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31.
Menezes PH Gonçalves SM Hallwass F Silva RO Bieber LW Simas AM 《Organic letters》2003,5(10):1601-1604
[reaction: see text] Several (77)Se NMR experiments were performed by titrating a sample of selenides with the chiral shift reagent methylbenzylamine (MBA), followed by acquisition of (77)Se NMR spectra. Eventually, we observed the appearance of two anisochronous resonances, with a relatively large separation, from 37 to 56 Hz, corresponding to the formation of the diastereomeric complexes. This methodology avoids derivatization processes, and the studied compound can be easily recovered from the NMR tube. 相似文献
32.
The obtention of (tetradecachloro-4-oxidotriphenylmethyl)–. M+ (M=Li, Na, K, n-Bu4N) salts in ethereal solution and the isolation of some alkaline complexed salts (M=Li-12C4, Na-18C6, K-18C6, K(THF)1–(H2O)3–4, n-Bu4N) are described and discussed. The association phenomena of these salts has been studied by electronic spectroscopy, osmometry and electron spin resonance. Linear correlations between radii counterions and the position maxima of the electronic spectra bands permit the study of the species present in solution (free ions, ion pairs and quadrupolar aggregates). 相似文献
33.
34.
C.?GarciaEmail author A.?Durán R.?Moreno 《Journal of Sol-Gel Science and Technology》2005,34(3):211-217
Functional coatings incorporating different types of particles developed by the sol–gel method have been proposed in the last few years for diverse applications. This work focuses on the preparation of homogeneous coatings prepared from stable suspensions with 10 wt% of glass and glass ceramic particles in a hybrid organic–inorganic solution as dispersing media. For this purpose, the pH was shifted up to 6–7 by adding tetrapropylammonium hydroxide (TPAH) which behaves as a cationic surfactant being probably adsorbed on the particles surface, while the sol maintains stable. Rheological measurements were performed to study the stability of the suspensions prepared at different conditions such as the kind and concentration of dispersant and the pH conditions. After sintering at 450∘C/30 min, coatings around 2 μ m in thickness were obtained. 相似文献
35.
Atomic charges and delocalization indexes (DIs) for a series of carbonyl compounds comprising dimethyl ketone, acetaldehyde, acetic acid, methyl acetate, acetamide, methyl vinyl ketone, divinyl ketone, and benzoic acid were studied using two different atomic partitionings: the QTAIM and the Hirshfeld (stockholder) scheme. The resonance model, traditionally employed to explain the reactivity of these compounds, is not in line with the total atomic charges and DIs calculated by both methodologies. However, the resonance model is supported to some extent by the pi charges and pi DIs calculated by both schemes, but the calculated values indicate that the pi population delocalizes only to a small degree. Although the absolute values of QTAIM and stockholder atomic charges are significantly different, the pi charges and the values of the DIs show similar trends for all the atoms and molecules of this study; this is especially the case for the pi DIs. A study of the electron density on the level of a single MO performed for CO, H2CO, F2CO, and H2CS reveals that the differences in the atomic sigma charges computed with both partitionings can be traced back to their different treatment of interatomic regions. 相似文献
36.
Durán JD Ramos-Tejada MM Arroyo FJ González-Caballero F 《Journal of colloid and interface science》2000,229(1):118-122
Because of their particular electric surface properties and crystal structure, most clay minerals possess a very high ion exchange capacity. Furthermore, the surface charge distribution is anisotropic: while faces of the laminar clay particles have a negative, pH-independent charge, edges may be positive or negative, depending on pH. In this work, we propose to contribute new data on particle-particle interaction and charge distribution, by means of measurements of the low-frequency dielectric dispersion (LFDD) of the clay suspensions. Because of the nonspherical shape of clay particles, there are no theoretical models capable of explaining the experimental relaxation spectra. Hence, we limit ourselves to obtaining indirect information by comparing LFDD spectra in different experimental conditions. The quantities of interest in LFDD are the value of the low-frequency dielectric constant, epsilon'(r)(0), and the characteristic or relaxation frequency, omega(cr). These two parameters were measured varying the weight fraction, straight phi, of clay (0.5, 1, and 1.5% w/v) and the pH of the dispersion medium (5, 7, and 9), while maintaining the ionic strength constant ([NaCl]=10(-4) M). It was found that the characteristic relaxation frequency of the dielectric constant was pH-dependent, with a significant minimum at pH 7 in all cases. The results are interpreted as the superposition of two independent relaxation phenomena, associated with edges and faces. With respect to the weight fraction influence, we have found a linear behavior of epsilon'(r)(0) with straight phi at pH 9, indicating the existence of no significant interaction between particles. However, at pH 7 a slight deviation of linearity is observed, and at pH 5 we observe a clearly nonlinear behavior, indicating a stronger degree of interaction between particles. This is in good agreement with the initial assumption that at acid pH values, the electric surface charge of faces is negative, whereas the edges possess a positive charge, thus favoring attractive face-to-edge interaction. Copyright 2000 Academic Press. 相似文献
37.
