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101.
102.
Häussermann U 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(7):1471-1478
The Group 15 elements P, As, Sb, and Bi all have layered structures consisting of six-membered rings under ambient conditions and attain the body-centered cubic (bcc) structure at the highest pressures applied. In the intermediate pressure region, however, phosphorus and its heavier congeners behave profoundly differently. In this region P first attains the open packed simple cubic (sc) structure for a wide range of pressures and then transforms into the rarely observed simple hexagonal (sh) structure. For the heavier congeners complex, incommensurately modulated host-guest structures emerge as intermediate pressure structures. We investigated the high-pressure behavior of P and As by ab initio density functional calculations in which pseudopotentials and a plane wave basis set were employed. The incommensurately modulated high-pressure structure of As was approximated by a supercell. Our calculations reproduced the experimentally established pressure stability ranges of the sc and sh structures for P and the host-guest structure for As very well. We found that the sc and especially the sh structure are decisively stabilized by the admixture of d states in the occupied levels of the electronic structure. This admixture releases s-s antibonding states above the Fermi level (s-d mixing). With pressure, s-d mixing increases rapidly for P, whereas it remains at a low level for As. As a consequence, the band energy contribution to the total energy determines the structural stability for P in the intermediate pressure region, giving rise to simple packed structures. On the other hand, in the intermediate pressure region of the heavier Group 15 elements, a delicate interplay between the electrostatic Madelung energy and the band energy leads to the formation of complex structures. 相似文献
103.
Sergii Afonin Alexander Frey Sybille Bayerl Dahlia Fischer Parvesh Wadhwani Sevil Weinkauf Anne S Ulrich 《Chemphyschem》2006,7(10):2134-2142
Cell-penetrating peptides (CPPs) are short polycationic sequences that can translocate into cells without disintegrating the plasma membrane. CPPs are useful tools for delivering cargo, but their molecular mechanism of crossing the lipid bilayer remains unclear. Here we study the interaction of the HIV-derived CPP TAT (48-60) with model membranes by solid-state NMR spectroscopy and electron microscopy. The peptide induces a pronounced isotropic (31)P NMR signal in zwitterionic DMPC, but not in anionic DMPG bilayers. Octaarginine and to a lesser extent octalysine have the same effect, in contrast to other cationic amphiphilic membrane-active peptides. The observed non-lamellar lipid morphology is attributed to specific interactions of polycationic peptides with phosphocholine head groups, rather than to electrostatic interactions. Freeze-fracture electron microscopy indicates that TAT(48-60) induces the formation of rodlike, presumably inverted micelles in DMPC, which may represent intermediates during the translocation across eukaryotic membranes. 相似文献
104.
Margaret M. Harding Ulrich Koert Jean-Marie Lehn Annie Marquis-Rigault Claude Piguet Jay Siegel 《Helvetica chimica acta》1991,74(3):594-610
A general strategy for the synthesis of oligobipyridine ligands 2 – 5 containing from two to five 2,2′-bipyridine subunits, for helical metal complexes is described (sec Scheme). Both the unsubstituted parent strands ( a series) as well as their derivatives bearing fester or amide functions in the 4,4′-positions of the bipyridine moieties ( b – d series) have been obtained. 相似文献
105.
The selection of different diimines 4 a-c by alkaline earth ions from a virtual combinatorial library (VCL) is described. The products were stabilized by reduction to the diamines 6 a-c; this allowed easy analysis. The library can be directed toward different target molecules 6 a-c upon addition of alkaline earth ions with different radii. Competition experiments show the possibility of synthesizing the macrocycles 6 a, 6 b, and 6 c simultaneously when using Mg(2+), Ca(2+), and Ba(2+) as template ions. The scope of this thermodynamically controlled, reversible approach for macrocycle syntheses is illustrated. 相似文献
106.
