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181.
Stefan Müllegger Kathrin H?nel Thomas Strunskus Christof W?ll Adolf Winkler 《Chemphyschem》2006,7(12):2552-2558
Near-edge X-ray absorption fine structure (NEXAFS) spectroscopy has been applied to reveal the molecular arrangement of ultrathin oligophenyl films [p-quaterphenyl (4P) and p-hexaphenyl (6P)] on Au(111). In the half-monolayer films the molecules lie flat on the surface but still have a considerable inter-ring twist of 30 degrees -40 degrees , similar to the gas-phase conformation. In the saturated monolayer film the second half of the molecules is side-tilted by an angle of less than 66 degrees with respect to the surface. This arrangement is already similar to that in bulk net planes of thicker films parallel to the surface, that is, the 4P(211) and 6P(21-3) planes, respectively. 相似文献
182.
It has been shown that the “internal” isotope distribution within a given molecular species at the natural abundance level is accessible by a new method, SNIF-NMR, which is based on deuterium NMR. Relative internal factors, Ri/j,have been defined which enable the isotope content of a given site, i, to be compared to that of another molecular site, j, taken as the reference. Several referencing methods intended to provide direct access to relative , Ti , and , (D/H)i , site-specific parameters, are now discussed from both the theoretical and the experimental points of view. In the , which involves a time-consuming chemical transformation of the sample, the risk exists of more or leas systematic errors resulting from discriminating fractionation effects. However this technique offers, conversely, an interesting way of investigating kinetic isotope effects without the need for specific labelling. In spite of its lower spectral precision the has the advantage of being fast and less sensitive to systematic errois and may be used for direct rough routine determinations of the site-specific isotope contents. More precise results can be obtained, at the price of contaminating the sample, when an is added and signal heights are used, remembering however that the intensity parameters then have no strict physical meaning in terms of absolute isotope contents. The site-specific parameters, Ti and (D/H)i thus accessible, provide new information on the mechanisms of the fractionation effects occurring in natural conditions and examples are considered. 相似文献
183.
A novel Ugi-five-centre-four-component reaction (U-5C-4CR) of aldehydes, primary amines, trimethylsilylazide and 2-isocyanoethyltosylate yielding tetrazolopiperazine building blocks is described. 相似文献
184.
Tin dioxide SnO2−δ is a pronounced n-type electron conductor due to its oxygen deficiency. This study investigates the rate of chemical diffusion of oxygen in SnO2−δ single crystals, which is a crucial step in the overall stoichiometry change of the material. The chemical diffusion coefficient Dδ was determined from conductivity- and EPR-relaxation methods. The temperature dependence was found to be . The dependence on crystal orientation, dopant content and oxygen partial pressure was below experimental error. The latter observation leads to the conclusion that the chemical diffusion coefficient is close to the diffusion coefficient of oxygen vacancies. Along with the relaxation process resulting from the chemical diffusion of oxygen, additional processes were observed. One of these was attributed to complications in the defect chemistry of the material. The relevance of the results for the kinetics of drift processes of Taguchi sensors is discussed. 相似文献
185.
186.
Ignacio Alfonso Covadonga Astorga Vicente Gotor 《Journal of inclusion phenomena and macrocyclic chemistry》2005,53(1-2):131-137
Electrospray ionization mass espectrometry (ESI-MS) has been used for the study of a cyclam derivative noncovalent interactions.
At acidic pH, diprotonated macrocycle bound to different anionic species were observed. The selectivity shown by competitive
experiments is rationalized with the help of semiempirical theoretical calculations. At basic pH, the base peak corresponded
to the macrocycle-alkaline metal complexes, and again competition experiments showed different binding strength. Finally,
experiments carried out in the presence of transition metal salts allowed the detection of the complexes present in the mixture
and revealed their different kinetic behavior. 相似文献
187.
Bernd GüNTHER 《中国科学B辑(英文版)》2007,50(6)
The interaction between stabilizers and nanoparticles is one of the important factors to prepare stable magnetic fluids. The magnetic nano-size Fe3O4 core with single domain and the average grain size around 8-12 nm were prepared by chemical precipitation method. The O/Fe molar ratio of the particle surface was measured by X-ray photoelectron spectroscopy (XPS). The heat effects of stabilizers ad- sorption on nanoparticles were measured by solution calorimetry. The excess amount of oxygen was possibly the result of the hydroxygen formed on the surface of the nanoparticles. The heat effects showed that compounds containing carboxyl groups can be adsorbed chemically on magnetite by forming chemical bonds. The other stabilizers involving NH-groups, such as polyethylene-imine, can be adsorbed physically. The exothermic value is about half of the former case. 相似文献
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