Ricardo H. M. Godoi Ana F. L. Godoi Anna Worobiec Sandro J. Andrade Johan de Hoog Mary R. Santiago-Silva Rene Van Grieken 《Mikrochimica acta》2004,145(1-4):53-56
Biomass burning is an important primary and secondary source of aerosol particles. The presence of carbonaceous particles in the respirable size range makes the study of this fraction important in view of possible health and climatic effects. The annual burning of sugar cane plantations causes emission of huge amounts of pyrogenic particles. Aerosol samples were collected in Araraquara city, São Paulo state, Brazil, during the harvest season for fine and coarse particles and bulk; they were analysed by electron-probe microanalysis, including facilities for low-Z element determination (low-Z EPMA) and by energy-dispersive X-ray fluorescence (EDXRF), in order to investigate the elemental composition of individual particles and bulk samples, respectively. Numerical analysis of the EPMA results by hierarchical clustering shows high contributions of carbonaceous particles that can be distinguished mainly in two different types: biogenic and carbon-rich. Additionally, two significant contributions of aluminosilicate particles were identified: as rather pure aluminosilicates or mixed with carbonaceous species. The EDXRF results are compatible with those of aerosol particles in Amazon, which is nowadays one of the main sources of biogenic particles in the world. 相似文献
38.
The role of hydrogen bonding on the microscopic properties of supercooled methanol has been analyzed by means of molecular dynamics simulations. Thermodynamic, structural, and dynamical properties have been investigated in supercooled methanol. The results have been compared with those of an ideal methanol-like system whose molecules have the same dipole moment as the methanol but lack sites for hydrogen bonding. Upon cooling the methanol samples, translational relaxation times increase more rapidly than reorientational ones. This effect is much more important when hydrogen bonds are suppressed. Suppression of hydrogen bonds also results in lower critical temperatures for diffusion and for several characteristic relaxation time constants. The anisotropy of individual dynamics and the existence of dynamical heterogeneities have also been investigated. 相似文献
39.
Ricardo Castanedo 《Tetrahedron letters》2006,47(6):973-976
The Birch reduction-dialkylation reaction has been studied with different aromatic carboxylic acids and primary and secondary bromides. From these results it can be concluded that it is a reasonably general reaction. However, we found important exceptions with the primary bromides: allyl bromide, β-phenethyl bromide, and 5-bromo-2-methyl-2-pentene. The unusual behavior of allyl bromide is briefly discussed. 相似文献
40.
Improved ultrasonic extraction procedure for the determination of polycyclic aromatic hydrocarbons in sediments 总被引:6,自引:0,他引:6
The aim of this work was to optimize an ultrasonic extraction procedure for the determination of polycyclic aromatic hydrocarbons (PAHs) in sediments and to compare it with the reflux procedure using methanolic potassium hydroxide. Sample extracts were purified with a miniaturized silica gel chromatographic column and analyzed by gas chromatography-mass spectrometry (GC-MS). Ultrasonication using n-hexane-acetone (1:1, v/v) solvent mixture on dried homogenized marine sediment gave better precision (smaller relative standard deviation (RSD) values) and comparable quantities of individual PAH's compared to the reflux procedure. Ultrasonication with the n-hexane-acetone (1:1, v/v) mixture, utilizing four 15 min extraction cycles, was found to be sufficient for extracting PAHs from wet sediments. The optimized ultrasonic extraction procedure extracted aliphatic and aromatic hydrocarbons from the National Institute of Standards and Technology SRM 1941a with recoveries greater than 90%. The major advantages of ultrasonication compared to the reflux method are the lower extraction times, simplicity of the apparatus and extraction procedure. The optimized ultrasonication procedure has been used in our laboratory to extract hydrocarbons from naturally wet sediments from rivers, and coastal and marine areas. 相似文献