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21.
22.
J. S. Bradshaw J. Y. Hui Y. Chan B. L. Haymore R. M. Izatt J. J. Christensen 《Journal of heterocyclic chemistry》1974,11(1):45-49
Macroeyclic polyether sulfides have been prepared by reacting an oligoethylene glycol dichloride with a dimercaptan or sodium sulfide as reported in a previous paper (6). The following new compounds were prepared: 1,4,7-trithia(15-crown-5) (1); 1,4,10-trithia(15-crown-5) (II): 1,4,7,10-tetrathia(15-crown-5) (III); I-thia(18-crown-6) (IV); 1,4-dithia(18-crown-6) (V); 1,7-dithia(18-crown-6) (VI); 1,4,7-trithia(18-crown-6) (VII); 1,7-dithia(21-crown-7) (VIII); and 1,4,7-trithia(21-crown-7) (IX). The melting points of these and previously reported thia-crown compounds correlate with their structures. X-ray analyses of two thia-crown compounds indicate that the large sulfur atoms are directed away from the center of the ring. 相似文献
23.
Three methods have been developed for the analysis of Oltipraz in serum. A method suitable for routine use employs spiking with a homologous internal standard, off-line solid-phase extraction, high-performance liquid chromatographic separation, and optical absorbance detection at 450 nm. Method detection limit is about 1 ng/ml. A second method, less susceptible to bias from co-eluting interferences, uses a stable isotope-labeled internal standard, similar extraction and separation, and detection by thermospray mass spectrometry. Method detection limit is about 0.2 ng/ml. A third method was developed which can be used without specially synthesized internal standards. It uses on-line solid-phase extraction, with quantification by comparison with external standards. Method detection limit is about 3 ng/ml. Good agreement was observed between these methods and with similar and different methods run in other laboratories. Calibration curves were linear over the entire range which was investigated, i.e., up to 500 ng/ml. Coefficients of variation were similar for all three methods, being about 5%. 相似文献
24.
Piperazino-functionalized 2',3'-BcNA and 4'-C-hydroxymethyl-DNA are appropriate molecular architectures for the introduction of basic functionalities facing the major groove and the minor groove of nucleic acid duplexes, respectively. 4'-C-(N-Methylpiperazino)methyl-DNA monomers induce significantly increased thermal stability of a DNA:DNA duplex. 相似文献
25.
Margit L. Svendsen Jesper Wengel Otto DahlFinn Kirpekar Peter Roepstorff 《Tetrahedron》1993,49(48):11341-11352
Novel Oligodeoxynucleotide analogues containing 3′-C-threo-methylene phosphodiester internucleoside linkages were synthesized on automated DNA-synthesizers using the phosphoramidite approach. The sugar modified phosphoramidite building block 5 was obtained by phosphitylation of 1-(2,3-dideoxy-5-O-(4,4′-dimethoxytrityl)-3-C-hydroxymethyl-β-D-threo-pentofuranosyl)thymine (4) which was synthesized in only three steps from 5′-O-(4,4′-dimethoxytrityl)thymidine (1). The hybridization properties and enzymatic stability of the oligonucleotide analogues were studied by UV experiments. 17-Mers having one or three modifications in the middle or two modifications in each end hybridized to DNA with moderate lowered affinity compared to unmodified 17-mers (ΔTm 1–3°C per modification). Furthermore, the end-modified and all-modified oligonucleotides were stable towards snake venom phosphodiesterase. 相似文献
26.
With tetragonal distortions of tetrahedral d2 complexes as examples, nonadditive and additive ligand fields are compared computationally, using Kohn-Sham density functional theory (KS-DFT) and ligand-field theory to obtain 45 linear, parametrical equations. For each complex, a "data" reduction from three nonadditive-field parameters to two parameters of the additive field occurs. The complexes V and CrX4- (where X=F, Cl, Br, I) provide the two-dimensional spectrochemical series of the sigma and pi AOM parameters, which are known semiempirically for the halide ligands. The same parametrical results can be obtained from the Kohn-Sham orbital energies of the "average of configuration" computation. 相似文献
27.
J. L. Oscarson R. M. Izatt P. R. Brown Z. Pawlak S. E. Gillespie J. J. Christensen 《Journal of solution chemistry》1988,17(9):841-863
The aqueous reactions,
相似文献
28.
The Amsterdam Density Functional (ADF) package has been used to constrain Kohn-Sham DFT in such a fashion that a transition from KS-DFT to ligand-field theory in the form of the parametrical d(q)() model is completely well-defined. A relationship is established between the strong-field approximation of the parametrical d(2) model for the tetrahedral complexes VCl(4)(-) and VBr(4)(-) and certain fixed-orbital ADF-computed energies. In this way values for all the parameters of the d(2)() model may be computed, thus allowing the ADF results to be expressed in terms of a KS-DFT energy matrix that can be diagonalized. This means that the KS-DFT deficiency with regard to computation of nondiagonal elements has been overcome and the KS-DFT eigenenergies have become available through the KS-DFT mimicking of the ligand-field plus repulsion model. By using mutually orthogonal strong-field energy matrices, the mimicking has been further elucidated. The computed values for the empirical parameters of VCl(4)(-) and VBr(4)(-) are in good agreement with experimental data. The spectrochemical and the nephelauxetic series have been computed by including the remaining halide complexes and the quantitatively special position of F(-)() among the halides corroborated for both series. 相似文献
29.
Andersen KB Christensen E Berg RW Bjerrum NJ von Barner JH 《Inorganic chemistry》2000,39(16):3449-3454
A vacuum-tight cell for infrared spectroscopic investigations of extremely corrosive melts, e.g., molten fluorides, has been constructed and tested up to 750 degrees C. The cell has a gold-lined sample chamber and a diamond window transparent for the infrared light. It can be furnished with a gold piston that enables the recording of short-path-length FTIR spectra of liquid samples. Solutions of Nb(V) in LiF-NaF-KF eutectic (FLINAK) with and without oxide additions have been investigated by FTIR and Raman spectroscopy. The presence of NbF7(2-), NbOF5(2-), and NbO2F4(3-) complexes was established in the molten state at 600 degrees C. After solidification NbF7(2-) was still the only Nb(V) all-fluoro complex present. Three oxofluoro complexes, NbOF6(3-), NbOF5(2-), and NbO2F4(3-), have been identified in the solid state. Typical frequency regions for the different complexes are established. Finally, it was shown that K2NbF7 can be used as an indicator to determine the oxide content of the sample melts. 相似文献
30.
Reed M. Izatt Gypzy C. Lindh Jan F. Biernat Maria Bochenska Ronald L. Bruening Jerald S. Bradshaw James J. Christensen 《Journal of inclusion phenomena and macrocyclic chemistry》1989,7(5):487-499
The transport of alkali metal cations by several macrocycles possessing two sulfonamide groups as a part of an 18-, 20-, or 21-membered macroring has been studied. Some of these compounds were found to be more effective transport agents than the proton-ionizable pyridone- and triazole-containing crown ethers reported previously. The factors affecting transport, such as ring size, source and receiving phase pH, and the nature of the groups attached to the sulfonamide nitrogen atoms were examined. Also, extraction experiments by some of the ligands were performed. The behavior of sulfonamide type crowns in single and competitive transport of the alkali metal cations is explained. The mechanism of transport appears to be complex. Transport of one or two cations per molecule of the disulfonamide carriers occurs. Complexation of these cations appears to occur both within and outside the macrocycle cavity. Our results also suggest that kinetic factors may play a significant role in transport rates and selectivities.Deceased: September 5, 1987. 相似文献
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