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Ruthenium is a robust catalyst for a variety of applications in environmental heterogeneous catalysis. The catalytic performance of Ru/TiO2 materials, synthesized by using the deposition precipitation with urea method, was assessed in the catalytic oxidation of C3H8, varying the ruthenium loading. The highest catalytic reactivity was obtained for a Ru loading of 2 wt. % in comparison with the 1, 1.5, 3, and 4 wt. % Ru catalysts. The physicochemical properties of the synthesized materials were investigated by XRD, N2 adsorption, TEM, FT-IR pyridine, H2-TPR, and XPS. The size of ruthenium particles was found to be greatly dependent on the pretreatment gas (air or hydrogen) and the catalytic activity was enhanced by the small-size ruthenium metal nanoparticles, leading to changes in the reduction degree of ruthenium, which also increased the Brönsted and Lewis acidity. Metal to support charge transfer enhanced the reactant adsorption sites while oxygen vacancies on the interface enabled the dissociation of O2 molecules as revealed through DFT calculations. The outstanding catalytic activity of the 2Ru/TiO2 catalysts allowed to convert C3H8 into CO2 at reaction temperatures of about 100 °C. This high activity may be attributed to the metal/support interaction between Ru and TiO2, which promoted the reducibility of Ti4+/Ti3+ and Ru4+/Ru0 species, and to the fast migration of TiO2 lattice oxygen in the catalyst. Furthermore, the Ru/TiO2 catalyst exhibited high stability and reusability for 30 h under reaction conditions, using a GHSV of 45,000 h-1. The underlying alkane-metal interactions were explored theoretically in order to explain the C-H bond activation in propane by the catalyst.

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Semiconductors are essential for modern life since they are the basis of many current technologies that are related to better living standards. Some of them, characterized by the periodic assembling of metal cyanides with filled d-shell (nd10 ) constitute an interesting series of cyanide-based coordination polymers with physical properties such like anomalous anisotropic thermal expansion and quantum confinement effects related to the polymer's width that can be exploited for technological applications. Herein, the electronic structure of nd10 metal cyanide-based systems were studied both experimentally and through Density Functional Theory. The band gap found for one-dimensional (1D) -M-C≡N- (M=Cu, Ag, Au) and tetrahedral M-(C≡N)2 (M=Zn, Cd, Hg) systems can be attributed to Laporte-allowed π → ${\to }$ π* (Metal to Ligand Charge Transfer mechanism) combined with metal center (d → ${\to }$ s,p) electronic transitions. Aurophilic bonding was found on the AuCN structure, and a new forbidden electronic transition associated to its band gap is reported. Computed effective and reduced masses from carriers revealed that carrier mobility and quantum confinement effects are greater in 1D systems.

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A density functional theory + U systematic theoretical study was performed on the geometry, electronic structure, and energies of properties relevant for the chemical reactivity of TiO2 anatase. The effects of D3(BJ) dispersion correction and the Hubbard U value over the energies corresponding to the TiO2/Ti2O3 reduction reaction, the oxygen vacancy formation, and transition-metal doping were analyzed to attain an accurate and well-balanced description of these properties. It is suggested to fit the Hubbard correction for the metal dopant atom by taking as reference the observed low spin-high spin (HS) energy difference for the metal atom. PBEsol-D3 calculations revealed a distinct electronic ground state for the yttrium-doped TiO2 anatase surface depending upon the type of doping and interstitial or substitutional defects. Based on the calculations, it was found that a HS state explains the observed ferromagnetism in cobalt-substituted TiO2 anatase. The results presented herein might be relevant for further catalytic studies on TiO2 anatase using a large surface model that would be worthwhile for heterogeneous catalysis simulations.

