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61.
Chromatography has been an important tool in marine laboratories. Since the 1960s, marine laboratories have been involved in the analysis of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polycyclic aromatic hydrocarbons (PAHs), and brominated flame retardants (BFRs). Column chromatography and liquid chromatography (LC) techniques have been used, mainly in the clean-up phase, while gas chromatography (GC) has been used extensively in the final determination of these contaminants. Developments have been observed from the use of packed GC columns, via capillary columns to the use of heart-cut multi-dimensional GC and comprehensive multi-dimensional GC. The progress made in interlaboratory studies and the availability of certified reference materials are discussed. 相似文献
62.
We show that the two-photon resonances in the third-order susceptibility can be exploited to yield two-photon spectra of molecular gases at moderately high spectral resolution. This form of spectroscopy does not depend on the occurrence of processes (such as fluorescence of photoionization) leading to indirect methods of two-photon absorption. The method is direct and leads in principle to values for a two-photon cross section. Comparisons of two-photon and coherent anti-Stokes Raman resonances leads to ratios of Raman and two-proton cross sections independent of the laser powers and spatial characteristics. The technique is documented with rotationally resolved spectra of SO2 and NO. A value for |αxxαyy| of 1.5 × 10?52 cm6 was measured for the O12 (6) component of the (A)2Σ ← (X)2 Π transition of nitric oxide. 相似文献
63.
Amaresh RR Lakshmikantham MV Baldwin JW Cava MP Metzger RM Rogers RD 《The Journal of organic chemistry》2002,67(8):2453-2458
3,4-Cyanomethyl substituted thiophenes reacted with thionyl chloride in the presence of base to give dicyano substituted thieno(3,4-c)thiophenes. The use of selenium oxychloride furnished the corresponding cyano substituted seleno(3,4-c)thiophene. 1,2-Phenylenediacetonitriles gave the corresponding cyano substituted benzo(c)thiophenes and benzo(c)selenenophenes, respectively, upon reaction with thionyl chloride and selenium oxychloride in the presence of base. 相似文献
64.
Functional-based screening of crude β-galactosidase activities from 42 yeast strains resulted in the selection of a single
enzyme of potential interest as a digestive supplement. β-Galactosidase produced by Kluyveromyces marxianus DSM5418 was purified to homogeneity by a combination of gel filtration, ion-exchange, and hydroxylapatite chromatographies.
The denatured (123 kDa) and native molecular masses (251 kDa) suggest that the enzyme is a homodimer. The optimum pH and temperature
of the purified enzyme were 6.8 and 37°C, respectively. The unpurified β-galactosidase in particular displayed a high level
of stability when exposed to simulated intestinal conditions in vitro for 4 h. Matrix-assisted laser desorption ionization
mass sectrometry analysis revealed that the enzyme's trypsin-generated peptide mass fingerprint shares several peptide fragment
hits with β-galactosidases from Kluyveromyces lactis. This confirms the enzyme's identity and indicates that significant sequence homology exists between these enzymes. 相似文献
65.
The dipole strengths of the 4A2 → 4T1(F), 4T1(P), d-electron transitions of the cobalt(II) tetrahalides are found to decrease with an increase in temperature, in agreement with a dynamic ligand-polarisation model for the absorption mechanism. The reduction in dipole strength is accounted for by a decrease in the coulombic coupling between the quadrupole moment of the d-electron transition of the metal ion and the transient electric dipole moment induced in the ligands, due to the anharmonic increase in the mean bond length and the progressively larger mean-square amplitudes of the bending modes of the complex ion in its ground electronic state as the temperature is raised. 相似文献
66.
Bedford RB 《Chemical communications (Cambridge, England)》2003,(15):1787-1796
Palladacycles are amongst the most active catalysts in Heck-type carbon-carbon bond formation and related carbon-heteroatom bond forming reactions. For instance they have recently emerged as showing the highest activity in the Suzuki coupling of electronically challenging aryl chloride substrates. In addition to the high activity they display, their ease of synthesis, facile modification and comparative stability all act to enhance their appeal. 相似文献
67.
Rios R Jimeno C Carroll PJ Walsh PJ 《Journal of the American Chemical Society》2002,124(35):10272-10273
We have demonstrated the feasibility of the kinetic resolution of atropisomeric amides using the commercially avaliable AD-mix. To our knowledge, this methodology represents the first catalytic kinetic resolution of such compounds. Relative rates of up to 32 have been found for the kinetic resolution processes. We have also determined the barriers to rotation and half-lives of some of these amides. The half-lives range from 7 to 135 h at room temperature. 相似文献
68.
