57 research outputs found
Evolution of thin-wall configurations of texture matter
We consider the free matter of global textures within the framework of the
perfect fluid approximation in general relativity. We examine thermodynamical
properties of texture matter in comparison with radiation fluid and bubble
matter. Then we study dynamics of thin-wall selfgravitating texture objects,
and show that classical motion can be elliptical (finite), parabolical or
hyperbolical. It is shown that total gravitational mass of neutral textures in
equilibrium equals to zero as was expected. Finally, we perform the
Wheeler-DeWitt's minisuperspace quantization of the theory, obtain exact wave
functions and discrete spectra of bound states with provision for spatial
topology.Comment: intermediate research on nature of dual-radiation matter; LaTeX, 12
pages, 1 figure and epsfig style file included; slightly shortened version
was published in December issue of GR
Evaluation of the silver species nature in Ag-ITQ2 zeolites by the CO oxidation reaction
The authors thank the Spanish Ministry of Economy and Competitiveness through RTI2018-101784-B-I00 (MINECO/FEDER) and SEV-2016-0683 projects for the financial support. We gratefully acknowledge ALBA synchrotron for allocating beamtime (proposal 2015091414) and the CLAESS beamline staff for their help and technical support during our experiment. CG and NB thank the TUW Innovative Project GIP165CDGC. CG, SP, VT, NB and GR are thankful for financial support from the Austrian Science Fund (FWF) through projects DK+ Solids4Fun (W1243) and ComCat (I 1041-N28). I. Lopez Hernandez is grateful to Generalitat Valenciana and European Social Fund for the pre doctoral grant ACIF2017.López-Hernández, I.; García Yago, CI.; Truttmann, V.; Pollit, S.; Barrabés, N.; Rupprechter, G.; Rey Garcia, F.... (2020). Evaluation of the silver species nature in Ag-ITQ2 zeolites by the CO oxidation reaction. Catalysis Today. 345:22-26. https://doi.org/10.1016/j.cattod.2019.12.001S2226345Serhan, N., Tsolakis, A., Wahbi, A., Martos, F. J., & Golunski, S. (2019). Modifying catalytically the soot morphology and nanostructure in diesel exhaust: Influence of silver De-NOx catalyst (Ag/Al2O3). Applied Catalysis B: Environmental, 241, 471-482. doi:10.1016/j.apcatb.2018.09.068Góra-Marek, K., Tarach, K. A., Piwowarska, Z., Łaniecki, M., & Chmielarz, L. (2016). Ag-loaded zeolites Y and USY as catalysts for selective ammonia oxidation. Catalysis Science & Technology, 6(6), 1651-1660. doi:10.1039/c5cy01446hHu, X., Bai, J., Hong, H., & Li, C. (2016). Supercritical carbon dioxide anchored highly dispersed silver nanoparticles on 4A-zeolite and selective oxidation of styrene performance. CrystEngComm, 18(14), 2469-2476. doi:10.1039/c5ce02435hCerrillo, J. L., Palomares, A. E., Rey, F., Valencia, S., Pérez-Gago, M. B., Villamón, D., & Palou, L. (2018). Functional Ag-Exchanged Zeolites as Biocide Agents. ChemistrySelect, 3(17), 4676-4682. doi:10.1002/slct.201800432Dong, X.-Y., Gao, Z.-W., Yang, K.-F., Zhang, W.-Q., & Xu, L.-W. (2015). Nanosilver as a new generation of silver catalysts in organic transformations for efficient synthesis of fine chemicals. Catalysis Science & Technology, 5(5), 2554-2574. doi:10.1039/c5cy00285kSulaiman, K. O., Sudheeshkumar, V., & Scott, R. W. J. (2019). Activation of atomically precise silver clusters on carbon supports for styrene oxidation reactions. RSC Advances, 9(48), 28019-28027. doi:10.1039/c9ra05566eCoutiño-Gonzalez, E., Baekelant, W., Steele, J. A., Kim, C. W., Roeffaers, M. B. J., & Hofkens, J. (2017). Silver Clusters in Zeolites: From Self-Assembly to Ground-Breaking Luminescent Properties. Accounts of Chemical Research, 50(9), 2353-2361. doi:10.1021/acs.accounts.7b00295Liu, L., & Corma, A. (2018). Metal Catalysts for Heterogeneous