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Reactions for the palladium-catalyzed intramolecular cyclization of the o-bromoindole and the o-bromo-N-methyl-indole derivatives in the presence and absence of base (Cs2CO3) were explored through DFT calculations. For the base-free reactions, the palladium atom firstly interacts with the aromatic rings of the indole molecule to yield a stable adduct. Once this adduct has been formed, reaction proceeds readily to the oxidative addition intermediate that arises from the insertion of the metal atom into the C-Br bond of the organic fragment. Further steps leading to the paullone (or dimethyl paullone) product, mainly those involving the metalation and deprotonation of the inserted intermediate, are not energetically viable for these reactions. When the effect of the base on the metalation-deprotonation steps is modeled by replacing the bromide ion with CO32- in the metal-inserted structure, a feasible pathway connecting the oxidative addition intermediate with the paullone-type product was located for each of the investigated reactions. The results emerging from this study suggest that palladium can insert into the C-Br bond of the indole derivatives to yield the oxidative addition intermediate (without participation of the base). However, the metalation and deprotonation steps that evolve to the paullone-type product take place via a concerted action involving both the metal and the base. Metalation and deprotonation steps that evolve to the paullone-type product take place via a concerted action involving both the metal and the base.

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Previous studies have suggested beneficial effects in lithium-sulfur batteries containing iodide in a sulfur-based cathode or as an electrolyte additive. These effects include preventing electrolyte degradation and improving the cycle stability of Li-S cells. However, little is known regarding the underlying reasons of such performance improvements. In this work, we present a theoretical study of the halogen-doping effect on the delithiation (charge) process on a (Li2S)10 model structure representing a potential final discharge product. It is revealed that the electron polaron is the dominant charge carrier during the charge process, and iodine is a facilitating agent for lithium detachment from the lithium sulfide cluster. However, the graphene support was found as potentially slowing down the ionic transport during the delithiation process due to charge transfer exerted by the support to the doped cluster that may retain the positive ions in the particle.

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1-methyl-2-pyrrolidone (1m2p) is a solvent with proven abilities for 2D-solid exfoliation due to its extremely high surface tension. In principle, such a feature could be used also to induce the selective breaking of certain bonds in solids to obtain new materials. Such a hypothesis is demonstrated in this study for transition metal nitroprussides, where 2D solids are obtained from 3D frameworks by selective rupture of axial bonds. This contribution discusses the mechanism involved in such molecular manufacture. The crystal structure for the formed 2D solids was solved and refined from XRD powder patterns recorded using synchrotron radiation. Mössbauer, IR and Raman spectra provided fine details on the electronic structure of the resulting new series of layered materials. The experimental information was complemented with calculations for the molecule configuration in its non-activated and activated forms. In the obtained 2D solids, neighboring layers of about 1 nm of thickness remain separated by activated 1m2p molecules. The interaction between neighboring layers is of a physical nature, without the presence of a chemical bond between them, as corresponds to a 2D material.

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Energy profiles for the lowest lying triplet and singlet electronic pathways that link the reactants Zr + CH3CH3 with the products observed under matrix-isolation conditions were obtained from DFT and CASSCF-MRMP2 calculations. The insertion of the metal into the C-H bond of the organic molecule to yield the oxidative addition product is not favorable for any of the investigated channels. However, the inserted structure H-Zr-CH2CH3 can be obtained from two sequential reactions involving the radical species ZrH and CH2CH3. According to this scheme, a first reaction produces the radical fragments from the ground state of the reactants. Then, the radicals can recombine themselves in a second reaction to form the inserted species H-Zr-CH2CH3. As the triplet and singlet radical asymptotes ZrH + CH2CH3 that vary only in spin of the non-metallic fragment are degenerate, the rebounding of the radicals can occur through both multiplicity channels. It is shown that the low spin channel leads to the most stable structures of the dihydride ZrH2-(CH2)2 and the vinyl metal trihydride complexes ZrH3-CH=CH2 experimentally determined for this reaction under matrix-isolation conditions. The description attained for this interaction does not invoke interactions between the triplet and singlet electronic states emerging from the reactants, as proposed by other authors.

