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Highly ordered Pt alloy structures are proven effective to improve their catalytic activity and stability for the oxygen reduction reaction (ORR) for proton exchange membrane fuel cells. Here, we report a new approach to preparing ordered Pt3Co intermetallic nanoparticles through a facile thermal treatment of Pt nanoparticles supported on Co-doped metal-organic-framework (MOF)-derived carbon. In particular, the atomically dispersed Co sites, which are originally embedded into MOF-derived carbon, diffuse into Pt nanocrystals and form ordered Pt3Co structures. It is very crucial for the formation of the ordered Pt3Co to carefully control the doping content of Co into the MOFs and the heating temperatures for Co diffusion. The optimal Pt3Co nanoparticle catalyst has achieved significantly enhanced activity and stability, exhibiting a half-wave potential up to 0.92 V vs reversible hydrogen electrode (RHE) and only losing 12 mV after 30â¯000 potential cycling between 0.6 and 1.0 V. The highly ordered intermetallic structure was retained after the accelerated stress tests made evident by atomic-scale elemental mapping. Fuel cell tests further verified the high intrinsic activity of the ordered Pt3Co catalysts. Unlike the direct use of MOF-derived carbon supports for depositing Pt, we utilized MOF-derived carbon containing atomically dispersed Co sites as Co sources to prepare ordered Pt3Co intermetallic catalysts. The new synthesis approach provides an effective strategy to develop active and stable Pt alloy catalysts by leveraging the unique properties of MOFs such as 3D structures, high surface areas, and controlled nitrogen and transition metal dopings.
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Examining continuous seismic data recorded by a dense broadband seismic network throughout Taipei shows for the first time, the nature of seismic noise in this highly populated metropolitan area. Using 140 broadband stations in a 50 km × 69 km area, three different recurring, strong noise signals characterized by dominant frequencies of 2-20 Hz, 0.25-1 Hz, and < 0.2 Hz are explored. At frequencies of 2-20 Hz, the seismic noise exhibits daily and weekly variations, and a quiescence during the Chinese New Year holidays. The largest amplitude occurred at a station located only 400 m from a traffic-roundabout, one of the busiest intersections in Taipei, suggesting a possible correlation between large amplitude and traffic flow. The median daily amplitude for the < 0.2 Hz and 0.2-1.0 Hz frequency bands is mostly synchronized with high similarity between stations, indicating that the sources are persistent oceanic or atmospheric perturbations across a large area. The daily amplitude for the > 2 Hz band, however, is low, indicating a local source that changes on shorter length scales. Human activities responsible for the 2-40 Hz energy in the city, we discovered, are able to produce amplitudes approximately 2 to 1500 times larger than natural sources. Using the building array deployed in TAIPEI 101, the tallest building in Taiwan, we found the small but repetitive ground vibration induced by traffic has considerable effect on the vibration behavior of the high-rise building. This finding urges further investigation not only on the dynamic and continuous interaction between vehicles, roads, and buildings, but also the role of soft sediment on such interaction.
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Tantalum (Ta)-doped titanium oxide (TiO2) thin films are grown by plasma enhanced atomic layer deposition (PEALD), and used as both an electron transport layer and hole blocking compact layer of perovskite solar cells. The metal precursors of tantalum ethoxide and titanium isopropoxide are simultaneously injected into the deposition chamber. The Ta content is controlled by the temperature of the metal precursors. The experimental results show that the Ta incorporation introduces oxygen vacancies defects, accompanied by the reduced crystallinity and optical band gap. The PEALD Ta-doped films show a resistivity three orders of magnitude lower than undoped TiO2, even at a low Ta content (0.8-0.95 at.%). The ultraviolet photoelectron spectroscopy spectra reveal that Ta incorporation leads to a down shift of valance band and conduction positions, and this is helpful for the applications involving band alignment engineering. Finally, the perovskite solar cell with Ta-doped TiO2 electron transport layer demonstrates significantly improved fill factor and conversion efficiency as compared to that with the undoped TiO2 layer.
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In this study, spatial atomic layer deposition (sALD) is employed to prepare titanium dioxide (TiO2) thin films by using titanium tetraisopropoxide and water as metal and water precursors, respectively. The post-annealing temperature is varied to investigate its effect on the properties of the TiO2 films. The experimental results show that the sALD TiO2 has a similar deposition rate per cycle to other ALD processes using oxygen plasma or ozone oxidant, implying that the growth is limited by titanium tetraisopropoxide steric hindrance. The structure of the as-deposited sALD TiO2 films is amorphous and changes to polycrystalline anatase at the annealing temperature of 450 °C. All the sALD TiO2 films have a low absorption coefficient at the level of 10-3 cm-1 at wavelengths greater than 500 nm. The annealing temperatures of 550 °C are expected to have a high compactness, evaluated by the refractive index and x-ray photoelectron spectrometer measurements. Finally, the 550 °C-annealed sALD TiO2 film with a thickness of ~8 nm is applied to perovskite solar cells as a compact electron transport layer. The significantly enhanced open-circuit voltage and conversion efficiency demonstrate the great potential of the sALD TiO2 compact layer in perovskite solar cell applications.