Catalysis: From Single Atoms to Nanoclusters and Nanoparticles. Chemical Reviews, 118(10), 4981-5079. doi:10.1021/acs.chemrev.7b00776Zhao, J., & Jin, R. (2018). Heterogeneous catalysis by gold and gold-based bimetal nanoclusters. Nano Today, 18, 86-102. doi:10.1016/j.nantod.2017.12.009Zhang, B., Kaziz, S., Li, H., Hevia, M. G., Wodka, D., Mazet, C., … Barrabés, N. (2015). Modulation of Active Sites in Supported Au38(SC2H4Ph)24 Cluster Catalysts: Effect of Atmosphere and Support Material. The Journal of Physical Chemistry C, 119(20), 11193-11199. doi:10.1021/jp512022vZhang, B., Sels, A., Salassa, G., Pollitt, S., Truttmann, V., Rameshan, C., … Barrabés, N. (2018). Ligand Migration from Cluster to Support: A Crucial Factor for Catalysis by Thiolate‐protected Gold Clusters. ChemCatChem, 10(23), 5372-5376. doi:10.1002/cctc.201801474Natarajan, G., Mathew, A., Negishi, Y., Whetten, R. L., & Pradeep, T. (2015). A Unified Framework for Understanding the Structure and Modifications of Atomically Precise Monolayer Protected Gold Clusters. The Journal of Physical Chemistry C, 119(49), 27768-27785. doi:10.1021/acs.jpcc.5b08193Tsukuda, T., & Häkkinen, H. (2015). Introduction. Protected Metal Clusters - From Fundamentals to Applications, 1-7. doi:10.1016/b978-0-08-100086-1.00001-4Zhang, X., Qu, Z., Li, X., Wen, M., Quan, X., Ma, D., & Wu, J. (2010). Studies of silver species for low-temperature CO oxidation on Ag/SiO2 catalysts. Separation and Purification Technology, 72(3), 395-400. doi:10.1016/j.seppur.2010.03.012Kolobova, E., Pestryakov, A., Mamontov, G., Kotolevich, Y., Bogdanchikova, N., Farias, M., … Cortes Corberan, V. (2017). Low-temperature CO oxidation on Ag/ZSM-5 catalysts: Influence of Si/Al ratio and redox pretreatments on formation of silver active sites. Fuel, 188, 121-131. doi:10.1016/j.fuel.2016.10.037Ausavasukhi, A., Suwannaran, S., Limtrakul, J., & Sooknoi, T. (2008). Reversible interconversion behavior of Ag species in AgHZSM-5: XRD, 1H MAS NMR, TPR, TPHE, and catalytic studies. Applied Catalysis A: General, 345(1), 89-96. doi:10.1016/j.apcata.2008.04.026Shi, C., Cheng, M., Qu, Z., & Bao, X. (2005). On the correlation between microstructural changes of Ag-H-ZSM-5 catalysts and their catalytic performances in the selective catalytic reduction of NOx by methane. Journal of Molecular Catalysis A: Chemical, 235(1-2), 35-43. doi:10.1016/j.molcata.2004.10.045Afanasev, D. S., Yakovina, O. A., Kuznetsova, N. I., & Lisitsyn, A. S. (2012). High activity in CO oxidation of Ag nanoparticles supported on fumed silica. Catalysis Communications, 22, 43-47. doi:10.1016/j.catcom.2012.02.014Kolobova, E., Pestryakov, A., Shemeryankina, A., Kotolevich, Y., Martynyuk, O., Tiznado Vazquez, H. J., & Bogdanchikova, N. (2014). Formation of silver active states in Ag/ZSM-5 catalysts for CO oxidation. Fuel, 138, 65-71. doi:10.1016/j.fuel.2014.07.011Royer, S., & Duprez, D. (2010). Catalytic Oxidation of Carbon Monoxide over Transition Metal Oxides. ChemCatChem, 3(1), 24-65. doi:10.1002/cctc.201000378Soliman, N. K. (2019). Factors affecting CO oxidation reaction over nanosized materials: A review. Journal of Materials Research and Technology, 8(2), 2395-2407. doi:10.1016/j.jmrt.2018.12.012Du, M., Sun, D., Yang, H., Huang, J., Jing, X., Odoom-Wubah, T., … Li, Q. (2014). Influence of Au Particle Size on Au/TiO2 Catalysts for CO Oxidation. The Journal of Physical Chemistry C, 118(33), 19150-19157. doi:10.1021/jp504681fCorma, A., Fornés, V., Guil, J. ., Pergher, S., Maesen, T. L. ., & Buglass, J. . (2000). Preparation, characterisation and catalytic activity of ITQ-2, a delaminated zeolite. Microporous and Mesoporous Materials, 38(2-3), 301-309. doi:10.1016/s1387-1811(00)00149-9Joshi, C. P., Bootharaju, M. S., Alhilaly, M. J., & Bakr, O. M. (2015). [Ag25(SR)18]−: The «Golden» Silver Nanoparticle. Journal of the American Chemical Society, 137(36), 11578-11581. doi:10.1021/jacs.5b07088Aspromonte, S. G., Mizrahi, M. D., Schneeberger, F. A., López, J. M. R., & Boix, A. V. (2013). Study of the Nature and Location of Silver in Ag-Exchanged Mordenite Catalysts. Characterization by Spectroscopic Techniques. The Journal of Physical Chemistry C, 117(48), 25433-25442. doi:10.1021/jp4046269Veronesi, G., Deniaud, A., Gallon, T., Jouneau, P.