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41.
Klaus van Benthem Stephan Krämer Wilfried Sigle Manfred Rühle 《Mikrochimica acta》2002,138(3-4):181-193
An understanding of the correlation between microstructures and properties of materials require the characterization of the
material on many different length scales. Often the properties depend primarily on the atomistics of defects, such as dislocations
and interfaces. The different techniques of transmission electron microscopy allow the characterization of the structure and
of the chemical composition of materials with high spatial resolution to the atomic level: high resolution transmission electron
microscopy allows the determination of the position of the columns of atoms (ions) with high accuracy. The accuracy which
can be achieved in these measurements depends not only on the instrumentation but also on the quality of the transmitted specimen
and on the scattering power of the atoms (ions) present in the analyzed column.
The chemical composition can be revealed from investigations by analytical microscopy which includes energy dispersive X-ray
spectroscopy, mainly quantitatively applied for heavy elements, and electron energy-loss spectroscopy. Furthermore, the energy-loss
near-edge structure of EELS data results in information on the local band structure of unoccupied states of the excited atoms
and, therefore, on bonding. A quantitative evaluation of convergent beam electron diffraction results in information on the
electron charge density distribution of the bulk (defect-free) material.
The different techniques are described and applied to different problems in materials science. It will be shown that nearly
atomic resolution can be achieved in high resolution electron microscopy and in analytical electron microscopy. Recent developments
in electron microscopy instrumentation will result in atomic resolution in the foreseeable future. 相似文献
42.
Probing the water coordination of protein-targeted MRI contrast agents by pulsed ENDOR spectroscopy.
Stephan G Zech Wei-Chuan Sun Vincent Jacques Peter Caravan Andrei V Astashkin Arnold M Raitsimring 《Chemphyschem》2005,6(12):2570-2577
A novel methodology based on electron-nuclear double resonance (ENDOR) spectroscopy is used for the direct determination of the water coordination number (q) of gadolinium-based magnetic resonance imaging (MRI) contrast agents. Proton ENDOR spectra can be obtained at approximately physiological concentrations for metal complexes in frozen aqueous solutions either in the presence or absence of protein targets. It is shown that, depending on the structure of the co-ligand, the water hydration number of a complex in aqueous solution can be significantly different to when the complex is noncovalently bound to a protein. From the ENDOR spectra of the exchangeable protons, precise information on the metal-proton distance can be derived as well. These essential parameters directly correlate with the efficacy of MRI contrast agents and should therefore aid the development of novel, highly efficient compounds targeted to various proteins. 相似文献
43.
Vitamin-B12-Catalyzed C, C-Bond Formation: Synthesis of Jasmonates via Sequential Radical Reaction The Cbl-catalyzed electroreduction of 3-(2′-bromo-1′-ethoxyethoxy)cyclopenten ( 1a ) in presence of 1-cyanovinyl-acetate ( 8 ) gave, in a sequential radical reaction (5-exo-trig-cyclization of 1a followed by addition to 8 ), 1-cyano-2-(2′-ethoxy-hexahydro-2′H-cyclopenta[b] furan-4′-yl)ethyl acetate ( 10a ). This intermediate was transformed to methyl jasmonate ( 7 ; four steps) and epituberolide ( 9 ; three steps) in 20 and 31% yield, respectively, from cyclopent-2-en-l-ol. 相似文献
44.
Stephan Wehner 《Archive for Mathematical Logic》1995,34(3):183-196
To date the problem of finding a general characterization of injective enumerability of recursively enumerable (r.e) classes of r.e. sets has proved intractable. This paper investigates the problem for r.e. classes of cofinite sets. We state a suitable criterion for r.e. classesC such that there is a boundn with |-A|n for allAC. On the other hand an example is constructed which shows that Lachlan's condition (F) does not imply injective enumerability for r.e. classes of cofinite sets. We also look at a certain embeddability property and show that it is equivalent with injective enumerability for certain classes of cofinite sets. At the end we present a reformulation of property (F).Thank you for technical support, Wolfgang Eppler, for intellectual support, Alistair Lachlan, and for proof-reading, Martin Kummer. Thanks also to the anonymous referee 相似文献
45.
