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991.
Hydrophilic-interaction liquid chromatography (HILIC), reversed-phase chromatography (RPC) and porous graphitic carbon (PGC) chromatography are typically applied for liquid chromatographic separations of protein N-glycans. Hence the performances of these chromatography modes for the separation of fluorescently labeled standard glycan samples (monoclonal antibody, fetuin, ribonuclease-B) covering high-mannose and a broad range of complex type glycans were investigated. In RPC the retention of sialylated glycans was enhanced by adding an ion-pairing agent to the mobile phase, resulting in improved peak shapes for sialylated glycans compared to methods recently reported in literature. For ion pairing RPC (IP-RPC) and HILIC ultra-high performance stationary phases were utilized to maximize the peak capacity and thus the resolution. But due to the shallow gradient in RPC the peak capacity was lower than on PGC. Retention times in HILIC and IP-RPC could be correlated to the monosaccharide compositions of the glycans by multiple linear regression, whereas no adequate model was obtained for PGC chromatography, indicating the significance of the three-dimensional structure of the analytes for retention in this method. Generally low correlations were observed between the chromatography methods, indicating their orthogonality. The high selectivities, as well as the commercial availability of ultra-high performance stationary phases render HILIC the chromatography method of choice for the analysis of glycans. Even though for complete characterization of complex glycan samples a combination of chromatography methods may be necessary. 相似文献
992.
993.
The random phase approximation has been used to extend the Leibler theory for the stability limit of a homogeneous melt of A–B diblock copolymers to examine the onset of microphase and macrophase separation in a variety of ABC block copolymer systems. The stability limit is located by the divergence of the collective structure factor of the melt. We introduce and analyze three models for ABC block copolymers: linear triblocks, random comb copolymers where a fixed number of A and B teeth are placed randomly along a C backbone, and statistical comb copolymers, with A or B teeth spaced regularly, but with sequences constructed using a two parameter Markov process. We compute order-disorder stability boundaries for the segregation strength parameter χABN at threshold as a function of χACN, χBCN, composition, and other model parameters, and compare the results for the three different architectural models. An interesting “reentrant order-disorder transition” is located in several model phase diagrams, and is associated with a peculiar situation in which more incompatibility causes less segregation. In the case of statistical combs, macrophase separation into two liquid phases can be favored over microphase separation. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 849–864, 1997 相似文献
994.
Andreas K. Theophilou Nikitas I. Gidopoulos 《International journal of quantum chemistry》1995,56(4):333-336
In this article, we justify the use of standard Kohn-Sham (KS ) band structure theory for the calculation of the low-energy spectrum of metals and the density of states. For the higher spectrum, one can start the KS excited-state calculations by using as the first-order approximation the spin orbitals of the ground state. We next deal with the problem of degenerate states by using the subspace theory minimum principle. © 1995 John Wiley & Sons, Inc. 相似文献
995.
The Kohn-Sham exchange potential of finite systems is shown to approach different asymptotic limits on nodal surfaces of the energetically highest-occupied orbital than in other regions. This leads to barrier-well structures in the near asymptotic region, which have a strong influence on virtual orbitals and thus on excitation energies. Common approximations for the exchange potential do not exhibit these features. These asymptotic structures, however, can be correctly described by effective exact-exchange methods. Conditions for the presence of an asymptotic barrier well in the full exchange-correlation potential are discussed. 相似文献
996.
This paper presents a flatness-based approach for the solution of the feedforward control problem for a boundary controlled semilinear wave equation. The solution to a given piecewise analytical desired output trajectory is shown to be piecewise analytical, which allows the application of a formal power series approach on suitable subregions in adequate coordinates. The subregions are determined by the characteristic curves of the system passing through the non-analyticity points of the desired trajectory. Convergence of the solution is demonstrated and simulation results are given for some set of parameters. (© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
997.
This article introduces and analyzes a p-version FEM for variational inequalities resulting from obstacle problems for some quasi-linear elliptic partial differential
operators. We approximate the solution by controlling the obstacle condition in images of the Gauss–Lobatto points. We show
existence and uniqueness for the discrete solution u
p
from the p-version for the obstacle problem. We prove the convergence of u
p
towards the solution with respect to the energy norm, and assuming some additional regularity for the solution we derive
an a priori error estimate. In numerical experiments the p-version turns out to be superior to the h-version concerning the convergence rate and the number of unknowns needed to achieve a certain exactness of the approximation. 相似文献
998.
(NH4)2[Mo6Cl14] · H2O ( 1 ) was prepared from reactions of MoCl2 in ethanol with aqueous NH4Cl solution. It crystallizes in the monoclinic space group I2/a (no. 15), Z = 4 with a = 912.3(1), b = 1491.2(2), c = 1724.8(2) pm, β = 92.25(1)°; R1 = 0.023 (based on F values) and wR2 = 0.059 (based on F2 values), for all measured X‐ray reflections. The structure of the cluster anion can be given as [(Mo6Cl)Cl]2– (i = inner, a = outer ligands). Thermal stability studies show that 1 loses crystal water followed by the loss of NH4Cl above 350 °C to yield MoCl2. The water‐free compound (NH4)2[Mo6Cl14] ( 2 ) was synthesized by solid state reaction of MoCl2 and NH4Cl in a sealed quartz ampoule at 270 °C. No single‐crystals could be obtained. Decompositions of 1 and 2 under nitrogen and argon exhibited the loss of NH4Cl at about 350 °C. Decomposition under NH3 resulted in the formation of MoN and Mo2N at 540 °C and 720 °C, respectively. 相似文献
999.
The discrete logarithm problem in various finite abelian groups is the basis for some well known public key cryptosystems. Recently, real quadratic congruence function fields were used to construct a public key distribution system. The security of this public key system is based on the difficulty of a discrete logarithm problem in these fields. In this paper, we present a probabilistic algorithm with subexponential running time that computes such discrete logarithms in real quadratic congruence function fields of sufficiently large genus. This algorithm is a generalization of similar algorithms for real quadratic number fields.
1000.
We consider the scattering of plane, time-harmonic electromagnetic waves by a perfect conductor D. We first show that the set ?λ consisting of the span of a fixed linear combination of the electric and magnetic far-field patterns is dense in the space of square-integrable tangential vector fields defined on the unit sphere for all values of the wave number k ≠ 0 provided that Im k ≥0. We next consider the affine hull ??λ of ?λ and characterize the set ? in terms of electric Herglotz fields. This result is then used to derive an optimization scheme for solving the inverse scattering problem of determining D from a knowledge of ?λ and it is shown that this (unconstrained) optimization scheme has zero as its greatest lower bound. 相似文献