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81.
Yu Yang Maya Belghazi Arnaud Lagadec David J. Miller Steven B. Hawthorne 《Journal of chromatography. A》1998,810(1-2):149-159
The intermolecular interactions between organic solutes and sorbent matrices under subcritical water conditions have been investigated at a pressure of 50 bar and temperatures ranging from 50 to 250°C. Both polar and nonpolar organics (chlorophenols, amines, n-alkanes, and polycyclic aromatic hydrocarbons) and five different sorbent matrices (glass beads, alumina, Florisil, silica-bonded C18, and polymeric XAD-4 resins) were used. From the same matrix, the polar solutes always eluted at lower temperatures, while the moderately polar and nonpolar solutes only eluted at higher temperatures. Similar to matrix effects previously observed using supercritical carbon dioxide, the sorbent type greatly influenced the elution efficiency under subcritical water conditions. Lower temperatures are sufficient to elute a particular solute from glass beads, alumina, and Florisil, but higher temperatures (less polar water) are needed to elute the same solute from silica-bonded C18. The highest temperatures were required to elute aromatic organics from XAD-4. These matrix effects demonstrate that, while low temperature water can break inert or dipole interactions between solutes and glass beads, alumina, and Florisil, higher temperature water is required to interrupt the van der Waals attractions between solutes and silica-bonded C18, and even higher temperatures needed to overcome the π-electron interactions between aromatic solutes and XAD-4. 相似文献
82.
Dhungana S Miller MJ Dong L Ratledge C Crumbliss AL 《Journal of the American Chemical Society》2003,125(25):7654-7663
The coordination chemistry of an extracellular siderophore produced by Mycobacterium neoaurum, exochelin MN (ExoMN), is reported along with its pK(a) values, Fe(III) and Fe(II) chelation constants, and aqueous solution speciation as determined by spectrophotometric and potentiometric titration techniques. Exochelin MN is of particular interest as it can efficiently transport iron into pathogenic M. leprae, which is responsible for leprosy, in addition to its own parent cells. The Fe(III) coordination properties of ExoMN are important with respect to understanding the Fe(III) acquisition and uptake mechanism in pathogenic M. leprae, as the siderophores from this organism are very difficult to isolate. Exochelin MN has two hydroxamic acid groups and an unusual threo-beta-hydroxy-l-histidine available for Fe(III) chelation. The presence of threo-beta-hydroxy-l-histidine gives rise to a unique mode of Fe(III) coordination. The pK(a) values for the two hydroxamic acid moieties, the histidine imidazole ring and the alkylammonium groups on ExoMN, correspond well with the literature values for these moieties. Proton-dependent Fe(III)- and Fe(II)-ExoMN equilibrium constants were determined using a model involving sequential protonation of the Fe(III)- and Fe(II)-ExoMN complexes. These data were used to develop a model whereby deprotonation reactions on the surface of the complex in the second coordination shell result in first coordination shell isomerization. The overall formation constants were calculated: log beta(110) = 39.12 for Fe(III)-ExoMN and 16.7 for Fe(II)-ExoMN. The calculated pFe value of 31.1 is one of the highest among all siderophores and their synthetic analogues and indicates that ExoMN is thermodynamically capable of removing Fe(III) from transferrin. The E(1/2) for the Fe(III)ExoMN/Fe(II)ExoMN(-) couple was determined to be -595 mV from quasi-reversible cyclic voltammograms at pH = 10.8, and the pH-dependent E(1/2) profile was used to determine the Fe(II)-ExoMN protonation constants. 相似文献
83.
It is apparent that, in electro-chromatographic separations, the change of area undergone by the initial spot of test solution plays a part in the final interpretation of results almost as important as the actual movement of the centre of the spot.Several interesting facts have emerged from this research concerning the role of the carrier electrolyte on tlie movement, the spot size, and the stability of complex salts. 相似文献
84.
