Development by Mechanochemistry of La0.8Sr0.2Ga0.8Mg0.2O2.8 Electrolyte for SOFCs

In this work, a mechanochemical process using high-energy milling conditions was employed to synthesize La0.8Sr0.2Ga0.8Mg0.2O3-δ (LSGM) powders from the corresponding stoichiometric amounts of La2O3, SrO, Ga2O3, and MgO in a short time. After 60 min of milling, the desired final product was obtained without the need for any subsequent annealing treatment. A half solid oxide fuel cell (SOFC) was then developed using LSGM as an electrolyte and La0.8Sr0.2MnO3 (LSM) as an electrode, both obtained by mechanochemistry. The characterization by X-ray diffraction of as-prepared powders showed that LSGM and LSM present a perovskite structure and pseudo-cubic symmetry. The thermal and chemical stability between the electrolyte (LSGM) and the electrode (LSM) were analyzed by dynamic X-ray diffraction as a function of temperature. The electrolyte (LSGM) is thermally stable up to 800 and from 900 °C, where the secondary phases of LaSrGa3O7 and LaSrGaO4 appear. The best sintering temperature for the electrolyte is 1400 °C, since at this temperature, LaSrGaO4 disappears and the percentage of LaSrGa3O7 is minimized. The electrolyte is chemically compatible with the electrode up to 800 °C. The powder sample of the electrolyte (LSGM) at 1400 °C observed by HRTEM indicates that the cubic symmetry Pm-3m is preserved. The SOFC was constructed using the brush-painting technique; the electrode-electrolyte interface characterized by SEM presented good adhesion at 800 °C. The electrical properties of the electrolyte and the half-cell were analyzed by complex impedance spectroscopy. It was found that LSGM is a good candidate to be used as an electrolyte in SOFC, with an Ea value of 0.9 eV, and the LSM sample is a good candidate to be used as cathode

Synthesis, characterization and performance of robust poison-resistant ultrathin film yttria stabilized zirconia – nickel anodes for application in solid electrolyte fuel cells

We report on the synthesis of undoped ∼5 μm YSZ-Ni porous thin films prepared by reactive pulsed DC magnetron sputtering at an oblique angle of incidence. Pre-calcination of the amorphous unmodified precursor layers followed by reduction produces a film consisting of uniformly distributed tilted columnar aggregates having extensive three-phase boundaries and favorable gas diffusion characteristics. Similarly prepared films doped with 1.2 at.% Au are also porous and contain highly dispersed gold present as Ni-Au alloy particles whose surfaces are strongly enriched with Au. With hydrogen as fuel, the performance of the undoped thin film anodes is comparable to that of 10–20 times thicker typical commercial anodes. With a 1:1 steam/carbon feed, the un-doped anode cell current rapidly falls to zero after 60 h. In striking contrast, the initial performance of the Au-doped anode is much higher and remains unaffected after 170 h. Under deliberately harsh conditions the performance of the Au-doped anodes decreases progressively, almost certainly due to carbon deposition. Even so, the cell maintains some activity after 3 days operation in dramatic contrast with the un-doped anode, which stops working after only three hours of use. The implications and possible practical application of these findings are discussed.European Union 298300Ministerio de Economía y Competitividad MAT2013‐40852R, 201560E05

High performance novel gadolinium doped ceria/yttria stabilized zirconia/nickel layered and hybrid thin film anodes for application in solid oxide fuel cells

Magnetron sputtering under oblique angle deposition was used to produce Ni-containing ultra thin film anodes comprising alternating layers of gadolinium doped ceria (GDC) and yttria stabilized zirconia (YSZ) of either 200 nm or 1000 nm thickness. The evolution of film structure from initial deposition, through calcination and final reduction was examined by XRD, SEM, TEM and TOF-SIMS. After subsequent fuel cell usage, the porous columnar architecture of the two-component layered thin film anodes was maintained and their resistance to delamination from the underlying YSZ electrolyte was superior to that of corresponding single component Ni-YSZ and Ni-GDC thin films. Moreover, the fuel cell performance of the 200 nm layered an- odes compared favorably with conventional commercially available thick anodes. The observed dependence of fuel cell performance on individual layer thicknesses prompted study of equivalent but more easily fabricated hybrid anodes consisting of simultaneously deposited Ni-GDC and Ni-YSZ, which procedure resulted in exceptionally intimate mixing and interaction of the components. The hybrids exhibited very unusual and favorable I---V characteristics, along with exceptionally high power densities at high currents. Their discovery is the principal contribution of the present work.European Union's Seventh Framework Programme FP7/2007–2013Fuel Cells and Hydrogen Joint Technology Initiative under the T-CELL project, grant 298300MINECO (Spain), grants nº MAT2013-40852RJuan de la Cierva Programme FPDI-2013-1862

