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11.
Xerogels obtained from the acid-catalyzed and ultrasound stimulated hydrolysis of TEOS were submitted to heat treatment at temperatures ranging from 60 to 1100 °C and studied by small-angle X-ray scattering (SAXS). The SAXS intensity as a function of the modulus of the scattering vector q was obtained in the range from q0=0.19 to qm=4.4 nm−1. At 60 °C the xerogels exhibit an apparent surface fractal structure with a fractal dimension DS∼2.5 in a length scale ranging from 1/q1∼1 to 1/qm∼0.22 nm. This structure becomes extremely rough at 120 °C (DS∼3) and at 150 °C, it apparently converts to a mass fractal with a fractal dimension D∼2.4. This may mean an emptying of the pores with preservation of a share of the original mass fractal structure of the wet aged gel, for it had presented a mass fractal dimension D∼2.2. A well characterized porous structure formed by 2.0 nm mean size pores with smooth surface of about 380 m2/g is formed at 300 °C and remains stable until approximately 800 °C. At 900 °C the SAXS intensity vanishes indicating the disappearance of the pores in the probed length scale. The elimination of the nanopores occurs by a mechanism in which the number of pores diminishes keeping constant their mean size. The xerogels exhibit a foaming phenomenon above 900 °C and scatter following Porod's law as does a surface formed by a coarse structure. 相似文献
12.
郭冰 柳卫平 Trinczek M Lapi S Ames F Buckley K R D’Auria J M Jayamanna K Ruiz C Ruth T J 《中国物理 C》2006,30(7):675-679
加拿大TRIUMF实验室利用11C成功验证了一种产生高强度(~108ions/s)放射性束流的方法. 该方法不同于普通在线同位素分离方法, 它利用了13MeV的低能强流质子束, 可以产生一系列核天体物理实验感兴趣的高强度放射性束流. 相似文献
13.
M. A. Morón C. Romero F. R. Ruiz del Portal 《Journal of Optimization Theory and Applications》1996,91(3):643-649
The purpose of this paper is to seek utility functions satisfying a weak condition which guarantees that the utility optimum always belongs to the compromise set. This set is a special subset of the attainable or feasible set, which is generated through the application of the well-known operational research approach called compromise programming. It is shown that there are large families of utility functions satisfying this condition, thus reinforcing the value of compromise programming as a good surrogate of the traditional utility optimum.Thanks are due to the reviewers for their helpful suggestions. The English editing by Ms. Christine Méndez is appreciated. The authors have been supported by the Comisión Interministerial de Ciencia y Tecnología (CICYT), Madrid, Spain. 相似文献
14.
G. Ortega Zarzosa S. A. Palomares Sánchez J. R. Martánez Facundo Ruiz M. G. Sánchez-Loredo 《Journal of Sol-Gel Science and Technology》2005,35(1):5-11
Composites containing Pd aggregates dispersed in amorphous silica are of interest from both a fundamental and applied point of view because of their attractive catalytic properties. The silica powders added with palladium, prepared by the sol-gel method, were studied using X-ray diffraction, and IR- and UV-Vis-spectrophotometry. Silica xerogel samples were prepared using a ethanol/H2O/TEOS molar ratio of 4:11.6:1 and loaded with sodium tetrachloropalladate. The silica xerogel microstructure of the powders was studied as a function of annealing temperature. Attention was paid to the evolution of the glass matrix as well as the palladium aggregates in the SiO2 matrix. We found in our samples partial crystallization of the glass matrix in form of quartz and cristobalite phases with palladium oxide and metallic palladium phase at 1000∘C. The Rietveld refinement method was used in order to determine the percentage of the phase contents. 相似文献
15.
A study of the viability of three derivatizing reagents for obtaining amino acid profiles in honey through high performance liquid chromatography (HPLC) is presented. A method using diode array detection based on a reaction with diethyl ethoxymethylene malonate (DEMM) and two other methods using fluorescence detection based on derivatization with fluorenylmethyl chloroformate (FMOC-Cl) and 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC) have been developed. The three methods yield detection limits close to the ppb level, but vary in relation to other analytical characteristics. The use of methyl chloroformate derivatives allows the profile to be obtained with the greatest sensitivity within a short time frame. On applying such methods to honey samples of diverse botanical origin, we observe that the proline values obtained are always lower than those found using the official spectrophotometric method, thereby underlining the advisability of using HPLC methods to reduce uncertainty in these results. 相似文献
16.
Asymmetry and magnetism in bis(oximato)-bridged heterobimetallic compounds: a computational approach
Cano J Rodríguez-Fortea A Alemany P Alvarez S Ruiz E 《Chemistry (Weinheim an der Bergstrasse, Germany)》2000,6(2):327-333
A density functional study of exchange coupling was carried out for a series of heterobinuclear oximato-bridged transition metal complexes. Model calculations were used to examine the influence of the electronic configuration of the metal atoms on the coupling constants. This analysis was complemented by a study of the variation of the coupling constant with the most usual structural distortions within this family of compounds. The influence of the nature of the terminal ligands as well as that of the symmetry on the bridge were also investigated. 相似文献
17.