Ulrich Dierkes 《Inventiones Mathematicae》1995,122(1):453-473
We here prove pointwise curvature estimates for minimal hypersurfaces in singular spaces, using the integral curvature estimate and a generalized Simons inequality which were established recently. A further basic ingredient is a new Sobolev type inequality for stationary hypersurfaces.Oblatum 19-IX-1994This research was supported by the Deutsche Forschungsgemeinschaft through a Heisenberg award. Part of the work described here was carried out during visits to Dipartimento Matematica Applicata, University of Firenze and Department of Mathematics, Stanford University. The author would like to express his gratitude to both institutions for their kind hospitality and support. Also it is a pleasure to thank the referee for his useful comments concerning the formulation of the main theorem. 相似文献
107.
Ulrich Kohlenbach 《Archive for Mathematical Logic》1995,34(4):279-283
It is well-known (due to C. Parsons) that the extension of primitive recursive arithmeticPRA by first-order predicate logic and the rule of
2
0
-induction
2
0
-IR is
2
0
-conservative overPRA. We show that this is no longer true in the presence of function quantifiers and quantifier-free choice for numbersAC
0,0-qf. More precisely we show that :=PRA
2 +
2
0
-IR+AC
0,0-qf proves the totality of the Ackermann function, wherePRA
2 is the extension ofPRA by number and function quantifiers and
2
0
-IR may contain function parameters.This is true even forPRA
2 +
1
0
-IR+
2
0
-IR
–+AC
0,0-qf, where
2
0
-IR
– is the restriction of
2
0
-IR without function parameters.I am grateful to an anonymous referee whose suggestions led to an improved discussion of our results 相似文献
108.
A Ginzburg-Landau model with a scalar and a vector order parameter, which describe the concentration and orientation of the amphiphile, respectively, is used to study the phase diagram and the scattering intensity of binary amphiphilic systems. With increasing amphiphile concentration, the calculated phase diagram shows the typical sequence of ordered phases observed experimentally, that is micellar liquid cubic micellar hexagonal lamellar cubic bicontinuous invers hexagonal. The scattering intensity in the homogeneous phase is calculated in the oneloop approximation. In the vicinity of a phase transition to an ordered phase, the intensity is found to show a 1/q behavior for not too small wave vectorsq, followed by a small peak, and a 1/q
2 decay for large wave vectors, in agreement with experimental observations in theL
3-(or sponge-)phase.Dedicated to Prof. H. Wagner on the occasion of his 60th birthday 相似文献
109.
Thin PtSi films can be grown by evaporating Pt on Si(100) at RT and subsequent annealing of the system at 600–700 K. Contaminants like oxygen are known to have a strong influence on this reaction. In the present study we concentrate on the effect of oxygen partial pressure during the annealing on the silicide growth process. Under proper vacuum conditions annealing at 500 K leads to a homogeneous Pt2Si film which reacts around 600 K completely to PtSi. A substantial oxygen partial pressure ( 0.1 mbar) in contrast results in an incomplete reaction in the same temperature range: unreacted platinum remains at the surface separated from the silicide by an oxygen enriched layer.Presented at the Seminar on Secondary Electrons in Electron Spectroscopy, Microscopy, and Microanalysis, Chlum (The Czech Republic), 21–24 September, 1993.This work was supported by Deutsche Forschungsgemeinschaft (DFG) through Sonderforschungsbereich 292.We thank Dr. W. Platz (Deutsche Aerospace AG, Ottobrunn) for providing us with Pt evaporated Si-wafers and Th. Hierl (Lehrstuhl für Angewandte Physik, University of Erlangen-Nürnberg), who performed the RBS measurements for AES calibration. 相似文献
110.
Rafael Abela Christopher Baines Xavier Donath Dierk Herlach David Maden Ivan D. Reid Dieter Renker György Solt Ulrich Zimmermann 《Hyperfine Interactions》1994,87(1):1105-1110
TheSR Facility Instruments presently available at PSI and the envisaged medium- and long-term developments are presented. The plans focus on further upgrades of the existing instruments and the development of new techniques using the very high fluxes becoming available at PSI, in particular the setup of a beamline with a fast kicker for muons on request (MORE) and the development of very low energy muon beams. 相似文献