Cognition in informal caregivers: evidence from an English population study

BACKGROUND AND OBJECTIVES: The relationship between caregiving and cognition remains unclear. We investigate this association comparing four cognitive tasks and exploring the role of potential explanatory pathways such as healthy behaviours (healthy caregiver hypothesis) and depression (stress process model).D RESEARCH AND DESIGN METHODS: Respondents were from English Longitudinal Study of Ageing (ELSA) (N = 8910). Cognitive tasks included immediate and delayed word recall, verbal fluency and serial 7 subtraction. Series of hierarchical linear regressions were performed. Adjustments included socio-demographics, health related variables, health behaviours and depression. RESULTS: Being a caregiver was positively associated with immediate and delayed recall, verbal fluency but not with serial 7. For immediate and delayed recall, these associations were partially attenuated when adjusting for health behaviours, and depression. For verbal fluency, associations were partially attenuated when adjusting for depression but fully attenuated when adjusting for health behaviours. No associations were found for serial 7. DISCUSSIONS AND IMPLICATIONS: Our findings show that caregivers have higher level of memory and executive function compared to non-caregivers. For memory, we found that although health behaviours and depression can have a role in this association, they do not fully explain it. However, health behaviours seem to have a clear role in the association with executive function. Public health and policy do not need to target specifically cognitive function but other areas as the promotion of healthy behaviours and psychological adjustment such as preventing depression and promoting physical activity in caregivers

Designing bioactive porous titanium interfaces to balance mechanical properties and in vitro cells behavior towards increased osseointegration

Titanium implant failures are mainly related to stress shielding phenomenon and the poor cell interaction with host bone tissue. The development of bioactive and biomimetic Ti scaffolds for bone regeneration remains a challenge which needs the design of Ti implants with enhanced osseointegration. In this context, 4 types of titanium samples were fabricated using conventional powder metallurgy, fully dense, dense etched, porous Ti, and porous etched Ti. Porous samples were manufactured by space holder technique, using ammonium bicarbonate particles as spacer in three different ranges of particle size (100–200 μm, 250–355 μm and 355–500 μm). Substrates were chemically etched by immersion in fluorhydric acid at different times (125 and 625 s) and subsequently, were characterized from a micro-structural, topographical and mechanical point of view. Etched surfaces showed an additional roughness preferentially located inside pores. In vitro tests showed that all substrates were biocompatible (80% of cell viability), confirming cell adhesion of premioblastic cells. Similarly, osteoblast showed similar cell proliferation rates at 4 days, however, higher cell metabolic activity was observed in fully dense and dense etched surfaces at 7 days. In contrast, a significant increase of alkaline phosphatase enzyme expression was observed in porous and porous etched samples compared to control surfaces (dense and dense etched), noticing the suitable surface modification parameters (porosity and roughness) to improve cell differentiation. Furthermore, the presence of pores and rough surfaces of porous Ti substrates remarkably decreased macrophage activation reducing the M1 phenotype polarization as well M1 cell marker expression. Thus, a successful surface modification of porous Ti scaffolds has been performed towards a reduction on stress shielding phenomenon and enhancement of bone osseointegration, achieving a biomechanical and biofunctional equilibrium.Ministry of Economy and Competitiveness of Spain grant MAT2015-71284-PJunta de Andalucía – FEDER (Spain) Project Ref. P12-TEP-140

Transformation-Optics Description of Nonlocal Effects in Plasmonic Nanostructures

We develop an insightful transformation-optics approach to investigate the impact that nonlocality has on the optical properties of plasmonic nanostructures. The light-harvesting performance of a dimer of touching nanowires is studied by using the hydrodynamical Drude model, which reveals nonlocal resonances not predicted by previous local calculations. Our method clarifies the interplay between radiative and nonlocal effects in this nanoparticle configuration, which enables us to elucidate the optimum size that maximizes its absorption and field enhancement capabilitiesThis work was supported by the ESF plasmonbionanosense program, the Leverhulme Trust, and the Engineering and Physical Sciences Research Council (EPSRC

