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101.
Lee CH Na HK Yoon DW Won DH Cho WS Lynch VM Shevchuk SV Sessler JL 《Journal of the American Chemical Society》2003,125(24):7301-7306
Three calix[4]pyrroles bearing m-orcinol-derived diether straps of different lengths on one side of the tetrapyrrolic core have been synthesized and characterized. Structural information for an analogous diester bridged strapped system reported previously (Yoon, D. W.; Hwang, H.; Lee, C. H. Angew. Chem., Int. Ed. Engl. 2002, 41, 1757-1759) is also provided as are bromide and chloride anion affinities for all four systems determined by Isothermal Titration Calorimetry (ITC) in acetonitrile. Although both sets of the strapped calix[4]pyrroles displayed enhanced affinities for chloride and bromide anion, differences were seen among the various receptors that support the conclusion that the anion binding ability of calixpyrrole-type systems can be effectively tuned by modifying the length and nature of the bridging straps. In the specific case of the diether systems, the largest chloride affinity was seen with the shortest strap, whereas the largest affinity for bromide anion was recorded in the case of the longest strap. On the basis of these findings, as well as supporting (1)H NMR spectroscopic studies, it is postulated that not only cavity size per se, but also the ability of the aryl portion of the strap to serve as a CH hydrogen bond donor site are important in regulating the observed anion affinities. 相似文献
102.
[reaction: see text] A short and highly stereoselective synthesis of the novel steroid squalamine (1) was accomplished in nine steps from easily available methyl chenodeoxylcholanate 2. Our synthesis featured improved dehydrogenation of 4 followed by conjugate reduction to construct the trans AB-ring system and efficient asymmetric isopropylation of aldehyde 6 to introduce the C-24R-hydroxyl group. 相似文献
103.
Swenson J Schwartz GA Bergman R Howells WS 《The European physical journal. E, Soft matter》2003,12(1):179-183
The dynamics of propylene glycol (PG) and its oligomers 7-PG and PPG, with
(about 70 monomers), confined in a Na-vermiculite clay have been investigated by quasi-elastic neutron scattering and dielectric spectroscopy. The liquids are confined to a single molecular layer between the clay platelets, thus giving a true 2D liquid. The results show that the average relaxation time
, deduced from neutron scattering at a momentum transfer Q of about
, is in perfect agreement with the dielectric
-relaxation time, although neutron scattering does not only probe the main (
-) relaxation, but all motions of hydrogens on the experimental time scale. At room temperature
is proportional to Q
2, indicating that the relaxations are mainly due to ordinary translational diffusion. The most unexpected finding is that
(or the dielectric
-relaxation time) is almost unaffected by the 2D confinement, in contrast to the dielectrically active normal mode of PPG which is substantially slower in the confinement. Only the 7-mer has a significantly slower segmental translational diffusion in the clay. The results suggest that the interactions to the clay surfaces are weak and that the present 2D confinement has a very small influence on the time scale of all our observed relaxation processes, except the normal-mode relaxation.Received: 1 January 2003, Published online: 8 October 2003PACS:
61.25.Em Molecular liquids - 68.35.Ja Surface and interface dynamics and vibrations - 61.12.-q Neutron diffraction and scattering 相似文献
104.
We introduce a new variant of spectral interferometry, using spectrally dispersed ultrafast laser pulses and quadrature detection to measure optical thickness variations related to surface structure. We can resolve surface features with depths of 3 mm to 25 nm, using a lateral resolution of ~100mum . Quadrature detection gives a larger dynamic range and solves the sign ambiguity problem. This method has potential applications in device manufacture, optical communications, and error compensation in pulse shaping. 相似文献
105.
