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31.
The reactions of the molecular transition metal iodates A[CrO(3)(IO(3))] (A = K, Rb, Cs) with UO(3) under mild hydrothermal conditions provide access to four new, one-dimensional, uranyl chromatoiodates, Rb[UO(2)(CrO(4))(IO(3))(H(2)O)] (1) and A(2)[UO(2)(CrO(4))(IO(3))(2)] (A = K (2), Rb (3), Cs (4)). Under basic conditions, MoO(3), UO(3), and KIO(4) can be reacted to form K(2)[UO(2)(MoO(4))(IO(3))(2)] (5), which is isostructural with 2 and 3. The structure of 1 consists of one-dimensional[UO(2)(CrO(4))(IO(3))(H(2)O)](-) ribbons that contain uranyl moieties bound by bridging chromate and iodate anions as well as a terminal water molecule to create [UO(7)] pentagonal bipyramidal environments around the U(VI) centers. These ribbons are separated from one another by Rb(+) cations. When the iodate content is increased in the hydrothermal reactions, the terminal water molecule is replaced by a monodentate iodate anion to yield 2-4. These ribbons can be further modified by replacing tetrahedral chromate anions with MoO(4)(2)(-) anions to yield isostructural, one-dimensional [UO(2)(MoO(4))(IO(3))(2)](2)(-) ribbons. Crystallographic data: 1, triclinic, space group P(-)1, a = 7.3133(5) A, b = 8.0561(6) A, c = 8.4870(6) A, alpha = 88.740(1) degrees, beta = 87.075(1) degrees, gamma = 71.672(1) degrees, Z = 2; 2, monoclinic, space group P2(1)/c, a = 11.1337(5) A, b = 7.2884(4) A, c = 15.5661(7) A, beta = 107.977(1) degrees, Z = 4; 3, monoclinic, space group P2(1)/c, a = 11.3463(6) A, b = 7.3263(4) A, c = 15.9332(8) A, beta = 108.173(1) degrees, Z = 4; 4, monoclinic, space group P2(1)/n, a = 7.3929(5) A, b = 8.1346(6) A, c = 22.126(2) A, beta = 90.647(1) degrees, Z = 4; 5, monoclinic, space group P2(1)/c, a = 11.3717(6) A, b = 7.2903(4) A, c = 15.7122(8) A, beta = 108.167(1) degrees, Z = 4. 相似文献
32.
The interaction of aspartic acid with kaolinite was studied by potentiometric titrations and by adsorption measurements both at constant aspartate concentration (but varying pH) and at a constant pH of 5.5. The temperature was 25 degrees C, and the ionic medium 5 mM KNO3. Aspartic acid dissociation constants estimated from titrations agreed with those from the literature. The adsorption of aspartic acid to kaolinite was weak and varied only slightly with pH; 10-18% of 100 microM aspartic acid adsorbed to kaolinite at 100 m(2)L(-1) between pH 3 and 10. Data from the titrations and adsorption experiments were fitted closely by an extended constant-capacitance surface complexation model, in which monodentate outer-sphere complexes formed between deprotonated aspartic acid molecules and protonated sites on the variable-charge edges of the kaolinite crystals. There appeared to be no adsorption to the permanently charged crystal faces. 相似文献
33.
A homologous series of 2,4-dichlorobenzyl alkyl ethers (DCBEs) have been synthesized and purified for use as retention index calibrants and internal standards. They are stable, sensitive to ECD and FID and ideal for GC-MS, with base peaks at m/z 159/161. The retention index calibration against the n-alkanes for a linear temperature program (LTP) series is given and recommendations made for the most suitable members of the DCBE series for use as internal standards in organochlorine (OC) residue analysis. 相似文献
34.
RECENT ADVANCES IN POLARIZATION SPECTROSCOPY: PERSPECTIVES OF THE EXTENSION TO THE SOFT X-RAY REGION
In this paper we present a general review of some of the new branches in the field of optical activity that have been developed during the last five years. Also, the conditions under which circular intensity differential scattering can be measurable in the soft X-ray region of the spectrum are established. It is found that the parameter which determines the strength of the preferential interaction of chiral molecules with opposite circular polarizations at these high energies is the anisotropy of the atomic polarizabilities in the molecule. The possibility of extending the other techniques discussed here to shorter wavelengths, is also discussed. 相似文献
35.
