Analysis of Performance Losses and Degradation Mechanism in Porous La2-X NiTiO6-δ:YSZ Electrodes.

The electrode performance and degradation of 1:1 La2-xNiTiO6-δ:YSZ composites (x = 0, 0.2) has been investigated to evaluate their potential use as SOFC cathode materials by combining electrochemical impedance spectroscopy in symmetrical cell configuration under ambient air at 1173 K, XRD, electron microscopy and image processing studies. The polarisation resistance values increase notably, i.e., 0.035 and 0.058 Ωcm2 h-1 for x = 0 and 0.2 samples, respectively, after 300 h under these demanding conditions. Comparing the XRD patterns of the initial samples and after long-term exposure to high temperature, the perovskite structure is retained, although La2Zr2O7 and NiO appear as secondary phases accompanied by peak broadening, suggesting amorphization or reduction of the crystalline domains. SEM and TEM studies confirm the ex-solution of NiO with time in both phases and also prove these phases are prone to disorder. From these results, degradation in La2-xNiTiO6-δ:YSZ electrodes is due to the formation of La2Zr2O7 at the electrode-electrolyte interface and the ex-solution of NiO, which in turn results in the progressive structural amorphization of La18NiTiO6-δ phases. Both secondary phases constitute a non-conductive physical barrier that would hinder the ionic diffusion at the La2-xNiTiO6-δ:YSZ interface and oxygen access to surface active area.

Alterations in femoral neck strength following pelvic irradiation. A finite element analysis of simulated eccentric forces using bone density data derived from CT.

BACKGROUND AND PURPOSE: Radiotherapy is known to produce long-term skeletal complications. We aim to evaluate the biomechanical effect on femoral neck bone from hypothetical eccentric loads on pre- and post-radiotherapy CT-images for patients treated for rectal cancer. MATERIAL AND METHODS: Pre- and post-radiotherapy CT-images of rectal cancer from 10 patients were selected randomly. The cortical and trabecular bone was segmented by hand. The biomechanical simulations of 4 eccentric loads and one load aligned with the femoral neck axis were completed using finite element analysis (FEA) in both pre- and post-patient models. RESULTS: A comparative statistical study was completed of pre- and post-radiotherapy patient models of stress and displacement factors. Significant differences were found in eccentric loads in both factors. Natural load has a significant difference in stress, but no differences were found for displacements. The absolute difference in eccentric load applied to the anterior area location on the same patient implies from 5.3% to 40.5% of the stress yield values reported in previous studies. CONCLUSIONS: Loads applied to the anterior area of the femoral head must be considered in fracture simulations because the percentage of yield stress of pre- and post-irradiated bones shows a significant biomechanical change.

Application of Crosslinked Polybenzimidazole-Poly(Vinyl Benzyl Chloride) Anion Exchange Membranes in Direct Ethanol Fuel Cells.

Crosslinked membranes have been synthesized by a casting process using polybenzimidazole (PBI) and poly(vinyl benzyl chloride) (PVBC). The membranes were quaternized with 1,4-diazabicyclo[2.2.2]octane (DABCO) to obtain fixed positive quaternary ammonium groups. XPS analysis has showed insights into the changes from crosslinked to quaternized membranes, demonstrating that the crosslinking reaction and the incorporation of DABCO have occurred, while the 13C-NMR corroborates the reaction of DABCO with PVBC only by one nitrogen atom. Mechanical properties were evaluated, obtaining maximum stress values around 72 MPa and 40 MPa for crosslinked and quaternized membranes, respectively. Resistance to oxidative media was also satisfactory and the membranes were evaluated in single direct ethanol fuel cell. PBI-c-PVBC/OH 1:2 membrane obtained 66 mW cm-2 peak power density, 25% higher than commercial PBI membranes, using 0.5 bar backpressure of pure O2 in the cathode and 1 mL min-1 KOH 2M EtOH 2 M aqueous solution in the anode. When the pressure was increased, the best performance was obtained by the same membrane, reaching 70 mW cm-2 peak power density at 2 bar O2 backpressure. Based on the characterization and single cell performance, PBI-c-PVBC/OH membranes are considered promising candidates as anion exchange electrolytes for direct ethanol fuel cells.

