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71.
Ribeiro da Silva MD Gomes JR Gonçalves JM Sousa EA Pandey S Acree WE 《The Journal of organic chemistry》2004,69(8):2785-2792
The mean (N-O) bond dissociation enthalpies were derived for three 2-methyl-3-(R)-quinoxaline 1,4-dioxide (1) derivatives, with R = methyl (1a), ethoxycarbonyl (1b), and benzyl (1c). The standard molar enthalpies of formation in the gaseous state at T = 298.15 K for the three 1 derivatives were determined from the enthalpies of combustion of the crystalline solids and their enthalpies of sublimation. In parallel, accurate density functional theory-based calculations were carried out in order to estimate the gas-phase enthalpies of formation for the corresponding quinoxaline derivatives. Also, theoretical calculations were used to obtain the first and second N-O dissociation enthalpies. These dissociation enthalpies are in excellent agreement with the experimental results herewith reported. 相似文献
72.
J. J. Ramírez-García M. Jiménez-Reyes M. Solache-Ríos E. Fernández-Ramírez H. López-González A. Rojas-Hernández 《Journal of Radioanalytical and Nuclear Chemistry》2003,255(2):299-303
The solubility of europium at 0.02M, 0.1M and 0.7M NaClO4 ionic strength solutions was determined by a radiometric method and pEus-pCH diagrams were obtained. Hydrolysis constants were also determined at the same ionic strengths by pH titration and the values found were log *1 = -7.68±0.11, -8.07±0.10 and -8.20±0.11. The log K
sp values were -23.5±0.2, -22.7±0.2 and -21.9±0.2 for 0.02M, 0.1M and 0.7M NaClO4 ionic strengths, respectively, at 303 K under CO2-free conditions and the extrapolated value at zero ionic strength was log K
sp
0 = -24.15. The working pCH ranges for the calculation of the hydrolysis constants were selected from the pEus-pCH diagrams in the region where precipitation of europium oxide or hydroxide was less than 20%. Europium removal from aqueous solutions with zeolites was explored. 相似文献
73.
74.
Ramírez-Muñoz J 《Talanta》1966,13(1):87-101
Concepts of sensitivity in flame photometry are discussed. A distinction is made between sensitivity itself, concentration limits and dilution limits applied to qualitative and quantitative analysis by flame photometry. Sensitivity values, as well as the concentration limits, are considered from two different aspects: as a function of the slope of calibration curves-percentual values-and as a function of fluctutions-fluctuational values. The concepts are applied to the two main branches of flame photometry, emission and absorption. 相似文献
75.
Pérez-Mendoza M Gonzalez J Wright PA Seaton NA 《Langmuir : the ACS journal of surfaces and colloids》2004,20(18):7653-7658
We have measured the adsorption of methane and ethane to high pressure on SBA-2, a structured mesoporous silica composed of spheres connected by narrow channels. The experimental data were analyzed by carrying out Monte Carlo simulations of adsorption in pore structure models of different complexity and then adjusting the parameters of the models to match the Monte Carlo results to the experimental data. We found that a model based on single-sized spherical cavities was inadequate and that it is necessary to explicitly account for the interconnecting channels. Further, we found that despite the basic regularity of the SBA-2 structure, it is necessary to allow for a distribution of the sizes of both the cavities and the channels. These size distributions were obtained by fitting the parameters of the model to the experimental adsorption data, revealing detailed structural information not previously known for this material. The channels were found to be 5-15 A in diameter, while the cavities were 40-50 A in diameter. There is some evidence that the distribution of channel sizes leads to a percolation effect whereby the pore structure is not equally accessible to all adsorptives. 相似文献
76.
Páez-Hernández ME Aguilar-Arteaga K Valiente M Ramírez-Silva MT Romero-Romo M Palomar-Pardavé M 《Analytical and bioanalytical chemistry》2004,380(4):690-697
The results presented in this work deal with the prime application of activated composite membranes (ACMs) for the transport of Hg(II) ions in a continuous extraction–re-extraction system using di-(2-ethylhexyl)dithiophosphoric acid (DTPA) as carrier. The effects of variables such as the pH, the nature of the acid and the concentration of the casting solutions on the transport of Hg(II) are also investigated. When the ACM was prepared with a 0.5 M DTPA solution and when the feed solution contained 2.5×10–4 M Hg(II) in 0.1 M HCl, the amount of mercury extracted was greater than 76%. The re-extracted mercury was subsequently recovered by means of a stripping phase comprising 0.3 M thiourea solution in 2 M H2SO4, yielding 54% of the initial amount of mercury after transport had taken place for 180 min. 相似文献
77.
