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21.
Let A(X) be the space defined by Waldhausen whose homotopy groups define the algebraic K-groups of the space X and let
. Here (X) denotes the free loop space of X and Q denotes the functor . For X = Y, the suspension of a connected space Y, we shall prove that the homotopy fibers Ã(X), B(X) of the maps A(X) A (point), B(X) B (point) are equivalent as infinite loop spaces. 相似文献
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25.
The effectivity of solvents as electron pair donors 总被引:1,自引:0,他引:1
Y. Marcus 《Journal of solution chemistry》1984,13(9):599-624
The effectivity of solvents as electron pair donors, their donicity as expressed by their donor numbers DN, is reexamined. The linear dependence of the enthalpy and the Gibbs free energy for the reaction of donor solvents with antimony pentachloride is affirmed. Extension of the DN scale by other measured quantities, via their linear correlations for sets of solvents where both kinds of data are known is applied to Drago's E-C scale, Kamlet's scale, and Koppel's B scale. This extension, added to previous extensions employing Selbin's DI, II and Popov's 23Na, produces a DN scale for 170 solvents. The relation of DN measured for isolated solvent molecules in 1,2-dichloroethane to DN values measured for bulk solvents is examined by means of the scaled particle theory and solute-solvent interaction terms. A scale of normalized donor numbers DN
N
is presented. These values are practically the same as the scale, and for those solvents for which DN values are presented here and values are lacking, they can serve in their place for those preferring to use the scale for donor solvents. 相似文献
26.
Pradier CM Rubio C Poleunis C Bertrand P Marcus P Compère C 《The journal of physical chemistry. B》2005,109(19):9540-9549
Adhesion of bacterial strains on solid substrates is likely related to the properties of the outer shell of the micro-organisms. Aiming at a better understanding and control of the biofilm formation in seawater, the surface chemical composition of three marine bacterial strains was investigated by combining Fourier transform IR spectroscopy, X-ray photoelectron spectroscopy (XPS), and time-of-flight secondary-ion mass spectrometry (ToF-SIMS). The D41 strain surface showed evidence of proteins, as deduced from the NH2 and NCO XPS and ToF-SIMS fingerprints; this strain was found to adhere to stainless steel, glass, or Teflon surfaces in a much higher quantity (2 orders of magnitude) than the two other ones, DA and D01. The latter are either enriched in COOH or sulfates, and this makes them more hydrophilic and less adherent to all substrates. Correlations with physicochemical properties and adhesion seem to demonstrate the role of the external layer composition, in particular the role of proteins more than that of hydrophobicity, on their adhesion abilities. 相似文献
27.
Minko S Müller M Motornov M Nitschke M Grundke K Stamm M 《Journal of the American Chemical Society》2003,125(13):3896-3900
We report a route to fabricate two-level structured self-adaptive surfaces (SAS) of polymer materials. The first level of structure is built by a rough polymer film that consists of needlelike structures of micrometer size. The second level of structure is formed by the nanoscopic self-assembled domains of a demixed polymer brush irreversibly grafted onto the needles. By exposing the surface to solvents that are selective to one of the components of the brush, we reversibly tune the surface properties. The large-scale surface structure amplifies the response and enables us to control wettability, adhesion, and chemical composition of the surface over a wide range. 相似文献
28.
The perturbed-chain statistical associating fluid theory (PC-SAFT) is studied for a wide range of temperature, T, pressure, p, and (effective) chain length, m, to establish the generic phase diagram of polymers according to this theory. In addition to the expected gas-liquid coexistence, two additional phase separations are found, termed "gas-gas" equilibrium (at very low densities) and "liquid-liquid" equilibrium (at densities where the system is expected to be solid already). These phase separations imply that in one-component polymer systems three critical points occur, as well as equilibria of three fluid phases at triple points. However, Monte Carlo simulations of the corresponding system yield no trace of the gas-gas and liquid-liquid equilibria, and we conclude that the latter are just artefacts of the PC-SAFT approach. Using PC-SAFT to correlate data for polybutadiene melts, we suggest that discrepancies in modelling the polymer density at ambient temperature and high pressure can be related to the presumably artificial liquid-liquid phase separation at lower temperatures. Thus, particular care is needed in engineering applications of the PC-SAFT theory that aims at predicting properties of macromolecular materials. 相似文献
29.
Westerlund F Wilhelmsson LM Nordén B Lincoln P 《Journal of the American Chemical Society》2003,125(13):3773-3779
Detergent sequestration using micelles as a hydrophobic sink for dissociated drug molecules is an established technique for determination of dissociation rates. The anionic surfactant molecules are generally assumed not to interact with the anionic DNA and thereby not to affect the rate of dissociation. By contrast, we here demonstrate that the surfactant molecules sodium dodecyl sulfate (SDS), sodium decyl sulfate, and sodium octyl sulfate all induce substantial rate enhancements of the dissociation of intercalators from DNA. Four different cationic DNA intercalators are studied with respect to surfactant-induced dissociation. Except for the smallest intercalator, ethidium, the dissociation rate constants increase monotonically with surfactant concentration both below cmc and (more strongly) above cmc, much more than expected from electrostatic effects of increased counterion concentration. The rate enhancement, most pronounced for the bulky, multicationic, hydrophobic DNA ligands in this study, indicates a reduction of the activation energy for the ligand to pass out from a deeply penetrating intercalation site of DNA. The discovery that surfactants enhance the rate of dissociation of cationic DNA-intercalators implies that rate constants previously determined by micelle-sequestered dissociation may have been overestimated. As an alternative, more reliable method, we suggest instead the addition of excess of dummy DNA as an absorbent for dissociated ligand. 相似文献
30.
Ionizable residues play important roles in protein structure and activity, and proton binding is a valuable reporter of electrostatic interactions in these systems. We use molecular dynamics free energy simulations (MDFE) to compute proton pKa shifts, relative to a model compound in solution, for three aspartate side chains in two proteins. Simulations with explicit solvent and with an implicit, dielectric continuum solvent are reported. The implicit solvent simulations use the generalized Born (GB) model, which provides an approximate, analytical solution to Poisson's equation. With explicit solvent, the direction of the pKa shifts is correct in all three cases with one force field (AMBER) and in two out of three cases with another (CHARMM). For two aspartates, the dielectric response to ionization is found to be linear, even though the separate protein and solvent responses can be nonlinear. For thioredoxin Asp26, nonlinearity arises from the presence of two substates that correspond to the two possible orientations of the protonated carboxylate. For this side chain, which is partly buried and has a large pKa upshift, very long simulations are needed to correctly sample several slow degrees of freedom that reorganize in response to the ionization. Thus, nearby Lys57 rotates to form a salt bridge and becomes buried, while three waters intercalate along the opposite edge of Asp26. Such strong and anisotropic reorganization is very difficult to predict with Poisson-Boltzmann methods that only consider electrostatic interactions and employ a single protein structure. In contrast, MDFE with a GB dielectric continuum solvent, used for the first time for pKa calculations, can describe protein reorganization accurately and gives encouraging agreement with experiment and with the explicit solvent simulations. 相似文献