Understanding the Driving Mechanisms of Enhanced Luminescence Emission of Oligo(styryl)benzenes and Tri(styryl)-s-triazine.

This work is focused on unraveling the mechanisms responsible for the aggregation-induced enhanced emission and solid-state luminescence enhancement effects observed in star-shaped molecules based on 1,3,5-tris(styryl)benzene and tri(styryl)-s-triazine cores. To achieve this, the photophysical properties of this set of molecules were analyzed in three states: free molecules, molecular aggregates in solution, and the solid state. Different spectroscopy and microscopy experiments and DFT calculations were conducted to scrutinize the causative mechanisms of the luminescence enhancement phenomenon observed in some experimental conditions. Enhanced luminescence emission was interpreted in the context of short- and long-range excitonic coupling mechanisms and the restriction of intramolecular vibrations. Additionally, we found that the formation of π-stacking aggregates could block E/Z photoisomerization through torsional motions between phenylene rings in the excited state, and hence, enhancing the luminescence of the system.

Synergic Effect of Metal and Fluorine Doping on the Structural and Electrical Properties of La5.4MoO11.1-Based Materials.

Cationic and anionic frameworks of La5.4MoO11.1 proton conductors have been modified by means of metal (Ti4+, Zr4+, and Nb5+) and fluorine (F-) doping. This synergic effect leads to the stabilization of high-symmetry and single-phase polymorphs. The materials have been fully characterized by structural techniques, such as X-ray and neutron powder diffraction and transmission electron microscopy. The fluorine content was determined by ion chromatography. Impedance spectroscopy analysis under different atmospheres (dry and wet N2 and O2 and wet 5% H2-Ar) showed an improvement in the electronic conductivity under reducing conditions, making these materials potential candidates for hydrogen separation membranes.

Poly(Cyclohexene Phthalate) Nanoparticles for Controlled Dasatinib Delivery in Breast Cancer Therapy.

The effect on the activity in breast cancer models of the small tyrosine kinase inhibitor dasatinib (DAS), either alone or in combination with other antitumoral agents, has been recently explored. However, DAS is characterized by its low and highly pH-dependent solubility, which could lead to poor uptake of the drug limiting its tumoral efficacy. Thus far, the development of safe and efficient delivery vehicles of DAS to improve the therapeutic efficacy minimizing the toxicity profile is still required. In this work, a biodegradable and biocompatible polyester is assessed, for the first time, as raw material for the generation of polymeric nanoparticles (NPs). NPs of 100 nm with a narrow polydispersity were formulated for the encapsulation of DAS. The enzymatic and cellular degradation of the new drug delivery system has been studied, and the toxicity and blood compatibility evaluated for its potential clinical use. The new material used for the generation of nanoparticles led to encapsulate DAS in an efficient manner with quicker release DAS profile when compared with the FDA-approved biopolymer Polylactide. The new DAS-loaded polymeric nanocarrier gave a superior efficacy when compared to free DAS with no difference in the mechanism of action. The new NPs shown to be a promising DAS delivery system to be further evaluated for breast cancer treatment.

Relationship between the Structure and Transport Properties in the Ce1-xLaxO2-x/2 System.