Ruiz E Rodríguez-Fortea A Cano J Alvarez S Alemany P 《Journal of computational chemistry》2003,24(8):982-989
The application of theoretical methods based on the density functional theory with hybrid functionals provides good estimates of the exchange coupling constants for polynuclear transition metal complexes. The accuracy is similar to that previously obtained for dinuclear compounds. We present test calculations on simple model systems based on H. He and CH(2). He units to compare with Hartree-Fock and multiconfigurational results. Calculations for complete, nonmodeled polynuclear transition metal complexes yield coupling constants in very good agreement with available experimental data. 相似文献
18.
Gregorio Snchez Francisco Ruiz Joaquín Garcia M. Ramírez Carmen de Arellano Gregorio Lpez 《Helvetica chimica acta》1997,80(8):2477-2485
The hydroxo complex (Bu4N)2[Ni2(C6F5)4(μ-OH)2]reacts with 2,3,4,5,6-pentafluoro benzenamine (C6F5-NH2), 1,3-diaryltriaz-1-enes (ArNH? N=N? Ar, Ar = Ph, 4-MeC6H4, 4-MeOC6H4), 7-aza-1H-indole (= 1H-pyrrolo[2.3-b]pyridine; Hazind), N-phenylpyridin-2-amine(pyNHPh), and N-phenylpyridine-2-carboxamide (py-CONHPh) at room temperature in acetone to give the binuclear complexes (Bu4N)2[Ni2(C6F5)4(μ-C6F5NH)2] ( 1 ) and (Bu4N)2[{Ni(C6F5)2} 2(μ-OH)(μ-azind)] ( 2 ) and the mononuclear complexes Bu4N[Ni(C6F5)2(ArN3Ar)] ( 3 – 5 ), Bu4N[Ni(C6F5)2(pyNPh)] ( 6 ), and Bu4N[Ni(C6F5)2(pyCONPh)] ( 7 ). The hydroxo.complex (Bu4N)2[{Ni(C6F5)2-(μ-OH)}2] promotes the nucleophilic addition of water to pyridine-2-carbonitrile, 2-aminoacetonitrile, and 2-(dimethylamino)acetonitrile, and complexes 8 – 10 containing pyridine-2-carboxamidato, 2-aminoacetamidato and 2-(dimethylamino)acetamidato ligands are formed. Analytical (C, H, N) and spectroscopic (IR, 1H and 19F-NMR, and FAB-MS) data were used for structural assignments. A single-crystal X-ray diffraction study of (Bu4N)2[{Ni(C6F5)2}2(μ-OH)(μ-azind)] ( 2 ) established the binuclear nature of the anion; the two Ni-atoms are bridged by an OH group and a 7-aza-7H-indol-7-yl group, but the central Ni? O? Ni? N? C? N ring is not planar, the dihedral angle between the Ni? O? Ni and Ni? N? C? N? Ni planes being 84.4°. 相似文献
19.
Manuel Urbano Cuadrado Gonzalo Cerruela García Irene Luque Ruiz Miguel Ángel Gómez-Nieto 《Journal of mathematical chemistry》2006,40(1):15-27
A method for the treatment of long-dimensional chemical data arrays is presented in this work with the aim of maximising classification models. The method is based on the construction of fingerprints and the subsequent generation of a similarity matrix. The similarity calculation has been modified through a scaling process to take into account different significance shown by the variables. The method was applied to spectral measurements of wines and several aspects were studied, namely: threshold considered in the construction of fingerprints and patterns, weighting factor used for scaling, normalisation method, etc. The application of both Principal Components Analysis and Soft-Independent Modelling of Class Analogies to the similarity matrices gave better classifications of the information than those obtained using original data. 相似文献
20.
García ME Riera V Ruiz MA Sáez D Vaissermann J Jeffery JC 《Journal of the American Chemical Society》2002,124(48):14304-14305
Protonation of [Mo2Cp2(mu-H)(mu-PHR*)(CO)4] (Cp = eta5-C5H5, R* = 2,4,6-C6H2tBu3) with HBF4.OEt2 gives the hydridophosphinidene complex [Mo2Cp2(mu-H)(mu-PR*)(CO)4]BF4, which is easily deprotonated with H2O to give the known phosphinidene complex [Mo2Cp2(mu-PR*)(CO)4] in 95% yield. Reaction of the latter with I2 gives the unsaturated phosphinidene complex [Mo2Cp2I2(mu-PR*)(CO)2], which exhibits an intermetallic distance of 2.960(2) A. Irradiation of solutions of [Mo2Cp2(mu-PR*)(CO)4] with UV light gives a mixture of the triply bonded [Mo2Cp2(mu-PR*)(mu-CO)2] and the hydridophosphido derivative [Mo2Cp2(mu-H){mu-P(CH2CMe2)C6H2tBu2}(CO)4] as major species. The latter complex results from an intramolecular C-H bond cleavage from a tBu group and has been characterized by spectroscopy and an X-ray study. Irradiation in the presence of HCC(p-tol) results in the insertion of the alkyne into the Mo-P bond to give [Mo2Cp2{mu-eta1:eta2,kappa-C(p-tol)CHPR*}(CO)4] structurally characterized through an X-ray study. 相似文献