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61.
The N.M.R. Knight shift depends upon the conduction electron density at the nucleus under observation. An interpretation of its absolute magnitude in liquid metals cannot be undertaken in terms of a pseudopotential formulation, but relative changes of shift with some parameter such as temperature, volume or alloy composition can be investigated. Knight shift changes with concentration have been measured for a series of binary liquid alloys. Since application of a pseudopotential treatment is simplest when the two constituents have the same valency, the alloys chosen have mostly been of this type, e.g. In-Ga, In-Tl, Sn-Pb, Sb-Bi. Although theory predicts the correct qualitative behaviour of the shift changes, the precise theoretical predictions are very sensitive to details of both the pseudopotentials and the liquid structure factor. In the case of In-Sn and In-Pb, where the shifts of both constituents decrease with increasing indium content for In-Sn, but increase for In-Pb, the difference between the pseudopotentials of tin and lead does not appear to be sufficient to explain the observed differences in changes of shift. 相似文献
62.
63.
Aurélie Rolle Helen Seymour Pascal Roussel Annick Rubbens Rose-Noëlle Vannier 《Ionics》2008,14(6):477-482
The Ba2In2 − x
Sn
x
O5 + x/2 solid solution was confirmed up to x = 1 by solid-state reaction. X-ray diffraction at room and at elevated temperatures, Raman scattering and impedance spectroscopy
were used to characterise the samples. The structure refinement of the composition x = 0.1 from neutron diffraction data reveals that tin is preferentially located in the tetrahedral layers of the brownmillerite.
Paper presented at the 11th EuroConference on the Science and Technology of Ionics, Batz-sur-Mer, Sept. 9–15, 2007 相似文献
64.
Let G be a digraph (without parallel edges) such that every directed cycle has length at least four; let β(G) denote the size of the smallest subset X ? E(G) such that G?X has no directed cycles, and let γ(G) be the number of unordered pairs {u, v} of vertices such that u, v are nonadjacent in G. It is easy to see that if γ(G) = 0 then β(G) = 0; what can we say about β(G) if γ(G) is bounded?
We prove that in general β(G) ≤ γ(G). We conjecture that in fact β(G) ≤ ½γ(G) (this would be best possible if true), and prove this conjecture in two special cases:
相似文献
- when V(G) is the union of two cliques
- when the vertices of G can be arranged in a circle such that if distinct u, v, w are in clockwise order and uw is a (directed) edge, then so are both uv, vw.
65.
Koehler JJ Zhao J Jedlicka SS Porterfield DM Rickus JL 《The journal of physical chemistry. B》2008,112(47):15086-15093
Nitric oxide (NO) is an important cell-signaling molecule whose role in a variety of cellular processes such as differentiation and apoptosis depends strongly on its concentration and flux levels. This work describes and characterizes a novel nitric oxide releasing nanocomposite, capable of photostimulated NO flux that can by dynamically modulated in within a range of biological levels. This material mimics the common compartmentalization strategies used by living cells to achieve its novel features. The material is constructed by encapsulating a photosensitive nitric oxide donor within lipid vesicles with an average diameter of 150 nm. The vesicles are then doped into the interstitial liquid phase of a solid porous silica matrix, which has previously demonstrated biological compatibility and capabilities as a growth surface for mammalian cells. Stimulation by a light source produces a step increase in NO concentration within seconds. The NO flux at the surface of the material is measured to be 14 pmol-cm(-2) sec(-1) using a NO selective self-referencing amperometric microsensor. The NO concentration profile decreases with distance perpendicular to the surface as expected for diffusion from a surface through an aqueous environment. A pattern of one minute light pulses produced uniform pulses of increased NO concentration of one minute duration. A linear relationship exists between NO surface concentration and photon flux, and this relationship can be used to tune the material response. 相似文献
66.
Kevin Doyle Maxine Roberts Jenna Harvey Richard Hewer Matthias Zebisch Victor Rangel Meigang Gu Yiming Wu Lichao Yang Mark Carlton Lee Dawson Roland Bürli 《Helvetica chimica acta》2023,106(9):e202300080
Brain concentrations of nicotinamide adenine dinucleotide (NAD+), an important cellular co-factor, tend to decrease with age and in neurodegeneration. As the NADase cluster of differentiation 38 (CD38) significantly contributes to NAD+ consumption, we reasoned that CD38 inhibition may be of therapeutic value for CNS disorders. The new pyrazole compound was designed based on a known CD38 inhibitor and showed good inhibitory potency. Several attempts to co-crystallise this pyrazole with CD38 and cyclic adenosine diphosphate ribose (cADPR) culminated in a high-resolution X-ray structure, in which the pyrazolyl group in the new compound formed a covalent bond with one of the ribosyl units of cADPR. This reaction proceeded under retention of configuration and resulted in a neutral ribosyl-pyrazole conjugate that is embedded within the active site of the enzyme. An analysis of this structural complex gave rise to design principles that enabled the preparation of more potent CD38 inhibitors with drug-like properties. 相似文献
67.