La-doped CeO2 materials have been widely investigated for potential applications in different high-temperature electrochemical devices, such as fuel cells and ceramic membranes for hydrogen production. However, the crystal structure is still controversial, and different models based on fluorite, pyrochlore, and/or type-C structures have been considered, depending on the lanthanum content and synthesis method used. In this work, an exhaustive structural analysis of the Ce1-xLaxO2-x/2 system (0.2 < x ≤ 0.7) is performed with different techniques. The average crystal structure, studied by conventional X-ray diffraction, could be considered to be a disordered fluorite; however, the local structure, examined by electron diffraction and Raman spectroscopy, reveals a biphasic mixture of fluorite and C-type phases. The thermal and electrical properties demonstrate that the materials with x ≥ 0.4 are oxide ion proton conductors in an oxidizing atmosphere and mixed ionic electronic conductors in a reducing atmosphere. The water uptake and proton conductivity increase gradually with the increase in La content, suggesting that the formation of the C-type phase is responsible for the proton conduction in these materials.

Assessment of doxorubicin delivery devices based on tailored bare polycaprolactone against glioblastoma.

Bare polycaprolactones with controlled molar mass and dispersity were employed to manufacture biodegradable devices, which were applied for doxorubicin delivery in glioblastoma. Micro- and nanoscale devices were prepared by emulsion formation or by a combination of precipitation and hydrolysis. The carriers were characterized by scanning electron microscopy, dynamic light scattering techniques, thermogravimetric analysis and differential scanning calorimetry. The encapsulation parameters and drug-release profiles are discussed in order to evaluate the influence of different fundamental parameters, such as molar mass and dispersity value, pH, morphology or crystallinity, on the efficiency of the doxorubicin delivery systems. The ability of doxorubicin-loaded micro- and nanoscale devices to induce cellular toxicity in glioblastoma cells was also explored. A cell viability assay against C6 cells of doxorubicin-loaded nanocarriers showed higher cytotoxicity than doxorubicin-loaded microcarriers. In addition, doxorubicin-loaded nanocarriers also showed good antitumor profile in human tumoral cells and improved the security profile in relation to free doxorubicin in non-tumoral cells. Consistent with the assessment study described in this manuscript, the results provide a proof of concept for the suitability of the approach, based on bare polycaprolactone, to local controlled-sustained release of doxorubicin for the treatment of glioblastoma.

Trastuzumab-Targeted Biodegradable Nanoparticles for Enhanced Delivery of Dasatinib in HER2+ Metastasic Breast Cancer.

Dasatinib (DAS) is a multikinase inhibitor that acts on several signaling kinases. DAS is used as a second-line treatment for chronic accelerated myeloid and Philadelphia chromosome-positive acute lymphoblastic leukemia. The therapeutic potential of DAS in other solid tumours is under evaluation. As for many other compounds, an improvement in their pharmacokinetic and delivery properties would potential augment the efficacy. Antibody-targeted biodegradable nanoparticles can be useful in targeted cancer therapy. DAS has shown activity in human epidermal growth factor receptor 2 (HER2) positive tumors, so conjugation of this compound with the anti-HER2 antibody trastuzumab (TAB) with the use of nanocarriers could improve its efficacy. TAB-targeted DAS-loaded nanoparticles were generated by nanotechnology. The guided nanocarriers enhanced in vitro cytotoxicity of DAS against HER2 human breast cancer cell lines. Cellular mechanistic, release studies and nanoparticles stability were undertaken to provide evidences for positioning DAS-loaded TAB-targeted nanoparticles as a potential strategy for further development in HER2-overexpressing breast cancer therapy.

Metal-Doping of La5.4MoO11.1 Proton Conductors: Impact on the Structure and Electrical Properties.

La5.4MoO11.1 proton conductors with different metal doping (Ca2+, Sr2+, Ba2+, Ti4+, Zr4+, and Nb5+) have been prepared and structurally and electrically characterized. Different polymorphs are stabilized depending on the doping and cooling rate used during the synthesis process. The most interesting results are obtained for Nb-doping, La5.4Mo1- xNb xO11.1- x/2, where single compounds are obtained in the compositional range 0 ≤ x ≤ 0.2. These materials are fully characterized by structural techniques such as X-ray and neutron powder diffraction and transmission electron microscopy, which independently confirm the changes of polymorphism. Scanning electron microscopy and impedance spectroscopy measurements in dry/wet gases (N2, O2, and 5% H2-Ar) showed an enhancement of the sinterability and electrical properties of the materials after Nb-doping. Conductivity measurements under very reducing conditions revealed that these materials are mixed ionic-electronic conductors, making them potential candidates for hydrogen separation membranes.

