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81.
Solid-state 2H NMR spectroscopy is a well-established and versatile method to study molecular orientation and dynamics in selectively deuterated samples. Herein, we introduce a 2D 2H double-quantum (DQ) NMR experiment performed under fast magic-angle spinning with a slight offset of the magic angle (OMAS). The experiment combines 2H chemical-shift resolution with DQ-filtered quasistatic 2H line shapes. In this way, it is possible to separate 2H resonances and to independently determine 2H quadrupole couplings at multiple sites. While 2H chemical shifts are resolved in the 2H DQ dimension, the quadrupole parameters can be obtained from characteristic line shapes which are reintroduced in the second dimension by the magic-angle offset. The 2D 2H DQ OMAS experiment is demonstrated on L-histidine which was deuterated at multiple sites by recrystallisation from D2O. 相似文献
82.
A method for separation and chemical identification of products formed in nuclear reactions or nuclear decay is to slow down the recoil products in a gas and to transport them to a trap, where a detecting system is arranged. The sources for the recoil products are252Cf and224Ra. As transport phase we used nitrogen or argon and added chemical reagents such as methyl and ethyl radicals, chlorine, oxygen, carbon monoxide or methane. The chemical additives lead to selective and fast separation of certain elements. As examples the results of two experiments are presented:224Ra with ethyl radicals, and252Cf with chlorine-oxygen-nitrogen mixtures. The registration of the recoil products at the trap was measured as a function of temperature, pressure and composition of the reactive gas. 相似文献
83.
N. Pilz P. Hoffmann K. H. Lieser W. Dams K. H. Nelges 《Fresenius' Journal of Analytical Chemistry》1989,335(7):695-697
Summary A non-destructive method and an experimental set-up are described by which the Pu content in UO2/PuO2 mixed oxide (MOX) pellets and in fuel rods, respectively, can be determined. The K-lines of Pu are excited by external -radiation (192Ir) and measured by a high-purity Ge detector. A calibration curve is presented and the detection limits are plotted as function of the time of measuring.
Dedicated to Prof. Dr. G. Tölg on the occasion of his 60th birthday 相似文献
Zerstörungsfreie bestimmung von plutonium in kernbrennstoff-stäben und -pellets
Dedicated to Prof. Dr. G. Tölg on the occasion of his 60th birthday 相似文献
84.
W. A. Schönfeldt P. H. Mokler D. H. H. Hoffmann A. Warczak 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1986,4(2):161-176
For 3.6 MeV/u Sm q+ projectiles a hump in the projectile (L l +L α) x-ray emission cross section is seen as a function of charge stateq for highq with 46≦q≦52 (closed incomingL shell). This hump is attributed to the Resonant electron Transfer from the Xe target atom with simultaneous Excitation of anL 3-shell electron to theM shell. The cross section for thisL 3-shell RTE process has values up to 2·10?19 cm2, which is seen in single spectra already. To verify the existence of theL-shell RTE process for the studied collision system, extensive calculations have been carried out. Especially theL 3-shell fluorescence yield for the radiative stabilization process in the highly-charged projectile has been considered. Our calculatedq-dependent cross sections for the RTE process support the given interpretation. 相似文献
85.
1,3-Dimethylated hydrocarbon segments occur frequently as structural elements in polyketide natural products. The (13)C NMR chemical shifts of a series of model compounds containing such segments can be well reproduced by a combination of molecular mechanics and SOS-DFPT/IGLO calculations. (13)C NMR chemical shifts are calculated on MM3 geometries and are Boltzmann weighted according to the MM3 energies. On the basis of the resulting thermally averaged chemical shifts, all diastereomers of the model compounds can be unequivocally distinguished. Significant differences in chemical shifts occur at methyl groups and methylene groups that are adjacent to a single stereogenic center. The method is applied to predict the relative configuration of two stereocenters in the side chains of two natural products, sambutoxin and the bradykinin inhibitor L-755,897. 相似文献
86.
Efforts are described to design simple, fully flexible but conformationally preorganised omega-hydroxy-nonanoic acids that could serve as the conformation controlling unit in analogues of the potent protein-kinase C activator aplysiatoxin. Such analogues are macrodilactones incorporating the designed omega-hydroxy-nonanoic acid and 3,4-dihydroxy-pentanoic acid, which contains the pharmacophoric groups. The design process (replacement of CH(2) groups by an oxygen atom, annelation of a six-membered ring and placement of alkyl substituents) of the omega-hydroxy-nonanoic acids was monitored by force-field calculations. In the end of this process simple analogues of aplysiatoxin are proposed in which the proper disposition of the pharmacophoric groups is secured by a conformationally flexible but preorganised template structure as part of the macrodilactone ring. 相似文献
87.
