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161.
162.
Blanc F Copéret C Thivolle-Cazat J Basset JM Lesage A Emsley L Sinha A Schrock RR 《Inorganic chemistry》2006,45(23):9587-9592
Delayed-acquisition methods, namely, echo and constant-time-acquisition approaches, allow a significant improvement in resolution in the proton solid state NMR spectra of surface organometallic catalysts such as [syn-(SiO)Mo(=NAr)(=CH(t)Bu)(CH2(t)Bu)] and [(SiO)Re(C(t)Bu)(=CH(t)Bu)(CH2(t)Bu)] (syn/anti ratio = 1:1). This enables the observation of all of the proton resonances, which is not possible with the simple proton single-pulse technique under magic-angle spinning. For example, the methylene protons of the neopentyl ligands, buried in the large peak associated with all of the methyls in the 1H MAS spectrum, can easily be identified by recording a delayed-acquisition spectrum (resolution enhancement of a factor of 3 is obtained). Moreover, combining constant-time acquisition with heteronuclear carbon-proton correlation spectroscopy also improves the resolution of the 2D HETCOR spectra. 相似文献
163.
Mourran A Ziener U Möller M Suarez M Lehn JM 《Langmuir : the ACS journal of surfaces and colloids》2006,22(18):7579-7586
The 2D assembly of phthalhydrazide 1 and aminopyrimidine 2 derivatives equipped with C16 and C8 alkyl chains, respectively, on highly ordered pyrolytic graphite (HOPG) was studied by scanning tunneling microscopy. Well-defined, rather complex surface layer patterns emerge resulting from a delicate balance of (self-) complementary (strong) hydrogen bonds and van der Waals force-driven ordering of the alkyl substituents on the HOPG surface. The four different compounds and their 1:1 mixtures yield seven different 2D structures. Phthalhydrazide offers in principle three tautomeric forms, with the lactim/lactam being the most stable. Depending on the solvent, different morphologies can be obtained. In one case, the special self-assembly of achiral 1a leads to a 2D chiral packing with the left- and right-hand motifs present in different domains. We assume that pure 1a is expressed in its lactim/lactam form, whereas in a 1:1 mixture with 2a it switches to the bislactam form. These features display a process of dynamic diversity generation through tautomerism resulting in different nanostructures in response to environmental parameters. 相似文献
164.
Linke-Schaetzel M Anson CE Powell AK Buth G Palomares E Durrant JD Balaban TS Lehn JM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(7):1931-1940
A series of butterfly-type molecular constructs has been prepared in good yield by using a double Stille coupling synthetic protocol. They are composed of a terpyridine (terpy) scaffold and two wings composed of appended porphyrins that are capable of switching from an extended W geometry to a compact U geometry upon cation coordination of the terpy unit. The porphyrin moieties exist in the constructs either as free bases or they can be sequentially metallated, thus giving rise to wings of different "colours". Stationary and time-resolved emission studies of the HZn, ZnAu and Zn2Au constructs show that the electronic properties are strongly dependent on the geometry. In the extended W conformation an energy-transfer process is seen from the free base to the Zn-metallated porphyrin. In the U conformation in Zn2Au the donor luminescence resulting from the singlet excited state of the Zn wing is strongly, quenched not only due to the heavy atom effect but also due to a fast electron-transfer process to the ground state of the Au wing. Furthermore, the binding of (alpha,omega)-diamine substrates to the Zn(II)-porphyrin sites can also influence the conformation of the system. For the Zn2Zn construct, single-crystal diffraction experiments with synchrotron radiation allowed the structure to be solved by direct methods and fully refined; it shows the expected U conformation. The central Zn atom is six-coordinate, whereby the zinc atom is coordinated by the eta3-terpy ligand as well by monodentate and semi-chelating acetate anions. The structure is made rigid by hydrogen bonds involving the aqua ligands on the outer Zn centres and acetate oxygen atoms. The present system thus represents a double-trigger-modulated optomechanical switching device with selective substrate binding for either metal atoms or tailored ligands. Both energy- and electron-transfer processes can be controlled opening a means of improving the on/off ratio in future constructs. 相似文献
165.