-H., Villanova, J., Delangle, P., … Michaud-Soret, I. (2016). Visualization, quantification and coordination of Ag+ions released from silver nanoparticles in hepatocytes. Nanoscale, 8(38), 17012-17021. doi:10.1039/c6nr04381jVeronesi, G., Aude-Garcia, C., Kieffer, I., Gallon, T., Delangle, P., Herlin-Boime, N., … Carrière, M. (2015). Exposure-dependent Ag+release from silver nanoparticles and its complexation in AgS2sites in primary murine macrophages. Nanoscale, 7(16), 7323-7330. doi:10.1039/c5nr00353aHudson-Smith, N. V., Clement, P. L., Brown, R. P., Krause, M. O. P., Pedersen, J. A., & Haynes, C. L. (2016). Research highlights: speciation and transformations of silver released from Ag NPs in three species. Environmental Science: Nano, 3(6), 1236-1240. doi:10.1039/c6en90025aShimizu, K., Sugino, K., Kato, K., Yokota, S., Okumura, K., & Satsuma, A. (2007). Formation and Redispersion of Silver Clusters in Ag-MFI Zeolite as Investigated by Time-Resolved QXAFS and UV−Vis. The Journal of Physical Chemistry C, 111(4), 1683-1688. doi:10.1021/jp066995aChen, D., Qu, Z., Shen, S., Li, X., Shi, Y., Wang, Y., … Wu, J. (2011). Comparative studies of silver based catalysts supported on different supports for the oxidation of formaldehyde. Catalysis Today, 175(1), 338-345. doi:10.1016/j.cattod.2011.03.059Schuricht, F., & Reschetilowski, W. (2012). Simultaneous selective catalytic reduction (SCR) of NOx and N2O over Ag/ZSM-5 – Catalytic studies and mechanistic implications. Microporous and Mesoporous Materials, 164, 135-144. doi:10.1016/j.micromeso.2012.07.018Akolekar, D. B., & Bhargava, S. K. (2000). Adsorption of NO and CO on silver-exchanged microporous materials. Journal of Molecular Catalysis A: Chemical, 157(1-2), 199-206. doi:10.1016/s1381-1169(00)00055-8Liu, J., Krishna, K. S., Kumara, C., Chattopadhyay, S., Shibata, T., Dass, A., & Kumar, C. S. S. R. (2016). Understanding Au∼98Ag∼46(SR)60 nanoclusters through investigation of their electronic and local structure by X-ray absorption fine structure. RSC Advances, 6(30), 25368-25374. doi:10.1039/c5ra27396jChevrier, D. M., Yang, R., Chatt, A., & Zhang, P. (2015). Bonding properties of thiolate-protected gold nanoclusters and structural analogs from X-ray absorption spectroscopy. Nanotechnology Reviews, 4(2). doi:10.1515/ntrev-2015-0007Yamazoe, S., & Tsukuda, T. (2019). X-ray Absorption Spectroscopy on Atomically Precise Metal Clusters. Bulletin of the Chemical Society of Japan, 92(1), 193-204. doi:10.1246/bcsj.2018028
Ligand migration from cluster to support: a crucial factor for catalysis by Thiolate-protected gold clusters
Thiolate
protected
metal
clusters
are valuable
precursors
for the
design
of tailored
nanosized
catalysts.
Their
performance
can
be tuned
precisely
at atomic
level,
e.g. by the configuration/
type
of ligands
or by partial/complete
removal
of the ligand
shell
through
controlled
pre-treatment
steps.
However,
the
interaction
between
the ligand
shell
and
the oxide
support,
as
well
as ligand
removal
by oxidative
pre-treatment,
are
still
poorly
understood.
Typically,
it was
assumed
that
the thiolate
ligands
are simply
converted
into
SO
2
, CO
2
and
H
2
O. Herein,
we
report
the first
detailed
observation
of sulfur
ligand
migration
from
Au to the oxide
support
upon
deposition
and
oxidative
pre-treatment,
employing
mainly
S K-edge
XANES.
