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  • 1995-1999  (2,124)
  • 1998  (2,124)
  • Engineering  (644)
  • Theoretical, Physical and Computational Chemistry  (583)
  • Industrial Chemistry  (457)
  • Physics  (299)
  • Capillary electrophoresis  (140)
  • Nuclear reactions
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  • 1995-1999  (2,124)
Year
Keywords
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Zeitschrift für Lebensmittel-Untersuchung und -Forschung 206 (1998), S. 246-250 
    ISSN: 1431-4630
    Keywords: Key words Histamine ; Capillary electrophoresis ; Photometric determination ; Liquid liquid extraction ; Solid phase extraction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract  To determine levels of histamine, two methods were used, photometry in conjunction with two sample clean-up procedures, and capillary zone electrophoresis (CZE). The two sample clean-up procedures used were liquid liquid extraction (LLE) with n-butanol and solid phase extraction (SPE). Using CZE, the separation of histamine from the matrix was good. The other method, photometry, represents a classic and simple method, that can be employed for in situ measurement of histamine. We found that it was necessary to clean up the samples prior to photometry; if this was not done, the recorded levels of histamine were higher than those determined by CZE. In order to determine levels of histamine, both of these rapid tests were applied to ten different foodstuffs. The levels of histamine measured using photometry following either LLE or SPE were compared. The results indicated that photometry is a suitable method for the measurement of histamine, although the sample solutions have to be purified by either LLE or SPE. Samples do not need to be cleaned up before CZE because there is no interference between histamine and attendant material. Both sample clean-up procedures were applied to the following foodstuffs: tomatoes, sauerkraut, tuna, leaf spinach, cream spinach, white wine and mackerel. The differences of the measured values vary between 3% and 18% for LLE and 6% and 27% for SPE. For the other foodstuffs, such as beef, beer and non-alcoholic beer, only one sample clean-up procedure is suitable. LLE used for beef and beer leads to differences in measured levels of histamine between 18% and 50%, respectively, whereas SPE used for non-alcoholic beer leads to differences of 20%.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    European radiology 8 (1998), S. 849-857 
    ISSN: 1432-1084
    Keywords: Key words: Ultrasound ; Physics ; Vascular studies ; Vascular pathologies ; Ultrasonic contrast agents ; Clinical applications
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract. The choice of the optimal ultrasonic frequency for vascular studies is determined by the required resolution and penetration. Anatomical real-time two-dimensional imaging and blood flow studies provide complementary information. Intravascular scanning allows high-frequency ultrasound to be used, with correspondingly good spatial resolution. Contrast resolution is degraded by beam side lobes and the limited dynamic range of the ultrasonic pulse. The physics of ultrasonic scattering by blood, pulsed Doppler and duplex scanning and colour flow imaging performances determines the limits of clinical applications. Contrast agents enhance the echogenicity of blood, improving sensitivity and, through second harmonic detection, suppressing solid tissue echoes. Three-dimensional display, with segmentation by the presence of the flow signal, facilitates spatial perception. Clinical applications in vascular pathologies are summarised.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Space science reviews 84 (1998), S. 199-206 
    ISSN: 1572-9672
    Keywords: Nuclear reactions ; Nucleosynthesis ; Abundances ; Stars:Evolution ; Interior ; Rotation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract We first recall the observational and theoretical facts that constitute the so-called 3He problem. We then review the chemical anomalies that could be related to the destruction of 3He in red giants stars. We show how a simple consistent mechanism can lead to the destruction of 3He in low mass stars and simultaneously account for the low 12C/13C ratios and low lithium abundances observed in giant stars of different populations. This process should both naturally account for the recent measurements of 3He/H in galactic HII regions and allow for high values of 3He observed in some planetary nebulae. We propose a simple statistical estimation of the fraction of stars that may be affected by this process.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Chichester, West Sussex : Wiley-Blackwell
    Mathematical Methods in the Applied Sciences 21 (1998), S. 1-24 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We study the large time asymptotics of solutions u(x, t) of the wave equation with time-harmonic force density f(x)e-iωt, ω≥0, in the semi-strip Ω= (0, ∞)×(0, 1) for a given f∊C∞0(Ω). We assume that u satisfies the initial condition u=(∂/∂t)u=0 for t=0 and the boundary conditions u=0 for x2=0 and x2=1, and (∂/∂x1)u=αu for x1=0, with given α, -π≤α〈∞. Let Dα be the self-adjoint realization of -Δ in Ω with this boundary condition. For -π≤α〈0, Dα has eigenvalues λj=π2j2-α2, j=1, 2, … For j≥2 these eigenvalues are embedded in the continuous spectrum of Dα, σc(Dα)=[π2, ∞]. For α≥0, Dα has no eigenvalues. We consider the asymptotic behaviour of u(x, t), t→∞, as a function of α. In the case α=0 resonances of order √t at ω=πj, j=1, 2, …, were found in References 5 and 10. We prove that for α=-π there is a resonance of order t2 for ω=0 and resonances of order t for every ω〉0 (note that 0 is an eigenvalue of D-π). Moreover, for -π〈α〈0 there are resonances of order t at ω=√λj. The resonance frequencies are continuous functions of α for -π〈α〈0 and tend to πj, j=1, 2, … as α goes to zero.On the contrary in the case α〉0 there are no real resonances in the sense that the solution remains bounded in time as t→∞. Actually in this case, the limit amplitude principle is valid for all frequencies ω≥0. This rather striking behaviour of the resonances is explained in terms of the extension of the resolvent R(κ)=(Dα-κ2)-1 as a meromorphic function of κ into an appropriate Riemann surface. We find that as α crosses zero the real poles of R(κ) associated with the eigenvalues remain real, but go into a second sheet of the Riemann surface. This behaviour under perturbation is rather different from the case of complex resonances which has been extensively studied in the theory of many-body Schrödinger operators where the (real) eigenvalues embedded in the continuous spectrum turn under a small perturbation into complex poles of the meromorphic extension of the resolvent, as a function of the spectral parameter κ2. © 1998 by B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Chichester, West Sussex : Wiley-Blackwell
    Mathematical Methods in the Applied Sciences 21 (1998), S. 117-128 
    ISSN: 0170-4214
    Keywords: third-grade fluid ; existence ; uniqueness ; classical solution ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: The global existence and uniqueness of classical solution of steady motions of a third-grade fluid provided assumptions on positivness of μ (coefficient of viscosity) and α1, γ (material coefficients) is proved. © 1998 B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Chichester, West Sussex : Wiley-Blackwell
    Mathematical Methods in the Applied Sciences 21 (1998), S. 227-249 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: Integral equations associated with the basic boundary value problems for the Laplace and Stokes equations are considered. The integral operators for these integral equations are interpreted as the pseudodifferential operators, and their principal symbols are calculated. The symbols are obtained in terms of the principal curvatures and the coefficients of the first quadratic form of the boundary. As a consequence, the initial approximation is suggested for the iterative methods solving the integral equations. © 1998 by B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Chichester, West Sussex : Wiley-Blackwell
    Mathematical Methods in the Applied Sciences 21 (1998), S. 327-359 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: The boundary integral equation method is used to prove the convergence of the Drude-Born-Fedorov equations with variable coefficients, possibly non-smooth, to Maxwell's equations as chirality admittance tends to zero. © 1998 by B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Chichester, West Sussex : Wiley-Blackwell
    Mathematical Methods in the Applied Sciences 21 (1998), S. 565-588 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: New explicit stability conditions are derived for a linear integro-differential equation with periodic operator coefficients. The equation under consideration describes oscillations of thin-walled viscoelastic structural members driven by periodic loads. To develop stability conditions two approaches are combined. The first is based on the direct Lyapunov method of constructing stability functionals. It allows stability conditions to be derived for unbounded operator coefficients, but fails to correctly predict the critical loads for high-frequency excitations. The other approach is based on transforming the equation under consideration in such a way that an appropriate ‘differential’ part of the new equation would possess some reserve of stability. Stability conditions for the transformed equation are obtained by using a technique of integral estimates. This method provides acceptable estimates of the critical forces for periodic loads, but can be applied to equations with bounded coefficients only. Combining these two approaches, we derive explicit stability conditions which are close to the Floquet criterion when the integral term vanishes. These conditions are applied to the stability problem for a viscoelastic bar compressed by periodic forces. The effect of material and structural parameters on the critical load is studied numerically. © 1998 B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
    Additional Material: 5 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Chichester, West Sussex : Wiley-Blackwell
    Mathematical Methods in the Applied Sciences 21 (1998), S. 653-664 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: In order to maintain spectrally accurate solutions, the grids on which a non-linear physical problem is to be solved must also be obtained by spectrally accurate techniques. The purpose of this paper is to describe a pseudospectral computational method of solving integro-differential systems with quadratic performance index. The proposed method is based on the idea of relating grid points to the structure of orthogonal interpolating polynomials. The optimal control and the trajectory are approximated by the m th degree interpolating polynomial. This interpolating polynomial is spectrally constructed using Legendre-Gauss-Lobatto grid points as the collocation points, and Lagrange polynomials as trial functions. The integrals involved in the formulation of the problem are calculated by Gauss-Lobatto integration rule, thereby reducing the problem to a mathematical programming one to which existing well-developed algorithms may be applied. The method is easy to implement and yields very accurate results. An illustrative example is included to confirm the convergence of the pseudospectral Legendre method, and a comparison is made with an existing result in the literature. © 1998 B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
    Additional Material: 2 Tab.
