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31.
García-Río L Leis JR Moreira JA Araujo E Norberto F Ribeiro L 《The Journal of organic chemistry》2003,68(11):4330-4337
A kinetic study was carried out on the hydrolysis of two N-nitrosoguanidines, 1-nitroso-1-methyl-3-tolylsulfonylguanidine (TSGNO) and 1-nitroso-1-methyl-3-benzoylguanidine (BCGNO). We observed an absence of buffer catalysis using H(2)PO(4)(-)/HPO(4)(2)(-), H(3)BO(3)/H(2)BO(3)(-), and HCO(3)(-)/CO(3)(2)(-) regulators and a complex dependency of the rate constant on the pH. We discovered the existence of three simultaneous reaction paths: spontaneous decomposition of the neutral form of the N-nitrosoguanidine, decomposition of the monoanion, and decomposition through the form of the dianion. The analysis of the kinetic data has allowed us to obtain the acidity constant for the formation of the monoanion of the N-nitrosoguanidine, with values of p = 11.5. The reaction rate for the process through the monoanion, k(2), decreases as the acidity increases. The application of the principle of nonperfect synchronization shows that the basicity and reactivity do not correlate when there exists a possibility of stabilization of the negative charge by resonance. This behavior is consistent with the mechanism E1cB whereby the stabler the negative charge, the slower the elimination reaction. When dealing with the case of the elimination through the neutral form we observe that the reaction rate increases together with the capacity of stabilization of the positive charge on the nitrogen atom adjacent to the imino group. For the reaction through the dianion we used a maximum value of k(3) = 10(10) s(-)(1) to estimate the value of p for the formation of the dianion of the N-nitrosoguanidine, obtaining values of p < 24. 相似文献
32.
Cyclohexene transformation was used as test reaction to study the effect of lanthanum exchange on the catalytic behavior of HY zeolite cracking catalysts. Lanthanum has an overall positive effect increasing both acitivity and stability of HY zeolite and maximum selectivity towards isomerization products is obtained at higher conversion.
HY. , , HY. .相似文献
33.
S. Ribeiro Guevara A. Rizzo R. Sánchez M. Arribére 《Journal of Radioanalytical and Nuclear Chemistry》2003,258(3):583-595
Unsupported 210Pb fluxes were determined from sediment core inventories in lakes located in Northern Patagonia, Argentina. Total 210Pb, 226Ra, associated with supported 210Pb, and 137Cs specific activity profiles were measured by gamma-ray spectrometry. Unsupported 210Pb fluxes showed very low values when compared to other regions, with a 12 fold variation, ranging from 4 to 48 Bq m–2.y–1. The linear correlation observed between the 210Pb fluxes and137Cs cumulative fluxes in sediment cores sampled from water bodies within a zone with similar precipitation demonstrated that both radioisotopes behave in the same manner in these systems concerning the processes occurred from fallout to sediment deposition, and that there are no appreciable local or regional sources of unsupported 210Pb. Positive correlation of 210Pb fluxes with organic matter contents of the uppermost sediment core layers was also observed. 相似文献
34.
Guerreiro C. T. R. Ribeiro C. A. Crespi M. S. Torres C. 《Journal of Thermal Analysis and Calorimetry》2002,67(2):419-424
Magnesium ion was reacted with 5,7-dibromo-, 5,7-dichloro-, 7-iodo-and 5-chloro-7-iodo-8-hydroxyquinoline, in acetone/ammonium
hydroxide medium under constant stirring to obtain (I) Mg[(C9H4ONBr2)2]·2H2O; (II) Mg[(C9H4ONCl2)2]·3H2O; (III) Mg[(C9H5ONI)2]·2H2O and (IV)Mg[(C9H4ONICl)2]·2.5H2O complexes. The compounds were characterized by elemental analysis, IR spectra, ICP, TG-DTA and DSC.
Through thermal decomposition residues were obtained and characterized, by X-ray diffractometry, as a mixture of hexagonal
MgBr2 and cubic MgO to the (I) compound at 850°C; cubic MgO to the (II), (III) and (IV) compounds at750, 800 and 700°C, respectively.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
35.
