should be exposed to blood, on the other side of the less than a micrometre thin air-blood barrier. For the inhaled nanoparticles to promote coagulation, they need to bind lung epithelial-cell membrane parts and relocate them into the blood. To assess this hypothesis, we use advanced microscopy and spectroscopy techniques to show that the nanoparticles wrap themselves with epithelial-cell membranes, leading to the membrane's disruption. The membrane-wrapped nanoparticles are then observed to freely diffuse across the damaged epithelial cell layer relocating epithelial cell membrane parts over the epithelial layer. Proteomic analysis of the protein content in the nanoparticles wraps/corona finally reveals the presence of the coagulation-initiating factors, supporting the proposed causal link between the inhalation of nanoparticles and cardiovascular disease.

Axially aligned organic fibers and amorphous calcium phosphate form the claws of a terrestrial isopod (Crustacea).

Skeletal elements that are exposed to heavy mechanical loads may provide important insights into the evolutionary solutions to mechanical challenges. We analyzed the microscopic architecture of dactylus claws in the woodlice Porcellio scaber and correlated these observations with analyses of the claws' mineral composition with energy dispersive X-ray spectrometry (EDX), electron energy loss spectroscopy (EELS) and selected area electron diffraction (SAED). Extraordinarily, amorphous calcium phosphate is the predominant mineral in the claw endocuticle. Unlike the strongly calcified exocuticle of the dactylus base, the claw exocuticle is devoid of mineral and is highly brominated. The architecture of the dactylus claw cuticle is drastically different from that of other parts of the exoskeleton. In contrast to the quasi-isotropic structure with chitin-protein fibers oriented in multiple directions, characteristic of the arthropod exoskeleton, the chitin-protein fibers and mineral components in the endocuticle of P. scaber claws are exclusively axially oriented. Taken together, these characteristics suggest that the claw cuticle is highly structurally anisotropic and fracture resistant and can be explained as adaptations to predominant axial loading of the thin, elongated claws. The nanoscale architecture of the isopod claw may inspire technological solutions in the design of durable machine elements subjected to heavy loading and wear.

Gel-sol synthesis of rutile nanoparticles.

Titanium dioxide (TiO(2)) rutile nanoparticles were synthesized at temperatures below 100 °C using a gel-sol process that provides control of the final particles' characteristics, such as the nanoparticle size, morphology, crystal structure and crystallinity. The synthesized rutile nanoparticles were analyzed using X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results show that the gel-sol process allows control over the final nanoparticle characteristics with the proper choice of reaction parameters. The most profound influence on the nanoparticles' properties is achieved by the type and concentration of the acid used in the reaction mixture. The gel-sol synthesis resulted in anisotropic rutile nanoparticles that are 60-160 nm long, depending on the reaction parameters, and have an aspect ratio of about 5. A reaction mechanism is presented, explaining the influence of various reaction parameters on the characteristics of the TiO(2) nanoparticles.

Exoskeletal cuticle differentiation during intramarsupial development of Porcellio scaber (Crustacea: Isopoda).

Exoskeletal crustacean cuticle is a calcified apical extracellular matrix of epidermal cells, illustrating the chitin-based organic scaffold for biomineralization. Studies of cuticle formation during molting reveal significant dynamics and complexity of the assembly processes, while cuticle formation during embryogenesis is poorly investigated. This study reveals in the terrestrial isopod Porcellio scaber, the ultrastructural organization of the differentiating precuticular matrices and exoskeletal cuticles during embryonic and larval intramarsupial development. The composition of the epidermal matrices was obtained by WGA lectin labelling and EDXS analysis. At least two precuticular matrices, consisting of loosely arranged material with overlying electron dense lamina, are secreted by the epidermis in the mid-stage embryo. The prehatching embryo is the earliest developmental stage with a cuticular matrix consisting of an epicuticle and a procuticle, displaying WGA binding and forming cuticular scales. In newly hatched marsupial larva manca, a new cuticle is formed and calcium sequestration in the cuticle is evident. Progression of larval development leads to the cuticle thickening, structural differentiation of cuticular layers and prominent cuticle calcification. Morphological characteristics of exoskeleton renewal in marsupial manca are described. Elaborated cuticle in marsupial larvae indicates the importance of the exoskeleton in protection and support of the larval body in the marsupium and during the release of larvae in the external environment.

Influence of TEM specimen preparation on chemical composition of Pb(Mg1/3Nb2/3)O3-PbTiO3 single crystals.

