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131.
132.
The differences in the extent of electron-attachment reactions between thermal electrons and selected classes of organic molecules with high electron affinities were investigated. The investigations showed that interactions of thermal electrons with nitroaromatic compounds lead to the formation of neutral products with very low electron affinities. By contrast, a number of other analytes with high electron affinities such as polyhalogenated organic compounds, lead to products with high electron affinities. This difference was exploited to differentiate between nitroaromatic and polychlorinated organic compounds with a tandem arrangement consisting of two electron-capture detectors connected in series with an electron-attachment reactor. 相似文献
133.
134.
Maximilian Zieringer Abel Garcia‐Bernabé Dr. Burkhard Costisella Prof. Dr. Heiko Glatz Dr. Willi Bannwarth Prof. Dr. Rainer Haag Prof. Dr. 《Chemphyschem》2010,11(12):2617-2622
This paper describes the behavior of various generations of polyglycerol dendrimers that contain a perfluorinated shell. The aggregation in organic solvents is based on supramolecular fluorous–fluorous interactions, which can be described by means of 19F NMR spectroscopy. In order to study the interaction and aggregation phenomena of dendrimers with perfluorinated shell and perfluoro‐tagged guest molecules we investigated [G3.5]‐dendrimer with a perfluorinated shell in the presence of perfluoro‐tagged disperse red. Noteworthy, the interaction intensities varied in an unexpected manner depending on the equivalents of perfluoro‐tagged guest molecules added to the dendrimers in solution which then formed supramolecular complexes based on fluorous–fluorous interactions. We found that these complexes aggregated around residual air in the solvent to form stable micron‐sized bubbles. Their sizes correlated with the interaction intensities measured for certain dendrimer–guest molecule ratios. Degassing of the solutions led to a quasi phase separation between organic and fluorous phase, whereby the dendrimers formed the fluorous phases. Regassing the sample with air afforded bubbles of the initial size again. 相似文献
135.
136.
Nataliya Chumalo Galyna P. Nychyporuk Rainer Pöttgen Dariusz Kaczorowski 《Journal of solid state chemistry》2010,183(12):2963-2967
The indides Ce7Ni5±xGe3±xIn6 and Pr7Ni5±xGe3±xIn6 were synthesized from the elements by arc-melting of the components. Single crystals were grown via special annealing sequences. Both structures were solved from X-ray single crystal diffraction data: new structure type, P6/m, Z=1, a=11.385(2), c=4.212(1) Å, wR2=0.0640, 634F2 values, 25 variables for Ce7Ni4.73Ge3.27In6 and a=11.355(6), c=4.183(2) Å, wR2=0.0539, 563F2 values, 25 variables for Pr7Ni4.96Ge3.04In6. Both indides show homogeneity ranges through Ni/Ge mixing (M sites). This new structure type can be derived from the AlB2 structure type by a substitution of the Al and B atoms by CeM12 and NiIn6Ce3 polyhedra (tricapped trigonal prism). Magnetic susceptibility measurements on a polycrystalline sample of Ce7Ni5Ge3In6 indicated Curie-Weiss like paramagnetic behavior down to 1.71 K with the effective magnetic moment slightly reduced in relation to the value expected for trivalent cerium ions. No magnetic ordering is evident. 相似文献
137.
Peter Rapta Krzysztof R. Idzik Vladimír Lukeš Rainer Beckert Lothar Dunsch 《Electrochemistry communications》2010,12(4):513-516
The role of the chemical structure in an alternative charge stabilisation and a changing reactivity of star-shaped compounds with a central triazine ring linked to aryl groups like thiophene, furan or ethylenedioxythiophene synthesized by a Stille cross-coupling procedure, is followed by spectroelectrochemical measurements. While cathodic reduction leads to stable anion radicals with a delocalised spin on the central triazine moiety, dimerisation and oligomerisation occurs upon anodic oxidation. The stability of the charged states in the polymer film increased substantially using an EDOT (3,4-ethylenedioxythiophene) side group. The location of the charged states on the molecules has been proved by computations. These star-shaped molecules are excellent model structures for studies of the competition of dimerisation and oligomerisation processes based on the variation of the electron and spin distribution in the molecules. 相似文献
138.
Reinhard Miller James K. Ferri Aliyar Javadi Jürgen Krägel Nenad Mucic Rainer Wüstneck 《Colloid and polymer science》2010,288(9):937-950
The response of interfacial layers to deformations in size and shape depends on their composition. The corresponding main
mechanical quantities are elasticity and viscosity of dilation and shear, respectively. Hence, the interfacial rheology represents
a kind of two-dimensional equivalent to the traditional bulk rheology. Due to growing interest in the quantitative understanding
of foams and emulsions, more works are dedicated to studies on interfacial rheology. This overview presents the theoretical
basis for traditional and recently developed experimental tools and discusses their application to different interfacial systems.
