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81.
Thompson AL Parker D Fulton DA Howard JA Pandya SU Puschmann H Senanayake K Stenson PA Badari A Botta M Avedano S Aime S 《Dalton transactions (Cambridge, England : 2003)》2006,(47):5605-5616
The crystal structures of the hydrated salts of [Gd.DOTAM]3+ and its more hydrophobic derivative [Gd.]3+, bearing 4 alpha-phenylethyl groups, (both Gd and Yb salts) are reported and compared. The nature of the anion determines the degree of ordering in the lattice and the extent of hydration. These effects are correlated with the results of 17O and 1H NMR measurements of water exchange dynamics in solution. With [Gd.DOTAM]3+, structural ordering or the extent of hydration in the hydrated lattice follows the sequence Cl->Br->I- and this order also defines the water exchange rate in solution: 7.3, 19.5, 33.3x10(4) s-1 (298 K), respectively. For [Gd.]3+ salts, the measured relaxivity is determined purely by the outer sphere term and the water exchange rate at 298 K is very similar (typically 1x10(4) s-1) for chloride, bromide, iodide, acetate, triflate and nitrate salts, notwithstanding the different nature and extent of hydration found in the crystalline lattice. 相似文献
82.
Two-dimensional infrared spectroscopy was recently used to measure the vibrational couplings between carbonyl bonds located on DNA nucleobases (Krummel, A. T.; Mukherjee, P.; Zanni, M. T. J. Phys. Chem. B 2003, 107, 9165 and Krummel, A. T.; Zanni, M. T. J. Phys. Chem. B 2006, 110, 13991). Here, we extend the coupling model derived from these 2D IR experiments to simulate the vibrational absorption and vibrational circular dichroism (VCD) spectra of three double-stranded DNA oligomers: poly(dG)-poly(dC), poly(dG-dC), and dGGCC. Using this model, we determine that the VCD spectrum of A-form poly(dG)-poly(dC) is dominated by interactions between stacked bases, whereas the coupling between base pairs and stacked bases carries equal importance in the VCD spectrum of B-form poly(dG-dC). We also simulate the absorption and VCD spectra of dGGCC, which is a combination of A- and B-form configurations. These simulations give insight into the structural interpretation of VCD and absorption spectroscopies that have long been used to monitor DNA secondary structure and kinetics. 相似文献
83.
84.
We have experimentally demonstrated a pulse sequence for the acquisition of heterodyned two-dimensional infrared (2D IR) spectra that correlates the overtone and combination bands to the fundamental frequencies. The spectra are generated by Fourier transforming the time domain signal that is allowed to evolve during one- and two-quantum coherence times. In this manner, the overtone and combination bands appear along the two-quantum axis, resulting in a direct determination of the diagonal and off-diagonal anharmonicities. To demonstrate this pulse sequence, we have collected two-quantum 2D IR spectra of a ruthenium dicarbonyl complex, extracted the diagonal and off-diagonal anharmonicities, and simulated the spectra using an exciton model. Several polarization conditions are presented that suppress the diagonal or cross peaks and we have used them to improve the accuracy of the measurement. 相似文献
85.
86.
Magnetic field effects and renormalization of the long-range Coulomb interaction in carbon nanotubes
We develop two theoretical approaches for dealing with the low-energy effects of the repulsive interaction in one-dimensional electron systems. Renormalization Group methods allow us to study the low-energy behavior of the unscreened interaction between currents of well-defined chirality in a strictly one-dimensional electron system. A dimensional regularization approach is useful, when dealing with the low-energy effects of the long-range Coulomb interaction. This method allows us to avoid the infrared singularities arising from the long-range Coulomb interaction at D = 1. We can also compare these approaches with the Luttinger model, to analyze the effects of the short-range term in the interaction. Thanks to these methods, we are able to discuss the effects of a strong magnetic field B in quasi one-dimensional electron systems, by focusing our attention on Carbon Nanotubes. Our results imply a variation with B in the value of the critical exponent α for the tunneling density of states, which is in fair agreement with that observed in a recent transport experiment involving carbon nanotubes. The dimensional regularization allows us to predict the disappearance of the Luttinger liquid, when the magnetic field increases, with the formation of a chiral liquid with α = 0. 相似文献
87.