The influences of different transmission electron microscopy (TEM) specimen preparation techniques on the chemical composition of Pb(Mg1/3Nb2/3)O3-PbTiO3 (PMN-PT) single crystals was studied. Ion-milled samples where no cooling with liquid nitrogen (L-N2) was applied show permanently changed composition also deep inside the bulk material. When the PMN-PT samples were cooled to L-N2 temperature during the ion-milling process and in addition lower accelerating voltages were used, the chemical composition was altered only in the thinnest parts close to the specimen edge. Samples prepared using only tripod polishing technique show compositional irregularities close to the specimen edge. For the preparation of lead-containing samples, such as PMN-PT single crystals, a combination of tripod polishing and short Ar-ion-milling at low accelerating voltages while cooling the samples to liquid nitrogen temperature proved to be the most suitable to obtain artefact-free electron-transparent TEM lamellae.

Highly efficient TiO2-based microreactor for photocatalytic applications.

A photocatalytic, TiO2-based microreactor is designed and fabricated on a metal-titanium foil. The microchannel is mechanically engraved in the substrate foil, and a double-layered TiO2 anatase film is immobilized on its inner walls with a two-step synthesis, which included anodization and a hydrothermal treatment. X-ray diffraction (XRD) and scanning electron microscopy (SEM) confirm the presence of an approximately 10-µm-thick layer of titania nanotubes and anatase nanoparticles. The SEM and transmission electron microscopy (TEM) of the cross sections show a dense interface between the titanium substrate and the TiO2 nanotubes. An additional layer of TiO2-anatase nanoparticles on the top of the film provides a large, photocatalytic surface area. The metal-titanium substrate with a functionalized serpentine channel is sealed with UV-transparent Plexiglas, and four 0.8-mW UV LEDs combined with a power controller on a small printed-circuit board are fixed over the substrate. The photocatalytic activity and the kinetic properties for the degradation of caffeine are provided, and the longer-term stability of the TiO2 film is evaluated. The results show that after 6 months of use and 3600 working cycles the microreactor still exhibits 60% of its initial efficiency.

Calcium bodies of Titanethes albus (Crustacea: Isopoda): molt-related structural dynamics and calcified matrix-associated bacteria.

Crustaceans form a variety of calcium deposits in which they store calcium necessary for the mineralization of their exoskeletons. Calcium bodies, organs containing large amounts of calcium, have been reported in some terrestrial isopod crustaceans, but have not yet been extensively studied. We analyzed the architecture of these organs during the molt cycle in the isopod Titanethes albus. Two pairs of calcium bodies are positioned ventrolaterally in posterior pereonites of T. albus. Individual organs are epithelial sacs that contain material arranged in concentric layers delimited by thin laminae. As demonstrated by electron microscopy and fluorescence in situ hybridization, abundant bacteria are present within the calcium bodies. Regardless of the molt cycle stage, crystalline concretions are present in the central areas of the calcium bodies. Energy dispersive X-ray spectrometry of the concretions demonstrated that they are composed predominantly of calcium and phosphorus and selected area electron diffraction indicated the presence of hydroxyapatite. In molting animals, a glassy layer of mineralized matrix is formed between the envelope and the outermost lamina of the calcium body. This layer consists of an amorphous calcium mineral which contains less phosphorus than the central concretions and is resorbed after molt. Since changes in the mineralized matrix are synchronized with the molt cycle, the calcium bodies likely function as a storage compartment that complements sternal deposits as a source of calcium for the mineralization of the exoskeleton. Bacteria associated with the mineralized matrix of calcium bodies are evidently involved in calcium dynamics.

Bioactive glass enhances bone ingrowth into the porous titanium coating on orthopaedic implants.

PURPOSE: The aim of the study was to verify the ability of nanoparticulate bioactive glass (BAG) to infiltrate into the porous titanium (Ti) layer on Ti-based implants to promote osseointegration. METHODS: The porous titanium layer on Ti-based implants was impregnated with nanoparticulate BAG. The implants without or with BAG were implanted bilaterally in tibial holes of ten New Zealand white rabbits. The rabbits were sacrificed after ten weeks for examinations. Beside histological examination, EDXS analysis of polished cross-sections of explanted implants was also performed with the aim to quantitatively evaluate the bone-to-pore contact and bone-in-pore ratio. RESULTS: After ten weeks, EDXS analyses of cross-sections of the explanted implants confirmed that bioactive glass was fully resorbed and that the pores throughout the thickness of the porous titanium layer were to a large extent filled with a new bone. In the absence of bioactive glass, only the outer part of the porous layer was filled with bone. The implants without BAG in the porous Ti-layer exhibited similar bone-to-pore contact, while significant improvement of bone ingrowth into the pores was observed for the implants with BAG (38%), as opposed to those without it (22%). CONCLUSION: This study confirmed that the nanoparticulate bioactive glass within the porous titanium surface layer on implants promotes osseointegration and stimulates the formation of bone within the pores.

