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961.
For decades, solving the phase problem of x-ray scattering has been a goal that, in principle, could be achieved by means of n-beam diffraction (n-BD). However, the phases extracted by the actual n-BD phasing techniques are not very precise, mainly due to systematic errors that are difficult to estimate. We present an innovative theoretical approach and experimental procedure that, combined, eliminate two major sources of error. It is a high precision phasing technique that provides the triplet-phase angle with an error of about 2 degrees. 相似文献
962.
We propose a modification of special relativity in which a physical energy, which may be the Planck energy, joins the speed of light as an invariant, in spite of a complete relativity of inertial frames and agreement with Einstein's theory at low energies. This is accomplished by a nonlinear modification of the action of the Lorentz group on momentum space, generated by adding a dilatation to each boost in such a way that the Planck energy remains invariant. The associated algebra has unmodified structure constants. We also discuss the resulting modifications of field theory and suggest a modification of the equivalence principle which determines how the new theory is embedded in general relativity. 相似文献
963.
Asensio JL Cañada FJ Cheng X Khan N Mootoo DR Jiménez-Barbero J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2000,6(6):1035-1041
The conformational behavior of alpha-O-Man-(1-->1)-beta-Gal (1) and its C-analogue (2) has been studied using J/NOE NMR data, molecular mechanics, molecular dynamics, and ab initio calculations. The population distribution around the glycosidic linkages of 1 and 2 is rather different, especially for the alpha-Man linkage. A lower limit for the exo-anomeric effect in water has been experimentally determined. 相似文献
964.
A quantitative analysis of the XAS spectra of the tetracyanonickelate complex [Ni(CN)4]2- has been carried out. The simultaneous study of the EXAFS and XANES regions yielded complementary information regarding the geometric and electronic structures of the complex. XANES spectra were modeled by applying recently developed self-consistent, full multiple-scattering algorithms in the FEFF8 code (version 8 x 34). XANES spectra for clusters of different sizes (from 9 to 125 atoms) were computed and compared with experimental spectra. This region of the spectra was proportional to a broadened Ni p-density of states diagram above the Fermi level. Although the main features of the XANES spectra were reasonably reproduced by computations, the weak dependence of the theoretical spectra on cluster size contrasts with the close similarity between the experimental spectra of the solid and solution systems. Because of the special geometry of the complex, calculations with polarized light parallel and perpendicular to the molecular plane were carried out, yielding a reasonable reproduction of the experimental data from another report for cluster sizes equal to or higher than 45 atoms. The highly symmetric square planar structure of the complex was found to be responsible for the unusual amplitude of the multiple-scattering (MS) contributions to the EXAFS spectra. Spectra in this region were fitted using the FEFFIT EXAFS analysis program, taking into account only the MS paths that simultaneously have both a high amplitude, as calculated with the ab initio code FEFF, and a small Debye-Waller factor, as estimated by the independent-vibration approximation model. Fitting results yielded very similar structures for the Ni2+ complex in the solid state and in solution, though the larger Debye-Waller factors found for the solid suggest higher static disorder in this state. 相似文献
965.
An improved design of the transport detector is described that uses a pre-oxidized titanium ribbon as the transport medium. The titanium ribbon has a high loading capacity that permits a large proportion of the total column eluent to be taken into the sensing system. The solute is sensed by pyrolysis and the subsequent detection of pyrolysis products by a miniature argon detector. The pyrolyzer and sensor system is designed to ensure that all the pyrolysis products enter the detector with minimum dilution and band dispersion. As a result, the sensitivity of the detector (or minimum detectable concentration) has been reduced by approximately two orders of magnitude compared with the original design. The sensitivity of the system described to sucrose is 8 x 10(-8) g/mL, which is similar to the sensitivity of the fixed-wavelength UV detector to benzene (approximately 5 x 10(-8) g/mL). It would appear that the new design has potentially a sensitivity at least an order of magnitude lower than that reported here. 相似文献
966.
Solid-phase extraction of quaternary ammonium herbicides 总被引:1,自引:0,他引:1
This paper highlights recent advances in the solid-phase extraction (SPE) of quaternary ammonium herbicides in water, soil, plant and biological samples. After a brief introduction summarizing the properties of quaternary ammonium herbicides and the difficulties involved in measuring them, attention is paid primarily to solid supports used for isolation and concentration, pre-treatments required for the different matrices, and eluents applied for quantitative desorption of these analytes. The determination techniques used after SPE and applications of the proposed SPE methodology are also briefly discussed. 相似文献
967.
The application of two extreme models for diffusion in two-component systems to electrochemically determine equilibrium constants is discussed. The application of cyclic voltammetric, diferential pulse and rotating-disc electrode voltammetric data to elucidate the stoichiometry and formation constant of complex species by applying a generalization of the molar-ratio method is described. Molar-ratio experiments permit the distinction between the limiting diffusive regimes. The values of the equilibrium stability constants for complexation of phenethylamine and phenethylammonium ions by a 26-membered dioxotetraester crown of 3,5-disubstituted 1H-pyrazole as free ligand 1[L] and as dipyrazolate anion 1'[L(2-)]2Na(+), respectively, were determined. 相似文献
968.
969.
Muñoz de la Peña A Mahedero MC Espinosa-Mansilla A Bautista Sánchez A Reta M 《Talanta》1999,48(1):15-21
The spectral characteristics of the inclusion of 1-naphthalenacetamide in beta-cyclodextrin have been studied by luminescence methods. The addition of bromoalcohols or bromoalkanes produces a decrease of the fluorescence of the inclusion complex, giving rise to a new band corresponding to phosphorescence emission. The emission intensity is much higher in the presence of bromoalkanes than in the presence of bromoalcohols. The deoxygenation of the solutions is achieved by flowing nitrogen, by the addition of sodium sulphite and by a combination of both methods, which results in the most effective approach. The phosphorescence emission is produced in the turbid suspension formed in the presence of the bromoalkane. The formation of microcrystals seems necessary to obtain phosphorescence emission from the ternary system. 相似文献
970.
Reguera Edilso Yee-Madeira Hernani Fernández-bertran José Nuñez Lourdes 《Transition Metal Chemistry》1999,24(2):163-167
Ferrous salts of ten hexacyanometallates and three tetracyanometallates were obtained and their Mössbauer spectra interpreted according to recent structural models for these families of compounds. Ferrous ferrocyanide (Williamson White) and its ruthenium and osmium analogs prepared mechanochemically are stable for hours, allowing their study by Mössbauer spectroscopy and other related techniques. For ferrous salts of trivalent hexacyanometallate anions, the random distribution of anion vacancies is discarded and a model of two well defined relative positions of CN and H2O ligands around the Fe2+ is suggested. Iron was found octahedrally coordinated in tetracyanometallates. 相似文献