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L. A. Arrúa D. E. Ardissone O. D. Quiroga J. B. Rivarola 《Reaction Kinetics and Catalysis Letters》1995,56(2):383-389
A P–O–Ni catalyst was prepared, characterized and tested in the oxidative dehydrogenation of ethylbenzene. A kinetic model was proposed. The experimental observations and the predictions of the model are in good agreement. 相似文献
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Let F= {C1,C2,...,C} be a family of ndisjoint convex bodies in the plane. We say that a set Vof exterior light sources illuminates F, if for every boundary point of any member of Fthere is a point in Vsuch that is visible from ,i.e. the open line segment joining and is disjoint from F. An illumination system Vis called primitive if no proper subset of Villuminates F. Let pmax(F) denote the maximum number of points forming a primitive illumination system for F, and letpmax(n) denote the minimum of F) taken over all families Fconsisting of ndisjoint convex bodies in the plane. The aim of this paper is to investigate the quantities pmax(F) and pmax(n). 相似文献
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Di Nicola C Galindo A Hanna JV Marchetti F Pettinari C Pettinari R Rivarola E Skelton BW White AH 《Inorganic chemistry》2005,44(9):3094-3102
Seven novel R2Sn(IV)-oxydiacetate (oda) and -iminodiacetate (ida) compounds of the form [R2Sn(oda)(H2O)]2 (R = Me, nBu, and Ph) (1-3), [(R2SnCl)2(oda)(H2O)2]n (R = Et, iBu, and tBu) (4-6), and [Me2Sn(ida)(MeOH)]2 (7) have been synthesized and characterized by IR, 1H, 13C, and 119Sn NMR (solution), solid-state 119Sn CPMAS NMR, and (119m)Sn M?ssbauer spectroscopy. The crystal structure of [Me2Sn(oda)(H2O)]2, 1, shows it to be dinuclear (centrosymmetric), with two seven-coordinated tin atoms, bridged by one arm of the carboxylate group from each oda. By contrast, the crystal structure of [(Et2SnCl)2(oda)(H2O)2]n, 4, comprises a zigzag polymeric assembly containing a pair of different alternating subunits, {Et2SnCl(H2O)} and {Et2SnCl(H2O)(oda)}, which are connected by way of bridging oda carboxylates, thus giving seven-coordinate tin centers in both components. Finally, the structure of [Me2Sn(ida)(MeOH)]2, 7, also centrosymmetric dinuclear, is comprised of a pair of mononuclear units with seven-coordinate tin. The 119Sn solid-state CPMAS NMR and (119m)Sn Mossbauer suggest the presence of seven-coordinate Sn metal atoms in some derivatives and the existence of two different tin sites in the [(R2SnCl)2(oda)(H2O)2]n compounds. 相似文献
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Claudia R. Rivarola Sonia G. Bertolotti Carlos M. Previtali 《Journal of polymer science. Part A, Polymer chemistry》2001,39(24):4265-4273
The photopolymerization of acrylamide (AA) initiated by the metallic complex tris(2,2′‐bipyridine)ruthenium(II) [Ru(bpy)3+2] in the presence of aliphatic and aromatic amines as co‐initiators was investigated in aqueous solution. Aromatic amines, which are good quenchers of the emission of the metal‐to‐ligand‐charge‐transfer excited state of the complex, are more effective co‐initiators than those that do not quench the luminescence of Ru(bpy)3+2, such as aliphatic amines and aniline. Laser‐flash photolysis experiments show the presence of the reduced form of the complex, Ru(bpy)3+1, for all the amines investigated. For aliphatic amines, the yield of Ru(bpy)3+1 increases with temperature, and on the basis of these experiments, a metal‐centered excited state is proposed as the reactive intermediate in the reaction with these amines. The decay of the transient Ru(bpy)3+1 is faster in the presence of AA. This may be understood by an electron‐transfer process from Ru(bpy)3+1 to AA, regenerating Ru(bpy)3+2 and producing the radical anion of AA. It is proposed that this radical anion protonates in a fast process to give the neutral AA radical, initiating in this way the polymerization chain. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 4265–4273, 2001 相似文献
