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11.
Canevali C Mari CM Mattoni M Morazzoni F Nodari L Ruffo R Russo U Scotti R 《The journal of physical chemistry. B》2005,109(15):7195-7202
The mechanism of NO interaction with nanosized Ru(Pd,Pt)-doped SnO(2) was studied by electron paramagnetic resonance, M?ssbauer, and electric resistance measurements. Three steps were proposed for the reaction between the semiconductor oxide and the gaseous component: (i) the formation of bielectronic oxygen vacancies (V(o)) in SnO(2); (ii) their single-ionization (V(o)(*)) with injection of electrons into the SnO(2) conduction band; (iii) the subsequent transfer of electrons from V(o)(*) to [Ru(Pd,Pt)](4+). The last process induces the formation of further oxygen vacancies which reduce the transition metal centers to lower oxidation states; the redox processes is enhanced and the electrical resistance in transition metal-doped SnO(2) is stronger modified with respect to the undoped material. 相似文献
12.
Franca Graiff 《Meccanica》1967,2(2):69-74
Summary When relativistic theory amalgamates space and time into event, other magnitudes of classical mechanics merge or superimpose. In special relativity it is still easy to find them again by referring to the inertial frame of reference, but general relativity presents them to us as already identified in the curvatures of the Riemannian universe, which admits of no inertial frames, except local ones. It is a search for particular magnitudes and relations (such as momentum and conservation laws), physically interpretablein the classical sense, which specifies a privileged frame. Starting from this frame of reference, the present Note sets out to define the energy-momentum density and super-potentials that give rise, in the same frame, to the known integral results due to the Einstein and Freud psendotensors. Thus the snags arising out of the transformation laws of these pseudotensors are eliminated at the same time.
Study conducted under the auspices of the mathematical teams of the Consiglio Nazionale delle Ricerche. 相似文献
Sommario Quando, nelle teorie relativistiche, si sostituisce alle grandezze spazio e tempo la loro fusione nell'evento, altre grandezze della meccanica classica si fondono e sovrappongono. Nella relatività ristretta è ancora agevole ritrovarle, riferendosi all'osservatore inerziale; ma la Relatività generale ce le presenta già fuse nelle curvature dell'Universo riemanniano, che non ammette osservatori inerziali, se non locali. E' la ricerca di particolari grandezze e relazioni, (come la quantità di moto e le leggi di conservazione), fisicamente interpretabili nel senso classico, che precisa un riferimento privilegiato. Valendosi di questo riferimento, vengono definiti, nella presente Nota, densità di energia-quantità di moto e superpotenziali che danno luogo, nello stesso riferimento, ai noti risultati integrali dovuti agli pseudo-tensori di Einstein e Freud. Risultano così eliminati, nello stesso tempo, gli inconvenienti dovuti alle leggi di trasformazione di questi pseudo-tensori.
Study conducted under the auspices of the mathematical teams of the Consiglio Nazionale delle Ricerche. 相似文献
13.
Dalva E. C. Ferreira Wagner B. De Almeida Ademir Neves Willian R. Rocha 《International journal of quantum chemistry》2010,110(5):1048-1055
Density functional theory (DFT) calculations with different exchange‐correlation functionals were performed for a mixed valence Fe(II)/Fe(III) binuclear complex with μ‐methoxo and two μ‐carboxylate bridging ligands, (1) with geometry optimizations being performed for all possible spin multiplicities (MS = 2, 4, 6, 8, and 10). Within the exchange‐correlation functionals studied, only the hybrid GGA functionals B3P and B3LYP and also the pure GGA functional RPBE, predicts the geometry with high spin (S = 9/2) to be more stable than the geometry with low spin state (S = 1/2) by 20 kcal/mol, in agreement with the experimental findings. These functionals also predict the same stability order for the different spin states, being MS = 10>8>6>2>4. The meta‐GGA functionals TPSS and TPSSh and also the pure GGA functionals BLYP and BP86 predict different stability orders. The computed average EPR g‐tensor, gav, of 2.03, at the B3LYP level, is in good agreement with the experimental findings. Heisenberg exchange coupling constants, J, were calculated within the broken‐symmetry formalism, at the B3LYP level, showing that the two iron centers are antiferromagnetic coupling, with a very weak coupling constant of about ?7 cm?1, in good agreement with the experimental value. Additionally, the effect of using different multiplicities of the reference geometries on the computed J value is discussed. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 相似文献
14.