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A systematic study of the electronic structure of polycyclic hydrocarbons from naphthalene to a system containing 80 fused benzene has been carried out. Geometries were optimized for closed shell singlet, open shell singlet, triplet and multiplet states at B3LYP/cc-pVDZ level of theory, D1 (second order Møller-Plesset) and D1 (second-order approximate coupled-cluster) diagnostics have been calculated for studied molecules. Complete active space self-consistent field (10,10)/6-31G(d) single point energy calculations have been carried out for all optimized structures. Multireference character of the ground state becomes important when the number of atoms in the polycyclic hydrocarbon exceeds 40-50. At this point, D1 diagnostics reaches 0.04-0.05 and the squared configuration interaction expansion coefficient for dominant configuration drops to about 0.6. However, only for the three largest systems predominantly polyradicalic ground states have been detected. All other polycyclic hydrocarbons showing significant multiconfigurational character of singlet ground state have only two dominant configurations which are closed shell singlet and doubly excited singlet, respectively. Thus, small polycyclic hydrocarbons have mostly single reference singlet ground state, the medium size systems have notably multireference ground state (singlet or triplet) with only moderate polyradicalic character. The ground state of largest systems is singlet polyradical.

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Metal-free, Zn-, Cd-, and Hg-containing one-dimensional tetraphenylporphyrin arrays containing up to eight repeat units were modeled at the PBE/def2-SVP level of theory with D3 empirical dispersion correction. Two different configurations--face to face (F) and parallel displaced (P)--were detected, the latter being the most stable for all types of nanoarrays. According to the calculations, the binding that occurs in nanoarrays is mostly due to dispersion, with binding energies of 33-35 kcal/mol seen for the metal-free nanoarrays and energies of 37-40 kcal/mol for the metal-containing ones. The band gaps, estimated as the S0 → S1 excitation energies and extrapolated to the infinite chain limit using the TD-CAM-B3LYP/def2-SVP model, were close to 2 eV; the band gap size was barely dependent on the nature of the metal and the number of repeat units in the nanoarray. The ionization potentials and electron affinities were greatly influenced by the number of repeat units due to delocalization of polarons across each nanoarray. Polaron delocalization and the related reorganization energies were clearly dependent on the nature of the metal. For the metal-free and Zn-containing nanoarrays, the reorganization energies for hole and electron transport decreased linearly with 1/n, where n is the number of repeat units in the nanoaggregate. The reorganization energies therefore reach zero for an infinitely long chain. These energies for Cd- and Hg-containing nanoarrays were found to be one order of magnitude higher for both hole and electron transport due to the localization of polarons in these nanoarrays.

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The results obtained from CASSCF-MRMP2 calculations are used to rationalize the singlet complexes detected under matrix-isolation conditions for the reactions of laser-ablated Zr((3)F) atoms with the CH3F and CH3CN molecules, without invoking intersystem crossings between electronic states with different multiplicities. The reaction Zr((3)F) + CH3 F evolves to the radical products ZrF· + ·CH3. This radical asymptote is degenerate to that emerging from the singlet channel of the reactants Zr((1)D) + CH3 F because they both exhibit the same electronic configuration in the metal fragment. Hence, the caged radicals obtained under cryogenic-matrix conditions can recombine through triplet and singlet paths. The recombination of the radical species along the low-multiplicity channel produces the inserted structures H3C-Zr-F and H2C=ZrHF experimentally detected. For the Zr((3)F) + CH3 CN reaction, a similar two-step reaction scheme involving the radical fragments ZrNC· + ·CH3 explains the presence of the singlet complexes H C-Zr-NC and H2 C=Zr(H)NC revealed in the IR-matrix spectra upon UV irradiation.

