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31.
Charmont P Sakellariou D Emsley L 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2002,154(1):136-141
In this article a method is suggested for restricting a sample (spatial localization) by preparing the magnetization with a phase-modulated radiofrequency pulse which inverts magnetization only over a very narrow range of radiofrequency field strengths. This is the most efficient method, in terms of sensitivity, of restricting the sample to improve rf homogeneity. The method is demonstrated by using it to improve the resolution obtained in a homonuclear dipolar decoupling experiment. 相似文献
32.
Heise H Sakellariou D Meriles CA Moulé A Pines A 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2002,156(1):146-151
In a recent publication we presented a method to obtain highly resolved NMR spectra in the presence of an inhomogeneous B(0) field with the help of a matched RF gradient. If RF gradient pulses are combined with "ideal" 90 degrees pulses to form inhomogeneous z rotation pulses, the line broadening caused by the B(0) gradient can be refocused, while the full chemical shift information is maintained. This approach is of potential use for NMR spectroscopy in an inhomogeneous magnetic field produced by an "ex-situ" surface spectrometer. In this contribution, we extend this method toward two-dimensional spectroscopy with high resolution in one or both dimensions. Line narrowing in the indirect dimension can be achieved by two types of nutation echoes, thus leading to depth-sensitive NMR spectra with full chemical shift information. If the nutation echo in the indirect dimension is combined with a stroboscopic acquisition using inhomogeneous z-rotation pulses, highly resolved two-dimensional correlation spectra can be obtained in matched field gradients. Finally, we demonstrate that an INEPT coherence transfer from proton to carbon spins is possible in inhomogeneous B(0) fields. Thus, it is possible to obtain one-dimensional (13)C NMR spectra with increased sensitivity and two-dimensional HETCOR spectra in the presence of B(0) gradients of 0.4 mT/cm. These schemes may be of some value for ex-situ NMR analysis of materials and biological systems. 相似文献
33.
François Beniere Dimitris Kostopoulos K.V. Reddy 《Journal of Physics and Chemistry of Solids》1980,41(7):727-734
The self-diffusion coefficients of Na+ and I?, as well as the ionic conductivity, are measured in Na(I) single crystals, pure and doped with Ca2+ ions. The computer analysis of the whole set of data shows that the atom transport in Na(I) is ensured essentially by the free vacancies with a very small contribution (~4%) of the vacancy pairs. The thermodynamic parameters of vacancy formation and migration are derived by taking the long range interactions into account (activity coefficients on the concentrations and relaxation factors on the mobilities). The respective entropies of Schottky defect formation, cation migration and anion migration are equal to 7.64, 3.23 and 2.91 k while the corresponding enthalpies are equal to 2.00, 0.58 and 0.77 eV. 相似文献
34.
Let be a random -CNF formula formed by selecting uniformly and independently out of all possible -clauses on variables. It is well known that if , then is unsatisfiable with probability that tends to 1 as . We prove that if , where , then is satisfiable with probability that tends to 1 as .
Our technique, in fact, yields an explicit lower bound for the random -SAT threshold for every . For our bounds improve all previously known such bounds.
35.
Grohol D Papoutsakis D Nocera DG 《Angewandte Chemie (International ed. in English)》2001,40(8):1519-1521
36.
Dimitris S. Achilias Alexandros K. Nikolaidis George P. Karayannidis 《Journal of Thermal Analysis and Calorimetry》2010,102(2):451-460
Kinetics of the in situ bulk polymerization of methyl methacrylate in the presence of organomodified montmorillonite (MMT)
was investigated using differential scanning calorimetry (DSC) and gravimetrically. Different amount and types of MMT under
the trade names Cloisite were employed. Using DSC, the amount of heat released versus time, under isothermal conditions, was
recorded, and eventually, the time evolution of polymerization rate and monomer conversion was calculated. Results on the
variation of monomer conversion with reaction time were in good agreement to corresponding from the gravimetric measurements.
The nanocomposites prepared were characterized with WAXD, TEM and FTIR, and their glass transition temperature, T
g, was measured with DSC. Depending on the added amount of nano-MMT, either exfoliated or intercalated structures were obtained.
An enhancement of the polymerization rate with the presence of the nanoparticles was observed especially in the gel effect
region. This was accompanied by a higher T
g and average molecular weight, as measured by GPC, of all nanocomposites compared to neat PMMA. 相似文献
37.
Sotiria Karagiovanaki Alexandros Koutsioubas Nikolaos Spiliopoulos Dimitris L. Anastassopoulos Alexandros A. Vradis Chris Toprakcioglu Angeliki Elina Siokou 《Journal of polymer science. Part A, Polymer chemistry》2010,48(14):1676-1682
We have studied the adsorption of end-attaching block copolymer chains inside the cylindrical pores of nanoporous alumina. Highly asymmetric PS-PEO block copolymers, with a small PEO anchoring block and a long PS dangling block, were allowed to adsorb onto porous alumina substrates with an average pore diameter of ∼200 nm from toluene solution. The adsorption process was monitored using FTIR spectroscopy, whereas depth profile analysis was performed by means of XPS and Ar+ ion sputtering. It is found that the PS-PEO adsorption kinetics in porous alumina are ∼4 orders of magnitude slower than the corresponding case of a flat alumina substrate. It appears that chains adsorbed near the pore entrance early on tend to form a barrier for chains entering the pore at later times, thereby slowing down the adsorption process significantly. This effect is much more pronounced for large chains whose dimensions are comparable with the pore diameter. The equilibrium adsorbance value is also affected by chain size due to the additional entropic penalty associated with chain confinement, the adsorbance falling substantially when the chain dimensions become comparable with the pore diameter. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1676–1682, 2010 相似文献
38.
Dimitris Kalaitzakis 《Tetrahedron》2010,66(48):9431-9439
The stereoselective reduction of α-substituted-β-hydroxy ketones for the preparation of the corresponding optically pure 2-monosubstituted or 2-disubstituted-1,3-diols is described. These transformations proceed in high optical purities and yields. Ketoreductases were able to catalyze the formation of either the syn or the anti diol, depending on the enzyme. By replacing the α-alkyl substituent for an OAc moiety, in low conversion time (≤24 h), ketoreductases catalyzed the formation of the OAc-protected 1,2,3-triol, in high yield and with high optical purity (>99% de, >99% ee). This is a simple and highly stereoselective method for the synthesis of different diastereomers of chiral diols. 相似文献
39.
Bougas L Sofikitis D Everest MA Alexander AJ Rakitzis TP 《The Journal of chemical physics》2010,133(17):174308
We report the measurement of the spin polarization of hydrogen (SPH) atoms by (2+1) laser-induced fluorescence, produced via the photodissociation of thermal HBr molecules with circularly polarized 193 nm light. This scheme, which involves two-photon laser excitation at 205 nm and fluorescence at 656 nm, offers an experimentally simpler polarization-detection method than the previously reported vacuum ultraviolet detection scheme, allowing the detection of SPH atoms to be performed more straightforwardly, from the photodissociation of a wide range of molecules and from a variety of collision experiments. 相似文献
40.
A biocatalytic cascade reaction was designed for the stereoselective synthesis of optically pure 2-alkyl-1,3-diols employing two enzymes. The cascade process consists of two consecutive steps: a stereoselective diketone reduction and a hydroxy ketone reduction. Chiral diols were formed by the addition of ketoreductases in the same vessel, in high stereoselectivity and chemical yield, without the isolation of the intermediate β-hydroxy ketones. 相似文献