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11.
W M Niessen M A de Kraa E R Verheij P J Bergers G F La Vos U R Tjaden J van der Greef 《Rapid communications in mass spectrometry : RCM》1989,3(1):1-4
On-line sample pretreatment by means of the phase-system switching approach is an interesting technique for the analysis of aqueous samples, e.g., plasma, by means of supercritical-fluid chromatography. In order to analyse plasma samples the following analytical procedure is used. The plasma sample is injected on to a short precolumn, which is washed with water and subsequently dried with nitrogen. Next, the solutes are desorbed with the supercritical mobile phase, analysed with packed-column supercritical-fluid chromatography and detected with either a UV detector or a mass spectrometer, equipped with a moving-belt interface. The herbicide diuron is selected as a test compound to study the feasibility of this approach. Using a selective detector the procedure is sufficiently sensitive to detect diuron in plasma, but not appropriate to detect the diuron metabolites in a post-mortem plasma sample. These have been identified with liquid chromatography/mass spectrometry. The detection limit of diuron in plasma using the procedure described is about 30 ng/mL. 相似文献
12.
13.
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
14.
Nelly A. Kachurovskaya Georgii M. Zhidomirov Rutger A. van Santen 《Research on Chemical Intermediates》2004,30(1):99-103
Periodical calculations of Zn(II) metal cation stabilization in cationic positions with distantly placed aluminium ions has been performed for high-silica ferrierite. It was found that decrease of the stabilization energy at large distances between Al ions (more than 10 Å) is about of 2 eV in comparison with nearest possible position of two Al ions in the zeolite lattice and weekly depended on following increase of the Al-Al distance. Main changes in stabilization energy occured within a 3-Å interval of these distances. Only for the localizations of both Al ions in one zeolite ring zinc cationic form is more stable than hydrogen form. 相似文献
15.
We give a criterion to decide if a given w-homogeneous derivation on A?k[X1,X2,X3] is locally nilpotent. We deduce an algorithm which decides if a k-subalgebra of A, which is finitely generated by w-homogeneous elements, is the kernel of some locally nilpotent derivation. 相似文献
16.
17.
A.M. van der Kraan 《Hyperfine Interactions》1998,111(1-4):23-34
In modern society the application of catalysts, and hence, research in the field of catalysis, is becoming more and more important. In the strongly increasing chemical industry most reaction processes are performed with the aid of catalysts. Knowledge about the structure of the active sites present at the surface of catalysts will facilitate the design of new catalysts with better performances. Such knowledge can be obtained by Mössbauer spectroscopy, which is an excellent in-situ characterization technique due to the high penetrating power of the γ-radiation used and the sensitivity of the spectral parameters for the chemical state and local environment of the Mössbauer atoms. 相似文献
18.
W. von der Linden 《Applied Physics A: Materials Science & Processing》1995,60(2):155-165
The reconstruction of physical quantities from (computer-) experimental data is very often hampered by the presence of noise, insufficient information and above all by the ill-posed nature of the underlying inversion problem. It will be demonstrated that the maximum entropy concepts is particularly suited for this type of data-analysis problems. It is based on Bayesian statistics and provides a consistent probabilistic theory to obtain unbiased results, independent of any model assumptions. This is particularly desirable if there is no additional information to justify these hypotheses. If, on the other hand, additional prior knowledge is available, it can be effectively incorporated into the computation, leading to more stringent confidence intervals. 相似文献
19.
Q. Gong R. N tzel P.J. van Veldhoven T.J. Eijkemans J.H. Wolter 《Journal of Crystal Growth》2005,280(3-4):413-418
We report on the shape transition from InAs quantum dashes to quantum dots (QDs) on lattice-matched GaInAsP on InP(3 1 1)A substrates. InAs quantum dashes develop during chemical-beam epitaxy of 3.2 monolayers InAs, which transform into round InAs QDs by introducing a growth interruption without arsenic flux after InAs deposition. The shape transition is solely attributed to surface properties, i.e., increase of the surface energy and symmetry under arsenic deficient conditions. The round QD shape is maintained during subsequent GaInAsP overgrowth because the reversed shape transition from dot to dash is kinetically hindered by the decreased ad-atom diffusion under arsenic flux. 相似文献
20.
Many recent algorithmic approaches involve the construction of a differential equation model for computational purposes, typically
by introducing an artificial time variable. The actual computational model involves a discretization of the now time-dependent differential system, usually
employing forward Euler. The resulting dynamics of such an algorithm is then a discrete dynamics, and it is expected to be
“close enough” to the dynamics of the continuous system (which is typically easier to analyze) provided that small – hence
many – time steps, or iterations, are taken. Indeed, recent papers in inverse problems and image processing routinely report
results requiring thousands of iterations to converge. This makes one wonder if and how the computational modeling process
can be improved to better reflect the actual properties sought.
In this article we elaborate on several problem instances that illustrate the above observations. Algorithms may often lend
themselves to a dual interpretation, in terms of a simply discretized differential equation with artificial time and in terms
of a simple optimization algorithm; such a dual interpretation can be advantageous. We show how a broader computational modeling
approach may possibly lead to algorithms with improved efficiency.
AMS subject classification (2000) 65L05, 65M32, 65N21, 65N22, 65D18 相似文献