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  • 10
    Electronic Resource
    Electronic Resource
    Chichester, West Sussex : Wiley-Blackwell
    Mathematical Methods in the Applied Sciences 21 (1998), S. 701-718 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: This article establishes the existence of a trapped-mode solution to a linearized water-wave problem. The fluid occupies a symmetric horizontal channel that is uniform everywhere apart from a confined region which either contains a thin vertical plate spanning the depth of the channel or has indentations in the channel walls; the forces of gravity and surface tension are operative. A trapped mode corresponds to an eigenvalue of the composition of an inverse differential operator and a Neumann-Dirichlet operator for an elliptic boundary-value problem in the fluid domain. The existence of such an eigenvalue is established by extending previous results dealing with the case when surface tension is absent. © 1998 B.G. Teubner Stuttgart-John Wiley & Sons, Ltd.
    Additional Material: 5 Ill.
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  • 11
    Electronic Resource
    Electronic Resource
    Chichester, West Sussex : Wiley-Blackwell
    Mathematical Methods in the Applied Sciences 21 (1998), S. 501-517 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: In this paper an initial-boundary-value problem in one-space dimension is studied for the Broadwell model extended to a gas mixture undergoing bimolecular reactions. Techniques of semigroup of bounded positive operators in a suitable Banach space are used to prove existence and uniqueness of the solution on bounded time intervals whose length depends on the initial data. © 1998 B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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  • 12
    Electronic Resource
    Electronic Resource
    Chichester, West Sussex : Wiley-Blackwell
    Mathematical Methods in the Applied Sciences 21 (1998), S. 685-700 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: In the present work, the problem of electromagnetic wave propagation in three-dimensional stratified media is studied. The method of decoupling the electric and magnetic fields is implemented, and the spectral approach is adopted, componentwise, to the vector equation involving the electric field. Operational calculus of self-adjoint, positive operators in suitable Hilbert spaces is used to solve the corresponding initial value problems. The spectral families of these operators for the cases of the whole space and of a finite layer are constructed. A discussion on the applicability of the obtained results to physical problems is also included. © 1998 B.G. Teubner Stuttgart-John Wiley & Sons Ltd.
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  • 13
    Electronic Resource
    Electronic Resource
    Chichester, West Sussex : Wiley-Blackwell
    Mathematical Methods in the Applied Sciences 21 (1998), S. 757-780 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: In this paper we prove under the assumption of small initial data the global existence of a classical solution to the equations in viscoelasticity, associated with a free damping boundary condition. We also show that if we choose the initial data large enough, blow up will occur in finite time. © 1998 B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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  • 14
    Electronic Resource
    Electronic Resource
    Chichester, West Sussex : Wiley-Blackwell
    Mathematical Methods in the Applied Sciences 21 (1998), S. 797-821 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We consider the thermoelastic plate system,utt-γΔutt+Δ2u+αΔθ=0,θt-κΔθ-αΔut=0 and we make a comparison between the models in which γ=0 and γ〉0. We conclude that in the first case the plate system is of a parabolic type, while when γ〉0 the corresponding system has a hyperbolic behaviour. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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  • 15
    Electronic Resource
    Electronic Resource
    Chichester, West Sussex : Wiley-Blackwell
    Mathematical Methods in the Applied Sciences 21 (1998), S. 883-894 
    ISSN: 0170-4214
    Keywords: solitary wave ; stability ; long wave-short wave resonance equations ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: This paper concerns the orbital stability for solitary waves of the Long Wave-Short Wave resonance equations. Since the abstract results of Grillakis et al. [7, 8] cannot be applied directly, we can extend the abstract stability theory and use the detailed spectral analysis to obtain the stability of the solitary waves. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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  • 16
    Electronic Resource
    Electronic Resource
    Chichester, West Sussex : Wiley-Blackwell
    Mathematical Methods in the Applied Sciences 21 (1998), S. 1049-1066 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We consider particle transport in a three-dimensional convex region V, bounded by the regular surface ∂V. We assume that particles are specularly reflected by ∂V and that a source q is assigned on ∂V; more general non-homogeneous boundary conditions are also discussed. The problem is non-linear because the boundary condition is not homogeneous. We prove existence of a unique strict solution and by using the theory of semigroups we derive the explicit expression of such a solution in terms of the boundary source q. In the appendix, we indicate how some properties of affine operators can be used to derive the solution. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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  • 17
    Electronic Resource
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    Chichester, West Sussex : Wiley-Blackwell
    Mathematical Methods in the Applied Sciences 21 (1998), S. 1085-1105 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: A phase-field model based on the Coleman-Gurtin heat flux law is considered. The resulting system of non-linear parabolic equations, associated with a set of initial and Neumann boundary conditions, is studied. Existence, uniqueness, and regularity results are proved. An asymptotic analysis is also carried out, in the case where the coefficient of the interfacial energy term tends to 0. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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  • 18
    Electronic Resource
    Electronic Resource
    Chichester, West Sussex : Wiley-Blackwell
    Mathematical Methods in the Applied Sciences 21 (1998), S. 1115-1148 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We apply the Child-Langmuir asymptotics of the Vlasov-Poisson system to the case of a bipolar diode, i.e. a vacuum diode where two species of particles of opposite electric charge are flowing. This leads to a simplified model which, if at least one of the two injected currents is not too large, has a unique solution. Moreover, in that case, the currents flowing inside the diode are limited by the so-called bipolar Child-Langmuir currents. In the case of large currents, other solutions may appear, and the formation of virtual electrodes may occur inside the diode. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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  • 19
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    Chichester, West Sussex : Wiley-Blackwell
    Mathematical Methods in the Applied Sciences 21 (1998), S. 1107-1113 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: In this paper we consider the Cauchy problem for the equation∂u/∂t + u ∂u/∂x + u/x = 0 for x 〉 0, t ≥ 0, with u(x, 0) = u0-(x) for x 〈 x0, u(x, 0) = u0+(x) for x 〉 x0, u0-(x0) 〉 u0+(x0). Following the ideas of Majda, 1984 and Lax, 1973, we construct, for smooth u0- and u0+, a global shock front weak solution u(x, t) = u-(x, t) for x 〈 φ(t), u(x, t) = u+(x, t) for x 〉 φ(t), where u- and u+ are the strong solutions corresponding (respectively) to u0- and u0+ and the curve t → φ(t) is defined by dφ/dt (t) = 1/2[u-(φ(t), t) + u+(φ(t), t)], t ≥ 0 and φ(0) = x0.© 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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  • 20
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    Chichester, West Sussex : Wiley-Blackwell
    Mathematical Methods in the Applied Sciences 21 (1998), S. 1195-1206 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: A variational approach to a non-linear non-local identification problem related to the non-linear transport equation is studied. Introducing a similarity transformation, the problem is formulated as an identification problem for a non-linear differential equation of second order with an additional non-local condition. For the solution of the forward problem stability in H1-norm with respect to the identification parameter is obtained. Using this result the existence of a solution to the identification problem is proved. Some results of computational experiments are given. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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  • 21
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    Chichester, West Sussex : Wiley-Blackwell
    Mathematical Methods in the Applied Sciences 21 (1998), S. 1233-1267 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We consider the plate equation in a polygonal domain with free edges. Its resolution by boundary integral equations is considered with double layer potentials whose variational formulation was given in Reference 25. We approximate its solution (u, (∂u/∂n)) by the Galerkin method with approximated spaces made of piecewise polynomials of order 2 and 1 for, respectively, u and (∂u/∂n). A prewavelet basis of these subspaces is built and equivalences between some Sobolev norms and discrete ones are established in the spirit of References 14, 16, 30 and 31. Further, a compression procedure is presented which reduces the number of nonzero entries of the stiffness matrix from O(N2) to O(N log N), where N is the size of this matrix. We finally show that the compressed stiffness matrices have a condition number uniformly bounded with respect to N and that the compressed Galerkin scheme converges with the same rate than the Galerkin one. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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  • 22
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1287-1296 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: The relativistic Vlasov-Maxwell-Fokker-Planck system is used in modelling distribution of charged particles in plasma. It consists of a transport equation coupled with the Maxwell system. The diffusion term in the equation models the collisions among particles, whereas the viscosity term signifies the dynamical frictional forces between the particles and the background reservoir. In the case of one space variable and two momentum variables, we prove the existence of a classical solution when the initial density decays fast enough with respect to the momentum variables. The solution which shares this same decay condition along with its first derivatives in the momentum variables is unique. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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  • 23
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1415-1439 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We consider reactive mixtures of dilute polyatomic gases in full vibrational non-equilibrium. The governing equations are derived from the kinetic theory and possesses an entropy. We recast this system of conservation laws into a symmetric conservative form by using entropic variables. Following a formalism developed by the authors in a previous paper, the system is then rewritten into a normal form, that is, in the form of a quasilinear symmetric hyperbolic-parabolic system. Using a result of Vol'pert and Hudjaev, we prove local existence and uniqueness of a bounded smooth solution to the Cauchy problem. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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  • 24
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1479-1494 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: Approximate solutions of the non-linear Boltzmann equation, which have the structure of the linear combination of three global Maxwellians with arbitrary hydrodynamical parameters, are considered. Some sufficient conditions which allow the error between the left- and the right-hand sides of the equation tend to zero, and which are calculated either in the mixed metric or in the pure integral metric, are obtained. The class of the distributions, which minimized this error for the arbitrary Knudsen number, is found. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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  • 25
