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151.
The separation of wide molecular mass (Mr) ranges of macromolecules using frit inlet asymmetrical flow field-flow fractionation (FI-AFlFFF) has been improved by implementing a combination of field and flow programming. In this first implementation, field strength (governed by the cross flow-rate through the membrane-covered accumulation wall) is decreased with time to obtain faster elution and improved detection of the more strongly retained (high Mr) materials. The channel outlet flow-rate is optionally held constant, increased, or decreased with time. With circulation of the flow exiting the accumulation wall to the inlet frit, the dual programming of cross flow and channel outlet flow could be implemented using just two pumps. With this flow configuration, the channel outlet flow-rate is always equal to the channel inlet flow-rate, and these may be programmed independently of the cross flow-rate through the membrane. FI-AFlFFF retains its operational advantage over conventional asymmetrical flow FFF (AFlFFF). Unlike conventional AFlFFF, FI-AFlFFF does not require time consuming, and experimentally inconvenient, sample focusing and relaxation steps involving valve switching and interruption of sample migration. The advantages of employing dual programming with FI-AFlFFF are demonstrated for sets of polystyrene sulfonate standards in the molecular mass range of 4 to 1000 kDa. It is shown that programmed FI-AFlFFF successfully expands the dynamic separation range of molecular mass. 相似文献
152.
A series of 3-monosubstituted, 3,3′-disubstituted, and 3,5-disubstitted perhydro-7a-methyloxazolo[3,4-c]oxazoles has been synthesised. Some indication of the predominant conformations of these systems and of the related perhydro-imidazo[1,5-c]thiazoles is obtainable from the magnitude of the geminal coupling constants of the methylene group protons situated between the heteroatoms. 相似文献
153.
Summary Naturally occurring waters in the oxidized zone of a Pb-Zn orebody have been collected where they are responsible for the formation of solid hydrozincite, Zn5(OH)6(CO3)2. The solutions were analysed and the computer programme COMICS used to describe the complex ion distribution in each case. From the results, the solubility product for hydrozincite has been recalculated as log KSP=–14.9(0.1). This value has been used to calculate the fields of stability of some secondary zinc minerals and illustrates the reason for the apparently anomalous stability of hydrozincite in nature, compared with what might be expected from considerations of earlier data. 相似文献
154.
Monteux C Williams CE Bergeron V 《Langmuir : the ACS journal of surfaces and colloids》2004,20(13):5367-5374
The adsorption and complexation of polystyrene sulfonate (a highly charged anionic polyelectrolyte) and a series of cationic surfactants, alkyltrimethylammonium bromide, CnTAB, n = 8-16, at the air-water interface has been studied by combining surface tension and ellipsometry measurements. We find that increasing the chain length of the surfactant from 8 to 10 carbons leads to a sharp increase in adsorption of PSS/CnTAB complexes. When the surfactant tail length is further increased to 12 and 14 carbons, surface adsorption becomes less favored than macroscopic phase separation, resulting in a partial surface depletion. Furthermore, we find that when surface tensions are plotted against surfactant/monomer molar concentration ratio, all data collapse to a single curve. This result shows that the surfactant-polymer molar ratio, s/p, is a key parameter for tuning the surface activity of the complexes formed. 相似文献
155.
The L3/L2 white-line intensity ratio in transition-metal oxides deviates widely from the statistical value of 2 : 1 but shows interesting systematics. In a series of oxides of a given metal, the ratio reaches a maximum for the d5 configuration (e.g. MnO) and a minimum for the d0 configuration (e.g. KMnO4). In a series of monoxides, sesquioxides and dioxides of different metals, the ratio is again a maximum at the d5 configuration and decreases as the configuration changes towards d0 or d10. Our results, obtained by electron energy-loss spectroscopy, carried out in an electron microscope, are interpreted on an atomic mechanism involving spin-spin coupling. According to this model, the L2 transition probability decreases in the progression d0 to d5 whereas the L3 transition probability decreases beyond d5. 相似文献
156.
[reaction: see text] The first examples of free radical-mediated vinyl amination are described by nonconventional vinyl radical addition to azomethine nitrogen. This new vinyl amination protocol is mild and provides convenient synthetic access to nonstabilized N,N-dialkyl enamines and tandem bond-forming processes. 相似文献
157.
Summary [Fe(3,3'-bipyridazine)3]2+ has a negligible rate of dissociation in water at pH 7, and in 0.05 mol dm–3 HO– at ionic strength 1.00 mol dm–3 (NaNO3) at 298.2 K, the second-order rate constant involving HO– is only 3.3 x 10–5 dm3 mol–1 s–1. Examination of kinetic and other data and results for it wide variety oftris-diimine complexes of FeII related compounds, indicates that dissociation takes placevia attack at the ligand. The significance of the various possible intermediates is assessed and it is evident that a previously postulated intramolecular transfer of HO– from the ligand to the metal atom, with associated metal-nitrogen bond fission, is important in the reaction. A general scheme for dissociation of these kinds of compounds is set out.Part XXX: R. D. Gillard, R. P. Houghton and J. N. Tucker,J. Chem. Soc., Dalton Trans., submitted for publication.Present address: Department of Chemistry. University of Nottingham, University Park, Nottingham NG7 2RD U.K. 相似文献
158.
As part of an effort to synthesize the polyene macrolide antibiotics, a comparison of several methods of polyene synthesis has been carried out with the finding that superior results were obtained using the Wollenberg vinyl ether method. 相似文献
159.
160.
Denis W. Clack Leon A. P. Kane-Maguire David H. Knight Peter A. Williams 《Transition Metal Chemistry》1980,5(1):376-378
Summary Molecular orbital calculations using-, the INDO method have been carried out fm the [FeL(CN)4]2 and [FeLH(CN)4] complexes, as well as for the tree ligands, with L 2 × pyridine, 1,10-phenanthroline.2,2-bipyridyl. 2,2-rimidine, 2, 3,3-bipyridazine and 4.4-bipyrimidine. Calculations of residual charge at carbon atoms in the ligand rings. correlating with relative nucleophilicity of the compounds, corresponds with observed differences of rate of reaction of the complex [FeI;]2 With nucleophiles. 相似文献