Extraordinary absorption of sound in porous lamella-crystals

We present the design of a structured material supporting complete absorption of sound with a broadband response and functional for any direction of incident radiation. The structure which is fabricated out of porous lamellas is arranged into a low-density crystal and backed by a reflecting support. Experimental measurements show that strong all-angle sound absorption with almost zero reflectance takes place for a frequency range exceeding two octaves. We demonstrate that lowering the crystal filling fraction increases the wave interaction time and is responsible for the enhancement of intrinsic material dissipation, making the system more absorptive with less material.The work was supported by the Spanish Ministry of Science and Innovation and European Union FEDER through project FIS2011-29734-C02-01. J.C. gratefully acknowledges financial support from the Danish Council for Independent Research and a Sapere Aude grant (12-134776). V. R. G. gratefully acknowledges financial support from the ''Contratos Post-Doctorales Campus Excelencia Internacional'' UPV CEI-01-11.Christensen, J.; Romero García, V.; Picó Vila, R.; Cebrecos Ruiz, A.; Garcia De Abajo, FJ.; Mortensen, NA.; Willatzen, M.... (2014). Extraordinary absorption of sound in porous lamella-crystals. Scientific Reports. 4(4674). https://doi.org/10.1038/srep04674S44674Mei, J. et al. Dark acoustic metamaterials as super absorbers for low-frequency sound. Nat. Commun. 3, 756 (2012).Leroy, V., Strybulevych, A., Scanlon, M. G. & Page, J. Transmission of ultrasound through a single layer of bubbles. Eur. Phys. J. E 29, 123 (2009).Leroy, V., Bretagne, A., Fink, M. H. W., Tabeling, P. & Tourin, A. Design and characterization of bubble phononic crystals. Appl. Phys. Lett. 95, 171904 (2009).Thomas, E. L. Applied physics: Bubbly but quiet. Nature 462, 990 (2009).Romero-García, V., Sánchez-Pérez, J. V. & Garcia-Raffi, L. M. Tunable wideband bandstop acoustic filter based on two-dimensional multiphysical phenomena periodic systems. J. Appl. Phys. 110, 014904 (2011).Garcia-Chocano, V. M., Cabrera, S. & Sanchez-Dehesa, J. Broadband sound absorption by lattices of microperforated cylindrical shells. Appl. Phys. Lett. 101, 184101 (2012).Kushwaha, M. S., Halevi, P., Dobrzynski, L. & Djafari-Rouhani, B. Acoustic band structure of periodic elastic composites. Phys. Rev. Lett. 71, 2022 (1993).Vasseur, J. O. et al. Experimental and Theoretical Evidence for the Existence of Absolute Acoustic Band Gaps in Two-Dimensional Solid Phononic Crystals. Phys. Rev. Lett. 86, 3012 (2001).Liu, Z. et al. Locally Resonant Sonic Materials. Science 289, 1734 (2000).Christensen, J., Martin-Moreno, L. & Garcia-Vidal, F. J. All-angle blockage of sound by an acoustic double-fishnet metamaterial. Appl. Phys. Lett. 97, 134106 (2010).Botten, L. C., Craig, M. S., McPhedran, R. C., Adams, J. L. & Andrewartha, J. R. The finitely conducting lamellar diffraction grating. Optica Acta 28, 1087 (1981).McPhedran, R. C., Botten, L. C., Craif, M. S., Neviere, M. & Maystre, D. Lossy lamellar gratings in the quasistatic limit. Optica Acta 29, 289 (1982).Kravets, V. G., Schedin, F. & Grigorenko, A. N. Plasmonic blackbody: Almost complete absorption of light in nanostructured metallic coatings. Phys. Rev. B 78, 205405 (2008).Sondergaard, T. et al. Plasmonic black gold by adiabatic nanofocusing and absorption of light in ultra-sharp convex grooves. Nat. Commun. 3, 969 (2012).Clapham, P. B. & Hurtley, M. C. Reduction of Lens Reflexion by the Moth Eye Principle. Nature Vol. 244, 281 (1973).Garcia-Vidal, F. J., Pitarke, J. M. & Pendry, J. B. Effective Medium Theory of the Optical Properties of Aligned Carbon Nanotubes. Phys. Rev. Lett. 78, 4289 (1997).Yang, Z., Ci, L., Bur, J. A., Lin, S. & Ajayan, P. M. Experimental Observation of an Extremely Dark Material Made By a Low-Density Nanotube Array. Nano Lett. 8, 446 (2008).Garcia-Vidal, F. J. Metamaterials: Towards the dark side. Nat. Photonics 2, 215 (2008).Mizunoa, K. et al. A black body absorber from vertically aligned single-walled carbon nanotubes. Proc. Natl. Acad. Sci. USA 106, 6044 (2009).Lidorkis, E. & Ferrari, A. C. Photonics with Multiwall Carbon Nanotube Arrays. ACS Nano 3, 1238 (2009).Beenakker, C. W. J. & Brouwer, P. W. Distribution of the reflection eigenvalues of a weakly absorbing chaotic cavity. Physica E 9, 463 (2001).Lafarge, D., Lemarinier, P., Allard, J. F. & Tarnow, V. Dynamic compressibility of air in porous structures at audible frequencies. J. Acoust. Soc. Am. 102, 1995 (1997), With the macroscopic parameters: ϕ = 0.94, α∞ = 1, σ = 20000 Nm−4s and Λ = Λ′ = 0.41 μm.García de Abajo, F. J. Colloquium: Light scattering by particle and hole arrays. Rev. Mod. Phys. 79, 1267–1290 (2007)