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    Chichester, West Sussex : Wiley-Blackwell
    Mathematical Methods in the Applied Sciences 21 (1998), S. 1519-1542 
    ISSN: 0170-4214
    Keywords: non-hyperbolic systems ; two-phase flows ; dispersion terms ; symmetrization ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: The paper considers a system of partial differential equations of convection dispersion type, modelling a stratified two-phase fluid flow. Local existence in time is proved for a sufficiently smooth initial data, given in the set of physically admissible states. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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  • 26
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1559-1569 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: In this paper we study the motion of an elastic conducting wire in a magnetic field. The motion of the conductor induces a current in the wire (Faraday's law) which, in turn produces a force on the wire. We consider the linear equation obtained by linearizing the resulting equations of motion about an equilibrium solution. This is a hyperbolic partial differential equation with a non-local term. We prove existence and uniqueness of a weak solution of an initial-boundary value problem for this equation. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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  • 27
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1637-1654 
    ISSN: 0170-4214
    Keywords: generalized Stokes equations ; incompressible flow ; least-squares ; finite element method ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: In this paper we are concerned with a weighted least-squares finite element method for approximating the solution of boundary value problems for 2-D viscous incompressible flows. We consider the generalized Stokes equations with velocity boundary conditions. Introducing the auxiliary variables (stresses) of the velocity gradients and combining the divergence free condition with some compatibility conditions, we can recast the original second-order problem as a Petrovski-type first-order elliptic system (called velocity-stress-pressure formulation) in six equations and six unknowns together with Riemann-Hilbert-type boundary conditions. A weighted least-squares finite element method is proposed for solving this extended first-order problem. The finite element approximations are defined to be the minimizers of a weighted least-squares functional over the finite element subspaces of the H1 product space. With many advantageous features, the analysis also shows that, under suitable assumptions, the method achieves optimal order of convergence both in the L2-norm and in the H1-norm. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1619-1635 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We consider the two-parameter non-linear Sturm-Liouville problems. By using the variational method on general level sets, the variational eigenvalues are obtained. The purpose of this paper is to study the properties of these variational eigenvalues with respect to the parameter of general level sets. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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  • 29
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 187-226 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We study the limit behaviour of solution of Poisson's equation in a class of thin two-dimensional domains, both simply connected or single-hollowed, as its thickness becomes very small. The method is based on a transformation of the original problem into another posed on a fixed domain, obtention of a priori estimates and convergence results when thickness parameter tends to zero. As an important application of abstract results we obtain the limit expressions for functions appearing in elastic beam theories as torsion and warping functions. In this way, we provide a mathematical justification and a correct definition of torsion, warping and Timoshenko functions and constants that should be used in the open and closed thin-walled elastic beam theories. © 1998 by B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 269-279 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: The generalized Möbius function and Möbius inversion formula are applied to a multiplicative semigroup. A general mathematical method based on this Möbius inversion is presented to solve inversion problems of expansions with unequally weighted terms. By this method, all the inverse lattice problems in physics can be solved concisely. The solutions of four inverse lattice problems: the Fibonacci structure, the square lattice structure, the bcc and the hcp lattice structures are given. These are difficult to be solved by other methods. © 1998 by B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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  • 31
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 361-374 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We use the eigenfunction expansion of Green's function of Dirichlet problems to obtain sampling theorems. The analytic properties of the sampled integral transforms as well as the uniform convergence of the sampling series are proved without any restrictions on the integral transforms. We obtain a one- and multi-dimensional versions of sampling theorems. In both cases the sampling series are written in terms of Lagrange-type interpolation expansions. Some examples and the truncation error as well as the stability of the obtained sampling expansions are discussed at the end of the paper. © 1998 B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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  • 32
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 393-416 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We consider a dynamical von Kármán system in the presence of thermal effects. Our model includes the possibility of a rotational inertia term in the system. We show that the total energy of the solution of such system decays exponentially as t→+∞. The decay rates we obtain are uniform on bounded sets of the energy space. The main ingredients of our method of proof are suitable properties of a decoupled system, the energy method and the compactness of the nonlinear map associated to the von Kármán system. © 1998 B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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  • 33
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 479-488 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: This short article discusses the spectrum of the Neumann Laplacian in the infinite domain Ω⊂∝n, n ≥2 created by inserting a compact obstacle P into the uniform cylinder Ω0 =(-∞, ∞)×Ω′. The main result is the existence of at least one embedded eigenvalue when P is an (n -2)-dimensional surface whose unit normal is parallel to Ω′ at each point of P . The special case when P is symmetric about {0}×Ω′ is also treated. It is shown that there is at least one symmetric eigenvector and, when P is sufficiently long, at least one antisymmetric eigenvector. © 1998 B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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  • 34
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 551-564 
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    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We prove the existence of solutions to the three-dimensional elastoplastic problem with Hencky's law and Neumann boundary conditions by elliptic regularization and the penalty method, both for the case of a smooth boundary and of an interior two dimensional crack. It is shown, in particular, that the variational solution satisfies all boundary conditions. © 1998 B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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  • 35
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 251-268 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: The propagation of Hölder regularity of the solutions to the 3D Euler equations is discussed. Our method is a special semi-linearization of the vorticity equation combined with the classical Schauder interior estimates. © 1998 by B.G. Teubner Stuttgart-John Wiley & Sons Ltd.
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  • 36
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 433-461 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: This paper is concerned with the solution of Maxwell equations in the modelling of the scattering of a time-harmonic electromagnetic wave by an obstacle located in a two-layered medium. The use of the Silver-Müller radiation condition in each layer is shown to provide a well-posed scattering problem. The analysis is based on the study of the Green tensor, which allows to relate the radiation condition to an integral representation formula. The analyticity properties of the scattering problem with respect to the frequency are then investigated. This gives rise to a limiting absorption principle and furnishes a characterization of the resonances. © 1998 B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 489-499 
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    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We apply our recently developed distributional technique [2, 3] to study time-domain asymptotics. This enables us to present a rigorous mathematical discussion and extensions of the results given by Chapman [1] and subsequent workers in this field. The present analysis is facilitated by defining functions which are distributionally small at infinity. We find that one of the advantages of using this technique is that multidimensional extensions can be derived very easily. © 1998 B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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  • 38
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 519-549 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: This paper is concerned with a specific finite element strategy for solving elliptic boundary value problems in domains with corners and edges. First, the anisotropic singular behaviour of the solution is described. Then the finite element method with anisotropic, graded meshes and piecewise linear shape functions is investigated for such problems; the schemes exhibit optimal convergence rates with decreasing mesh size. For the proof, new local interpolation error estimates for functions from anisotropically weighted spaces are derived. Finally, a numerical experiment is described, that shows a good agreement of the calculated approximation orders with the theoretically predicted ones. © 1998 B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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  • 39
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 605-617 
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    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: This paper presents a general method of analysis for investigating the whirl stability of a rotor-bearing system whose appendage is flexibly attached to the spinning shaft. Sufficient conditions of asymptotic stability involving system different parameters are derived based on Liapunov's theory. An inclusive analysis of the effect of the combined flexibilities of the elastic attachment of the appendage to the shaft and the two end bearings coupled with the other various parameters of the system on the dynamic stability is presented. © 1998 B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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  • 40
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 665-684 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We investigate the steady compressible Navier-Stokes equations near the equilibrium state v = 0, ρ = ρ0 (v the velocity, ρ the density) corresponding to a large potential force. We introduce a method of decomposition for such equations: the velocity field v is split into a non-homogeneous incompressible part u (div (ρ0u) = (0) and a compressible (irrotational) part ∇φ. In such a way, the original complicated mixed elliptic-hyperbolic system is split into several ‘standard’ equations: a Stokes-type system for u, a Poisson-type equation for φ and a transport equation for the perturbation of the density σ = ρ - ρ0. For ρ0 = const. (zero potential forces), the method coincides with the decomposition of Novotny and Padula [21]. To underline the advantages of the present approach, we give, as an example, a ‘simple’ proof of the existence of isothermal flows in bounded domains with no-slip boundary conditions. The approach is applicable, with some modifications, to more complicated geometries and to more complicated boundary conditions as we will show in forthcoming papers. © 1998 B.G. Teubner Stuttgart-John Wiley & Sons Ltd.