The present paper studies the properties of Hubbard-like models in high spatial dimensionsD. In a first par the limit of infinite dimension and its main features-i.e.i) the mapping onto a generalized atomic model with an additional auxiliary field andii) the validity of the local approximation for the self-energy-are worked out in a systematic (1/D)-expansion. Since the hopping matrix elements have to be properly scaled with the dimensionD, the (1/D)-expansion is also an expansion in the hopping amplitude. Thus for small hopping theD-limit may serve as a proper approximation for finite-dimensional systems. The second part of the paper adopts the hybridisation-perturbation theory of the single impurity Anderson model in order to construct a perturbation theory for the auxiliary field of the generalized atom which can also be interpreted as an expansion in the hopping amplitude. The non-crossing approximation (NCA) is used to study the antiferromagnetic phase transtion of theD-Hubbard model in the case of half filling: the critical temperature, the antiferromagnetic order parameter and the free energy of the lattice system are calculated. The NCA-results are in quite good agreement with recent results from the imaginary-time discretisation method. 相似文献
46.
47.
Nonribosomal peptide synthetases (NRPS) are multimodular biocatalysts that bacteria and fungi use to assemble many complex peptides with broad biological activities. The same modular enzymatic assembly line principles are found in fatty acid synthases (FAS), polyketide synthases (PKS), and most recently in hybrid NRPS/PKS multienzymes. FAS as well as PKS are known to function as homodimeric enzyme complexes, raising the question of whether NRPS may also act as homodimers. To test this hypothesis, biophysical methods (size exclusion chromatography, analytical equilibrium ultracentrifugation, and chemical crosslinking) and biochemical methods (two-affinity-tag-system and complementation studies with enzymes being inactivated in different catalytic domains) were applied to NRPS subunits from the gramicidin S (GrsA-ATE), tyrocidine (TycB(1)-CAT and TycB(2-3)-AT.CATE), and enterobactin (EntF-CATTe) biosynthetic systems. These methods had revealed the dimeric structure of FAS and PKS previously, but all three NRPS systems investigated are functionally active as monomers. 相似文献
48.
Stephan Weinbruch Michael Wentzel Manfred Kluckner Peter Hoffmann Hugo M. Ortner 《Mikrochimica acta》1997,125(1-4):137-141
In this paper procedures for the characterization of individual aerosol particles by element mapping in the electron microprobe are presented. The number, size and qualitative chemical composition of particles is derived from a combination of secondary or backscattered electron images and element distribution maps. Accuracy of the size distribution and reliability of the qualitative analysis procedure were checked with silicate samples. In order to obtain a semi-quantitative estimate of the chemical composition of individual particles the count rates taken from element distribution maps are corrected for matrix and geometric effects using particle ZAF procedures.Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday 相似文献
49.
Starting from earlier work by Baudler we introduce a chemical heuristic for the systematic deduction and classification of covalent partial structures of phosphorus in polycyclic phosphanes, phosphorus-rich polycyclic phosphides, and allotropes of phosphorus except the black forms. This approach is used to direct ab initio techniques (which also confirm the rules) in the quest for as yet unknown forms of molecular or macromolecular phosphorus. Based on calculated stabilities of systematically generated structural alternatives we rationalize the stabilities of Hittorf's phosphorus and of molecular P4, confirm the possible existence of at least one other crystalline allotropic form of phosphorus, and provide insight into the probable structure of amorphous red phosphorus. In total, the combined approach of chemical heuristics and large scale ab initio calculations presented in this work supplies a coherent chemical understanding of covalent polyphosphorus structures. 相似文献
50.
A high-performance liquid chromatography-mass spectrometry method has been developed for the simultaneous determination of native carnitine and eight acylcarnitines in urine. The procedure uses a solid-phase extraction on a cation-exchange column and the separation is performed without derivatization within 17 min on a reversed-phase C8 column in the presence of a volatile ion-pairing reagent. The detector was an ion trap mass spectrometer and quantification was carried out in the MS-MS mode. Validation was done for aqueous standards at ranges between 0.75 and 200 micromol/l, depending on the compound. Carnitine was quantified in urine and comparison with a radioenzymatic assay gave a satisfactory correlation (R2 = 0.981). The assay could be successfully applied to the diagnostic of pathological acylcarnitines profile of metabolic disorders in urines of patients suffering from different organic acidurias. 相似文献