Organocatalytic,Asymmetric Eliminative [4+2] Cycloaddition of Allylidene Malononitriles with Enals: Rapid Entry to Cyclohexadiene‐Embedding Linear and Angular Polycycles
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Dr. Nicoletta Brindani Dr. Gloria Rassu Dr. Luca Dell'Amico Dr. Vincenzo Zambrano Dr. Luigi Pinna Dr. Claudio Curti Dr. Andrea Sartori Prof. Dr. Lucia Battistini Prof. Dr. Giovanni Casiraghi Prof. Dr. Giorgio Pelosi Dr. Daniela Greco Prof. Dr. Franca Zanardi 《Angewandte Chemie (International ed. in English)》2015,54(25):7386-7390
A direct aminocatalytic synthesis has been developed for the chemo‐, regio‐, diastereo‐, and enantioselective construction of densely substituted polycyclic carbaldehydes containing fused cyclohexadiene rings. The chemistry utilizes, for the first time, remotely enolizable π‐extended allylidenemalononitriles as electron‐rich 1,3‐diene precursors in a direct eliminative [4+2] cycloaddition with both aromatic and aliphatic α,β‐unsaturated aldehydes. The generality of the process is demonstrated by approaching 6,6‐, 5,6‐, 7,6‐, 6,6,6‐, and 6,5,6‐fused ring systems, as well as biorelevant steroid‐like 6,6,6,6,5‐ and 6,6,6,5,6‐rings. A stepwise reaction mechanism for the key [4+2] addition is proposed as a domino bis‐vinylogous Michael/Michael/retro‐Michael reaction cascade. The utility of the malononitrile moiety as traceless activating group of the dicyano nucleophilic substrates is demonstrated. 相似文献
15.
Simone Zanella Dr. Michele Mingozzi Alberto Dal Corso Dr. Roberto Fanelli Dr. Daniela Arosio Prof. Dr. Marco Cosentino Dr. Laura Schembri Dr. Franca Marino Dr. Marta De Zotti Prof. Dr. Fernando Formaggio Dr. Luca Pignataro Prof. Dr. Laura Belvisi Prof. Dr. Umberto Piarulli Prof. Dr. Cesare Gennari 《ChemistryOpen》2015,4(5):633-641
A dual-action ligand targeting both integrin αVβ3 and vascular endothelial growth factor receptors (VEGFRs), was synthesized via conjugation of a cyclic peptidomimetic αVβ3 Arg-Gly-Asp (RGD) ligand with a decapentapeptide. The latter was obtained from a known VEGFR antagonist by acetylation at the Lys13 side chain. Functionalization of the precursor ligands was carried out in solution and in the solid phase, affording two fragments: an alkyne VEGFR ligand and the azide integrin αVβ3 ligand, which were conjugated by click chemistry. Circular dichroism studies confirmed that both the RGD and VEGFR ligand portions of the dual-action compound substantially adopt the biologically active conformation. In vitro binding assays on isolated integrin αVβ3 and VEGFR-1 showed that the dual-action conjugate retains a good level of affinity for both its target receptors, although with one order of magnitude (10/20 times) decrease in potency. The dual-action ligand strongly inhibited the VEGF-induced morphogenesis in Human Umbilical Vein Endothelial Cells (HUVECs). Remarkably, its efficiency in preventing the formation of new blood vessels was similar to that of the original individual ligands, despite the worse affinity towards integrin αVβ3 and VEGFR-1. 相似文献
16.
Stabilization of Titanium Dioxide Nanoparticles at the Surface of Carbon Nanomaterials Promoted by Microwave Heating
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Rui Zhang Prof. Dr. Saveria Santangelo Dr. Enza Fazio Prof. Dr. Fortunato Neri Dr. Massimiliano D'Arienzo Prof. Dr. Franca Morazzoni Prof. Dr. Yihe Zhang Prof. Dr. Nicola Pinna Dr. Patrícia A. Russo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(42):14901-14910
TiO2 is frequently combined with carbon materials, such as reduced graphene oxide (RGO), to produce composites with improved properties, for example for photocatalytic applications. It is shown that heating conditions significantly affect the interface and photocatalytic properties of TiO2@C, and that microwave irradiation can be advantageous for the synthesis of carbon‐based materials. Composites of TiO2 with RGO or amorphous carbon were prepared from reaction of titanium isopropoxide with benzyl alcohol. During the synthesis of the TiO2 nanoparticles, the carbon is involved in reactions that lead to the covalent attachment of the oxide, the extent of which depends on the carbon characteristics, heating rate, and mechanism. TiO2 is more efficiently stabilized at the surface of RGO than amorphous carbon. Rapid heating of the reaction mixture results in a stronger coupling between the nanoparticles and carbon, more uniform coatings, and smaller particles with narrower size distributions. The more efficient attachment of the oxide leads to better photocatalytic performance. 相似文献
17.