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  • 41
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 619-651 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We consider acoustic scattering from an obstacle inside an inhomogeneous structure. We prove in the paper that if the outside inhomogeneity is known then the obstacle and possible inside inhomogeneity are uniquely determined by the fixed energy far field data. The proof is based on new mapping properties of layer potentials in spaces that specify one point. © 1998 B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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  • 42
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 939-967 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: The linear problem for the velocity potential around a slightly curved thin finite wing is considered under the Joukowskii-Kutta hypothesis. The exponents of possible singularities of solutions at angular points on wing's trailing edge are expressed in terms of eigenvalues of mixed boundary value problems for the Beltrami-Laplace operator on the hemisphere and the semicircle. These singularities have a structure such that the circulation function turns out to be continuous in interior angular points of the trailing edge. In the case of trapezoidal shape of the wing ends there occur square-root singularities of the velocity field at the trailing edge endpoints and the same singularities, of course, are extended along the lateral sides of the wake behind the wing. It is proved that for any angular point on the trailing edge the exponents of all above-mentioned singularities form a countable set in the upper complex half-plane with the only accumulation point at infinity. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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  • 43
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 985-1014 
    ISSN: 0170-4214
    Keywords: Vlasov-Poisson-Fokker-Planck ; long-time behaviour ; fundamental solutions ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We study the long-time behaviour of solutions of the Vlasov-Poisson-Fokker-Planck equation for initial data small enough and satisfying some suitable integrability conditions. Our analysis relies on the study of the linearized problems with bounded potentials decaying fast enough for large times. We obtain global bounds in time for the fundamental solutions of such problems and their derivatives. This allows to get sharp bounds for the decay of the difference between the solutions of the Vlasov-Poisson-Fokker-Planck equation and the solution of the free equation with the same initial data. Thanks to these bounds, we get an explicit form for the second term in the asymptotic expansion of the solutions for large times. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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  • 44
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1067-1084 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: An initial-value problem modelling coagulation and fragmentation processes is studied. The results of earlier papers are extended to models where either one or both of the rates of coagulation and fragmentation depend on time. An abstract integral equation, involving the solution operator to the linear fragmentation part, is investigated via the contraction mapping principle. A unique global, non-negative, mass-conserving solution to this abstract equation is shown to exist. The latter solution is used to generate a global, non-negative, mass-conserving solution to the original non-autonomous coagulation and multiple-fragmentation equation. © 1998 B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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  • 45
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1185-1194 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: In this paper we prove the global existence and study decay property of the solutions to the initial boundary value problem for the quasi-linear wave equation with a dissipative term without the smallness of the initial data. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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  • 46
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1207-1226 
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    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: Reaction random-walk systems are hyperbolic models to describe spatial motion (in one dimension) with finite speed and reactions of particles. Here we present two approaches which relate reaction random-walk equations with reaction diffusion equations. First, we consider the case of high particle speeds (parabolic limit). This leads to a singular perturbation analysis of a semilinear damped wave equation. A initial layer estimate is given. Secondly, we consider the case of a transcritical bifurcation. We use techniques similar to that of the Ginzburg-Landau method to find a modulation equation for the amplitude of the first unstable mode. It turns out that the modulation equation is Fisher's equation, hence near the bifurcation point travelling wave solutions are obtained. The approximation result and the corresponding estimate is given in terms of the bifurcation parameter. Both results are based on an a priori estimate for classical solutions which follows from explicit representations of the solution of the linear telegraph equation. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1365-1377 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: In the article the problem of regulation of the cardiovascular system is investigated from the point of view of control process theory. This problem was reduced to finding the optimal control in the sense of speed in a bilinear system. In the first part of the article the possibility of applying Saburov's method for the solution to bilinear control problems is considered. The second part of the article is devoted to the application of this method to a concrete problem from practical medicine. The method has allowed the complete synthesis of an optimal control to be carried out  -  the sliding mode takes place and it was investigated completely. The results obtained are interesting from the point of view of control process theory, and testify to the high efficiency of the method. The final results allow concrete recommendations about the regulation of the cardiovascular system. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1399-1413 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: The steady-state equations for a charged gas or fluid consisting of several components, exposed to an electric field, are considered. These equations form a system of strongly coupled, quasilinear elliptic equations which in some situations can be derived from the Boltzmann equation. The model uses the duality between the thermodynamic fluxes and the thermodynamic forces. Physically motivated mixed Dirichlet-Neumann boundary conditions are prescribed. The existence of generalized solutions is proven. The key of the proof is a transformation of the problem by using the entropic variables, or electro-chemical potentials, which symmetrize the equations. The uniqueness of weak solutions is shown under the assumption that the boundary data are not far from the thermal equilibrium. A general uniqueness result cannot be expected for physical reasons. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1343-1363 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We consider an elastic plate with the non-deformed shape ΩΣ := Ω \ Σ, where Ω is a domain bounded by a smooth closed curve Γ and Σ ⊂ Ω is a curve with the end points {γ1, γ2}. If the force g is given on the part ΓN of Γ, the displacement u is fixed on ΓD := Γ \ ΓN and the body force f is given in Ω, then the displacement vector u(x) = (u1(x), u2(x)) has unbounded derivatives (stress singularities) near γk, k = 1, 2   u(x) = ∑2k, l=1 Kl(γk)r1/2kSCkl(θk) + uR(x)     near γk.Here (rk, θk) denote local curvilinear polar co-ordinates near γk, k = 1, 2, SCkl (θk) are smooth functions defined on [-π, π] and uR(x) ∊ {H2(near γk)}2. The constants Kl(γk),   l = 1, 2, which are called the stress intensity factors at γk (abbr. SIFs), are important parameters in fracture mechanics. We notice that the stress intensity factors Kl(γk) (l = 1, 2;  k = 1, 2) are functionals Kl(γk) = Kl(γk; L, Ω, Σ) depending on the load L, the shape of the plate Ω and the shape of the crack Σ. We say that the crack Σ is safe, if Kl(γk; Ω)2 + K2(γk; Ω)2 〈 RẼ. By a small change of Ω the shape Σ can change to a dangerous one, i.e. we have K1(γk; Ω)2 + K2(γk; Ω)2 ≥ RẼ. Therefore it is important to know how Kl(γk) depends on the shape of Ω.For this reason, we calculate the Gâteaux derivative of Kl(γk) under a class of domain perturbations which includes the approximation of domains by polygonal domains and the Hadamard's parametrization Γ(τ) := {x + τφ(x)n(x);  x ∊ Γ}, where φ is a function on Γ and n is the outward unit normal on Γ. The calculations are quite delicate because of the occurrence of additional stress singularities at the collision points {γ3, γ4} = ΓD ∩ ΓN.The result is derived by the combination of the weight function method and the Generalized J-integral technique (abbr. GJ-integral technique). The GJ-integrals have been proposed by the first author in order to express the variation of energy (energy release rate) by extension of a crack in a 3D-elastic body. This paper begins with the weak solution of the crack problem, the weight function representation of SIF's, GJ-integral technique and finish with the shape sensitivity analysis of SIF's. GJ-integral Jω(u; X) is the sum of the P-integral (line integral) Pω(u, X) and the R-integral (area integral) Rω(u, X). With the help of the GJ-integral technique we derive an R-integral expression for the shape derivative of the potential energy which is valid for all displacement fields u ∊ H1. Using the property that the GJ-integral vanishes for all regular fields u ∊ H2 we convert the R-integral expression for the shape derivative to a P-integral expression. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1543-1558 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: It is shown that a stochastic system of N interacting particles in a slab approximates, in the Boltzmann-Grad limit, a one-dimensional Boltzmann equation with diffusive boundary conditions. © 1998 B. G. Teubner Stuttgart-John Wiley & Sons, Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1571-1591 
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    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: The asymptotic behaviour of solutions of certain semilinear elliptic Dirichlet boundary value problems defined on a semi-infinite cylinder is investigated by means of energy arguments and maximum principles. Various hypotheses are made on the form of the semilinear term, and in some cases it is found that the rate of decay of solutions is faster than the optimal decay rate for harmonic functions. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1655-1679 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: In this paper the problem of collision analysis for a mobile robot operating in a planar environment with moving objects (obstacles) is addressed. The pattern of motion of the potential obstacles cannot be predicted; only a bound on their maximum velocity is available. Based on this information, at its current position the robot constructs the Hazard Region that corresponds to the path it contemplates. If the Hazard Region contains at least one obstacle, then there is a potential for this obstacle to collide with the robot (in which case perhaps another path should be planned). We first derive the solution for Hazard Region for two standard path primitives, a straight line segment and a circular arc segment; the solution is exact, except for one special case (for which the approximation error is estimated). This result is then applied to a more complex case when the path presents a combination of those primitives. Such are, for example, the optimal (shortest) paths with constrained curvature (known as Dubins paths [3]), which connect two points, each with a prescribed direction of motion. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1681-1704 
    ISSN: 0170-4214
    Keywords: stratified medium ; acoustic waves ; self-adjoint operators ; spectrum ; limiting absorption principle ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We consider the acoustic propagator A=-∇·c2∇ in the strip Ω={(x, z)∊∝2∣0〈z〈H} with finite width H〉0. The celerity c depends for large ∣x∣ only on the variable z and describes the stratification of Ω: it is assumed to be in L∞(Ω), bounded from below by cmin〉0, such that there exists M〉0 with c(x, z)=c1(z) if x〈 -M and c(x, z)=c2(z) if x〉M. We look at the propagator A as a ‘perturbation’ of the free propagators Aj in Ω associated to the velocities cj, j=1, 2, and implement a ‘perturbative’ method, adapting ideas of Majda and Vainberg. The spectrum of A is defined in section 2, a limiting absorption principle is proved in section 3 outside of a countable set Γ(A). The points of Γ(A) can only accumulate at the left of the thresholds of the free propagators. The needed material about Aj, j=1, 2, and some technical estimates for A are given in Appendix. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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  • 54
