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31.
The synthesis and structural characterization of a rare example of a uranyl complex possessing three equatorial ligands, [M(THF)2][UO2(N(SiMe3)2)3] (3a, M = Na; 3b, M = K), are described. The sodium salt 3a is prepared by protonolysis of [Na(THF)2]2[UO2(N(SiMe3)2)4], whereas the potassium salt 3b is obtained via a metathesis reaction of uranyl chloride UO2Cl2(THF)2 (4) with 3 equiv of K[N(SiMe3)2]. A single-crystal X-ray diffraction study of 3a revealed a trigonal-bipyramidal geometry about uranium, formed by two axial oxo and three equatorial amido ligands, with average U=O and U-N bond distances of 1.796(5) and 2.310(4) A, respectively. One of the oxo ligands is also coordinated to the sodium counterion. 1H NMR spectroscopic studies indicate that THF adds reversibly as a ligand to 3 to expand the trigonal bipyramidal geometry. The degree to which the coordination sphere in 3 is electronically satisfied with only three amido donors is suggested by (1) the reversible THF coordination, (2) a modest elongation in the bond distances for a five-coordinate U(VI) complex, and (3) the basicity of the oxo ligands as evidenced in the contact to Na. The vibrational spectra of the series of uranyl amido complexes [UO2(N(SiMe3)2)n]2-n (n = 2-4) are compared, to evaluate the effects on the axial U=O bonding as a function of increased electron density donated from the equatorial region. Raman spectroscopic measurements of the nu 1 symmetric O=U=O stretch show progressive axial bond weakening as the number of amido donors is increased. Crystal data for [Na(THF)2][UO2(N(SiMe3)2)3]: orthorhombic space group Pna2(1), a = 22.945(1) A, b = 15.2830(7) A, c = 12.6787(6) A, z = 4, R1 = 0.0309, wR2 = 0.0524. 相似文献
32.
Atomically flat monolayer and trilayer films of polydiacetylenes have been prepared on mica and silicon using a horizontal deposition technique from a pure water subphase. Langmuir films of 10,12-pentacosadiynoic acid (I) and N-(2-ethanol)-10,12-pentacosadiynamide (II) were compressed to 20 mN/m and subsequently polymerized by UV irradiation at the air-water interface. Blue and red forms of the films were prepared by varying exposure times and incident power. Polymerization to the blue-phase films produced slight contractions of 2 and 5% for the films of II and I, respectively. Longer UV exposures yielded red-phase films with dramatic film contraction of 15 and 32% for II and I, respectively. The horizontal deposition technique provided transfer ratios of unity with minimal film stress or structure modification. Atomic force microscopy images revealed nearly complete coverage of the substrate with atomically flat films. Crystalline domains of up to 100 micrometers of highly oriented polydiacetylene molecules were observed. The results reported herein provide insight into the roles of molecular packing and chain orientations in converting the monomeric film to the polymerized blue and red phases. Copyright 2000 Academic Press. 相似文献
33.
M. B. Cooper P. A. Burns B. L. Tracy M. J. Wilks G. A. Williams 《Journal of Radioanalytical and Nuclear Chemistry》1994,177(1):161-184
Re-suspension studies on soils contaminated with plutonium during nuclear weapons tests were performed by use of a mechanical dust-raising apparatus. Airborne dust was analyzed in terms of mass and241Am activities for particle sizes less than 7 m. The AMAD was determined as 4.8 to 6 m, for re-suspended soil. Also, surface soil was characterized in the laboratory by means of sieving and microparticle classification, yielding mass and241Am activity distributions with respect to size. Data indicate the granularity of plutonium contamination at both major and minor trial sites. Depth profile analyses for undisturbed, areas demonstrate that most (74% on average) of the americium and plutonium activity is found in the top 10 mm of soil. Plutonium and americium activities were found to be enhanced in the inhalable fraction over their values, in the total soil, and the enhancement factors were similar in re-suspended dust and surface soil. Observed enhancement factors ranged from 3.7 to 32.5. 相似文献
34.