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Pt alloy nanoparticles supported on Vulcan XC-72 (Pt/C) are the most effective catalysts for kinetically sluggish oxygen reduction reaction (ORR) in proton exchange membrane fuel cells. However, significant performance degradation has been observed with the Pt/C catalysts due to agglomeration and Ostwald ripening of Pt nanoparticles largely resulting from the corrosion of carbon supports. Here, we developed a Pt alloy catalyst through annealing Pt nanoparticles deposited on nitrogen/metal co-doped large-size graphene tubes (NGTs). The in-situ formation of PtM (M: Co and Ni) alloy during the annealing process contributes to the improvement of the catalytic activity and stability. During the accelerated stress tests (AST), after 20 000 potential cycles (0.6-1.0 V vs. RHE), the retained electrochemical surface area (ECSA) of the PtM/NGT catalyst is more than 2 times larger than that of the Pt/C catalyst. As for the AST tests of carbon corrosion, after 30 000 potential cycles (1.0-1.5 V vs. RHE) at room temperature, the NGT morphologies are well maintained and no ECSA loss of this PtM catalyst is observed, indicating excellent corrosion-resistance. Even at harsher 60 °C, the PtM/NGT catalyst exhibits only insignificant loss (6 mV) of E1/2 while the Pt/C catalyst shows significant degradation (47 mV loss in E1/2). The improved stability of PtM/NGT catalyst is attributed to the highly graphitized NGTs and possible synergistic effects between the NGT carbon support and the PtM alloy nanoparticles.
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PURPOSE: The mitogenic action of PDGF has been shown to associate with reactive oxygen species (ROS) generation, but the mechanism leading to ROS production and subsequent cell proliferation is not clear. We investigated the upstream membrane-bound target proteins involved in PDGF-stimulated signal transduction in human lens epithelial cell (HLE B3), using specific inhibitors and transfected cells. METHODS: PDGF (1 ng/ml)-stimulated ROS generation was measured using fluorescent reaction of DCFDA by confocal microscope in live HLE B3 cells. Western blot analysis was used to determine the activated MAP kinases in cell lysates. Specific inhibitors used in this study were: AG1296 for PDGF receptor (PDGFR); AG1517 for EGF receptor (EGFR); pertussis toxin for cytokine-binding G protein coupled receptor (GPCR); PP1 for Src-family kinases; LY294002 for phosphatidylinositol-3 kinase (PI3K). Small GTP-binding proteins Rac and Ras were studied using transfectants of dominant negative Rac (Rac N17), Ras (Ras N17) or constitutively active Rac (Rac V12). Cell proliferation was quantified using BrdU incorporation method. RESULTS: Inhibitions of PDGF receptor kinase, the docking protein component Src-family kinases, and the survival element PI3K all eradicated PDGF-stimulated ROS production and corroborated with the suppressed cell growth. These inhibitions also attenuated the activated ERK1/2, JNK, and Akt, all downstream targets of the above factors. Interestingly, inhibiting GPCR or EGFR also showed the same effect but to a lesser degree. Co-inhibiting receptors to PDGF and EGF with or without co-inhibiting GPCR eradicated the PDGF signaling system completely. Transiently transfected cells with plasmid from small GTP-binding proteins Rac N17 or Ras N17 diminished PDGF action in ROS generation, cell proliferation and MAP kinase activation, while cells with Rac V12 enhanced the PDGF effect. CONCLUSIONS: Our data clarified the potential mechanism of PDGF signaling in the lens epithelial cells, in which concerted efforts of the upstream components of PDGF receptor kinase, Src-family kinases, PI3K, Rac, and Ras proteins are required. This report also provided novel findings that GPCR and EGF receptors may control PDGF signaling in the lens epithelial cells via integrative signaling and transactivation mechanisms, respectively.