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 25-42 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: Considered is the rotation of a robot arm or rod in a horizontal plane about an axis through the arm's fixed end and driven by a motor whose torque is controlled. The model was derived and investigated computationally by Sakawa and co-authors in [7] for the case that the arm is described as a homogeneous Euler beam. The resulting equation of motion is a partial differential equation of the type of a wave equation which is linear with respect to the state, if the control is fixed, and non-linear with respect to the control.Considered is the problem of steering the beam, within a given time interval, from the position of rest for the angle zero into the position of rest under a certain given angle.At first we show that, for every L2-control, there is exactly one (weak) solution of the initial boundary value problem which describes the vibrating system without the end condition.Then we show that the problem of controllability is equivalent to a non-linear moment problem. This, however, is not exactly solvable. Therefore, an iteration method is developed which leads to an approximate solution of sufficient accuracy in two steps. This method is numerically implemented and demonstrated by an example. © 1998 by B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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  • 55
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 59-91 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: A time-dependent Ginzburg-Landau-type model of a superconducting-normal-superconducting junction is presented. The existence and the uniqueness of the solutions are proved. When the data of the model are symmetric of some kinds, the solutions turns out to be symmetric of some kinds. In this symmetric case, an approximate model with the small thickness of the normal material in the middle of the junction as coefficients of a differential system is established for the sake of numerical computations. And also the existence and the uniqueness of the solution to this approximate model are set up. © 1998 by B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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  • 56
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 165-185 
    ISSN: 0170-4214
    Keywords: boundary integral equations ; boundary finite element ; free edge polygonal plate ; hypersingular kernels ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We consider the problem of a polygonal plate with free edges. It is a boundary value problem for the biharmonic operator on a polygon with Neumann boundary conditions. Its resolution is studied via boundary integral equations. A variational formulation of the boundary problem obtained by a double-layer potential is given. Finally, we implement the method and give numerical results. © 1998 B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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  • 57
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 129-163 
    ISSN: 0170-4214
    Keywords: wavelets on closed surfaces ; Dirichlet's and Neumann's problem ; scaling function ; scale discrete wavelets ; integral formulas ; exact fully discrete wavelet transform ; band-limited harmonic wavelets ; Runge-Walsh approximation ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: Wavelets on closed surfaces in Euclidean space ∝3 are introduced starting from a scale discrete wavelet transform for potentials harmonic down to a spherical boundary. Essential tools for approximation are integration formulas relating an integral over the sphere to suitable linear combinations of function values (resp. normal derivatives) on the closed surface under consideration. A scale discrete version of multiresolution is described for potential functions harmonic outside the closed surface and regular at infinity. Furthermore, an exact fully discrete wavelet approximation is developed in case of band-limited wavelets. Finally, the role of wavelets is discussed in three problems, namely (i) the representation of a function on a closed surface from discretely given data, (ii) the (discrete) solution of the exterior Dirichlet problem, and (iii) the (discrete) solution of the exterior Neumann problem. © 1998 by B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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  • 58
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 417-432 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We state a 1D model with quasi-stationary gas flows approximation for a carbon reactivity test in the production of silicon. The mathematical problem we formulate is a non-linear boundary value problem for a third-order ordinary differential equation with non-linear boundary conditions, which are non-local in time. We prove existence and uniqueness of a classical solution and provide a numerical example. © 1998 B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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  • 59
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 281-325 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: We present a bending model for a shallow arch, namely the type of curved rod where the curvature is of the order of the diameter of the cross section. The model is deduced in a rigorous mathematical way from classical tridimensional linear elasticity theory via asymptotic techniques, by taking the limit on a suitable re-scaled formulation of that problem as the diameter of the cross section tends to zero. This model is valid for general cases of applied forces and material, and it allows us to calculate displacements, axial stresses, bending moments and shear forces. The equations present a more general form than in the classical Bernoulli-Navier bending theory for straight slender rods, so that flexures and extensions are proved to be coupled in the most general case. © 1998 by B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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  • 60
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 375-392 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: In this work we analyse a model for radiative heat transfer in materials that are conductive, grey and semitransparent. Such materials are for example glass, silicon, water and several gases. The most important feature of the model is the non-local interaction due to exchange of radiation. This, together with non-linearity arising from the well-known Stefan-Boltzmann law, makes the resulting heat equation non-monotone. By analysing the terms related to heat radiation we prove that the operator defining the problem is pseudomonotone. Hence, we can prove the existence of weak solution in the cases where coercivity can be obtained. In the general case, we prove the solvability of the system using the technique of sub and supersolutions. © 1998 B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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  • 61
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 589-603 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: In the paper we study the problem of control by means of a heat source g for a thermoelastic system of equationsutt - ρ∇·p(θ, ∇u) - νΔut + DΔ2 u = f, cv(θ, ∇u)θt - κΔθ - ρθ[pθ (θ, ∇u)·∇ut] - ν∣∇ut∣2 = g, in a two-dimensional domain, where both viscosity ν and rigidity D are positive. Such a system has been considered in our former papers, and existence of solutions as well as uniqueness have been obtained. Here we prove the continuity and differentiability of solutions under somewhat stronger assumptions. An example of a control problem and necessary optimality conditions are presented. The system has an interpretation as a plate reinforced with shape memory alloy (SMA) wire mesh. © 1998 B. G. Teubner Stuttgart-John Wiley & Sons Ltd.
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  • 62
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 719-731 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: The exact solutions for the KdV and the Calogero-Degasperis-Fokas mKdV equations can be obtained by the AKNS class. The technique developed relies on the construction of the wave functions which are solutions of the associated AKNS system; that is, a linear eigenvalue problem in the form of a system of first order partial differential equations. The method of characteristics is used and Bäcklund transformations (BTs) are employed to generate two new solutions from the old. © 1998 B.G. Teubner Stuttgart-John Wiley & Sons Ltd.
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  • 63
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 781-795 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: In this paper we consider the boundary value problem for a semilinear equation□u(t, x)-μu(t, x)+aum(t, x)=0, μ〉0, a∊ℜ in the interior domain. We find a time global classical solution with exponential decay property by using singular hyperbolic equation. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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  • 64
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 895-906 
    ISSN: 0170-4214
    Keywords: geometrical inverse problems ; crack detection ; identifiability ; stability ; Lipschitz stability ; Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: This paper deals with the detection of emergent plane cracks, by using boundary measurements. An identifiability result (uniqueness of the solution) is first proved. Then, we look at the stability of this solution with respect to the measurement. A weak stability result is proved, as well as a Lipshitz stability result for straight cracks, by using domain-derivative techniques. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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  • 65
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1467-1477 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: In this paper, the existence, both locally and globally in time, the uniqueness of solutions and the non-existence of global solutions to the initial boundary value problem of a generalized Modification of the Improved Boussinesq equation utt-uxx-uxxtt=σ(u)xx are studied and a few examples are discussed. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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  • 66
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    Mathematical Methods in the Applied Sciences 21 (1998), S. 1593-1617 
    ISSN: 0170-4214
    Keywords: Engineering ; Numerical Methods and Modeling
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mathematics
    Notes: In this paper we study the following problem:ut-Δu=-f(u) in Ω×(0, T)≡QT,∂u ∂n=g(u) on ∂Ω×(0, T)≡ST,u(x, 0)=u0(x) in Ω, where Ω⊂∝N is a smooth bounded domain, f and g are smooth functions which are positive when the argument is positive, and u0(x)〉0 satisfies some smooth and compatibility conditions to guarantee the classical solution u(x, t) exists. We first obtain some existence and non-existence results for the corresponding elliptic problems. Then, we establish certain conditions for a finite time blow-up and global boundedness of the solutions of the time-dependent problem. Further, we analyse systems with same kind of boundary conditions and find some blow-up results. In the last section, we study the corresponding elliptic problems in one-dimensional domain. Our main method is the comparison principle and the construction of special forms of upper-lower solutions using related equations. © 1998 B. G. Teubner Stuttgart - John Wiley & Sons, Ltd.
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  • 67
    ISSN: 1612-1112
    Keywords: Capillary electrophoresis ; Airborne particles ; Humic-like substances
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A considerable fraction of the refractory organic carbon in airborne particulate matter is to be attributed to humic-like substances (HULIS). Such atmospheric HULIS isolated from different air dust samples by a microscale extraction procedure were characterized by capillary electrophoresis (CE). For fractionation of HULIS the working conditions of the CE system were optimized using a borate buffer (pH 8.2), polyacrylamide (PAA) coated, fused-silica capillary and polyethylene glycol as sieving modifier. Using CE under optimized conditions, HULIS produced electropherograms showing well resolved and reproducible signals.
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  • 68
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    Chromatographia 47 (1998), S. 249-256 
    ISSN: 1612-1112
    Keywords: Capillary electrophoresis ; Cyclodextrin mobile phase additives ; Synthetic food colorants ; Selectivity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A high-performance capillary electrophoresis method with diode-array detection has been developed for analysis of synthetic food colorants. The influence of buffer composition on the separation of the food colorants was examined, as were the effects of α-, β- and γ-c-yclodextrins on analyte migration behavior. Eight food colorants were completely separated within 10 min using pH 9.5 borax—NaOH buffer containing 5 mM β-cyclodextrin. Experimental results indicate that the relative standard deviations of analyte migration times were〈0.88% under the optimized separation condition. Correlation coefficients of the linear calibration plots of the analytes exceeded 0.998. The method was suitable for determination of the quantities of synthetic food colorantsi in ice cream bars and fruit soda drinks.
