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31.
Hans Beat Bürgi Hermann Gehrer Peter Strickler Fritz Karl Winkler 《Helvetica chimica acta》1976,59(7):2558-2565
Crystals of the title compound are triclinic, a = 27.87 Å, b = 10.77 Å, c = 12.94 Å, α 73.1°, β 116.1°, γ 120.0°, space group P1 . The structure consists of octanuclear ions: Eight Cd(II) ions are found at the corners of a distorted cube, the center of the cube is occupied by an iodide, the twelve thioglycolate sulfur atoms bridge the twelve edges of the cube thereby forming a distorted icosahedron. Cadmium ions are either five or seven coordinate. The phase problem for this structure was solved using a combination of very high and very low E-values. 相似文献
32.
On addition, at neutral reaction, of increasing amounts of AlCl3 solutions to 0.005 m Na-silicate solutions, in which the silicate anions are monomeric, amorphous, almost Na+-free precipitates are formed being at first characterised by a higher atomic Al:Si ratio than the total Al:Si mixing ratio. With increasing Al:Si addition, the Al:Si ratio of the precipitates increases until — at a 3:1 ratio in both the liquid and the solid phase — a definite, “saturated” compound, {[(OH)2AlO]3SiOH · aq}, is formed. In this compound the silicate anions are monomeric and not condensable at room temperature. This is valid, too, for precipitates from Al:Si > 3 which contain, besides the “saturated” compound, free Al hydroxide. The first-mentioned precipitates with Al:Si < 3, however, contain polymeric Si units which easily condense to more high-polymeric silicate anions. 相似文献
33.
We evaluate the force-length relation for short model chains. It is shown that this relation is markedly different when evaluated for static and dynamic model chains with rigid segments. The relation also differs for chains with rigid segments when they are isolated and coupled to a canonical heatbath, respectively. Furthermore, it is derived that the variation of the masses along the chain only has a small influence on the force-length relation. On the other hand, restricting the motion of the chain by walls perpendicular to the chain extension has a pronounced effect. We especially find that in this situation the chain has a finite equilibrium length.Dedicated to Professor W. Pechhold on the occasion of his 60th birthday 相似文献
34.
Knippenberg S Nixon KL Mackenzie-Ross H Brunger MJ Wang F Deleuze MS François JP Winkler DA 《The journal of physical chemistry. A》2005,109(41):9324-9340
Results of a study of the valence electronic structure of norbornene (C(7)H(10)), up to binding energies of 30 eV, are reported. Experimental electron momentum spectroscopy (EMS) and theoretical Green's function and density functional theory approaches were utilized in this investigation. A stringent comparison between the electron momentum spectroscopy and theoretical orbital momentum distributions found that, among the tested models, the combination of the Becke-Perdew functional and a polarized valence basis set of triple-zeta quality provides the best representation of the electron momentum distributions for all 19 valence orbitals of norbornene. This experimentally validated model was then used to extract other molecular properties of norbornene (geometry, infrared spectrum). When these calculated properties are compared to corresponding results from independent measurements, reasonable agreement is typically found. Due to the improved energy resolution, EMS is now at a stage to very finely image the effective topology of molecular orbitals at varying distances from the molecular center, and the way the individual atomic components interact with each other, often in excellent agreement with theory. This will be demonstrated here. Green's Function calculations employing the third-order algebraic diagrammatic construction scheme indicate that the orbital picture of ionization breaks down at binding energies larger than about 22 eV. Despite this complication, they enable insights within 0.2 eV accuracy into the available ultraviolet emission and newly presented (e,2e) ionization spectra. Finally, limitations inherent to calculations of momentum distributions based on Kohn-Sham orbitals and employing the vertical depiction of ionization processes are emphasized, in a formal discussion of EMS cross sections employing Dyson orbitals. 相似文献
35.
Raimund Winkler 《Fresenius' Journal of Analytical Chemistry》1973,267(4):261-266
Zusammenfassung Eisen-55 wurde in Neuherberg bei München seit März 1970 in monatlich gesammelten Luftstaubproben und seit Januar 1971 in Monatsniederschlagsproben bestimmt. Nach dem Veraschen der Proben wurde Eisen durch Extraktion' mit Di-iso-propyläther abgetrennt. Zur weiteren Entfernung störender Radionuklide des Fallouts wurde eine Ionenaustauschertrennung angeschlossen. Nach der elektrolytischen Abscheidung des Eisens auf Kupferplättchen wurden die Röntgenspektren mit einem Proportionalzähler sowie einem Si(Li)-Detektor aufgenommen.Die mittlere spezifische Luftaktivität betrug in Neuherberg 1,0 fCi/m3 im Jahr 1970 (ab März), 1,2 fCi/m3 im Jahr 1971 und 0,36 fCi/m3 im Jahr 1972. Die dem Boden durch den Niederschlag zugeführte Aktivität wurde zu 697 pCi/m2 · Jahr für 1971 und 178 pCi/m2 · Jahr für 1972 bestimmt.Vortrag anläßlich der Tagung Spurenanalyse, 2. bis 5. April 1973 in Erlangen. 相似文献
36.
