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11.
Kowalewski J Effemey M Jokisaari J 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2002,157(2):171-177
Multiple-field (4.7, 9.4, 14.1 T) carbon-13 relaxation data are reported for hexamethylenetetramine (HMTA) in the cryosolvent D(2)O/DMSO at 243 K. Under these conditions, the reorientational motion of HMTA is outside of the extreme narrowing range and the relaxation data can be subjected to a quantitative interpretation. Because of the high symmetry of the HMTA molecule, the reorientation must be isotropic. Treating the reorientation as a small-step rotational diffusion of a rigid body, we obtain a rotational correlation time of 1.0 ns and a carbon-proton dipole-dipole coupling constant corresponding to an effective internuclear distance of 114. 2 pm. The harmonic vibrational correction to the dipole-dipole coupling constant, based on a known force field, yields an NMR estimate of the r(alpha) distance of 110.8 +/- 0.3 pm. 相似文献
12.
Bertini I Kowalewski J Luchinat C Parigi G 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2001,152(1):103-108
Cross-correlated relaxation caused by the interference of nuclear dipole-dipole interaction and the Curie spin relaxation (DD-CSR cross relaxation) is generalized to treat the case of anisotropic magnetic susceptibility, including the important case where the latter originates from zero-field splitting. It is shown that the phenomenon of DD-CSR cross relaxation is absolutely general and to be expected under any electronic configuration. The results of the generalization are presented for a model system, and the consequences for paramagnetic metalloproteins are illustrated with an example of cerium(III)-substituted calbindin. The effects of the magnetic anisotropy are found to be substantial. 相似文献
13.
Kaikkonen A Kowalewski J 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2000,146(2):297-310
A relaxation network has been calculated for multipolar AMX systems under application of a spin-locking RF field. Systems of this type are of interest in the study of proteins with fractional 2H enrichment. All possible auto- and cross-correlation terms involving dipolar, quadrupolar, and CSA interactions have been taken into account. The results show the presence of spectral densities at zero frequency for interactions associated with the locked nuclei, which are nonvanishing in the absence of fast motions. In addition, the application of a spin-locking field blocks certain cross-correlation interactions, thereby considerably simplifying the relaxation network. 相似文献
14.
Two-dimensional, shell-cross-linked nanoparticle arrays. 总被引:2,自引:0,他引:2
Q Ma E E Remsen T Kowalewski K L Wooley 《Journal of the American Chemical Society》2001,123(19):4627-4628
15.
16.
Nicolaus Kowalewski 《Mathematische Annalen》1908,65(4):528-537
Ohne Zusammenfassung 相似文献
17.
Bain AD Baron M Burger SK Kowalewski VJ Rodríguez MB 《The journal of physical chemistry. A》2011,115(33):9207-9216
Cyclohexane is an extremely flexible molecule that oscillates, at room temperature, between two clearly distinct and extreme conformations that cannot be distinguished at room temperature; so much so that the NMR spectrum is a single line that includes all 12 protons be they axial or equatorial. This raises the interesting question as to what happens when there are equal substituents at the 1 and 4 carbon atoms of the ring. Therefore substitution in the 1,4-positions in the cyclohexane ring has been the subject of considerable interest because some form of interconversion between extreme conformations could lead to the existence of a rather unusual behavior. To study this problem, the interconversion in (di- or tetra-1,4)-substituted six-membered cyclohexane-type rings, trans-1,4-dibromo-1,4-dicyanocyclohexane, was found to be a particularly suitable candidate. Although X-ray diffraction studies on the crystalline solid found the molecule to be centrosymmetric, it still shows a significant dipole moment μ in solution, as determined with a procedure that leads to the vapor phase values of μ. Furthermore, the low magnetic field proton NMR spectrum at ambient temperature appears as a single line, a situation that changes with increasing field intensity and different solvents. Both these effects are attributed to dynamics, because small distortions can easily disrupt the exact cancellation of the individual dipoles (which are quite strong) associated with each end of the molecule. The molecule can exist in two forms, with both the bromines in an axial geometry or both in an equatorial position. Interconversion between these forms is observed, as in the parent cyclohexane. The single NMR line observed at low magnetic fields is due to fast exchange and requires that the two forms have roughly equal populations. Spectra obtained at low temperature confirm this, and variable-temperature studies allow measurement of the rates, leading to an enthalpy of activation of 62 kJ mol(-1). More details of the interconversion are provided by some new calculation methods. Even for a relatively small molecule like this, calculation of a full potential energy surface is prohibitive. However, methods are now available to follow the molecule along the reaction coordinate in quite an efficient way. The results of these calculations lead to an extremely detailed picture of chair-chair interconversion in a di- and tetrasubstituted six-membered ring of the cyclohexane family. 相似文献
18.
19.
On the basis of the experimental results described in detail in the following sections an explanation of the mechanism of liquid modifier in chalk filled PP action was proposed. After concluding that liquid modifier does not change the sample morphology and crystallinity it was stated that it facilitates filler particles translocation in polymer matrix during deformation. Such translocations are the necessary condition for saturation of volume increase of the sample due to void formation in the process of polymer filler separation preserving the sample from its premature fracture. The most important physicochemical parameter of liquid modifier seems to be its molecular weight. This parameter determines liquids ability to migrate in micropore structure arising under stress and thus to act as a cracking agent. The possibility of the importance of more efficient heat dissipation in the sample was shown indicating the role of better thermal contacts in the sample in the case of modified chalk used as a filler. Such picture of mechanism of liquid modifier action leads also to two important conclusions: Due to polymer filler separation by means of liquid layer no further filler particles surface processing, as in some cases, is needed. The method of modification can be easily generalized for other polymers especially other polyolefins [19], [20] as physicochemical requirements for liquid are known. 相似文献
20.
Jan Almlf Edwin Haselbach Felicjan Jachimowicz Jozef Kowalewski 《Helvetica chimica acta》1975,58(8):2403-2409
The electrostatic potential (EP.) for aceheptylene (I) is calculated using ab-initio wavefunctions. In addition, the EP. around I is approximated by a monopole expression, using wavefunctions from various semiempirical procedures as a basis. It is found that the previously noted discrepancy between the thoretical prediction of differential nuclophilicity of the individual unsaturated C-atoms in 3,5,8,10-tetramethyl-aceheptylene(II) and the experimental results of protonation is removed, if instead of local atomic charges, the EP. around II, approximated by that of I is considered. 相似文献