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941.
Verdier L Sakhaii P Zweckstetter M Griesinger C 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2003,163(2):353-359
In this paper we show that water insoluble compounds dissolved in poly-gamma-benzyl-glutamate are amenable to the measurement of a number of homo- and heteronuclear dipolar couplings. The sensitivity and experimental precision of dipolar couplings are sufficient to obtain a good match with the structure. In order to achieve the necessary precision for H,C dipolar couplings between protons and carbons that are not directly bound a new method for the measurement of heteronuclear long range couplings is introduced that allows a one-parameter fit to a HSQC-based experiment as reference experiment. The methodology is applied to menthol (1R, 3S, 4R). 相似文献
942.
Eleven bis-ureas have been synthesized, and some of their properties are reported. Several of these compounds form supramolecular polymers in organic solvents. The self-association is shown by FTIR spectroscopy to display cooperativity at two levels. The first level of cooperativity is due to the synergistic association of the two urea functions of a single molecule. The second level of cooperativity is revealed by the fact that the formation of dimers is less favored than that of long oligomers. 相似文献
943.
Synthesis and characterization of Co/CdSe core/shell nanocomposites: bifunctional magnetic-optical nanocrystals 总被引:3,自引:0,他引:3
Kim H Achermann M Balet LP Hollingsworth JA Klimov VI 《Journal of the American Chemical Society》2005,127(2):544-546
Nanocomposite materials provide the possibility for multifunctional properties in contrast with their more-limited single-component counterparts. Here, we report the synthesis and characterization of the first all-inorganic core/shell hybrid magnetic-optical nanoparticle, cobalt/cadmium selenide. The core/shell nanocrystals are prepared in a facile one-pot reaction, and their microstructure is analyzed using low- and high-resolution transmission electron microscopy. Using magnetic and optical characterization, we demonstrate bifunctional behavior, whereby the core retains the magnetic properties of the starting Co nanoparticle, and the shell emits similarly to a single-component CdSe nanoparticle. Interestingly, while the coercivity was found to be unchanged by shell formation, the blocking temperature for the composite structure was observed to be substantially lower (Co: >350 K; Co/CdSe: 240 K). In addition, we observed that at low temperatures (20 K) shell CdSe photoluminescence (PL) decay was very rapid (<1 ns). In contrast, nanocrystalline CdSe PL decay is typically much slower at such temperatures (>50 ns). Finally, we propose possible explanations for the unusual magnetic and optical behavior of the core/shell hybrid nanostructures. 相似文献
944.
Iuga D Morais C Gan Z Neuville DR Cormier L Massiot D 《Journal of the American Chemical Society》2005,127(33):11540-11541
We show for the first time that it is possible to acquire high-resolution heteronuclear NMR correlation experiments in solid state between second-order-broadened half integer quadrupolar nuclei (i.e., 27Al and 17O) using the scalar J-coupling. The sensitivity of the experiment is dramatically improved at high fields (gain proportional to the fourth power of the principal field) with a combination of signal enhancement techniques. This turns a challenging experiment into a real tool. We apply this experiment to characterize a calcium aluminate glass in which we prove the presence of tricluster mu3 oxygen sites and describe the signature of their directly bonded aluminum sites. Applications involve a large range of possible pairs of quadrupolar nuclei in different materials, such as glasses, porous or mesoporous framework materials, zeolites, hybrid organic-inorganic, and bioinvolved materials. 相似文献
945.
Maron L Werkema EL Perrin L Eisenstein O Andersen RA 《Journal of the American Chemical Society》2005,127(1):279-292
The net reaction of monomeric Cp'(2)CeH [Cp' = 1,3,4-(Me(3)C)(3)(C(5)H(2))] in C(6)D(6) with C(6)F(6) is Cp'(2)CeF, H(2), and tetrafluorobenzyne. The pentafluorophenylmetallocene, Cp'(2)Ce(C(6)F(5)), is formed as an intermediate that decomposes slowly to Cp'(2)CeF and C(6)F(4) (tetrafluorobenzyne), and the latter is trapped by the solvent C(6)D(6) as a [2+4] cycloadduct. In C(6)F(5)H, the final products are also Cp'(2)CeF and H(2), which are formed from the intermediates Cp'(2)Ce(C(6)F(5)) and Cp'(2)Ce(2,3,5,6-C(6)F(4)H) and from an unidentified metallocene of cerium and the [2+4] cycloadducts of tetra- and trifluorobenzyne with C(6)D(6). The hydride, fluoride, and pentafluorophenylmetallocenes are isolated and characterized by X-ray crystallography. DFT(B3PW91) calculations have been used to explore the pathways leading to the observed products of the exergonic reactions. A key step is a H/F exchange reaction which transforms C(6)F(6) and the cerium hydride into C(6)F(5)H and Cp'(2)CeF. This reaction starts by an eta(1)-F-C(6)F(5) interaction, which serves as a hook. The reaction proceeds via a sigma bond metathesis where the fluorine ortho to the hook migrates toward H with a relatively low activation energy. All products observed experimentally are accommodated by pathways that involve C-F and C-H bond cleavages. 相似文献
946.
