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Leif Schrder Christian Schmitz Peter Bachert 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2004,171(2):87
Proton NMR resonances of the endogenous metabolites creatine and phosphocreatine ((P)Cr), taurine (Tau), and carnosine (Cs, β-alanyl-l-histidine) were studied with regard to residual dipolar couplings and molecular mobility. We present an analysis of the direct 1H–1H interaction that provides information on motional reorientation of subgroups in these molecules in vivo. For this purpose, localized 1H NMR experiments were performed on m. gastrocnemius of healthy volunteers using a 1.5-T clinical whole-body MR scanner. We evaluated the observable dipolar coupling strength SD0 (S = order parameter) of the (P)Cr-methyl triplet and the Tau-methylene doublet by means of the apparent line splitting. These were compared to the dipolar coupling strength of the (P)Cr-methylene doublet. In contrast to the aliphatic protons of (P)Cr and Tau, the aromatic H2 (δ = 8 ppm) and H4 (δ = 7 ppm) protons of the imidazole ring of Cs exhibit second-order spectra at 1.5 T. This effect is the consequence of incomplete transition from Zeeman to Paschen-Back regime and allows a determination of SD0 from H2 and H4 of Cs as an alternative to evaluating the multiplet splitting which can be measured directly in high-resolution 1H NMR spectra. Experimental data showed striking differences in the mobility of the metabolites when the dipolar coupling constant D0 (calculated with the internuclear distance known from molecular geometry in the case of complete absence of molecular dynamics and motion) is used for comparison. The aliphatic signals involve very small order parameters S ≈ (1.4 − 3) × 10−4 indicating rapid reorientation of the corresponding subgroups in these metabolites. In contrast, analysis of the Cs resonances yielded S ≈ (113 − 137) × 10−4. Thus, the immobilization of the Cs imidazole ring owing to an anisotropic cellular substructure in human m. gastrocnemius is much more effective than for (P)Cr and Tau subgroups. Furthermore, 1H NMR experiments on aqueous model solutions of histidine and N-acetyl-l-aspartate (NAA) enabled the assignment of an additional signal component at δ = 8 ppm of Cs in vivo to the amide group at the peptide bond. The visibility of this proton could result from hydrogen bonding which would agree with the anticipated stronger motional restriction of Cs. Referring to the observation that all dipolar-coupled multiplets resolved in localized in vivo 1H NMR spectra of human m. gastrocnemius collapse simultaneously when the fibre structure is tilted towards the magic angle (θ ≈ 55°), a common model for molecular confinement in muscle tissue is proposed on the basis of an interaction of the studied metabolites with myocellular membrane phospholipids. 相似文献
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The control of piecewise-deterministic processes is studied where only local boundedness of the data is assumed. Moreover the discount rate may be zero. The value function is shown to be solution to the Bellman equation in a weak sense; however the solution concept is strong enough to generate optimal policies. Continuity and compactness conditions are given for the existence of nonrelaxed optimal feedback controls. 相似文献
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By using a sheaf-theoretical language, we introduce a notion of deformation quantization allowing not only for formal deformation parameters but also for real or complex ones as well. As a model for this approach to deformation quantization, we construct a quantization scheme for cotangent bundles of Riemannian manifolds. Here, we essentially use a complete symbol calculus for pseudodifferential operators on a Riemannian manifold. Depending on a scaling parameter, our quantization scheme corresponds to normally ordered, Weyl or antinormally ordered quantization. Finally, it is shown that our quantization scheme induces a family of pairwise isomorphic strongly closed star products on a cotangent bundle. 相似文献
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Guy Schmitz 《国际化学动力学杂志》2007,39(1):17-21
At bromide concentrations higher than 0.1 M, a second term must be added to the classical rate law of the bromate–bromide reaction that becomes ?d[BrO3?]/dt = [BrO3?][H+]2(k1[Br?] + k2[Br?]2). In perchloric solutions at 25°C, k1 = 2.18 dm3 mol?3 s?1 and k2 = 0.65 dm4 mol?4 s?1 at 1 M ionic strength and k1 = 2.60 dm3 mol3 s?1and k2 = 1.05 dm4 mol?4 s?1 at 2 M ionic strength. A mechanism explaining this rate law, with Br2O2 as key intermediate species, is proposed. Errors that may occur when using the Guggenheim method are discussed. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 39: 17–21, 2007 相似文献
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G.Biju Kumar Hetal.V Patel Amrish C Shah Markus Trenkle Christine J Cardin 《Tetrahedron: Asymmetry》1996,7(12):3391-3396
N-Arylsulfonamides of (R)- and (S)-2-amino-1-butanol, on condensation with aromatic aldehydes produced diastereomerically pure 2-aryl-3-arenesulfonyl 4-ethyl-1,3-oxazolidines. The absolute configurations of one enantiomeric pair have been determined from two fully refined X-ray structures, supplemented by nmr data. 相似文献
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Markus Hegland Jochen Garcke Vivien Challis 《Linear algebra and its applications》2007,420(2-3):249-275
The combination technique has repeatedly been shown to be an effective tool for the approximation with sparse grid spaces. Little is known about the reasons of this effectiveness and in some cases the combination technique can even break down. It is known, however, that the combination technique produces an exact result in the case of a projection into a sparse grid space if the involved partial projections commute.
The performance of the combination technique is analysed using a projection framework and the C/S decomposition. Error bounds are given in terms of angles between the spanning subspaces or the projections onto these subspaces. Based on this analysis modified combination coefficients are derived which are optimal in a certain sense and which can substantially extend the applicability and performance of the combination technique. 相似文献
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