Summary A simple procedure for the determination of salicylanilide and paratoluene sulphonamide in paints has been worked out. Salicylanilide is determined by ethanol extraction and subsequent measuring of the UV-absorption spectrum, and also by determining the nitrogen content according to Kjeldahl. For the determination of para-toluene sulphonamide three different methods are employed, viz., the Kjeldahl determination of the nitrogen content, the determination of the sulphur content by burning the sample in an oxygen flask and subsequent determination of sulphate, and also by measuring the UV-absorption spectrum, the last method being only a semi-quantitative check.
Part II: Hoffmann, E., B. Bursztyn, and A. Saracz: Z. analyt. Chem. 207, 432 (1965). 相似文献
Zusammenfassung Ein einfaches Verfahren zur Bestimmung von Salicylanilid und p-Toluolsulfonamid in Anstrichfarben wird beschrieben. Die Salicylanilidbestimmung erfolgt durch Äthanolextraktion und anschließende Messung des UV-Absorptionsspektrums sowie durch Stickstoffbestimmung nach Kjeldahl. Zur Bestimmung von p-Toluolsulfonamid dient ebenfalls die Stickstoffbestimmung nach Kjeldahl, sowie die Schwefelbestimmung durch Verbrennung in Sauerstoff mit anschließender Sulfatbestimmung und auch die UV-Absorptionsspektrometrie, letztere jedoch nur als halb quantitative Kontrollmethode.
Part II: Hoffmann, E., B. Bursztyn, and A. Saracz: Z. analyt. Chem. 207, 432 (1965). 相似文献
88.
The etch rate ofn-type Si in diluted HF solutions was investigated as a function of the bias voltage applied to the Si/electrolyte interface in the dark and under illumination. It was observed that the etch rate depends very sensitively on the minority carrier flow through this interface. For an illumination intensity of 5.3×1016 photons/cm2 s (=550nm) and the depleted Si/electrolyte interface biased slightly (less than 1 V) in reverse, the etch rate is increased by a factor of more than 1000 as compared to the etch rate under open-circuit condition. This effect can be used to create etch patterns during device processing without prior masking the semiconductors. Using the same effect it should be possible to trim the thickness of Si layers on (semi-) insulating substrates for the fabrication of enhancement-mode FETs. 相似文献
89.
Treatment of methyl 2-(1-hydroxyalkyl)prop-2-enoates 1 with conc. HBr solution afforded methyl (Z)-2-(bromomethyl)alk-2-enoates 2 , which were transformed regioselectively into N-substituted methyl (E)-2- (aminomethyl)alk-2-enoates 3 (SN2 reaction) and into N-substituted methyl 2-(1-aminoalkyl)prop-2-enoates 4 (SN2′ reaction). Regiocontrol of nucleophilic attack by amine was accomplished simply by choice of solvent, the SN2 reaction occurring in MeCN and the SN2′ reaction in petroleum ether. Hydrolysis and lactamization afforded β-lactams 7 and 8 , containing an exocyciic alkylidene and methylidene group at C(3), respectively. 相似文献
90.
Knez M Sumser MP Bittner AM Wege C Jeske H Hoffmann DM Kuhnke K Kern K 《Langmuir : the ACS journal of surfaces and colloids》2004,20(2):441-447
We studied the adsorption behavior and surface chemistry of the tobacco mosaic virus (TMV) on well-defined metal and insulator surfaces. TMV serves as a tubular supramolecular model system with precisely known surface termination. We show that if the surface chemistry of the substrate and the pH-dependent chemistry of the molecular surface match, for example, by hydrogen bonding, a strong adsorption occurs, and lateral movement is impeded. Due to the immobilization, the virion can be imaged by atomic force microscopy (AFM) in contact mode. We also used self-assembled monolayers with an acyl chloride group to induce covalent bonding via ester formation. Noncontact AFM proved that TMV keeps its cylindrical cross section only under weak adsorption conditions, that is, on hydrophobic surfaces, while on hydrophilic substrates a deformation occurs to maximize the number of interacting chemical groups. 相似文献