Conse-
quently,
thiolate
ligand
migration
not only
produces
clean
Au
cluster
surfaces
but
also
the
surrounding
oxide
support
is
modified
by sulfur-containing
species,
with
pronounced
effects
on catalytic
propertiesPeer ReviewedPostprint (published version
Singular shell embedded into a cosmological model
We generalize Israel's formalism to cover singular shells embedded in a
non-vacuum Universe. That is, we deduce the relativistic equation of motion for
a thin shell embedded in a Schwarzschild/Friedmann-Lemaitre-Robertson-Walker
spacetime. Also, we review the embedding of a Schwarzschild mass into a
cosmological model using "curvature" coordinates and give solutions with
(Sch/FLRW) and without the embedded mass (FLRW).Comment: 25 pages, 2 figure
Adsorption and reaction of CO on (Pd–)Al2O3 and (Pd–)ZrO2: vibrational spectroscopy of carbonate formation
γ-Alumina is widely used as an oxide support in catalysis, and palladium nanoparticles supported by alumina represent one of the most frequently used dispersed metals. The surface sites of the catalysts are often probed via FTIR spectroscopy upon CO adsorption, which may result in the formation of surface carbonate species. We have examined this process in detail utilizing FTIR to monitor carbonate formation on γ-alumina and zirconia upon exposure to isotopically labelled and unlabelled CO and CO2. The same was carried out for well-defined Pd nanoparticles supported on Al2O3 or ZrO2. A water gas shift reaction of CO with surface hydroxyls was detected, which requires surface defect sites and adjacent OH groups. Furthermore, we have studied the effect of Cl synthesis residues, leading to strongly reduced carbonate formation and changes in the OH region (isolated OH groups were partly replaced or were even absent). To corroborate this finding, samples were deliberately poisoned with Cl to an extent comparable to that of synthesis residues, as confirmed by Auger electron spectroscopy. For catalysts prepared from Cl-containing precursors a new CO band at 2164 cm−1 was observed in the carbonyl region, which was ascribed to Pd interacting with Cl. Finally, the FTIR measurements were complemented by quantification of the amount of carbonates formed via chemisorption, which provides a tool to determine the concentration of reactive defect sites on the alumina surface
Effect of COMBinAtion therapy with remote ischemic conditioning and exenatide on the Myocardial Infarct size: a two-by-two factorial randomized trial (COMBAT-MI)
Remote ischemic conditioning (RIC) and the GLP-1 analog exenatide activate different cardioprotective pathways and may have additive effects on infarct size (IS). Here, we aimed to assess the efficacy of RIC as compared with sham procedure, and of exenatide, as compared with placebo, and the interaction between both, to reduce IS in humans. We designed a two-by-two factorial, randomized controlled, blinded, multicenter, clinical trial. Patients with ST-segment elevation myocardial infarction receiving primary percutaneous coronary intervention (PPCI) within 6 h of symptoms were randomized to RIC or sham procedure and exenatide or matching placebo. The primary outcome was IS measured by late gadolinium enhancement in cardiac magnetic resonance performed 3–7 days after PPCI. The secondary outcomes were myocardial salvage index, transmurality index, left ventricular ejection fraction and relative microvascular obstruction volume. A total of 378 patients were randomly allocated, and after applying exclusion criteria, 222 patients were available for analysis. There were no significant interactions between the two randomization factors on the primary or secondary outcomes. IS was similar between groups for the RIC (24 ± 11.8% in the RIC group vs 23.7 ± 10.9% in the sham group, P = 0.827) and the exenatide hypotheses (25.1 ± 11.5% in the exenatide group vs 22.5 ± 10.9% in the placebo group, P = 0.092). There were no effects with either RIC or exenatide on the secondary outcomes. Unexpected adverse events or side effects of RIC and exenatide were not observed. In conclusion, neither RIC nor exenatide, or its combination, were able to reduce IS in STEMI patients when administered as an adjunct to PPCI
Infrared Studies on Bimetallic Copper/Nickel Catalysts Supported on Zirconia and Ceria/Zirconia