We have evaluated the potential of near-infrared spectroscopy (NIRS) as a technique for rapid analysis of lactate in whole blood. To test the NIRS technique, a comparison was made with a standard clinical method using whole blood samples taken from five exercising human subjects at three different stage of exercise. To expand lactate concentration within the physiological range, standard additions method was used to generate 45 unique data points. Spectra were collected over the 2050-2400 nm spectral range with a 1 mm optical path length quartz cell. Reference lactate concentrations in the samples were determined by enzymatic measurements. Estimates and calibration of the lactate concentration with NIRS was made using partial least squares (PLS) regression analysis and leave-N-out cross validation on second derivative spectra. Separate calibrations were determined from each of the subject samples and cumulative PRESS was used to determine the number of PLS factors in the final model. The results from the PLS model presented are generated from the five individual calibration coefficient vectors and provided a correlation coefficient of 0.978 and a standard error of cross validation of 0.65 mmol l−1 between the enzymatic assay and the NIRS technique. To study the parameters that impact the spectra baseline and the correlation between the calculated model and the data, referenced measurements of lactate against baseline spectrum were made for each individual. A correlation coefficient of 0.992 and a standard error of cross validation of 0.21 mmol l−1 were found. The results suggest that NIRS may provide a valuable tool to assess physiological status for both research and clinical needs. 相似文献
35.
[structure: see text]. Macromolecules 1c and 2c bearing multiple redox-active sites are synthesized by an efficient palladium-catalyzed coupling of 2,5-dimethoxytolylmagnesium bromide with readily available hexakis(4-bromophenyl)benzene and tetrakis(4-bromophenyl)methane. These macromolecular electron donors undergo reversible oxidation at a constant potential of 1.15 V vs SCE to yield robust, multiply charged cation radicals that are isolated in pure form using SbCl(5) as an oxidant. These nanometer-size cation-radical salts are shown to act as efficient "electron sponges" toward a variety of electron donors. 相似文献
36.
The use of xanthene, triphenylmethane and other basic dye cations as reagents for the determination of anions is reviewed. Elements and anions determined include Sb, Tl, Ga, Au, Te, In, Zn, Ta, Hg, Re, Sn, U, Os, B, Cr, Ag, ClO(4)(-), PO(4)(-), SO(4)(2-) and NO(3)(-). Difficulties encountered in developing satisfactory procedures involving basic dyes are discussed. Procedures for the purification and analysis of basic dye samples are outlined. 相似文献
37.
A work force includes workers of m types. The worker categories are ordered, with type-1 workers the most highly qualified, type-2 the next, and so on. If the need arises, a type-k worker is able to substitute for a worker of any type j greater than k (k = 1, ..., m - 1). For 7-day-a-week operation, daily requirements are for at least Dk workers of type-k or better, of which at least dk must be precisely type-k. Formulas are given to find the smallest number and most economical mix of workers, assuming that each worker must have 2 off-days per week and a given fraction of weekends off. Algorithms are presented which generate a feasible schedule, and provide work stretches between 2 and 5 days, and consecutive weekdays off when on duty for 2 weekends in a row, without additional staff. 相似文献
38.
39.
40.
D. Thorburn Burns N. Chimpalee M. Harriott 《Fresenius' Journal of Analytical Chemistry》1992,342(9):734-736
Summary A flow-injection manifold with mixing chamber has been developed for the determination of phosphate by reaction with molybdate and crystal violet. The insoluble blue dye salt is kept in colloidal solution with poly(vinyl alcohol) and measured at 560 nm. The injection rate is 100 h–1. The detection limit is 0.01 g PO
4
3–
/ml based on 250 l injection volumes. The system has been applied to the determination of phosphate in serum samples and after appropriate mineralisation to organic compounds and to plant materials. 相似文献