D'Arienzo M Carbajo J Bahamonde A Crippa M Polizzi S Scotti R Wahba L Morazzoni F 《Journal of the American Chemical Society》2011,133(44):17652-17661
The promising properties of anatase TiO(2) nanocrystals exposing specific surfaces have been investigated in depth both theoretically and experimentally. However, a clear assessment of the role of the crystal faces in photocatalytic processes is still under debate. In order to clarify this issue, we have comprehensively explored the properties of the photogenerated defects and in particular their dependence on the exposed crystal faces in shape-controlled anatase. Nanocrystals were synthesized by solvothermal reaction of titanium butoxide in the presence of oleic acid and oleylamine as morphology-directing agents, and their photocatalytic performances were evaluated in the phenol mineralization in aqueous media, using O(2) as the oxidizing agent. The charge-trapping centers, Ti(3+), O(-), and O(2)(-), formed by UV irradiation of the catalyst were detected by electron spin resonance, and their abundance and reactivity were related to the exposed crystal faces and to the photoefficiency of the nanocrystals. In vacuum conditions, the concentration of trapped holes (O(-) centers) increases with increasing {001} surface area and photoactivity, while the amount of Ti(3+) centers increases with the specific surface area of {101} facets, and the highest value occurs for the sample with the worst photooxidative efficacy. These results suggest that {001} surfaces can be considered essentially as oxidation sites with a key role in the photoxidation, while {101} surfaces provide reductive sites which do not directly assist the oxidative processes. Photoexcitation experiments in O(2) atmosphere led to the formation of Ti(4+)-O(2)(-) oxidant species mainly located on {101} faces, confirming the indirect contribution of these surfaces to the photooxidative processes. Although this work focuses on the properties of TiO(2), we expect that the presented quantitative investigation may provide a new methodological tool for a more effective evaluation of the role of metal oxide crystal faces in photocatalytic processes. 相似文献
18.
Vitor C Almeida Willian F Costa Jorge Nozaki Cláudio C Oliveira 《Analytical sciences》2006,22(3):445-448
A new spectrophotometric method involving flow injection analysis and textile dye aggregation effect is proposed. The method is based on the aggregation effect of Blue Procion HEGN at pH 3, which relocates its maximum absorption wavelength from 620 to 776 nm, avoiding the interference of other blue textile dyes. For this task, a simple and robust flow injection system was designed, which became a very stable analytical method. When the system was applied to Blue Procion determination in effluent of textile industry, precise results were observed (RSD < 2% within 1.0 and 5.0 mg l(-1) HEGN). The analytical frequency was 80 measurements per hour; the analytical curve was linear from 1.0 to 5.0 mg l(-1) HEGN; the detection limit considering three times the standard deviation of the blank solution (n = 10) was estimated as 0.03 mg l(-1) HEGN; and recoveries between 95% and 105% were found. The system consumes 20 mg of sodium citrate and 125 microl of the sample per determination. No baseline drift was observed during extended (5 h) operation periods. 相似文献
19.
Roberto Sigfrido Gallegos Olea Luce Maria Brandão Torres Luiz Carlos Roque Nidia Franca Roque 《Magnetic resonance in chemistry : MRC》1994,32(6):378-379
The 13C NMR chemical shifts of the triterpenes glutinol, glutinone and acetylglutinol were measured and analysed. 相似文献
20.
Coluccio ML Ciardelli G Bertoni F Silvestri D Cristallini C Giusti P Barbani N 《Macromolecular bioscience》2006,6(6):403-411
The preparation of an enzymatic controlled drug release system from blends of PVA/starch/alphaA, in the form of films, is described. It was shown that alphaA hydrolyses the starch within these films, resulting in a time-dependent change of the porosity in the matrix. Films were characterized by calorimetric analysis to study the interactions between the enzyme and the polymeric constituents at the molecular level. The presence of alphaA, in fact, influenced the PVA crystallization in the blends. Release tests and permeability experiments were carried out to evaluate the transport properties of the films. An increase in porosity and permeability was observed by increasing alphaA content (16-28 wt.-%). Films loaded with theophylline and caffeine were also prepared to analyze drug release properties of the matrix. Drug release kinetics were coherent with the measured changes in porosity: at higher alphaA concentrations the amount of released drug increased under the influence of diffusion and erosion processes. The results obtained are promising for the realization of drug delivery devices for a rapid release or for the release of poorly soluble drugs which usually remain entrapped in the matrix.SEM images of a PVA/starch/alphaA film before (A) and after (B) the erosion. 相似文献