ABSTRACT: Infrared spectroscopy has been employed for a detailed characterization of ZrO(2) and CeO(2)/ZrO(2) supported nickel and copper/nickel catalysts to be utilized for methane decomposition. Adsorption of CO at 303 K was performed in order to determine the surface composition and accessible adsorption sites. Alloy formation occurred during reduction, as indicated by a red-shift of the vibrational band of CO on Ni: by 27 cm(−1) on nickel-rich CuNi alloy, by 34 cm(−1) on 1:1 Cu:Ni and by 36 cm(−1) on copper-rich CuNi alloy. CuNi alloy formation was confirmed by X-ray absorption spectroscopy during reduction revealing a considerably lower reduction temperature of NiO in the bimetallic catalyst compared to the monometallic one. However, hydrogen chemisorption indicated that after reduction at 673 K copper was enriched at the surface of the all bimetallic catalysts, in agreement with IR spectra of adsorbed CO. In situ IR studies of methane decomposition at 773 K demonstrated that the addition of Cu to Ni strongly reduced coking occurring preferentially on nickel, while maintaining methane activation. Modification of the zirconia by ceria did not have much effect on the adsorption and reaction properties. Ceria-zirconia and zirconia supported samples exhibited very similar properties and surface chemistry. The main difference was an additional IR band of CO adsorbed on metallic copper pointing to an interaction of part of the Cu with the ceria. GRAPHICAL ABSTRACT: [Figure: see text
Practical guidelines for rigor and reproducibility in preclinical and clinical studies on cardioprotection
The potential for ischemic preconditioning to reduce infarct size was first recognized more than 30 years ago. Despite extension of the concept to ischemic postconditioning and remote ischemic conditioning and literally thousands of experimental studies in various species and models which identified a multitude of signaling steps, so far there is only a single and very recent study, which has unequivocally translated cardioprotection to improved clinical outcome as the primary endpoint in patients. Many potential reasons for this disappointing lack of clinical translation of cardioprotection have been proposed, including lack of rigor and reproducibility in preclinical studies, and poor design and conduct of clinical trials. There is, however, universal agreement that robust preclinical data are a mandatory prerequisite to initiate a meaningful clinical trial. In this context, it is disconcerting that the CAESAR consortium (Consortium for preclinicAl assESsment of cARdioprotective therapies) in a highly standardized multi-center approach of preclinical studies identified only ischemic preconditioning, but not nitrite or sildenafil, when given as adjunct to reperfusion, to reduce infarct size. However, ischemic preconditioning—due to its very nature—can only be used in elective interventions, and not in acute myocardial infarction. Therefore, better strategies to identify robust and reproducible strategies of cardioprotection, which can subsequently be tested in clinical trials must be developed. We refer to the recent guidelines for experimental models of myocardial ischemia and infarction, and aim to provide now practical guidelines to ensure rigor and reproducibility in preclinical and clinical studies on cardioprotection. In line with the above guideline, we define rigor as standardized state-of-the-art design, conduct and reporting of a study, which is then a prerequisite for reproducibility, i.e. replication of results by another laboratory when performing exactly the same experiment
Pt-MgZnCuAl hydrotalcite-derived catalysts in the reduction of nitrates using continuous and batch reactors
International audienceThe role of acid-base properties and reconstruction degree of the hydrotalcite-derived materials (MgZn- CuAl) in the catalytic hydrogenation of nitrates reaction is studied. In addition, the catalysts have been tested in a batch and continuous reactor to evaluate the influence of the reactor configuration on the catalytic performance. The characterizations of the samples have been performed by XRD, TPR, BET, TEM and MBOH test reaction. A clearly influence of the acid-base properties of the catalysts, modulated by the Zn incorporation, is observed with an increase in the nitrogen selectivity. Besides the common operational parameter differences between work in continuous and discontinuous systems, it shows great differences in the reconstruction degree of the samples. Higher reconstruction leads to higher nitrate reduction and a decrease of nitrite production
The dynamic structure of Au38(SR)24 nanoclusters supported on CeO2 upon pretreatment and CO oxidation
Atomically precise thiolate protected Au nanoclusters Au38(SC2H4Ph)24 on CeO2 were used for in-situ (operando) extended X-ray absorption fine structure/diffuse reflectance infrared fourier transform spectroscopy and ex situ scanning transmission electron microscopy–high-angle annular dark-field imaging/X-ray photoelectron spectroscopy studies monitoring cluster structure changes induced by activation (ligand removal) and CO oxidation. Oxidative pretreatment at 150 °C “collapsed” the clusters’ ligand shell, oxidizing the hydrocarbon backbone, but the S remaining on Au acted as poison. Oxidation at 250 °C produced bare Au surfaces by removing S which migrated to the support (forming Au+-S), leading to highest activity. During reaction, structural changes occurred via CO-induced Au and O-induced S migration to the support. The results reveal the dynamics of nanocluster catalysts and the underlying cluster chemistry.Peer ReviewedPostprint (author's final draft
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