Yang J Welby JL Meyerhoff ME 《Langmuir : the ACS journal of surfaces and colloids》2008,24(18):10265-10272
A universal nitric oxide (NO) generating surface is assembled via Layer-by-Layer (LbL) deposition of sodium alginate (Alg) and organoselenium modified polyethyleneimine (SePEI) on quartz and polymeric substrates. The immobilized SePEI species is capable of catalytically decomposing S-nitrosothiol species (RSNO) to NO in the presence of thiol reducing agents (e.g., glutathione, cysteine, etc.). The stepwise buildup of the multilayer films is monitored by UV-vis spectroscopy, SEM and surface contact angle measurements. X-ray photoelectron spectroscopy is used to study the stoichiometry between the polyanion and polycation, and also the presence of Se in the catalytic LbL film. A reductive annealing process is necessary to improve the stability of freshly coated multilayer films via chain rearrangement. Chemiluminescence measurements illustrate the ability of the LbL films to generate NO from S-nitrosoglutathione (GSNO) in the presence of glutathione (GSH). Enhanced NO fluxes can be achieved by increasing the number of catalytic (SePEI/Alg) bilayers coated on the substrates. Nitric oxide generation is observed even after prolonged contact with sheep whole blood. Preliminary applications of this LbL on silicone rubber tubings and polyurethane catheters reveal similar NO generation behavior from these biomedical grade polymeric substrates. 相似文献
68.
Diaminohydroxymethyl (1) and triaminomethyl (2) radicals were generated by femtosecond collisional electron transfer to their corresponding cations (1+ and 2+, respectively) and characterized by neutralization-reionization mass spectrometry and ab initio/RRKM calculations at correlated levels of theory up to CCSD(T)/aug-cc-pVTZ. Ion 1+ was generated by gas-phase protonation of urea which was predicted to occur preferentially at the carbonyl oxygen with the 298 K proton affinity that was calculated as PA = 875 kJ mol-1. Upon formation, radical 1 gains vibrational excitation through Franck-Condon effects and rapidly dissociates by loss of a hydrogen atom, so that no survivor ions are observed after reionization. Two conformers of 1, syn-1 and anti-1, were found computationally as local energy minima that interconverted rapidly by inversion at one of the amine groups with a <7 kJ mol-1 barrier. The lowest energy dissociation of radical 1 was loss of the hydroxyl hydrogen atom from anti-1 with ETS = 65 kJ mol-1. The other dissociation pathways of 1 were a hydroxyl hydrogen migration to an amine group followed by dissociation to H2N-C=O* and NH3. Ion 2+ was generated by protonation of gas-phase guanidine with a PA = 985 kJ mol-1. Electron transfer to 2+ was accompanied by large Franck-Condon effects that caused complete dissociation of radical 2 by loss of an H atom on the experimental time scale of 4 mus. Radicals 1 and 2 were calculated to have extremely low ionization energies, 4.75 and 4.29 eV, respectively, which belong to the lowest among organic molecules and bracket the ionization energy of atomic potassium (4.34 eV). The stabilities of amino group containing methyl radicals, *CH2NH2, *CH(NH2)2, and 2, were calculated from isodesmic hydrogen atom exchange with methane. The pi-donating NH2 groups were found to increase the stability of the substituted methyl radicals, but the stabilities did not correlate with the radical ionization energies. 相似文献
70.
Let Σ be a (connected) surface of “complexity” κ; that is, Σ may be obtained from a sphere by adding either ½κ handles or κ crosscaps. Let ρ ≥ 0 be an integer, and let Γ be a “ρ-representative drawing” in Σ; that is, a drawing of a graph in Σ so that every simple closed curve in Σ that meets the drawing in < ρ points bounds a disc in Σ. Now let Γ′ be another drawing, in another surface Σ′ of complexity κ′, so that Γ and Γ′ are isomorphic as abstract graphs. We prove that. (i) If ρ ≥ 100 log κ/ log log κ (or ρ ≥ 100 if κ ≤ 2) then κ′ ≥ κ, and if κ′ = κ and Γ is simple and 3-connected there is a homeomorphism from Σ to Σ′ taking Γ to Γ′, and. (ii) if Γ is simple and 3-connected and Γ′ is 3-representative, and ρ ≥ min (320, 5 log κ), then either there is a homeomorphism from Σ to Σ′ taking Γ to Γ′, or κ′ ≥ κ + 10-4 ρ2. © 1996 John Wiley & Sons, Inc. 相似文献