88.
Amber L. Norman 《Tetrahedron letters》2008,49(26):4153-4155
The R-isomer of ISO-1, a 3,5-disubstituted Δ2-isoxazoline, has been implicated as a potential therapeutic agent for the treatment of Type 1 Diabetes via the antagonism of macrophage migration inhibitory factor (MIF). Δ2-Isoxazolines can be prepared by the palladium(II)-mediated cyclization of substituted β,γ-unsaturated oximes. While this reaction results in racemic mixtures, we have developed a stereoselective variant of this method based on the incorporation of an enantiomeric palladium complex in the reaction mixture. The use of chiral bisoxazoline ligands in the palladium(II)-mediated ring closure reaction has been shown to enhance the enantiomeric excess due to chirality at C5 of the Δ2-isoxazoline. 相似文献
89.
A series of cyclometalated platinum(II) complexes have been prepared, [PtL(n)Cl], containing N--C--N-coordinating, terdentate ligands based on 1,3-dipyridylbenzene (HL(1)), incorporating aryl substituents at the central 5 position of the ligand. All of the new complexes are intensely luminescent in a degassed solution at 298 K (phi = 0.46-0.65 in CH(2)Cl(2)) with lifetimes in the microsecond range (7.9-20.5 micros). The introduction of the aryl substituents leads to a red shift in the lowest-energy, intense charge-transfer absorption band compared to [PtL(1)Cl] (401 nm in CH(2)Cl(2)), in the order H < mesityl < 2-pyridyl < 4-tolyl < 4-biphenylyl < 2-thienyl < 4-(dimethylamino)phenyl (431 nm in CH(2)Cl(2)), which correlates with the decreasing order of oxidation potentials. A similar order is also observed in the emission maxima, ranging from 491 nm for [PtL(1)Cl] to 588 nm for the 4-(dimethylamino)phenyl-substituted complex. The emission spectra of all of the complexes, except for the amino-substituted compound, are highly structured in a dilute solution in CH(2)Cl(2), and the emission is assigned to excited states of primarily (3)LC (ligand-centered) character. At higher concentrations, self-quenching accompanied by structureless excimer emission centered at 700 nm is observed, but the aryl groups attenuate the self-quenching compared to the parent compound [PtL(1)Cl], particularly for the most sterically hindered mesityl complex. The introduction of the strongly electron-donating 4-dimethylamino substituent leads to a switch in the nature of the lowest-energy excited state from (3)LC to one of primarily intraligand charge-transfer (ILCT) character in CH(2)Cl(2): this complex displays a structureless and much broader emission band than the other compounds and a high degree of positive solvatochromism. No excimer emission is observed in CH(2)Cl(2), and self-quenching is an order of magnitude lower than that for the other complexes. However, in nonpolar solvents such as CCl(4), the ILCT state is destabilized, such that the (3)LC remains the lowest-energy excited state. Reversible switching between the ILCT and (3)LC states can also be achieved in a CH(2)Cl(2) solution by protonation of the amine, with an accompanying large change in the emission maxima of >100 nm. The X-ray structures of the biphenylyl- and methyl-substituted complexes are reported, together with those of the 2-pyridyl- and mesityl-substituted ligands and the key synthetic intermediate 1-bromo-3,5-di(2-pyridyl)benzene. 相似文献
90.
Organolanthanide-mediated hydrophosphination and ethylene polymerization are coupled in a catalytic cycle to produce diphenylphosphine-terminated polyethylenes. The resulting polymers were characterized by 1H, 13C, and 31P NMR, GPC, and DSC and compared spectroscopically to the model compound, 1-eicosyldiphenylphosphine oxide. High activities (107 g polymer/(mol Ln.atm ethylene.h)) and narrow polydispersities were observed in the polymerization/chain transfer process. Polyethylene molecular weights were found to be inversely proportional to diphenylphosphine concentration, supporting a chain transfer mechanism. The present discovery represents the first case in which an electron-rich phosphine functions efficiently as a chain transfer agent in a single-site fn/d0-mediated olefin polymerization process. 相似文献