Radiomics of CT Features May Be Nonreproducible and Redundant: Influence of CT Acquisition Parameters.

Purpose To identify the reproducible and nonredundant radiomics features (RFs) for computed tomography (CT). Materials and Methods Two phantoms were used to test RF reproducibility by using test-retest analysis, by changing the CT acquisition parameters (hereafter, intra-CT analysis), and by comparing five different scanners with the same CT parameters (hereafter, inter-CT analysis). Reproducible RFs were selected by using the concordance correlation coefficient (as a measure of the agreement between variables) and the coefficient of variation (defined as the ratio of the standard deviation to the mean). Redundant features were grouped by using hierarchical cluster analysis. Results A total of 177 RFs including intensity, shape, and texture features were evaluated. The test-retest analysis showed that 91% (161 of 177) of the RFs were reproducible according to concordance correlation coefficient. Reproducibility of intra-CT RFs, based on coefficient of variation, ranged from 89.3% (151 of 177) to 43.1% (76 of 177) where the pitch factor and the reconstruction kernel were modified, respectively. Reproducibility of inter-CT RFs, based on coefficient of variation, also showed large material differences, from 85.3% (151 of 177; wood) to only 15.8% (28 of 177; polyurethane). Ten clusters were identified after the hierarchical cluster analysis and one RF per cluster was chosen as representative. Conclusion Many RFs were redundant and nonreproducible. If all the CT parameters are fixed except field of view, tube voltage, and milliamperage, then the information provided by the analyzed RFs can be summarized in only 10 RFs (each representing a cluster) because of redundancy.

Exchange Bias Optimization by Controlled Oxidation of Cobalt Nanoparticle Films Prepared by Sputter Gas Aggregation.

Porous films of cobalt nanoparticles have been obtained by sputter gas aggregation and controllably oxidized by air annealing at 100 °C for progressively longer times (up to more than 1400 h). The magnetic properties of the samples were monitored during the process, with a focus on the exchange bias field. Air annealing proves to be a convenient way to control the Co/CoO ratio in the samples, allowing the optimization of the exchange bias field to a value above 6 kOe at 5 K. The occurrence of the maximum in the exchange bias field is understood in terms of the density of CoO uncompensated spins and their degree of pinning, with the former reducing and the latter increasing upon the growth of a progressively thicker CoO shell. Vertical shifts exhibited in the magnetization loops are found to correlate qualitatively with the peak in the exchange bias field, while an increase in vertical shift observed for longer oxidation times may be explained by a growing fraction of almost completely oxidized particles. The presence of a hummingbird-like form in magnetization loops can be understood in terms of a combination of hard (biased) and soft (unbiased) components; however, the precise origin of the soft phase is as yet unresolved.

ß-NaMnO2: a high-performance cathode for sodium-ion batteries.

There is much interest in Na-ion batteries for grid storage because of the lower projected cost compared with Li-ion. Identifying Earth-abundant, low-cost, and safe materials that can function as intercalation cathodes in Na-ion batteries is an important challenge facing the field. Here we investigate such a material, ß-NaMnO2, with a different structure from that of NaMnO2 polymorphs and other compounds studied extensively in the past. It exhibits a high capacity (of ca. 190 mA h g(-1) at a rate of C/20), along with a good rate capability (142 mA h g(-1) at a rate of 2C) and a good capacity retention (100 mA h g(-1)after 100 Na extraction/insertion cycles at a rate of 2C). Powder XRD, HRTEM, and (23)Na NMR studies revealed that this compound exhibits a complex structure consisting of intergrown regions of α-NaMnO2 and ß-NaMnO2 domains. The collapse of the long-range structure at low Na content is expected to compromise the reversibility of the Na extraction and insertion processes occurring upon charge and discharge of the cathode material, respectively. Yet stable, reproducible, and reversible Na intercalation is observed.