This paper argues that curvelets provide a powerful tool for representing very general linear symmetric systems of hyperbolic differential equations. Curvelets are a recently developed multiscale system [7, 9] in which the elements are highly anisotropic at fine scales, with effective support shaped according to the parabolic scaling principle width ≈ length2 at fine scales. We prove that for a wide class of linear hyperbolic differential equations, the curvelet representation of the solution operator is both optimally sparse and well organized.
- It is sparse in the sense that the matrix entries decay nearly exponentially fast (i.e., faster than any negative polynomial) and
- well organized in the sense that the very few nonnegligible entries occur near a few shifted diagonals.
947.
We consider a nonrelativistic electron interacting with a classical magnetic field pointing along the -axis and with a quantized electromagnetic field. Because of the translation invariance along the -axis, we consider the reduced Hamiltonian associated with the total momentum along the -axis and, after introducing an ultraviolet cutoff and an infrared regularization, we prove that the reduced Hamiltonian has a ground state if the coupling constant and the total momentum along the -axis are sufficiently small. Finally, we determine the absolutely continuous spectrum of the reduced Hamiltonian and we prove that the renormalized mass of the electron is greater than its bare one. To cite this article: L. Amour et al., C. R. Acad. Sci. Paris, Ser. I 340 (2005). 相似文献
948.
It is difficult to hear out individually the components of a "chord" of equal-amplitude pure tones with synchronous onsets and offsets. In the present study, this was confirmed using 300-ms random (inharmonic) chords with components at least 1/2 octave apart. Following each chord, after a variable silent delay, listeners were presented with a single pure tone which was either identical to one component of the chord or halfway in frequency between two components. These two types of sequence could not be reliably discriminated from each other. However, it was also found that if the single tone following the chord was instead slightly (e.g., 1/12 octave) lower or higher in frequency than one of its components, the same listeners were sensitive to this relation. They could perceive a pitch shift in the corresponding direction. Thus, it is possible to perceive a shift in a nonperceived frequency/pitch. This paradoxical phenomenon provides psychophysical evidence for the existence of automatic "frequency-shift detectors" in the human auditory system. The data reported here suggest that such detectors operate at an early stage of auditory scene analysis but can be activated by a pair of sounds separated by a few seconds. 相似文献
949.
Thresholds for detecting interaural phase differences (IPDs) in sinusoidally amplitude-modulated pure tones were measured in seven normal-hearing listeners and nine listeners with bilaterally symmetric hearing losses of cochlear origin. The IPDs were imposed either on the carrier signal alone-not the amplitude modulation-or vice versa. The carrier frequency was 250, 500, or 1000 Hz, the modulation frequency 20 or 50 Hz, and the sound pressure level was fixed at 75 dB. A three-interval two-alternative forced choice paradigm was used. For each type of IPD (carrier or modulation), thresholds were on average higher for the hearing-impaired than for the normal listeners. However, the impaired listeners' detection deficit was markedly larger for carrier IPDs than for modulation IPDs. This was not predictable from the effect of hearing loss on the sensation level of the stimuli since, for normal listeners, large reductions of sensation level appeared to be more deleterious to the detection of modulation IPDs than to the detection of carrier IPDs. The results support the idea that one consequence of cochlear damage is a deterioration in the perceptual sensitivity to the temporal fine structure of sounds. 相似文献
950.
Bioanalogue models of composite cell envelopes were designed by electrostatically driven self-assembly of actin shells inside giant vesicles. Viscoelastic relaxation moduli were measured between 0.03 and 20 s as a function of actin density by magnetic bead microrheometry. The shear relaxation spectra exhibited by the composite shells compare well with those of natural cell envelopes and bulk entangled actin networks. Absolute value of the shear modulus was measured for the first time by deformation field mapping. Shear and bending moduli agree well with values obtained by bead fluctuations analysis. 相似文献