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41.
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Mössbauer spectra and X-ray diffraction data have been recorded for compounds in the solid solution series FexTi3?xO5, 0 ? x ? 1. Compounds with x > 0.35 have the orthorhombic pseudobrookite structure, and those with x < 0.35 a monoclinic distortion of it. Ferrous ions in the fourfold and eightfold sites give rise to separate quadrupole doublets in the Mössbauer spectra, and thus it has been possible to determine the site occupancy as a function of composition by a least-square analysis of the spectra. The Mössbauer method has also proved to be a sensitive tool for the investigation of the orthorhombic-monoclinic distortion. 相似文献
44.
Koumi P Green HE Hartley S Jordan D Lahec S Livett RJ Tsang KW Ward DM 《Electrophoresis》2004,25(14):2227-2241
The demand for high-throughput DNA profiling has increased with the introduction of national DNA databases and has led to the development of automated methods of short tandem repeat (STR) profile production; however, a potential bottleneck still exists at the gel electrophoresis stage. Capillary electrophoresis sequencers capable of processing 96 samples with considerably reduced manual intervention are now available. In this paper, we compare the ABI Prism 377 slab-gel sequencer currently used by the Forensic Science Service with three leading capillary array electrophoresis instruments: the ABI Prism 3700, the Amersham MegaBACE 1000 and the 16-capillary ABI Prism 3100. We describe the experiments used to evaluate and validate these platforms for forensic use with the STR multiplex Ampf/STR SGMplus [1, 2], along with comparative data from the ABI Prism 377 sequencer. 相似文献
45.
The trans 1,2-phenylseleno acetate, acetamide, alcohol and nitrile of cyclohexane may be oxidized at selenium by halogens and the phenylseleno moiety displaced by halide to give high yields of 1,2 halide-containing products with cis geometry. 相似文献
46.
Treatment of dimethyl ketene with ethoxyacetylene 1a, 1-ethoxyoct-1-yne 1b, and 1-ethoxytetrade-1-yne 1c afforded the 3-ethoxycyclobutenones 2a–c. Hydrolysis of 2a–c with dilute hydrochloric acid gave the cyclobutane-1,3-diones 3a–c. The 1H NMR spectra of these compounds indicate that in CDCl3 solution 2,2-dimethylcyclobutane-1,3-dione 3a exists as the diketone, whereas the 2,2,4-trialkylcyclobutane-1,3-diones 3b and 3c exist as the monoenols. 相似文献
47.
N. I. Ward S. A. Kerr T. Otsuka 《Journal of Radioanalytical and Nuclear Chemistry》1987,115(1):113-123
Due to the interaction with components present in natural waters, radionuclides may be present in different physico-chemical forms, varying in size, charge and density. The distribution pattern will influence the transport, mobility and biological uptake of the radionuclides. Size fractionation based on hollow fiber is useful for the determination of the size distribution pattern of radionuclides in natural waters. Furthermore, a continuous mixing and separation system has been developed for the investigation of the association of radionuclides with naturally occurring colloids. Results based on radionuclides in waste water from the Forsmark nuclear power plant, Sweden, will illustrate the potential usefulness of the technique. 相似文献
48.
Pyrazines and quinoxalines bearing 2-substituents that direct ortho metalation reacted with lithium 2,2,6,6-tetramethylpiperidide to produce 2-substituted-3-lithiopyrazines and quinoxalines. These lithio reagents reacted with N-methoxy-N-methylbenzamide to give good to moderate yields of 3-substituted pyrazinyl or quinoxalinylphenylmethanones. The 3-methylthio substituents of some ketone products were oxidized to methylsulfonyl groups that were susceptible to nucleophilic displacement. 相似文献
49.
Hughes RP Meyer MA Tawa MD Ward AJ Williamson A Rheingold AL Zakharov LN 《Inorganic chemistry》2004,43(2):747-756
Reaction of Pd(TMEDA)(CH(3))(2) [TMEDA = tetramethylethylenediamine] with fluoroalkyl iodides R(F)I affords a series of square planar Pd(II) complexes Pd(TMEDA)(CH(3))(R(F)) [R(F) = CF(2)CF(3) (9), CFHCF(3) (10), CH(2)CF(3) (11)], presumably by oxidative addition followed by reductive elimination of CH(3)I. The solid-state structures of each compound have been determined by single crystal X-ray diffraction studies, allowing the effect of increasing alpha-fluorination on the structural trans-influence of alkyl ligands to be examined. In these compounds there is no significant difference observed in the trans-influence of the three fluorinated alkyl ligands toward the trans-N atom, although a significant cis-influence on the neighboring methyl ligand is apparent. Oxidative addition of the same series of fluoroalkyl ligands to the corresponding Pt(TMEDA)(CH(3))(2) affords octahedral Pt(IV) complexes trans-Pt(TMEDA)(CH(3))(2)(R(F))I [R(F) = CF(2)CF(3) (12), CFHCF(3) (13), CH(2)CF(3) (14)] as the kinetic products. In each case, subsequent isomerization to the corresponding all cis-isomers is observed; in the case of 13, the stereocenter at the alpha-carbon results in two diastereomeric cis-isomers, which are formed at different rates. The molecular structures of 13 and its more stable all cis-isomer 16b have been crystallographically determined. Kinetic studies of the trans-cis isomerization reactions show the mechanism to involve a polar transition state, presumably involving iodide dissociation, followed by rearrangement of the cation, and iodide recombination. High dielectric solvents increase the rate, but solvent coordinating ability has no effect. Dissolved salts (LiI, LiOTf) show normal accelerative salt effects, with no inhibition in the case of added iodide, consistent with the formation of an intimate ion pair intermediate. The kinetic parameters show that the trans-effects of fluoroalkyl ligands in these compounds follow the order expected from the relative sigma-donor properties of the ligands, with CF(2)CF(3) < CFHCF(3) < CH(2)CF(3). 相似文献
50.
Burnaby Munson Ta-Min Feng Harry D. Ward Roger K. Murray 《Journal of mass spectrometry : JMS》1987,22(9):606-609
Analysis of the isobutane chemical ionization mass spectra of hexenols, cyclohexenols and various syn/anti pairs of bicyclic and tricyclic homoallylic alcohols shows that: (i) the spectra of the allylic alcohols are dominated by [M + H – H2O]+ and [M + C4H9–H2O]+ ions and contain traces of [M + H]+ ions; (ii) [M + H]+ ions are prominent in the spectra of acyclic and certain cyclic homoallylic alcohols; and (iii) [M + H]+ ions dominate the spectra of other acyclic unsaturated alcohols. The [M + H]+ ions may result from either: (a) protonation of the hydroxyl group, followed by a very rapid intramolecular proton transfer from the protonated hydroxyl group to the carbon–carbon double bond or internal solvation of the protonated hydroxyl group by the carbon–carbon double bond; and/or (b) direct protonation of the carbon–carbon double bond with significant internal solvation of the resulting carbocation by the hydroxyl group, which may lead to carbon–oxygen bond formation to give a protonated cyclic ether. The consequences of placing various geometric constraints on the possible intramolecular interactions between the hydroxyl group and the carbon–carbon double bond in unsaturated alcohols are explored. 相似文献