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191.
Armin C. Schneider Christoph Pasel Michael Luckas Klaus Gerhard Schmidt Jan-Dirk Herbell 《Journal of solution chemistry》2004,33(3):257-273
The single ion activity coefficients of hydrogen and chloride ions in aqueous HCl solutions have been estimated at 25°C at concentrations up to 1 mol-kg–1, using potentiometric measurements with ion-selective electrodes and appropriate calibration procedures. Two methods are described for an internal calibration of the electrodes in the extended Debye–Hückel concentration range. The results are compared to the conventional pH calibration with external buffer solutions. Since the latter calibration method does not account for the liquid junction potential E
J which arises at the reference electrode, the resulting activity coefficients are quite different in HCl solutions of higher concentration. These differences between internal and external calibration decrease significantly, when a correction for E
J is introduced into the conventional pH calibration. Hence, in solutions of higher ionic strength the accuracy of the conventional pH electrode calibration using buffer solutions is very limited, when exact H+ activities are required. The consistency of the results indicates that the liquid junction potentials in the examined systems calculated by the Henderson/Bates approximation are of reasonable precision. 相似文献
192.
Tandem intramolecular silylformylation-allyl(crotyl)silylation reactions have been developed that allow the highly efficient synthesis of polyketide fragments. The substrates are subjected to Rh(I)-catalyzed silylformylation to afford β-(diallyl)silyl aldehydes which undergo spontaneous uncatalyzed allylsilylation. This unusual spontaneous allylsilylation reaction is driven by strain release Lewis acidity, which arises from the ∼95° O-Si-C bond angle in the oxasilacyclopentane product of the silylformylation reaction. The methodology has been developed both for alkene and alkyne substrates, may be used to establish as many as three stereocenters, and has been shown to be amenable to use in an iterative fashion. 相似文献
193.
This paper defines a set of material compatibility constraints for use in order promising mixed integer programs. The constraints always represent a necessary condition for compatibility and, in certain cases, are both necessary and sufficient. The underlying analysis represents incompatibilities using bipartite graphs and applies results from the perfectly matchable subgraph polytope. 相似文献
194.
This paper investigates regression quantiles (RQ) for unstable autoregressive models. The uniform Bahadur representation of the RQ process is obtained. The joint asymptotic distribution of the RQ process is derived in a unified manner for all types of characteristic roots on or outside the unit circle. It involves stochastic integrals in terms of a sequence of independent and identically distributed multivariate Brownian motions with correlated components. The related L-estimator is also discussed. The asymptotic distributions of the RQ and the L-estimator corresponding to the nonstationary componentwise arguments can be transformed into a function of a normal random variable and a sequence of i.i.d. univariate Brownian motions. This is different from the analysis based on the LSE in the literature. As an auxiliary theorem, a weak convergence of a randomly weighted residual empirical process to the stochastic integral of a Kiefer process is established. The results obtained in this paper provide an asymptotic theory for nonstationary time series processes, which can be used to construct robust unit root tests. 相似文献
195.
196.
Classical electrodynamics based on the Maxwell–Born–Infeld field equations coupled with a Hamilton–Jacobi law of point charge motion is partially quantized. The Hamilton–Jacobi phase function is supplemented by a dynamical amplitude field on configuration space. Both together combine into a single complex wave function satisfying a relativistic Klein–Gordon equation that is self-consistently coupled to the evolution equations for the point charges and the electromagnetic fields. Radiation-free stationary states exist. The hydrogen spectrum is discussed in some detail. Upper bounds for Born's “aether constant” are obtained. In the limit of small velocities of and negligible radiation from the point charges, the model reduces to Schrödinger's equation with Coulomb Hamiltonian, coupled with the de Broglie–Bohm guiding equation. 相似文献
197.
We have prepared glucose and cellobiose conjugates at the phenolic 3- and hydroxylic 17-positions of the pure anti-estrogenic compound fulvestrant (ICI 182,780), which has recently been approved in the USA for the treatment of advanced postmenopausal breast cancer. Glycosylation at the 17-position was achieved most effectively using pivaloyl protection of the sugar imidates employed, which we found suppressed the competing transacylation reaction and led to improved yields of the product glycosides. 相似文献
198.
Lakshmi N. Roy Rabindra N. Roy Cole E. Denton Sean R. LeNoue Chandra N. Roy Shahaf Ashkenazi Thomas B. Williams Daniel R. Church Michael S. Fuge Kartik N. Sreepada 《Journal of solution chemistry》2006,35(4):605-624
The values of the second dissociation constant, K
2, and related thermodynamic quantities of the ampholyte bis[(2-hydroxyethyl)amino]acetic acid (BICINE) have been determined at temperatures from 5 to 55 ∘C. The pH values of six equimolal buffer solutions, and four buffer solutions having ionic strengths (I = 0.16 mol⋅kg−1) similar to those in blood plasma, have been evaluated at 12 temperatures from 5 to 55 ∘C using the Bates–Guggenheim convention. The liquid junction potentials (E
j
) between the buffer solutions of BICINE and saturated KCl solution of the calomel electrode at 25 and 37 ∘C have been estimated by measurement with a flowing junction cell. These values of E
j
have been used to ascertain the operational pH values at 25 and 37 ∘C. The pK
2 values at 25 and 37 ∘C are 8.333 and 8.156, respectively. The thermodynamic quantities associated with the second acid dissociation have been calculated from the values of pK
2 as a function of temperature. The zwitterionic buffer BICINE was shown to be useful as a pH standard in the region close to that of blood serum. 相似文献
199.
A graph with n vertices that contains no triangle and no 5-cycle and minimum degree exceeding n/4 contains an independent set with at least (3n)/7 vertices. This is best possible. The proof proceeds by producing a homomorphism to the 7-cycle and invoking the No Homomorphism Lemma. For k ≥ 4, a graph with n vertices, odd girth 2k+1, and minimum degree exceeding n/(k+1) contains an independent set with at least kn/(2k+1) vertices; however, we suspect this is not best possible. © 1993 John Wiley & Sons, Inc. 相似文献
200.
Michael Bildhauer 《manuscripta mathematica》1998,97(3):389-406
H?lder continuity up to the free boundary is proved for minimizing solutions if they meet the supporting surface in an angle
which is bounded away from zero. The problem is localized by proving the continuity of the distance function, a result which
is also true for stationary points.
Received: 14 April 1998 相似文献