Flexible Bonding of the Phosph(V)azane Dianions [S(E)P(µ-NtBu)]22-

Oxidation of the P(III) dianion [S-P(µ-NtBu)]22- (1) with elemental sulphur, selenium and tellurium gives the P(V) dianions [(S)(E)P(µ-NtBu)]22- (E = S (6a), Se (6b), Te (6c)). Although 6c proves to be too unstable, the S,S-dianion 6a and ambidentate S,Se-dianion 6b are readily transferred intact to main group and transition metal elements, producing a range of new cage and coordination compounds. While their coordination characteristics are in many ways similar to closely-related isoelectronic phosph(V)azane anions [(E)(RN=)P(µ-NtBu)]22-, the sterically unhindered nature of 6 introduces an expanded range of coordination modes, i.e., facial S,S- and Se,Se-bonding as well as side-on S,Se-coordination. All of these bonding modes are observed for the amibidentate S,Se dianion 6b.We thank the EU (ERC Advanced Grant for DSW, Erasmus grant for AJP), Cambridge Australia Scholarships (FJR) and the Cambridge Trust (AJP, FJR) and the PPF (AJP) for funding and the Spanish MINECO-AEI and the European Union (ESF) for a Ramon y Cajal contract (RG-R, RYC-2015–19035)

Smart Nanoparticles as Advanced Anti-Akt Kinase Delivery Systems for Pancreatic Cancer Therapy

Pancreatic cancer is one of the deadliest cancers partly due to late diagnosis, poor drug delivery to the target site, and acquired resistance to therapy. Therefore, more effective therapies are urgently needed to improve the outcome of patients. In this work, we have tested self-assembling genetically engineered polymeric nanoparticles formed by elastin-like recombinamers (ELRs), carrying a small peptide inhibitor of the protein kinase Akt, in both PANC-1 and patient-derived pancreatic cancer cells (PDX models). Nanoparticle cell uptake was measured by flow cytometry, and subcellular localization was determined by confocal microscopy, which showed a lysosomal localization of these nanoparticles. Furthermore, metabolic activity and cell viability were significantly reduced after incubation with nanoparticles carrying the Akt inhibitor in a time- and dose-dependent fashion. Self-assembling 73 ± 3.2 nm size nanoparticles inhibited phosphorylation and consequent activation of Akt protein, blocked the NF-κB signaling pathway, and triggered caspase 3-mediated apoptosis. Furthermore, in vivo assays showed that ELR-based nanoparticles were suitable devices for drug delivery purposes with long circulating time and minimum toxicity. Hence, the use of these smart nanoparticles could lead to the development of more effective treatment options for pancreatic cancer based on the inhibition of Akt

Monovinyl sulfone beta-cyclodextrin. A flexible drug carrier system

Cyclodextrins have been conjugated to target various receptors and have also been functionalized with carbohydrates for targeting specific organs. However, this approach is based on a rigid design that implies the ad hoc synthesis of each cyclodextrin-targeting agent conjugate. We hypothesized that: 1) a modular design that decouples the carrier function from the targeting function leads to a flexible system, 2) combining the reactivity of the vinyl sulfone group toward biomolecules that act as targeting agents with the ability of cyclodextrin to form complexes with a wide range of drugs may yield a versatile system that allows the targeting of different organs with different drugs, and 3) the higher reactivity of histidine residues toward the vinyl sulfone group can be exploited to couple the cyclodextrin to the targeting system with a degree of regioselectivity. As a proof of concept, we synthesized a monovinyl sulfone beta-cyclodextrin (module responsible for the payload), which, after coupling to recombinant antibody fragments raised against Trypanosoma brucei (module responsible for targeting) and loading with nitrofurazone (module responsible for therapeutic action) resulted in an effective delivery system that targets the surface of the parasites and shows trypanocidal activity