Summary The kinetics of the solvolysis of thetrans-[Coen2Cl2]+ cation (en = 1,2-diaminoethane) have been investigated over a range of temperatures in water with added ethanonitrile which has much less effect on the solvent structure than the acohols already used as co-solvents with water for this solvolysis. However, the non-linear relationship obtained for the variation of log (rate constant) with the reciprocal of the dielectric constant at constant temperature shows that the effect of changing solvent structure is still important, although, as expected from the absence of pronounced extrema in the variation with composition in water + ethanonitrile of physical properties which are influenced by such changes in solvent structure, the enthalpy and entropy of activation for the solvolysis vary smoothly with composition. The application of a free energy cycle shows that changes in solvent structure affect the pentacoordinated cobalt(III) ion in the transition state more than the hexacoordinated cobalt(III) ion in the initial state. 相似文献
36.
A. Hinz J. S. Wells A. G. Maki 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1987,5(4):351-358
Heterodyne frequency measurements are reported for absorption transitions of N2O in the frequency range from 1257 to 1335 cm?1. The measurements use a CO laser as a transfer oscillator whose frequency is measured directly against combinations of frequencies of two stabilized CO2 lasers whose frequencies are well known. A tunable diode laser is locked to the N2O absorption feature and the frequency difference is measured between the diode laser and the CO laser. Thev 3 fundamental bands of the15N14N16O and14N15N16O isotopes are reported. Measurements are also given for the 0002–0001, 0201–0200, and 0221–0220 vibrational transitions of N2O. A table of frequencies is given for the 0002–0000 band near 2560 cm?1 based on these and earlier measurements. 相似文献
37.
Claude Delseth Luhata Tolela Carl Djerassi Paul J. Scheuer Robert J. Wells 《Helvetica chimica acta》1979,62(1):101-109
The steroidal components of 2 marine sponges, Terpios zeteki (from Hawaii) and Dysidea herbacea (from Australia) were fractionated through a combination of chromatographic methods, including reversed phase HPLC., and were analyzed by a combination of physical methods, including high resolution GC.-MS. and 360 MHz 1H-NMR. T. zeteki contains 6 conventional 5α-stanols which comprise 91% of the sterol mixture, and traces (0.5%) of a new C26 sterol, 5α-24-norcholestan-3β-ol. Minor amounts of conventional Δ5-sterols (6.5%) and of a single Δ4-3-ketosteroid (1.5%) were also present. In contrast, the Australian sponge (D. herbacea) contains 3 Δ5,7-sterols which comprise 1.5% of the sterol mixture, and one new C29 sterol, (24 Z)-stigmasta-5,7,24(28)-trien-3β-ol, as the major component (75%). In addition, minor amounts of conventional 5α-stanols (0.5%), Δ5-sterols (5%) and 5α-Δ7-sterols (18%) were present in this complex sterol mixture. The possible dietary or endosymbiotic origins of these sterols are discussed. 相似文献
38.
Chevreux G Potier N Van Dorsselaer A Bahloul A Houdusse A Wells A Sweeney HL 《Journal of the American Society for Mass Spectrometry》2005,16(8):1367-1376
Among the myosin superfamily, myosin VI differs from all others by a reverse directionality and a particular motility. Little structural information is available for myosin VI. It is known that it binds one calmodulin (CaM) by means of a single "IQ motif" and that myosin VI contains a specific insert located at the junction between the motor domain (MD) and the lever arm, likely to play a critical role for the unusual motility previously observed. Electrospray ionization mass spectrometry (MS) was used to determine the CaM and Ca2+ stoichiometries in several myosin VI constructs. In particular, the experimental conditions required for the observation of multiprotein/Ca2+ noncovalent assemblies are detailed for two truncated MD constructs (less than 20 kDa) and for three full MD constructs (more than 90 KDa). The specificity of the detected stoichiometries is discussed for each construct and the resolving power of Time of Flight mass spectrometry is stressed, in particular for the detection of metal ions binding to high molecular weight complexes. MS reveals a new CaM binding site for myosin VI and highlights a different behavior for the five myosin VI constructs versus Ca2+ binding. In addition to these stoichiometry based experiments, gas-phase dissociation analyses on intact complexes are described. They reveal that Ca2+ transfer between protein partners occurs during the dissociation process for one construct with a full MD. Charge-transfer and dissociation behavior has allowed to draw structural assumptions for the interaction of the MD with the CaM N-terminal lobe. 相似文献
39.
Hexamethylditin in methanol solution reacts rapidly with mercuric chloride to yield mercury and trimethyltin chloride. With alkylmercuric salts the reaction is complex, yielding tetraalkyltin and/or dialkylmercury, depending upon the reactivity of the alkylmercuric salt. An electrophilic substitution mechanism involving trimethylstannyl mercurials as transient intermediates is suggested. The reaction of hexaalkylditin with diarylmercury is suggested to follow a homolyric pathway. 相似文献
40.