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  • 69
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    Chromatographia 48 (1998), S. 355-359 
    ISSN: 1612-1112
    Keywords: Capillary electrophoresis ; Cathodic flow electrode ; Electrolyte buffer depletion ; Reproductibility and precision
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The effects of electrolyte buffer depletion is well recognised and regular replacement of the electrolyte can prevent poor reproducibility. We have further investigated the effect of electrolyte depletion and produced a modified cathodic flow electrode to improve reproducibility using minimal volumes of electrolytes.
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  • 70
    ISSN: 1612-1112
    Keywords: Capillary electrophoresis ; Enantiomers ; Epinephrine ; Experimental designs ; Optimization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A capillary electrophoretic method using a chiral selector was optimized by experimental design for the enantioresolution of epinephrine enantiomers. Two β-cyclodextrins derivatives, namely heptakis-2,6-di-O-methyl-β-cyclodextrin and carboxy-methyl-β-cyclodextrin, respectively neutral and charged, were used as chiral selectors employing an uncoated capillary. By using a statistical experimental design in which all factors are varied at the same time, it was possible to optimize the method with regard to the resolution between peaks and the two migration times. A fractional factorial design and a central composite design were used. A compromise between conflicting goals, such as maximization of resolution and minimization of analysis time, was found by means of a desirability function D. Balancing these goals against each other, the most acceptable solution to the problem was found and the optimized method gave a fast separation with complete resolution between the adrenaline enantiomers. The response surfaces obtained confirmed the robustness of the method.
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  • 71
    ISSN: 1612-1112
    Keywords: Capillary electrophoresis ; pK A determination ; Indirect UV detection ; Alkyl-alkyl phosphonic acids
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Capillary electrophoresis (CE) has proved to be a fast and convenient method for the determination of the dissociation constants of non-UV absorbing solutes in the acidic pK A range (2.0–2.5). The electroosmotic flow was reversed by washing the capillary with 0.2% polybren aqueous solution. A series of background electrolytes was prepared with phenylphosphonic acid (pK A=1.29) and β-alanine (pK A=3.55) with the same ionic strength and a high buffer capacity in order to improve the repeatability (0.1–0.2 %) of the electrophoretic mobility and to determine the values of pK A accurately. This procedure was applied to the determination of the dissociation constants of several alkyl-alkylphosphonic acids whose pK A values have not yet been published in the literature. In this work, their dissociation constants have been found to vary between 1.91 and 2.34 for alkyl-methylphosphonic acids and between 2.10 and 2.38 for alkyl-ethylphosphonic acids.
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  • 72
    ISSN: 1612-1112
    Keywords: Capillary electrophoresis ; Aldehydes ; Hydrazino benzene sulfonic acid ; Water analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A method has been developed for the analysis of environmentally important aldehydes in rain water. The method is based on the derivatization of the aldehydes with hydrazino benzene sulfonic acid, separation of the hydrazones formed by capillary electrophoresis and UV detection at 280 nm. Derivatization was shown to be complete in 15 min at 50°C. The aldehyde derivatives could be separated from each other and from the excess of reagent using a pH 9 borate buffer as background electrolyte, with an analysis time of less than 6 min. The repeatability was better than 0.5% for the peak mobilities and in the order of 2–5% for the peak areas. Detection limits of 0.8–3 μmol L−1 (0.02–0.2 ppm) were obtained. The method was applied for the determination of formaldehyde and acetaldehyde in rain water samples.
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  • 73
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    Chromatographia 48 (1998), S. 569-575 
    ISSN: 1612-1112
    Keywords: Capillary electrophoresis ; Oligonucleotides ; Dextran ; Polymer solution ; Purity testing
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Capillary gel electrophoresis (CGE) has been recognized as an effective method for the analysis of oligonucleotides. CGE using polymer solutions is especially useful and effective compared with that using crosslinked gels, because of easy change of media. Replacement of media leads to the reproducible separation of analytes. We have investigated CGE analysis of oligonucleotides of less than 20 bases employing various kinds of polymers. Polyacrylamide, dextrin, dextran, pullakin, and poly(ethylene glycol) were used as sieving matrixes at concentrations of 0–30 %. Polydeoxythymidylic acids [p(dT)11–20] were used as a test sample. These small oligonucleotides were successfully resolved on the basis of their base number by CGE using some of these polymer solutions. In particular, dextran was found to be effective and baseline separation was observed when a 30 % dextran solution was employed. Some validations such as linearity and reproducibility were also established and this method was found to be an adequate quality control method for small oligonucleotides. Finally, CGE using a 30 % dextran solution was successfully applied to impurity profiling of some synthetic oligonucleotides.
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  • 74
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    Chromatographia 48 (1998), S. 739-744 
    ISSN: 1612-1112
    Keywords: Capillary electrophoresis ; Nucleotides ; Inorganic cations ; Complexation with Mg and Ca
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The complexation equilibrium between nucleotides (ATP, ADP) and inorganic cations (Mg2+, Ca2+) has been studied by capillary electrophoresis. The equilibrium constant and the stoichiometry of nucleotide-inorganic cation complexes can be deduced from the dependence of the electrophoretic mobility of each nucleotide on the negative logarithm of the inorganic cation concentration. The experimental values of complexation constants determined by CE compare favorably with those in the literature. As expected, Mg2+ forms more stable complexes with ATP (logK=2.30 and 4.10 at pH 5 and 8, respectively) than with ADP (logK=1.92 and 3.15 at pH 5 and 8, respectively). In the pH range 4–8, the stoichiometry of ADP-Mg2+ and ADP-Ca2+ complexes is always 1∶1 whereas that of the complexes between these cations and ATP depends on pH-hence ATP-Mg2+ and ATP-Ca2+ complexes have 1∶1 stoichiometry at pH 5 and 1∶2 at pH 8.
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  • 75
    ISSN: 1612-1112
    Keywords: Capillary electrophoresis ; Conductivity tuning ; Chiral separation ; Peak symmetry ; Resolution expression
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Different approaches how to handle the electromigration dispersion process that occurs in separation and determination of enantiomers are presented. The use of cyclodextrins as chiral selectors in resolution enantiomers involves the possibility to tune the conductivity of the sample band in order to obtain symmetrical and efficient peaks. Determination of impurities that migrate in the rear part of an overloaded main peak can be accomplished if the conductivity of the background electrolyte (BGE) is adapted to the conductivity of the sample band. This strategy was shown in determination of the content of D-sotalol in a mixture of L and D-sotalol. The efficiency and the symmetry of the overloaded L-sotalol peak was substantially improved by substitution of tetrabutylammonium ions for tetrapentylammonium ions as co-ions in the BGE. In this system it was possible to determine 0.2% w/w of the chiral impurity D-sotalol. A resolution model is presented and used qualitatively in the study where the complexation between the tetraalkyllammonium ions and the cyclodextrins is taken into account.
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  • 76
    ISSN: 1612-1112
    Keywords: Capillary electrophoresis ; Succinic and levulinic acid ; Indirect UV detection ; Standard addition method
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary This paper describes an capillary electrophoresis (CE) method used to quantify both succinic acid and levulinic acid in an industrial production process. Measurement was performed by CE with indirect UV detection, using potassium hydrogen phthalate as the UV-absorbing additive. The electrolyte composition used was 5 mM potassium hydrogen phthalate at pH 7.0 containing 0.25 mM cetyl trimethylammonium bromide (CTAB) as an electrosmotic flow (EOF) modifier to reverse the EOF. The method provides for improved sensitivity by employing an extended path length capillary, and for identification and quantification by the use of a standard addition method.
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  • 77
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    Chromatographia 47 (1998), S. 219-224 
    ISSN: 1612-1112
    Keywords: Capillary electrophoresis ; Beta-blockers ; Protein separation ; Drug separation ; Guaran ; Buffer modifier
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Guaran, a neutral polysaccharide, has been used as a buffer modifier to improve the separation of basic proteins and drugs. Migration reproductibility, peak shape and efficiency were improved when 0.1% guaran was added to the buffer. The concentration of guaran, ionic strength, and pH of buffer solution were optimized to obtain the optimum separation of proteins. Possible separation efficiencies of 700,000 plates per meter were obtained for test proteins. The relative standard deviation (% RSD) of the migration time of all test proteins was less than 0.5%. Improved separation of β-blockers was also observed when guaran was added to the buffer.
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  • 78
    ISSN: 1612-1112
    Keywords: Capillary electrophoresis ; DNA fragments ; Cellulose derivatives ; Sieving cellulose matrix
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A rapid, robust and reproducible method providing excellent separation performance and simplicity using a 0.5% MC-4000 methyl cellulosic sieving medium in DB-1 coated capillaries has been developed. The method is suitable for qualitative comparison of DNA restriction profiles for fragments in the size range 100–1000 base pairs (bp). Efficiencies up to 8.5 million plates/m (1057 bp fragment) were recorded. Peak resolution of 6 bp (291/297 bp, 335/341 bp) and 4 bp (238/242 bp, 341/345 bp) was achieved. In addition, 1 bp partial resolution of 123/124 bp and 298/297 bp was obtained. Run-to-run (n=15), day-to-day (n=4), and capillary-to-capillary (n=3) variations of 0.1–0.2% RSD, 0.3–0.5% RSD, and 0.1–0.3% RSD, respectively, were observed. The MC-4000 sieving matrix was found to be better than hydroxypropyl methyl cellulose and hydroxypropyl cellulose, in terms of both performance and stability in the DB-1 coated capillaries. The efficiency and resolution in DB-WAX capillaries were inferior to those obtained in DB-1 capillaries. The commercially available DB-1 capillaries were stable for months in the sieving medium at pH 8.3 and could be regenerated to provide high efficiency after accidental current breaks.