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Células Epiteliales/efectos de los fármacos , Cristalino/citología , Cristalino/efectos de los fármacos , Factor de Crecimiento Derivado de Plaquetas/farmacología , Especies Reactivas de Oxígeno/metabolismo , Transducción de Señal/efectos de los fármacos , Proliferación Celular/efectos de los fármacos , Células Cultivadas , Activación Enzimática/efectos de los fármacos , Inhibidores Enzimáticos/farmacología , Células Epiteliales/citología , Receptores ErbB/antagonistas & inhibidores , Humanos , Proteínas Quinasas Activadas por Mitógenos/metabolismo , Toxina del Pertussis/farmacología , Inhibidores de las Quinasa Fosfoinosítidos-3 , Receptores Acoplados a Proteínas G/antagonistas & inhibidores , Receptores del Factor de Crecimiento Derivado de Plaquetas/antagonistas & inhibidores , Tirfostinos/farmacología , Proteínas de Unión al GTP rac/metabolismo , Proteínas ras/metabolismo , Familia-src Quinasas/antagonistas & inhibidoresRESUMEN
Clinical abnormalities in cystathionine-beta-synthase (CBS) deficiency, a key enzyme in the trans-sulfuration pathway, associate with many eye disorders. However, little is known about this enzyme in the eye. The goal of this study is to examine the distribution of CBS in the various regions of the eye, including conjunctiva, cornea, iris, lens, vitreous, retina and optic nerve using fresh eyes from both pigs (6 months) and humans (4-82 years). We have found that pig eye showed the highest CBS protein presence in cornea, conjunctiva and iris, followed by retina and optic nerve. The whole lens had a relatively lower amount and vitreous body had none. CBS protein distribution in the human eyes showed a similar pattern, with high level in the anterior segments but much lower amount in retina and optic nerve. CBS in anterior segments remained high throughout the lifespan, but retinal CBS showed a trend of age-dependent increase. The presence of CBS in human and pig eye tissues was further confirmed by RT-PCR, CBS activity assay, both showed similar distribution profiles as the Western blot analysis. This is the first evidence of the presence of CBS enzyme in the eye outside of the lens, which indicates that a functional trans-sulfuration pathway may be present in various eye tissues.
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Cistationina betasintasa/metabolismo , Ojo/enzimología , Estrés Oxidativo/fisiología , Porcinos/metabolismo , Adolescente , Adulto , Anciano , Anciano de 80 o más Años , Envejecimiento/metabolismo , Animales , Niño , Preescolar , Cistationina betasintasa/genética , Ojo/metabolismo , Expresión Génica , Humanos , Persona de Mediana Edad , ARN Mensajero/genética , Reacción en Cadena de la Polimerasa de Transcriptasa Inversa/métodos , Transducción de Señal/fisiología , Especificidad de la Especie , Distribución TisularRESUMEN
Low level of reactive oxygen species (ROS) has been shown to play an important role in host defense and mediating mitogen-stimulated cell signaling in several cell types. This study is to identify the mitogen-induced endogenous ROS generation and the range of exogenous H(2)O(2) that initiate redox signaling and cell proliferation in human lens epithelial cells (HLE B3), using platelet-derived growth factor (PDGF) as a model. To detect ROS generation, serum starved HLE cells (1.6 million) were loaded with fluorescent dye, 2',7'-dichlorofluorescin diacetate (DCFH-DA), before exposing to PDGF (1 ng ml(-1)). The fluorescence generated from the oxidant-sensitive DCFH, the intracellular product of DCFH-DA hydrolysate, was immediately measured in live cells by confocal laser light microscopy (lambda(Ex)=488 nm, lambda(Em)=522 nm, laser power=10%). PDGF-stimulated cells showed strong transient fluorescence during the 60 min while no fluorescence could be seen in the unstimulated cells. The PDGF-induced fluorescence could be suppressed with cells preloaded with N-acetyl-L-cysteine (NAC, 30 mm), catalase (1 mg ml(-1)), or D-mannitol (100mm). The ability of catalase to penetrate and function in HLE cells was confirmed by western blot, enzyme activity and immunofluorescence microscopic analyses. PDGF induced DNA synthesis within one hour as measured by (3)H-thymidine incorporation, and transiently activated the mitogen-activated protein kinases (MAPKs) of ERK1/2 and JNK. PDGF-stimulated DNA synthesis and MAPK activation were eliminated in the presence of catalase or mannitol. Low levels of H(2)O(2) (10-20 microm) mimicked PDGF in both MAPK stimulation and cell proliferation. In conclusion, the mitogenic stimulus function of PDGF in HLE cells appears to be mediated via ROS to activate MAPKs and cell proliferation, which can be mimicked by low levels of H(2)O(2). It is proposed that the physiological function of ROS, the redox signaling, is present in the HLE cells and may play an important role in the development and maintenance of the lens.