Baxley PA Booth NO Hodgkiss WS 《The Journal of the Acoustical Society of America》2000,107(3):1301-1323
Matched-field replica models based on an inaccurate knowledge of geoacoustic parameters such as bottom attenuation, shear, and interfacial sound-speed discontinuities, can predict an incorrect number of propagating modes for a shallow-water channel. The resulting degradation in the matched-field ambiguity surface can be substantially reduced by obtaining optimal replica models via modal-sum-limit optimization or bottom-property inversion. The use of these techniques for multi-tone (70, 95, 145, and 195 Hz) source-tow data recorded near San Diego during the first Shallow-Water Evaluation Cell Experiment (SWellEX-1) significantly increased matched-field correlation levels and improved source localization relative to results obtained with a previous nonoptimized model. The predicted number of propagating modes was also reduced substantially. The inversion for bottom properties (attenuation, interfacial sound-speed discontinuities, no shear) provided sediment attenuation estimates which agree well with Hamilton's models and were an order-of-magnitude greater than that used in the nonoptimized model, which accounts for the reduction in the number of modes. A simulated modal decomposition using the inverted optimal replica model verifies the number of modes predicted by the modal-sum-limit optimization. 相似文献
106.
Functional magnetic resonance imaging with intermolecular multiple-quantum coherences 总被引:4,自引:0,他引:4
Richter W Richter M Warren WS Merkle H Andersen P Adriany G Ugurbil K 《Magnetic resonance imaging》2000,18(5):489-494
For the first time, we demonstrate here functional magnetic resonance imaging (fMRI) using intermolecular multiple-quantum coherences (iMQCs). iMQCs are normally not observed in liquid-state NMR because dipolar interactions between spins average to zero. If the magnetic isotropy of the sample is broken through the use of magnetic field gradients, dipolar couplings can reappear, and hence iMQCs can be observed. Conventional (BOLD) fMRI measures susceptibility variations averaged over each voxel. In the experiment performed here, the sensitivity of iMQCs to frequency variations over mesoscopic and well-defined distances is exploited. We show that iMQC contrast is qualitatively and quantitatively different from BOLD contrast in a visual stimulation task. While the number of activated pixels is smaller in iMQC contrast, the intensity change in some pixels exceeds that of BOLD contrast severalfold. 相似文献
107.
We present a k-space approximation that directly relates a pulse sequence to its residual pattern of z-directed magnetization M(z), in a manner akin to the k-space approximation for small tip-angle excitation. Our approximation is particularly useful for the analysis and design of tagging sequences, in which M(z) is the important quantity-as opposed to the transverse magnetization components M(x) and M(y) considered in selective excitation. We demonstrate that our approximation provides new insights into tagging, can be used to design novel tag patterns, and, more generally, may be applied to selective presaturation sequences for purposes other than tagging. 相似文献
108.
Varnum WS Delamater ND Evans SC Gobby PL Moore JE Wallace JM Watt RG Colvin JD Turner R Glebov V Soures J Stoeckl C 《Physical review letters》2000,84(22):5153-5155
Inertial confinement fusion implosions using capsules with two concentric shells separated by a low density region (double shells) are reported which closely follow one dimensional (1D) radiatively driven hydrodynamics simulations. Capsule designs which mitigate Au M-band radiation asymmetries appear to correspond more closely to 1D simulations than targets lacking mitigation of hohlraum drive M-band nonuniformities. One capsule design achieves over 50% of the unperturbed 1D calculated yield at a convergence ratio of 25.5, comparable to that of a double-shell design for an ignition capsule at the National Ignition Facility. 相似文献
109.
110.
Harding DJ Gruene P Haertelt M Meijer G Fielicke A Hamilton SM Hopkins WS Mackenzie SR Neville SP Walsh TR 《The Journal of chemical physics》2010,133(21):214304
The geometric structures of small cationic rhodium clusters Rh(n)(+) (n = 6-12) are investigated by comparison of experimental far-infrared multiple photon dissociation spectra with spectra calculated using density functional theory. The clusters are found to favor structures based on octahedral and tetrahedral motifs for most of the sizes considered, in contrast to previous theoretical predictions that rhodium clusters should favor cubic motifs. Our findings highlight the need for further development of theoretical and computational methods to treat these high-spin transition metal clusters. 相似文献