Cabeza M Heuze I Bratoeff E Ramírez E Martínez R 《Chemical & pharmaceutical bulletin》2001,49(5):525-530
The objective of this study was to synthesize several new pregnane derivatives and evaluate them as antiandrogens. From the commercially available 16-dehydropregnenolone acetate (7), two new steroidal compounds were synthesized: 17alpha-hydroxy-17beta-methyl-16beta-phenyl-D-homoandrosta-1,4,6-triene-3,20-dione (18) and 17alpha-acetoxy-17beta-methyl-16beta-phenyl-D-homoandrosta-1,4,6-triene-3,20-dione (19). The 5alpha-reductase inhibitory effect of the new compounds 18 and 19 together with the previously synthesized intermediates 7, 8, 13, 16, and 17 was determined in three different models: gonadectomized hamster flank organs diameter size, incorporation of [1,2-(14)C]sodium acetate into lipids in flank organs and conversion of [3H]testosterone (T) to [3H]dihydrotestosterone (DHT) by Penicillium crustosum. The evaluation of these steroids was carried out with three different controls: one group was treated with vehicle, the second with T and the third group with T plus finasteride. The pharmacological results from this work demonstrated that T significantly increases the diameter of the pigmented spot on the flank organs (p<0.05) as well as the incorporation of labeled sodium acetate into lipids in gonadectomized hamster flank organs (from 0.125 to 0.255 nmol per gland). In this study we also observed that broth of Penicillium crustosum converted [3H]T to [3H]DHT in a manner comparable to that of the flank organs. All experiments indicated that finasteride as well as steroids 7, 8, 13, 16-19 reduced significantly the conversion of T to DHT in P. crustosum. These compounds also decrease the size of the pigmented spot in the flank organs as well as reducing the incorporation of radiolabeled sodium acetate into lipids; T and the control sample (treated with vehicle only) were used for comparison. Apparently the presence of the 4,6-diene-3,20-dione moiety and also the C-17 ester group produce a higher inhibitory effect on the parameters used. PPThe data from this study indicated also that the three models used for the pharmacological evaluation exhibited comparable results. 相似文献
78.
Guerrero-Alvarez JA Moncayo-Bautista A Ariza-Castolo A 《Magnetic resonance in chemistry : MRC》2004,42(6):524-533
The relative configuration of 11 1,4-diazaspiro[4.5]decanes (1a-1j and 1m), 15 1,4-oxazaspiro[4.5]decanes (2a-2o) and 10 1,4-dioxaspiro[4.5]decanes (3a-3n) substituted at the 2-, 6-, 7- or 8-position by a methyl group or using the tert-butyl group as a model for the ananchomeric structure is reported. The relative stereochemistry was analyzed by 1H, 13C, 15N and 17O NMR and all isomers present were characterized spectroscopically. Compounds with a methyl group in the six-membered ring show a chair conformation preference with the methyl group in the equatorial position. Compounds with one or two nitrogens exhibit a tautomeric equilibrium between the imine-diazolidine forms, as demonstrated by IR and 13C NMR. 相似文献
79.
Castro JL López Ramírez MR López Tocón I Otero JC 《Journal of colloid and interface science》2003,263(2):357-363
Raman and SERS spectra of phenylacetic acid and alpha-phenylglycine on silver sols have been recorded at several concentrations and pH values. The alpha-phenylglycine has been also studied in D(2)O. The respective vibrational assignments have been proposed and the analysis of the SERS spectra has made it possible to conclude that phenylacetic acid links to the metal through its carboxylate group only, while alpha-phenylglycine links also through its amino group. In both cases the aromatic ring seems to be almost perpendicular to the metal surface. On the other hand, the contribution of the charge transfer (CT) mechanism to the enhancement of the SERS spectra has been calculated as well and it is found to be very important in both molecules. The band most enhanced by this mechanism is that of vibration 8a, mainly in alpha-phenylglycine. 相似文献
80.
A simple and versatile method for the synthesis of acetals from aldehydes and ketones using bismuth triflate 总被引:1,自引:0,他引:1
Leonard NM Oswald MC Freiberg DA Nattier BA Smith RC Mohan RS 《The Journal of organic chemistry》2002,67(15):5202-5207
Acetals are obtained in good yields by treatment of aldehydes and ketones with trialkyl orthoformate and the corresponding alcohol in the presence of 0.1 mol % Bi(OTf)3.4H2O. A simple procedure for the formation of acetals of diaryl ketones has also been developed. The conversion of carbonyl compounds to the corresponding 1,3-dioxolane using ethylene glycol is also catalyzed by Bi(OTf)3.4H2O (1 mol %). Two methods, both of which avoid the use of benzene, have been developed. 相似文献