Ordered mesoporous carbons obtained by a simple soft template method as sulfur immobilizers for lithium-sulfur cells.

Carbon materials with ordered mesoporous structures were synthesized using soft template methods and then activated by CO2 treatment. Sulfur was incorporated in these carbons via a simple chemical deposition method in aqueous solutions and the resulting composites were tested as electrodes in Li-S cells. The electrochemical results showed that well-ordered mesoporous carbons perform better than those with a random mesopore arrangement (wormhole-like mesoporous structure). The mesopore ordering yields a framework of well-connected empty sites that results in an enhancement of both the charge carrier mobility and the reversibility of the electrochemical reaction. Although the activation with CO2 partially destroys the mesopore arrangement, which adversely affects the electrode performance, it notably increases the surface area and the micropore content which improves the connectivity between the mesopores. The final observation was an irrelevant effect of the activation process at low current densities. However, at higher rates the activated carbon composite delivered higher capacities. The hierarchical pore structure formed by micro- and mesopores should guarantee the required fast mobility of the Li(+).

A new anode for solid oxide fuel cells with enhanced OCV under methane operation.

A new SOFC anode material based upon oxygen excess perovskite related phases has been synthesised. The material shows better electrochemical performance than other alternative new anodes and comparable performance to the state-of-art of the electrodes, Ni-YSZ cermets, under pure hydrogen. Furthermore, this material shows an enhanced performance under methane operation with high open circuit voltages, i.e. 1.2-1.4 V at 950 degrees C, without using steam excess. The effect of the anode configuration was tested in one and four layer configurations. The optimised electrode polarisation resistances were just 0.12 ohm cm(2) and 0.36 ohm cm(2), at 950 degrees C, in humidified H(2) and humidified CH(4), respectively. Power densities of 0.5 W cm(-2) and 0.35 W cm(-2) were obtained in the same conditions. A very low anodic overpotential of 100 mV at 1 A cm(-2) was obtained under humidified H(2) at 950 degrees C. Samples were tested for two days in reducing and oxidising conditions, alternating heating and cooling processes from 850 degrees C to 950 degrees C, showing stable electrode performance and open circuit voltages. The results show that the substituted strontium titanates are very promising anode materials for SOFC.

Disruption of extended defects in solid oxide fuel cell anodes for methane oxidation.

Point defects largely govern the electrochemical properties of oxides: at low defect concentrations, conductivity increases with concentration; however, at higher concentrations, defect-defect interactions start to dominate. Thus, in searching for electrochemically active materials for fuel cell anodes, high defect concentration is generally avoided. Here we describe an oxide anode formed from lanthanum-substituted strontium titanate (La-SrTiO3) in which we control the oxygen stoichiometry in order to break down the extended defect intergrowth regions and create phases with considerable disordered oxygen defects. We substitute Ti in these phases with Ga and Mn to induce redox activity and allow more flexible coordination. The material demonstrates impressive fuel cell performance using wet hydrogen at 950 degrees C. It is also important for fuel cell technology to achieve efficient electrode operation with different hydrocarbon fuels, although such fuels are more demanding than pure hydrogen. The best anode materials to date--Ni-YSZ (yttria-stabilized zirconia) cermets--suffer some disadvantages related to low tolerance to sulphur, carbon build-up when using hydrocarbon fuels (though device modifications and lower temperature operation can avoid this) and volume instability on redox cycling. Our anode material is very active for methane oxidation at high temperatures, with open circuit voltages in excess of 1.2 V. The materials design concept that we use here could lead to devices that enable more-efficient energy extraction from fossil fuels and carbon-neutral fuels.