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    Chromatographia 48 (1998), S. 331-346 
    ISSN: 1612-1112
    Keywords: Peak integration ; Baseline determination ; Quantitation ; Capillary electrophoresis ; Chromatography
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Peak integration is still a major source of error in analytical techniques such as chromatography (LC and GC), aapillary electrophoresis (CE), spectrosocpy, and electrochemistry. If the baseline is complex, e.g. because of matrix effects, or if the peak shape is irregular, e.g. because of peak tailing, the results are often not satisfactory when classical procedures are used. These shortcomings arise because of the stepwise appearance of the chromatogram. An algorithm that copies the human method of considering baseline and peaks as a whole has already been introduced. Here the use of a straight line as a baseline model led to an improvement in several instances. The baseline is, however, usually not exactly straight and rigid. A baseline model with flexible properties is more advantageous. Thus the smoothing cubic spline function is applied in this work. Here the rigidity can be controlled by use of a parameterp k. The prediction interval of the spline is used for iterative distinction between baseline and peak regions. Afterwards straightforward optimization of the peak boundaries is applied. More than 50 series of consecutive injections of the same sample (n=40 on average) were used to test the performance of this procedure. The same raw data have been integrated by means of the algorithm described here and by use of commercially available software. The reproducibility of the main component peak are within the series was taken as a measure of integration quality. Typically the new procedure reducesRSD % by approximately 33% (e.g. from 1.5% to 1.0%). The improvement is even more impressive for difficult samples with complex matrices, e.g. blood plasma or polymer excipients. for such samples improvements of up to a factor of 6 are obtained.
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  • 80
    ISSN: 0894-3230
    Keywords: Menschutkin reaction ; duality of SN1, SN2 mechanisms ; benzyl tosylates ; Yukawa-Tsuno equation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rate data for the Menschutkin reaction between strongly activated Z-substituted benzyl p-toluenesulfonates and Y-substituted N,N-dimethylanilines in acetonitrile at 35 °C fit the equation, kobs  =  k1 + k2 [DMA], which is consistent with concurrent first- and second-order processes. The k1 and k2 values for each substrate were separated based on the above equation. The SN1 rate constant, k1, is unaffected by the nature of the nucleophile, whereas the SN2 rate constant, k2, increased with the electron-donating substituent of the N,N-dimethylaniline. The substituent effect on the k1 values is linearly correlated by the Yukawa-Tsuno equation with ρ  =  -5.2 and r  =  1.3. The unimolecular reaction can be regarded as a classical SN1 mechanism. In contrast, that on the k2 values shows an upward curvature when analyzed by the Brown σ+ treatment. These results are ascribed to the simultaneous and independent occurrence of SN1 and SN2 mechanisms in the present Menschutkin reaction. © 1998 John Wiley & Sons, Ltd.
    Additional Material: 6 Ill.
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  • 81
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    Journal of Physical Organic Chemistry 11 (1998), S. 231-231 
    ISSN: 0894-3230
    Keywords: Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: No Abstract
    Type of Medium: Electronic Resource
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  • 82
    ISSN: 0894-3230
    Keywords: calorimetry ; IR spectra ; ketones ; solvation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solution enthalpies of n-hexane, acetone, butan-2-one and octan-2-one in a series of tetrachloromethane-acetonitrile mixtures and the carbonyl stretching absorption frequencies in the IR spectra of these ketones were determined. It was found that over the whole range of concentrations (varying from neat tetrachloromethane up to neat acetonitrile) the solvation enthalpy of these compounds can be obtained additively from the contributions of the alkyl and carbonyl fragments. The solvent effect on the solvation enthalpy of the carbonyl group was found to be satisfactorily correlated with the corresponding IR frequency shifts of the C=O group. It was also found that the sensitivities of the carbonyl IR frequencies to the solvent composition are different for various ketones. From both IR and calorimetric data, the preferential solvation parameters were evaluated. The differences between the IR spectroscopic and calorimetric data are discussed. © 1998 John Wiley & Sons, Ltd.
    Additional Material: 4 Ill.
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  • 83
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    Journal of Physical Organic Chemistry 11 (1998), S. 261-272 
    ISSN: 0894-3230
    Keywords: 1-substituted 2-pyrrolidinones ; C=O stretching frequencies ; solvent effects ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In an effort to model solute-solvent interactions, the C=O stretching frequencies of five 1-substituted 2-pyrrolidinones and four other carbonyl-containing compounds were measured for 30 common solvents. These were then correlated with four empirical parameter sets and one theoretical (computational) parameter set. While an empirical parameter set gave the best correlation equations, the theoretical parameter equations are physically and statistically significant. Solvent volume, polarizability and hydrogen bond donor acidity (capacity) terms are significant in the correlation equations. © 1998 John Wiley & Sons, Ltd.
    Additional Material: 14 Tab.
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  • 84
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    Journal of Physical Organic Chemistry 11 (1998), S. 232-240 
    ISSN: 0894-3230
    Keywords: P - S bond cleavage ; hydroperoxidolysis ; nerve agent VX ; molecular orbital calculations ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The P - S bond cleavage process in the hydroperoxidolysis of a model system for the nerve agent VX was studied using ab initio and semiempirical molecular orbital methods. Aqueous solvation effects were included through single-point calculations using the semiempirical SM5.2PD/A continuum solvation model and geometries optimized at the HF/MIDI! level of theory. The predominant pathway for P - S bond cleavage involves pseudorotation of a low-energy trigonal bipyramidal intermediate followed by apical ligand ejection. In aqueous solution, the free energy barriers for these processes are found to be 14.3 and 4.6 kcal mol-1, respectively, with electronic energies calculated at the MP2/cc-pVDZ//HF/MIDI! level of theory. By comparison with another continuum model of solvation (PCM), it is concluded that the SM5.2PD/A model performs well even for hypervalent phosphorus species, in spite of not having included any such molecules in the model's parameterization set. © 1998 John Wiley & Sons, Ltd.
    Additional Material: 4 Ill.
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  • 85
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    Journal of Physical Organic Chemistry 11 (1998), S. 407-410 
    ISSN: 0894-3230
    Keywords: gas-phase thermolysis ; N-methyl-N-phenyl-tert-butylsulfenamide ; morpholinyl-tert-butylsulfenamide ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: N-Methyl-N-phenyl-tert-butylsulfenamide (MPSA) and morpholinyl-tert-butylsulfenamide (MOSA) were thermolyzed in a stirred-flow reactor at temperatures of 340-390 °C and pressures of 7-13 Torr, using toluene as carrier gas, at residence times of 0.3-1.3 s. Isobutene was formed in 99% yield through first-order reactions having the following Arrhenius parameters (A,s-1, Ea, kJ mol-1): MPSA, log A  =  12.41 ± 0.02, Ea  =  158.8 ± 0.2; MOSA, log A  =  12.91 ± 0.22, Ea  =  159 ± 3. It is proposed that the elimination of isobutene takes place by unimolecular reaction mechanisms involving polar, four-center cyclic transition states, forming S-unsubstituted thiohydroxylamines as co-products. Thermochemical parameters, estimated by semiempirical AM1 calculations, are reported for the latter and for the parent molecules. © 1998 John Wiley & Sons, Ltd.
    Additional Material: 1 Ill.
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  • 86
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    Journal of Physical Organic Chemistry 11 (1998), S. 411-418 
    ISSN: 0894-3230
    Keywords: 2,2′-bisbenzimidazolyl ; tautomerism ; NMR ; semi-empirical calculations ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A dynamic NMR study of the tautomerism of 2,2′-bisbenzimidazolyl in DMSO-d6 and a mechanistic interpretation of the process, based on a stepwise, single-proton transfer and formation of a zwitterionic intermediate, are presented. This interpretation is substantiated by semi-empirical calculations of the postulated intermediate and transition state, that yield results which are compared with previous studies on related aliphatic systems. © 1998 John Wiley & Sons, Ltd.
    Additional Material: 5 Ill.
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  • 87
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    Journal of Physical Organic Chemistry 11 (1998), S. 397-406 
    ISSN: 0894-3230
    Keywords: bond dissociation energy ; acidity ; phenylsulfenylamides ; phenylsulfenylanilides ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Acidities and bond dissociation energies (BDEs) of the N-H bond in two phenylsulfenylamides, PhSNHBz and PhSNH-t-Bu, and four phenylsulfenylanilides, 4-GC6H4NHSPh, where G  =  MeO, H, Br and CN, were measured in order to compare the effects of substituents on acidities and BDEs of N - H bonds with those of C - H bonds. The effects of PhS groups on acidities and BDEs in a series of C - H acids were found to be comparable to those on acidities and BDEs of PhS in a similar series of N - H acids. Comparisons were also made of the effects of changing the oxidation state of sulfur in the series PhS, PhSO and PhSO2 on the acidities and BDEs of adjacent N - H and C - H bonds in weak acids. Hammett-type plots of pKHA values for phenyl benzyl sulfones (4-GC6H4CH2SO2Ph) and phenylsulfenylanilides (4-GC6H4NHSPh) were linear vs σp- values. A linear plot was obtained and explained for a plot of BDE of the N - H bonds in remotely substituted phenylsulfonylanilides with σ+ values. Plots of BDEs vs Eox(A-) were also linear for 4-substituted phenylsulfenylanilides (4-GC6H4NHSPh), phenylsulfonylanilides (4-GC6H4NHSO2Ph) and phenyl benzyl sulfones (4-GC6H4CH2SO2Ph). © 1998 John Wiley & Sons, Ltd.