Interplay between the structural and magnetic probes in the elucidation of the structure of a novel 2D layered [V4O4(OH)2(O2CC6H4CO2)4]·DMF.

The title compound has been synthesized under solvothermal conditions by reacting vanadium(V) oxytriisopropoxide with terephthalic acid in N,N-dimethylformamide. A combination of synchrotron powder diffraction, infrared spectroscopy, scanning and transmission electron microscopy, and thermal and chemical analysis elucidated the chemical, structural and microstructural features of a new 2D layered inorganic-organic framework. Due to the low-crystallinity of the final material, its crystal structure has been solved from synchrotron X-ray powder diffraction data using a direct space global optimization technique and subsequent constraint Rietveld refinement. [V(4)O(4)(OH)(2)(O(2)CC(6)H(4)CO(2))(4)]·DMF crystallizes in the monoclinic system (space group P2/m (No. 10)); cell parameters: a = 20.923(4) Å, b = 5.963(4) Å, c = 20.425(1) Å, ß = 123.70(6)°, V = 2120.1(9) Å(3), Z = 2. The overall structure can be described as an array of parallel 2D layers running along [-101] direction, consisting of two types of vanadium oxidation states and coordination polyhedra: face-shared trigonal prisms (V(4+)) and distorted corner-shared square pyramids (V(5+)). Both configurations form independent parallel chains oriented along the 2-fold symmetry crystallographic b-axis mutually interlinked with terephthalate ligands in a monodentate mode perpendicular to it. The morphology of the compound exhibits long nanofibers, with the growth direction along the layered [-101] axis. The magnetic susceptibility measurements show that the magnetic properties of [V(4)O(4)(OH)(2)(O(2)CC(6)H(4)CO(2))(4)]·DMF can be described by a linear antiferromagnetic chain model, with the isotropic exchange interaction of J = -75 K between the nearest V(4+) neighbours of S = 1/2.

Characterization of individual barium titanate nanorods and their assessment as building blocks of new circuit architectures.

In this work, we report on the integration of individual BaTiO(3) nanorods into simple circuit architectures. Polycrystalline BaTiO(3) nanorods were synthesized by electrophoretic deposition (EPD) of barium titanate sol into aluminium oxide (AAO) templates and subsequent annealing. Transmission electron microscopy (TEM) observations revealed the presence of slabs of hexagonal polymorphs intergrown within cubic grains, resulting from the local reducing atmosphere during the thermal treatment. Electrical measurements performed on individual BaTiO(3) nanorods revealed resistivity values between 10 and 100 Ω cm, which is in good agreement with typical values reported in the past for oxygen-deficient barium titanate films. Consequently the presence of oxygen vacancies in their structure was indirectly validated. Some of these nanorods were tested as proof-of-concept humidity sensors. They showed reproducible responses towards different moisture concentrations, demonstrating that individual BaTiO(3) nanorods may be integrated in complex circuit architectures with functional capacities.

Oriented cube-on-cube nanocrystal assembly of SrTiO3 tubules.

We report on an unusual crystallization phenomenon that results in the self-assembly of sub-micron tubules of crystalline SrTiO(3). The deposition of the tubular structures was done in the pores of anodized aluminum oxide templates by the electrophoretic deposition of SrTiO(3) sols and subsequent annealing. Homogeneous nucleation inside the pores produces a critical number of crystallites leading to their self-organization when the nanocrystals reach sizes that equal the mean free distances between the nuclei. Due to steric constraints the crystals start to organize in order to most efficiently fill the available surface of the pore walls. This process leads to the formation of domains containing a large number of idiomorphic SrTiO(3) nano-cubes that are self-aligned into almost perfect cube-on-cube and cube-to-wall registry, which makes up the walls of the tubules. The described mechanism shows the ability of nanocrystals with well defined morphologies to adapt spatial constraints and self-organize into desired geometries.

Retrieval process of high-resolution HAADF-STEM images.

A process for retrieving experimental high-resolution high-angle annular dark field (HAADF) scanning transmission electron microscopy (STEM) images, which are systematically distorted by environmental and/or instrumental instability in addition to the convolution influence of the probe, is demonstrated using a HAADF-STEM image of an antimony-rich basal plane inversion boundary in Sb2O3-doped ZnO ceramics recorded in the [0110] zone axis. The process includes a correction of the diffractogram of the HAADF-STEM image by referring to the diffractogram of a high-resolution transmission electron microscopy image of the same area. The corrected diffractogram is used for deconvolution processing combined with the maximum entropy method. The retrieved images show bright spots regarded as the object function. Thus, the processing of the experimental HAADF-STEM image provides almost a real projected atomic structure by reforming the systematic distortion and eliminating the effects of the probe function.