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Milanesio ME Alvarez MG Rivarola V Silber JJ Durantini EN 《Photochemistry and photobiology》2005,81(4):891-897
The photodynamic activities of a porphyrin-C60 dyad (P-C60) and its metal complex with Zn(II) (ZnP-C60) were compared with 5-(4-acetamidophenyl)-10,15,20-tris(4-methoxyphenyl)porphyrin (P), both in homogeneous medium-bearing photooxidizable substrates and in vitro on the Hep-2-human-larynx-carcinoma cell line. This study represents the first evaluation of dyads, with a high capacity to form a photoinduced charge-separated state, to act as agents to inactivate cells by photodynamic therapy (PDT). Absorption and fluorescence spectroscopic studies were performed in toluene and N,N-dimethylformamide (DMF). The emission of the porphyrin moiety in the dyads is strongly quenched by the attached fullerene C60 moiety. The singlet molecular oxygen, O2(1delta(g)), productions (phi(delta)) were determined using 9,10-dimethylanthracene (DMA). The values of phi(delta) were strongly dependent on the solvent's polarity. Comparable phi(delta) values were found for dyads and P in toluene, while O2(1delta(g)) production was significantly diminished for the dyads in DMF. In more polar solvent, the stabilization of charge-transfer state takes place, decreasing the efficiency of porphyrin triplet-state formation. Also, both dyads photosensitize the decomposition of L-tryptophan in DMF. In biological medium, no dark cytotoxicity was observed using sensitizer concentrations < or = 1 microM and 24 h of incubation. The uptake of sensitizers into Hep-2 was studied using 1 microM of sensitizer and different times of incubation. Under these conditions, a value of approximately 1.5 nmol/10(6) cells was found between 4 and 24 h of incubation. The cell survival after irradiation of the cells with visible light was dependent upon light-exposure level. A higher photocytotoxic effect was observed for P-C60, which inactivates 80% of cells after 15 min of irradiation. Moreover, both dyads keep a high photoactivity even under argon atmosphere. Thus, depending on the microenvironment where the sensitizer is localized, these compounds could produce biological photodamage through either an O2(1delta(g))-mediated photoreaction process or a free-radicals mechanism under low oxygen concentration. These results show that molecular dyads, which can form a photoinduced charge-separated state, are a promising model for phototherapeutic agents, with potential applications in cell inactivation by PDT. 相似文献
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Smita Basu Archana Mizar Tushar S. Basu Baul Eleonora Rivarola 《Hyperfine Interactions》2008,185(1-3):95-102
Several organotin(IV) compounds, viz., diorganotin(IV) compounds of the types Ph2SnLH (monomer), nBu2SnLH·OH2 (monomer), [Me2SnLH·OH2]2 (centrosymmetric dimer), [nBu2SnLH]3 (cyclic trinuclear), [Ph2SnLH] n (polymer), {[nBu2Sn(LH)]2O}2 (centrosymmetric tetranuclear), dinuclear di-/tri-mixed organotin(IV) compounds Ph2SnLH·Ph3SnCl (monomer) and triorganotin(IV) compounds of the types [Bz3SnLH]2 (centrosymmetric dimer) and [Me3SnL1H] n (Polymer) (LH = Schiff base carboxylate) have been studied in the solid state at liquid nitrogen temperature using 119Sn Mössbauer spectroscopy. The tin coordination geometry of the compounds determined from crystallography was correlated with the 119Sn Mössbauer results. 相似文献
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P. J. Meoli G. H. Olivera G. Saint-Martin O. A. Bernaola P. D. Fainstein R. D. Rivarola 《Radiation measurements》1997,28(1-6):25-26
The track radius calculation reported by Tombrello was applied to experimental data of tracks from several ions and energies in Makrofol E. Qualitative analysis of ion tracks in this material is discussed. These data were also compared with values calculated using the Continuum Distorted Wave-Eikonal Initial State approximation 相似文献