Schäfer M Fuchs R Budzikiewicz H Springer A Meyer JM Linscheid M 《Journal of mass spectrometry : JMS》2006,41(9):1162-1170
Structure elucidation of naturally occurring linear and cyclic peptidic compounds can be complicated by rearrangement reactions induced upon collision activation (CA) when parts of the molecule migrate, suggesting incorrect substitution patterns. Such complex rearrangements are examined and discussed for two iron complexing compounds produced by the bacterial genus Pseudomonas (so-called pyoverdins). Various MS2- and MS3-product ion experiments were performed using a quadrupole-ion trap (QIT) at low resolution and a FT-ICR at high resolution allowing accurate mass determinations. The results of the multidimensional study confirm the proposed processes. On the basis of the series of tandem-MS experiments the structure of a new pyoverdin from a P. fluorescens strain [PVD(D47)] is deduced. 相似文献
166.
Most of the studies devoted to elastography are focused on the estimation of the axial component of the strain. However when subjected to any load, whatever the direction, soft biological media deform in the three spatial dimensions. The aim of our work is to build a three dimensional strain mapping from data acquired with a 3D clinical sectorial probe. The estimation of radial strain is based on the estimation of local scaling factors. A method of cross-correlation of interpolated signals between adjacent radiofrequency lines was used to estimate the angular displacement and strain. For the sectorial strain estimation, the same displacement estimation technique has been implemented. The method has been tested on experimental data acquired on calibrated phantoms and compared to simulation. 相似文献
167.
J. Eid J.L. Santailler B. Ferrand A. Basset A. Passero R. Lewandowska C. Balloud J. Camassel 《Superlattices and Microstructures》2006,40(4-6):201
Cubic-silicon carbide crystals have been grown from carbon-rich silicon solutions using the travelling-zone method. To improve the growth process, we investigated the effect of controlling more tightly some of the growth parameters. Using such improved growth conditions, our best sample is a 12 mm diameter and 3 mm long 3C–SiC crystal. It is grown on a (0001) 2 off, 6H–SiC seed and has 111-orientation. The low amount of silicon inclusions results in a reduced internal stress, which is demonstrated by the consideration of μ-Raman spectra collected at room temperature on a large number of samples. 相似文献
168.
Anthony Delmas Yannick Le Maoult Jean-Marie Buchlin Thierry Sentenac Jean-José Orteu 《Experiments in fluids》2013,54(4):1-16
The goal of this study is to examine the perturbation induced by the convective effect (or mirage effect) on shape measurement and to give an estimation of the error induced. This work explores the mirage effect in different spectral bands and single wavelengths. A numerical approach is adopted and an original setup has been developed in order to investigate easily all the spectral bands of interest with the help of a CCD camera (Si, 0.35–1.1 μm), a near infrared camera (VisGaAs, 0.8–1.7 μm) or infrared cameras (8–12 μm). Displacements due to the perturbation for each spectral band are measured and finally some hints about how to correct them are given. 相似文献
169.
The structures of two different bovine muscles, the Semitendinosus (ST) and the Triceps brachii (TB), were studied using quantitative maps obtained by diffusion tensor imaging at 4.7 T. The estimated features were: mean diffusivity, intra- and inter-voxel anisotropy and fiber tract orientation angles. Significant differences in anisotropy (fractional anisotropy and lattice index), spatial variations of anisotropy and fiber tract orientation were detected between ST and TB, and are discussed. Accumulation of free water, which diffuses more freely and isotropically than in the rest of the muscle, was detected and localized in ST. These results underline the usefulness of diffusion tensor measurements to characterize muscle structure and help understand the mechanisms of post mortem water exudation. 相似文献
170.
We present developments in dynamic magnetic resonance imaging that allow internal structural muscle markers to be followed during heating. This monitoring is based on quantitative characterization of the experimental conditions and their temperature time course. A nonlinear image registration technique was optimized and applied to consecutively acquired images to measure the deformation fields in the muscle. A model coupling local deformation and temperature was obtained, which for the first time takes into account the variations of deformation and temperature in the sample. This modeling opens the way to a better understanding of the mechanisms responsible for mass loss and degradation of the textural properties of muscle during heating. 相似文献