To explore tertiary contact formation in alpha-synuclein, a natively unfolded protein implicated in Parkinson's disease, we have measured the rates of reaction between a powerful electron donor, the tryptophan (W) triplet excited state, and an acceptor, 3-nitro-tyrosine (Y(NO2)) in six different variants, probing loop sizes between 15 and 132 residues. Electron transfer rates decrease with loop size with the fastest contact time of 140 ns for the N-terminal pair and the slowest of 1.2 mus for the N- to C-terminal pair. Diffusion coefficients ranging from approximately 2 x 10-6 to approximately 10-5 cm2 s-1 were extracted from simultaneous fits of the W to Y(NO2) electron (triplet excited state) and energy transfer (singlet excited state) kinetics. 相似文献
37.
The spatial relaxation of electrons to homogeneous states under the action of space-independent electric fields is investigated
in helium, krypton, and N2 plasmas for various electric field strengths. These investigations are based on a new method recently developed for solving
the one-dimensional inhomogeneous electron Boltzmann equation in weakly ionized, collision-dominated plasmas. Elastic as well
as conservative inelastic collisions of electrons with gas atoms have been included in the kinetic treatment. The spatial
relaxation is caused by an imposed direct disturbance in the velocity distribution of the electrons on a spatial boundary.
A pronounced dependence of the relaxation structure and the resultant relaxation length on the atomic data of the electron
collision processes in different gases has been found. Furthermore the relaxation process sensitively depends on the electric
field strength in the region of medium field values. 相似文献
38.
Fazil O. Gülaar Franois Mermound F. Johann Winkler Armand Vuchs 《Helvetica chimica acta》1984,67(2):488-501
Ammonia chemical ionization (CI) mass spectra of various open-chain, cyclic and unsaturated C5- to C10-alcohols were obtained at source temperatures ranging from 60° to 250°C. The reactivity of the ammonia adduct ion MNH and its fragmentation channels are characteristic for substrate structure. Although strongly temperature-dependent, the spectra give nevertheless information on the OH-group environment as well as on the C-skeleton at any source temperature. Primary, secondary and tertiary alcohols as well as allylic and simple olefinic alcohols can be distinguished by their spectra, which show ammonium adduct ions [MNH4]+, adduct dehydrogenation ions [MNH4-H2], ammonium substitution ions [MNH4-H2O]+ and [M-OH]+-ions as the main characteristic peaks. Moreover, konfigurational assignments of stereoisomeric alcohols are possible for larger substrate-size and source-temperature ranges than with isobutane CI mass spectrometry. Homologous M NH-ions show molecular-size control of fragmentation and linear MNH-ions are less stable than branched isomers due to incomplete energy randomization. 相似文献
39.
In Arbuzov-type reactions CFnCl3?nSCl reacts with ROPCl2 (R = CH3, C2H5) to give CFnCl3?nSP(O)Cl2 (n = 3,2,1,0). The corresponding reaction with CF3SeX (X = Cl, Br) produces CF3SeP(O)Cl2 in good yields only in the presence of catalysts such as SbCl5 or BCl3. Reactions between P4 and the sulfenylchlorides produce (CFnCl3?nS)xPCl3?n (n = 3,2,1 and x = 1,2). On heating CFn′ Cl3?n′ SP(O)Cl2 (n′ = 2,1,0) decompose to P(O)Cl3 and SCFn′ Cl2?n′. During this process fluorination of P(O)Cl3 to P(O)F3 by SCF2 is observed. A Cl/Br exchange between CFnCl3?nSP(O)Cl2 (n = 3,2) and PBr3 was proved 19F? and 31P-NMR-spectroscopically.Chemical and physical properties of the newly synthesized compounds will be discussed. 相似文献
40.
Miller JE Grădinaru C Crane BR Di Bilio AJ Wehbi WA Un S Winkler JR Gray HB 《Journal of the American Chemical Society》2003,125(47):14220-14221
Near-UV irradiation of structurally characterized [Re(I)(CO)3(1,10-phenanthroline)(Q107H)](W48F/Y72F/H83Q/Y108W)AzM(II) [Az = Pseudomonas aeruginosa azurin, M = Cu, Zn]/[Co(NH3)5Cl]Cl2 produces a tryptophan radical (W108*) with unprecedented kinetic stability. After rapid formation (k = 2.8 x 106 s-1), the radical persists for more than 5 h at room temperature in the folded ReAzM(II) structure. The absorption spectrum of ReAz(W108*)M(II) exhibits maxima at 512 and 536 nm. Oxidation of K4[Mo(CN)8] by ReAz(W108*)Zn(II) places the W108*/W108 reduction potential in the protein above 0.8 V vs NHE. 相似文献