Wang Q Zakeeruddin SM Cremer J Bäuerle P Humphry-Baker R Grätzel M 《Journal of the American Chemical Society》2005,127(15):5706-5713
We report on cross surface ambipolar charge percolation within a monolayer of a molecular triad adsorbed on semiconducting or insulating mesoscopic metal oxide films. The triad consists of a triphenlyamine (TPA) donor and a perylenemonoimide (PMI) acceptor connected by a bithiophene (T2) bridge. The self-assembled PMI-T2-TPA monolayer exhibits p-type or n-type conduction depending on the potential that is applied to the conducting glass (FTO) electrode supporting the oxide films. Cross surface electron transfer is turned on at around -1.24 V (vs Fc+/Fc) where the PMI moiety is electroactive. The color of the film changes from red to blue during the reduction of the PMI. By contrast, lateral hole transfer is turned on at around 0.8 V (vs Fc+/Fc) where the TPA moiety becomes electroactive. The stepwise oxidation of the T2-TPA units at 0.79 and 1.28 V (vs Fc+/Fc) is associated with a color change of the film from red to black. Cyclic voltammetric as well as chronocoulometric and spectroelectrochemical measurements were applied to determine the percolation threshold for cross surface charge transfer and the diffusion coefficients for the electron and hole hopping process. The effect of oxide surface states on the lateral charge motion was also investigated. 相似文献
69.
Bowmaker GA Harris RK Assadollahzadeh B Apperley DC Hodgkinson P Amornsakchai P 《Magnetic resonance in chemistry : MRC》2004,42(9):819-826
Solid-state cross-polarization magic-angle spinning (CP/MAS) NMR spectra were recorded for the compounds [Ag(NH3)2]2SO4, [Ag(NH3)2]2SeO4 and [Ag(NH3))]NO3, all of which contain the linear or nearly linear two-coordinate [Ag(NH3)2]+ ion. The 109Ag CP/MAS NMR spectra show centrebands and associated spinning sideband manifolds typical for systems with moderately large shielding anisotropy, and splittings due to indirect 1J(109Ag,14N) spin-spin coupling. Spinning sideband analysis was used to determine the 109Ag shielding anisotropy and asymmetry parameters Deltasigma and eta from these spectra, yielding anisotropies in the range 1500-1600 ppm and asymmetry parameters in the range 0-0.3. Spectra were also recorded for 15N and (for the selenate) 77Se. In all cases the number of resonances observed is as expected for the crystallographic asymmetric units. The crystal structure of the selenate is reported for the first time. One-bond (107, 109Ag,15N) coupling constants are found to have magnitudes in the range 60-65 Hz. Density functional calculations of the Ag shielding tensor for model systems yield results that are in good agreement with the experimentally determined shielding parameters, and suggest that in the solid compounds Deltasigma and eta are reduced and increased, respectively, from the values calculated for the free [Ag(NH3)2]+ ion (1920 ppm and 0, respectively), primarily as a result of cation-cation interactions, for which there is evidence from the presence of metal-over-metal stacks of [Ag(NH3)2]+ ions in the solid-state structures of these compounds. 相似文献
70.
Reversible storage of molecular hydrogen by sorption into multilayered TiO2 nanotubes 总被引:4,自引:0,他引:4
Bavykin DV Lapkin AA Plucinski PK Friedrich JM Walsh FC 《The journal of physical chemistry. B》2005,109(41):19422-19427
The sorption of hydrogen between the layers of the multilayered wall of nanotubular TiO2 was studied in the temperature range of -195 to 200 degrees C and at pressures of 0 to 6 bar. Hydrogen can intercalate between layers in the walls of TiO2 nanotubes forming host-guest compounds TiO2 x xH2, where x < or = 1.5 and decreases at higher temperatures. The rate of hydrogen incorporation increases with temperature and the characteristic time for hydrogen sorption in TiO2 nanotubes is several hours at 100 degrees C. The rate of intercalate formation is limited by the diffusion of molecular hydrogen inside the multilayered walls of the TiO2 nanotube. 1H NMR-MAS and XRD data confirm the incorporation of hydrogen between the layers in the walls of TiO2 nanotubes. The nature and possible applications of the observed intercalates are considered. 相似文献