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1.
Zareen Ahkter Andrew J. Edwards Scott L. Ingham Jack Lewis Ana M. Martin Castro Paul R. Raithby Gregory P. Shields 《Journal of Cluster Science》2000,11(1):217-226
The reaction of the di-gold cation [Au2(dppx)]2+ with the heptanuclear cluster dianion [Os7(CO)20]2– affords the mixed metal cluster [Os7(CO)20{Au2(dppx)}] (x=m (1), e (2), b (3)). On standing, in solution, this complex undergoes decarbonylation to give the cluster [Os7(CO)19{Au2(dppx)}] (x=m (4), e (5), b (6)). The complexes have been characterised spectroscopically, and an X-ray structure determination of the dppm derivative shows that it contains a metal core based on an Os7 edge-bridged bicapped tetrahedron with the two
3-Au atoms capping adjacent triangular Os3 faces of the central tetrahedron. In an analogous reaction, the carbido anion [Os7(H)C(CO)19]– affords the neutral cluster [Os7C(CO)19{Au2(dppm)}] (7) when treated with [Au2(dppm)]2+ in the presence of base. 相似文献
2.
Potential energy curves have been computed for [C2H6]2+ ions and the results used to interpret the conspicuous absence of these ions in 2E mass spectra and in charge-stripping experiments. The energies and structures of geometry-optimized ground-state singlet and excited-state triplet [C2H6]2+ ions have been determined along with energies for different decomposition barriers and dissociation asymptotes. Although singlet and triplet [C2H6]2+ ions can exist as stable entities, they possess low energy barriers to decomposition. Vertical Franck-Condon transitions, involving electron impact ionization of ethane as well as charge-stripping collisions of [C2H6]+ ions, produce [C2H6]2+ ions which promptly dissociate since they are formed with energies in excess of various decomposition barriers. Appearance energies computed for doubly-charged ethane fragment ions are in accordance with experimental values. 相似文献
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A mass fragmentography (MF) assay is described for ten potential, minor urinary metabolites of codeine (C) and morphine (M). Samples were hydrolyzed, extracted, derivatized with Tri-Sil Z and analyzed by methane chemical ionization (CI)-MF. The method is sensitive to ca. 0.01 microgram/ml for all compounds with the exception of normorphine (NM) which was difficult to extract with chloroform. The sensitivity of the MF assay for NM was only ca. 0.10 microgram/ml. Various solvent systems were investigated for optimization of extraction efficiency of all metabolites. A separate method for the extraction of NM is reported which utilizes a solid buffer--solvent combination, i.e., potassium carbonate--isopropanol. This latter method provided the best overall recovery of NM (39.0 +/- 3.4%). Gas chromatographic (GC) retention times of C, M and metabolites are reported for three liquid phases (3%) on Gas-Chrom Q (100-120 mesh). Resolution of metabolites (as trisilyl derivatives) was best on Silar-5CP and this phase was used in metabolic studies of C and M. GC resolution was not complete for all compounds; however, selection of specific ions for monitoring by MF provided the required specificity for all compounds except the 6 alpha- and 6 beta-hydroxy isomers. CI spectra for all metabolites are reported. The MF assay was used for urinary analysis of samples from guinea pigs that received single doses of C (15 mg/kg) or M (8 mg/kg). Following C administration 6 alpha- and 6 beta-hydrocodol, 6 alpha, beta-hydromorphol (undifferentiated), HM and M were measured. Following M administration only 6 alpha, beta-hydromorphol was found. The amount of total metabolite as percent dose for each component was calculated as less than 1%. 相似文献
8.
Darwin P. R. Kint Antxon Martinez de Ilarduya Jordi J. Bou Sebastin Muoz‐Guerra 《Journal of polymer science. Part A, Polymer chemistry》2002,40(14):2276-2285
The methanolytic degradation of poly(ethylene terephthalate) (PET) copolymers containing nitroterephthalic units was investigated. Random poly(ethylene terephthalate‐co‐nitroterephthalate) copolyesters (PETNT) containing 15 and 30 mol % nitrated units were prepared from ethylene glycol and a mixture of dimethyl terephthalate and dimethyl nitroterephthalate. A detailed study of the influence of the nitro group on the methanolytic degradation rate of the nitrated bis(2‐hydroxyethyl) nitroterephthalate (BHENT) model compound in comparison with the nonnitrated bis(2‐hydroxyethyl) terephthalate (BHET) model compound was carried out. The kinetics of the methanolysis of BHENT and BHET were evaluated with high‐performance liquid chromatography and 1H NMR spectroscopy. BHENT appeared to be much more reactive than BHET. The methanolytic degradation of PET and PETNT copolyesters at 80 °C was followed by changes in the weight and viscosity, gel permeation chromatography, differential scanning calorimetry, scanning electron microscopy, and 1H and 13C NMR spectroscopy. The copolyesters degraded faster than PET, and the degradation increased with the content of nitrated units and occurred preferentially by cleavage of the ester groups placed at the meta position of the nitro group in the nitrated units. For both PET and PETNT copolyesters, an increase in crystallinity accompanied methanolysis. A surface degradation mechanism entailing solubilization of the fragmented polymer and consequent loss of mass was found to operate in the methanolysis of the copolyesters. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2276–2285, 2002 相似文献
9.
William H. Newsome J. Brian Shields 《International journal of environmental analytical chemistry》2013,93(3-4):295-304
A radioimmunoassay was developed capable of determining Aroclor 1260 in milk at levels of from 20 to 80 ppb and in blood from 2 to 16 ppb. The values obtained by radioimmunoassay correlate well with those determined by gas-liquid chromatography (r2 = 0.96 for milk and 0.99 for blood) but were lower. Antiserum was produced in rabbits and was specific for 2, 2′, 4, 4′, 5, 5′-hexachlorobiphenyl. It cross-reacted with congeners and isomers in Aroclor 1254 and 1260 to the extent that a 20% decrease in binding was observed with 0.1 ng of either mixture. The method requires preliminary cleanup of the extract on alumina and utilizes 25 % dimethyl sulfoxide in the assay medium to promote solubilization of the substrates. 相似文献
10.
Hydrogen Bond Cooperativity and the Three‐Dimensional Structures of Water Nonamers and Decamers
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Dr. Cristóbal Pérez Dr. Daniel P. Zaleski Nathan A. Seifert Dr. Berhane Temelso Prof. George C. Shields Prof. Zbigniew Kisiel Prof. Brooks H. Pate 《Angewandte Chemie (International ed. in English)》2014,53(52):14368-14372
Broadband rotational spectroscopy of water clusters produced in a pulsed molecular jet expansion has been used to determine the oxygen atom geometry in three isomers of the nonamer and two isomers of the decamer. The isomers for each cluster size have the same nominal geometry but differ in the arrangement of their hydrogen bond networks. The nearest neighbor O? O distances show a characteristic pattern for each hydrogen bond network isomer that is caused by three‐body effects that produce cooperative hydrogen bonding. The observed structures are the lowest energy cluster geometries identified by quantum chemistry and the experimental and theoretical O? O distances are in good agreement. The cooperativity effects revealed by the hydrogen bond O? O distance variations are shown to be consistent with a simple model for hydrogen bonding in water that takes into account the cooperative and anticooperative bonding effects of nearby water molecules. 相似文献