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Se estudiaron 100 recién nacidos sometidos a tratamiento con ventilación mecánica durante los años 1986 y 1987, en la Unidad de Cuidados Intensivos del Hospital Pediátrico Provincial de Villa Clara. El 57 % del total estuvo comprendido en el grupo de más de 2 500 g de peso al nacimiento y el 41 % de ellos tuvo un Aggar menor de 7. De los recién nacidos con edad entre 0 a 6 días al inicio de la ventilación fallecieron 17, los que representaron el 65,4 % de este grupo. Se pudo demostrar que en el 36 y el 17 %, respectivamente, del total de pacientes, la hipoxia perinatal y la enfermedad de la membrana hialina fueron las entidades que más motivaron la ventilación. Se comprobó la sobrevida en el 36 % del total de niños ventilados. Las complicaciones más comúnmente halladas fueron la sepsis y el borotrauma (AU)

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Se estudiaron 100 recién nacidos sometidos a tratamiento con ventilación mecánica durante los años 1986 y 1987, en la Unidad de Cuidados Intensivos del Hospital Pediátrico Provincial de Villa Clara. El 57 % del total estuvo comprendido en el grupo de más de 2 500 g de peso al nacimiento y el 41 % de ellos tuvo un Aggar menor de 7. De los recién nacidos con edad entre 0 a 6 días al inicio de la ventilación fallecieron 17, los que representaron el 65,4 % de este grupo. Se pudo demostrar que en el 36 y el 17 %, respectivamente, del total de pacientes, la hipoxia perinatal y la enfermedad de la membrana hialina fueron las entidades que más motivaron la ventilación. Se comprobó la sobrevida en el 36 % del total de niños ventilados. Las complicaciones más comúnmente halladas fueron la sepsis y el borotrauma

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Se estudiaron 104 pacientes que presentaron manifestaciones de fracaso multiorgánico (FMO) a su ingreso o en algún momento de su evolución en la unidad de cuidados intensivos (UCI) del Hospital Pediátrico de Santa Clara durante 1988. De ellos egresaron vivos 60 y fallecieron 44, con predominio de los menores de un año. La malnutrición por defecto fue un índice de mal pronóstico. El fracaso monofásico fue el de diagnóstico más frecuente. Las lesiones respiratorias y cardiovasculares constituyeron las causas iniciales de fracaso en un alto porcentaje de pacientes. Se observó una relación directa entre el número de sistemas en fallo y la mortalidad (AU)

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Se realizó un estudio sobre morbimortalidad en la UTI del ÿ Hospital Pediátrico Provincial Docente "José Luis Miranda" de ÿ Santa Clara durante el año 1986. Fueron sometidos a estudio, el ÿ total de pacientes que ingresaron en la misma durante dicho ÿ periodo, para lo que se agruparon por edades, sexo, provincia ÿ de origen, servicio de procedencia, estadía, diagnóstico al ÿ egreso y causa de fallecimiento. El total de ingresos durante el ÿ año fue de 774. Los menores de 1 año constituyeron el 51.9 porciento del ÿ total. La mayoría de los pacientes procedieron del Departamento de ÿ Urgencias. La enfermedad meningocócica continuó siendo la causa ÿ más frecuente de ingresos en la Unidad

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Se realizó un estudio sobre morbimortalidad en la UTI del ÿ Hospital Pediátrico Provincial Docente "José Luis Miranda" de ÿ Santa Clara durante el año 1986. Fueron sometidos a estudio, el ÿ total de pacientes que ingresaron en la misma durante dicho ÿ periodo, para lo que se agruparon por edades, sexo, provincia ÿ de origen, servicio de procedencia, estadía, diagnóstico al ÿ egreso y causa de fallecimiento. El total de ingresos durante el ÿ año fue de 774. Los menores de 1 año constituyeron el 51.9 porciento del ÿ total. La mayoría de los pacientes procedieron del Departamento de ÿ Urgencias. La enfermedad meningocócica continuó siendo la causa ÿ más frecuente de ingresos en la Unidad(AU)

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