Briggs CR Allen MJ O'Hagan D Tozer DJ Slawin AM Goeta AE Howard JA 《Organic & biomolecular chemistry》2004,2(5):732-740
The energies of the gauche and anti conformers of 2-fluoroethylamine, 2-fluoroethanol and their protonated analogues are calculated using density functional theory. Unlike the non protonated systems, the protonated systems show a strong gauche effect where the C-F and the C-(+)NH(3) or C-F and C-(+)OH(2) bonds are gauche rather than anti to each other. Single crystal X-ray diffraction studies of 2-fluoroethylammonium compounds identify the same conformational preference. 相似文献
85.
Akutsu H Akutsu-Sato A Turner SS Le Pevelen D Day P Laukhin V Klehe AK Singleton J Tocher DA Probert MR Howard JA 《Journal of the American Chemical Society》2002,124(42):12430-12431
Normal state conductivity and superconductivity together with bulk magnetic susceptibility and magnetization measurements have been measured for two molecular charge-transfer salts: beta' '-(ET)4[(H3O)Ga(C2O4)3]G (ET = bis(ethylenedithio)tetrathiafulvalene, G = pyridine for compound I and nitrobenzene for compound II). With the exception of the included guest molecules (G) the crystal structures are almost identical. Both show minima in their electrical transport at 130 K for I and at 160 K for II, but at lower temperatures their behaviors differ markedly. The resistance of I reaches a maximum at 50 K with a further small peak at 2 K and possible superconductivity only below 2 K, whereas that of II increases continuously down to 7.5 K, where an abrupt transition to a superconducting state occurs. 相似文献
86.
87.
S. T. Howard J. P. Huke I. W. Parsons S. J. Till 《International journal of quantum chemistry》1991,39(1):71-91
The usefulness of the MS -Xα method for calculating molecular transition properties is investigated in a study of NO2. Two-dimensional potential surfaces are obtained in C2v symmetry for the X?2A1/Ã2B2 system. Potential curves that approximately follow the asymmetric stretch coordinate are also presented: On investigation, no symmetry-broken solutions were found. At all nuclear geometries investigated, the muffin-tin sphere radii were chosen by an energy-minimization technique. The inclusion of corrections to the muffin-tin form of the Xα total energy is shown to be essential, if the computed surfaces are to be qualitatively correct. The transition dipole moment connecting the two states is evaluated as a function of nuclear coordinates, using the transition-state approximation. Finally, the radiative decay of a single vibronic level in NO2 is modeled and the relevance to experiment is discussed. 相似文献
88.
89.
Inorganic oxide core, polymer shell nanocomposite as a high K gate dielectric for flexible electronics applications 总被引:1,自引:0,他引:1
Maliakal A Katz H Cotts PM Subramoney S Mirau P 《Journal of the American Chemical Society》2005,127(42):14655-14662
Organic/inorganic core shell nanoparticles have been synthesized using high K TiO(2) as the core nanoparticle, and polystyrene as the shell. This material is easy to process and forms transparent continuous thin films, which exhibit a dielectric constant enhancement of over 3 times that of bulk polystyrene. This new dielectric material has been incorporated into capacitors and thin film transistors (TFTs). Mobilities approaching 0.2 cm(2)/V.s have been measured for pentacene TFTs incorporating the new TiO(2) polystyrene nanostructured gate dielectric, indicating good surface properties for pentacene film growth. This novel strategy for generating high K flexible gate dielectrics will be of value in improving organic and flexible electronic device performance. 相似文献
90.
Howard M. Colquhoun 《Transition Metal Chemistry》1981,6(1):57-59
Summary Ligating dinitrogen, in the complexes,trans-M(N2)2(Ph2PCH2CH2PPh2)2 (where M=Mo or W) may be acylated by trifluoroacetic anhydride, to give trifluoroacetyldiazenido complexes in high yield. Unlike corresponding reactions with acyl halides, trifluoroacetylation proceeds under nonradical conditions, and a mechanism analogous to that of protonation is suggested.Dinitrogen-derived ligands may also be acylated by (CF3CO)2O, so that the methyldiazenido ligand is converted into a methyl (trifluoroacetyl) hydrazido (2-) ligand, and the acetyldiazenido ligand undergoes transacylation to give a trifluoroacetyl diazenido derivative.New complexes were characterised by i.r.,19F and1H n.m.r. spectra, and by elemental analysis.Part 1 is ref. 10 相似文献