Ribeiro da Silva MA Gomes JR Ferreira AI 《The journal of physical chemistry. B》2005,109(27):13356-13362
The standard (p degrees = 0.1 MPa) molar enthalpies of formation of 2-, 3-, and 4-chloroaniline were derived from the standard molar energies of combustion, in oxygen, at T = 298.15 K, measured by rotating bomb combustion calorimetry. The Calvet high-temperature vacuum sublimation technique was used to measure the enthalpies of vaporization or sublimation of the three isomers. These two thermodynamic parameters yielded the standard molar enthalpies of formation of the three isomers of chloroaniline, in the gaseous phase, at T = 298.15 K, as 53.4 +/- 3.1 kJ.mol(-1) for 2-chloroaniline, 53.0 +/- 2.8 kJ.mol(-1) for 3-chloroaniline, and 59.7 +/- 2.3 kJ.mol(-1) for 4-chloroaniline. These values, which correct previously published data, were used to test the computational methodologies used. Therewith, gas-phase acidities, proton affinities, electron donor capacities, and N-H bond dissociation enthalpies were calculated and found to compare well with available experimental data for these parameters. 相似文献
36.
Ionic dynamics in room temperature molten salts (ionic liquids) containing 1-alkyl-3-methylimidazolium cations is investigated by molecular-dynamics simulations. Calculations were performed with united atom models, which were used in a previous detailed study of the equilibrium structure of ionic liquids [S. M. Urahata and M. C. C. Ribeiro, J. Chem. Phys. 120, 1855 (2004)]. The models were used in a systematic study of the dependency of several single particle time correlation functions on anion size (F-, Cl-, Br-, and PF6-) and alkyl chain length (1-methyl-, 1-ethyl-, 1-butyl-, and 1-octyl-). Despite of large mass and size of imidazolium cations, they exhibit larger mean-square displacement than anions. A further detailed picture of ionic motions is obtained by using appropriate projections of displacements along the plane or perpendicular to the plane of the imidazolium ring. A clear anisotropy in ionic displacement is revealed, the motion on the ring plane and almost perpendicular to the 1-alkyl chain being the less hindered one. Similar projections were performed on velocity correlation functions, whose spectra were used to relate short time ionic rattling with the corresponding long time diffusive regime. Time correlation functions of cation reorientation and dihedral angles of the alkyl chains are discussed, the latter decaying much faster than the former. A comparative physical picture of time scales for distinct dynamical processes in ionic liquids is provided. 相似文献
37.
D. T. Ribeiro C. Madzak A. Sarasin P. DI Mascio H. Sies C. F. M. Menck † 《Photochemistry and photobiology》1992,55(1):39-45
The effects of singlet oxygen (1O2), generated by the thermal decomposition of water soluble NDPO2 (endoperoxide of the disodium 3,3'-(1,4-naphthylidene) dipropionate), on a single-stranded shuttle vector were analysed. 1O2 induces a much higher level of breaks in the phosphodiester backbone of single-stranded than double-stranded DNA. This may be due to a higher accessibility of guanine residue, primarily damaged by 1O2. The damaged vector was transfected into monkey COS7 cells where single-stranded DNA was converted to the double-stranded replicative form DNA. After 3 days, extrachromosomal DNA was extracted and the plasmids rescued in E. coli to study mutagenesis. There is a significant increase in mutation frequency of damaged single-stranded DNA in comparison to untreated DNA. It is concluded that 1O2 induces breaks in the backbone of single-stranded DNA and that the 1O2-damaged molecules are mutated after passage through mammalian cells. 相似文献
38.
J. Pires M. Brotas de Carvalho F. R. Ribeiro E. G. Derouane 《Reaction Kinetics and Catalysis Letters》1991,43(2):313-319
The silicoaluminophosphate SAPO-37 as well as ZSM-20 zeolite have a faujaside-like structure and are potentially useful as catalysts. We report in this work different procedures to decompose the organic template occluded in SAPO-37. The texture of the final products was analyzed by means of nitrogen adsorption. The acid properties of SAPO-37 and ZSM-20 were also compared by IR measurements of adsorbed pyridine and related to the acidic properties of the presently commonly used cracking catalyst zeolite Y.
-37, ZSM-20 . , -37. . -37 ZSM-20 - . , .相似文献
39.
40.
Peter Schwendt Alena Oravcová Jarmila Tyršelová František Pavel?ík Jaromír Marek 《Polyhedron》1996,15(24):4507-4511
The vanadium(V) peroxo phosphato complex K7[V4O4(O2)8(PO4)]·9H2O has been obtained from the KVO3---KH2PO4---KOH---H2O2---H2O---C2H5OH system. The X-ray structural analysis revealed a tetranuclear anionic structure in which two dinuclear [V2O2(O)2)2(μ-η1 : η2-O2)2] units are connected by the μ4-PO4 group. 相似文献