While dilational rheology provides information on the composition of mixed interfacial layers, the shear rheology gives answers
essentially on structures formed at an interface. The most frequently used methods at present are the oscillating drop and
bubble tensiometry methods for dilational deformations and oscillating ring/bicone rheometers for shear deformations. 相似文献
139.
Tae-Soo You Jing-Tai Zhao Rainer Pttgen Walter Schnelle Ulrich Burkhardt Yuri Grin Gordon J. Miller 《Journal of solid state chemistry》2009,182(9):2430-2442
Two isoelectronic series, Eu(Ga1−xTtx)2 (Tt=Si, Ge, 0≤x≤1), have been synthesized and characterized by powder and single-crystal X-ray diffraction, physical property measurements, and electronic structure calculations. In Eu(Ga1−xSix)2, crystal structures vary from the KHg2-type to the AlB2-type, and, finally, the ThSi2-type structure as x increases. The hexagonal AlB2-type structure is identified for compositions 0.18(2)≤x<0.70(2) with Ga and Si atoms statistically distributed in the polyanionic 63 nets. As smaller Si atoms replace Ga atoms while the number of valence electrons increases, the lattice parameters, unit cell volumes, and Ga–Si distances in this phase region decrease significantly. Although aspects of X-ray diffraction results suggest puckering of the 63 nets for the Si-richest example of the AlB2-type Eu(Ga1−xSix)2, the complete experimental evidence remains inconclusive. On the other hand, in Eu(Ga1−xGex)2, six different structural types were observed as x varies. In addition to EuGa2 (KHg2-type; space group Imma) and EuGe2 (own structure type, space group P3¯m1), the ternary phases studied show four different structures: the AlB2-type for Ga-rich compositions; the YPtAs-type structure for EuGaGe; and two new structures, which are intergrowths of the YPtAs-type EuGaGe and EuGe2, for Ge-rich compositions. These two Ge-rich phases include: (1) Eu(Ga0.45(2)Ge0.55(2))2 containing two YPtAs-type motifs of EuGaGe plus one EuGe2 motif; and (2) Eu(Ga0.40(2)Ge0.60(2))2 containing one YPtAs-type motif alternating with a split site at and z=0.4798(2) with ca. 50% site occupancy by Ga and Ge along the c-axis. Magnetic susceptibilities of three Eu(Ga1−xGex)2 compounds display Curie–Weiss behavior above ca. 100 K, and show effective magnetic moments indicative of divalent Eu with a 4f7 electronic configuration, consistent with. X-ray absorption spectra (XAS). Density of states (DOS) and crystal orbital Hamilton population (COHP) analyses, based on first principles electronic structure calculations, rationalize the observed homogeneity ranges of the AlB2-type phases in both systems and the structural variations as a function of Tt content. 相似文献
140.
Tang X Houchins C Lau KC Ng CY Dressler RA Chiu YH Chu TS Han KL 《The Journal of chemical physics》2007,127(16):164318
Time-dependent wave packet quantum scattering (TWQS) calculations are presented for HD(+) (v = 0 - 3;j(0)=1) + He collisions in the center-of-mass collision energy (E(T)) range of 0.0-2.0 eV. The present TWQS approach accounts for Coriolis coupling and uses the ab initio potential energy surface of Palmieri et al. [Mol. Phys. 98, 1839 (2000)]. For a fixed total angular momentum J, the energy dependence of reaction probabilities exhibits quantum resonance structure. The resonances are more pronounced for low J values and for the HeH(+) + D channel than for the HeD(+) + H channel and are particularly prominent near threshold. The quantum effects are no longer discernable in the integral cross sections, which compare closely to quasiclassical trajectory calculations conducted on the same potential energy surface. The integral cross sections also compare well to recent state-selected experimental values over the same reactant and translational energy range. Classical impulsive dynamics and steric arguments can account for the significant isotope effect in favor of the deuteron transfer channel observed for HD(+)(v<3) and low translational energies. At higher reactant energies, angular momentum constraints favor the proton-transfer channel, and isotopic differences in the integral cross sections are no longer significant. The integral cross sections as well as the J dependence of partial cross sections exhibit a significant alignment effect in favor of collisions with the HD(+) rotational angular momentum vector perpendicular to the Jacobi R coordinate. This effect is most pronounced for the proton-transfer channel at low vibrational and translational energies. 相似文献