    Additional Material: 7 Tab.
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  • 88
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    Journal of Physical Organic Chemistry 11 (1998), S. 387-391 
    ISSN: 0894-3230
    Keywords: α-diamides ; 17O NMR ; conformation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 17O NMR spectra of several α-diamides were obtained at natural isotopic abundance in acetonitrile solution in order to study the conformations of these compounds in solution. The 17O NMR shifts vary with the intercarbonyl dihedral angle α in a sense opposite to that observed for α-diketones. © 1998 John Wiley & Sons, Ltd.
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  • 89
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    Journal of Physical Organic Chemistry 11 (1998), S. 392-396 
    ISSN: 0894-3230
    Keywords: 8-azaadenine ; tautomerism ; theoretical study ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The prototropic tautomerism of 8-azaadenine (azaade) was studied theoretically by means of ab initio methods, in both the gas phase and aqueous solution. A number of tautomeric forms were not included in the calculations after applying a stepwise elimination procedure based on both AM1 and HF/6-31G* energy values. The tautomers 9H-azaade, 8H-azaade and 7H-azaade survived to this elimination and their optimized geometries and energies were calculated at the MP2/6-31*//HF/6-31G* level. To include the solvent effects, two self-consistent reaction field method were used: (1) Onsager's SCRF with multipolar expansion up to the hexadecapolar term and (2) the isodensity polarizable continuum method (IPCM). Both methods produce similar results, although the latter represents better the situation in aqueous solution. The stability order in solution, 8H- 〉 9H- 〉 7H-azaade, differs slightly from that found in the gas phase, implying that in general the electrostatic effects in solution are important, but the intrinsic stability of these species in the gas phase overcomes the solvent effect. © 1998 John Wiley & Sons, Ltd.
    Additional Material: 1 Ill.
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  • 90
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    Journal of Physical Organic Chemistry 11 (1998), S. 377-377 
    ISSN: 0894-3230
    Keywords: Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: No abstract.
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  • 91
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    Journal of Physical Organic Chemistry 11 (1998), S. 419-425 
    ISSN: 0894-3230
    Keywords: 5-nitro-5′-dimethylamino-2,2′-bisthiophene ; π* probe dye ; cyclic voltammetry ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cyclic voltamograms of the solvatochromic dye 5-nitro-5′-dimethylamino-2,2′-bisthiophene (1), introduced recently as a sensitive π* probe, were recorded in different solvents. An EPR spectrum of the anionic radical of 1 in DMSO was obtained and compared with other spectra of analogous substituted bisthiophene radicals. It was found that the presence of a donor- acceptor pair of substituents in 1-⋅ reduces significantly the rotational barrier of the radical compared with the unsubstituted bithienyl radical anion 2-⋅. This is the result of an electronic repulsion between the donor ring fragment and the added electron in the coplanar radical, which does not exist in 2-⋅. © 1998 John Wiley & Sons, Ltd.
    Additional Material: 3 Ill.
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  • 92
    ISSN: 0894-3230
    Keywords: calix[4]resorcinarenes ; organophosphorus compounds ; solvatophobic interactions ; host-guest complexation ; high-performance liquid chromatography ; x-ray analysis ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Reversed-phase high-performance liquid chromatography [LiChrosorb RP-18,UV detection at 254 nm and acetonitrile-water (86:14,v/v) as mobile phase] was applied to studies of the host-guest complexation of tetraalkylcalix[4]resorcinareneoctols and their upper rim phosphoryl, sulfonyl and dialkylaminomethyl derivatives with some aromatic guests in the mobile phase. It was shown that the formation of the inclusion complexes results in changes in the retention of aromatic guests and improves their separation. Stability constants of the complexes were calculated from the dependences of the l/k′ values of the aromatic guest on the concentration of the calix[4]resorcinarene in the mobile phase. The molecular structure of 4,6,16,18-tetrahydroxy-10,12,22,24-tetrakis(dipropoxyphosphoryloxy)-2,8,14,20-tetramethylcalix[4]resorcinarene (12) was determined. Crystal data for 12 are P21/n, a  =  16.708(9) Å, b  =  18.683(6) Å, c  =  20.243(5) Å, β  =  95.75(3)°, V  =  6287(4) Å3 and Z  =  4. Compound 12 exists in a boat conformation, in which two opposite unsubstituted resorcinol rings of the macrocyclic skeleton lie in the plane formed by four methine bridges and two diphosphorylated rings are perpendicular to the plane. © 1998 John Wiley & Sons, Ltd.
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  • 93
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    Journal of Physical Organic Chemistry 11 (1998), S. 378-386 
    ISSN: 0894-3230
    Keywords: alkylboronic acids ; arylboronic acids ; ab initio ; MM3 ; molecular mechanics ; force field parameters ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The boronic acid functional group has been incorporated into various biologically important compounds. In order to study this class of compounds better with molecular mechanics, five alkyl- and arylboronic acids were calculated using ab initio methods (Spartan) at the RHF/6-31G* level. MM3 force field parameters were developed based on the theoretically calculated geometries, vibrational spectra, and torsional profiles. © 1998 John Wiley & Sons, Ltd.
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  • 94
    ISSN: 0894-3230
    Keywords: γ-lactones ; base-catalysed hydrolysis ; reactivity-structure correlations ; isobenzofuranones ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Rate coefficients were measured for the base-catalysed hydrolysis of a series of substituted 3-(phenoxy- or thiophenoxymethylene)-(Z)-1(3H)-isobenzfuranones (3-phenoxy- or thiophenoxymethylenephthalides) in 70% (v/v) aqueous dioxane at 30.0 °C, in addition to the carbonyl stretching frequencies in chloroform and tetrachloromethane following deconvolution and band separation, when required. The Hammett reaction constants for the alkaline hydrolysis of the 3-/4-substituted phenoxy and thiophenoxy series are ca 0.75 and 1.10, respectively. These results are related to electrostatic field and resonance effects. Successful correlations between the carbonyl stretching frequencies and substituent constants and the rates of alkaline hydrolysis were found. Computational studies using the semi-empirical AM1 method correctly model both the details of the mechanistic pathway and the substituent effects. © 1998 John Wiley & Sons, Ltd.
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  • 95
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    Journal of Physical Organic Chemistry 11 (1998), S. 437-447 
    ISSN: 0894-3230
    Keywords: inductive constants ; theoretical estimation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new model of the inductive effect is proposed, allowing highly accurate theoretical calculations of inductive constants for a diversity of substituents, using a simple and readily available system of mathematics. According to this approach, the inductive effect of a substituent is considered in terms of the additive influence of its constituent atoms. A constant inherent capacity for inductive interaction with a reactive center (with a four-coordinate carbon atom chosen for such a center), represented by an atomic constant σA, is ascribed to each atom. Values of σA for a wide variety of atoms are determined, and their physical meaning is revealed to elucidate to a certain extent the physical nature of the inductive effect. In addition, the proposed model permits the convenient use in calculations of group constants σG characterizing the inductive power of groups. Values of σG are determined for molecular fragments that are most widely dealt with in organic chemistry, and the use of σA or σG constants and of their superposition is shown to have, in most cases, little or no effect on the accuracy and reproducibility of the results obtained. It is also shown that, in terms of the developed approach, the inductive effect of a substituent is closely associated with its conformation. Theoretical inductive constants were calculated for 427 organic, aromatic, organometallic and charged substituents, and they showed perfect correlation with the corresponding experimental values. © 1998 John Wiley & Sons, Ltd.
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  • 96
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    Journal of Physical Organic Chemistry 11 (1998), S. 448-454 
    ISSN: 0894-3230
    Keywords: mandelic acid ; alkaline permanganate ; oxidation ; kinetics ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of the oxidation of mandelic acid (MA) by permanganate in aqueous alkaline medium at a constant ionic strength of 1.0 mol dm-3 were studied spectrophotometrically. The reaction shows first-order kinetics in [permanganate ion] and fractional order dependences in [MA] and [alkali]. Addition of products, manganate and aldehyde have no significant effect on the reaction rate. An increase in ionic strength and a decrease in dielectric constant of the medium increase the rate. The oxidation process in alkaline medium under the conditions employed in the present investigation proceeds first by formation of an alkali permanganate complex, which combines with mandelic acid to form another complex. The latter decomposes slowly followed by a fast reaction between the free radical of mandelic acid and another molecule of permanganate to give products. The reaction constants involved in the mechanism were derived. There is good agreement between the observed and calculated rate constants under different experimental conditions. The reaction was studied at different temperatures and activation parameters were computed with respect to the slow step of the proposed mechanism. © 1998 John Wiley & Sons, Ltd.
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  • 97
    ISSN: 0894-3230
    Keywords: Selective arylation ; exocyclic N-position ; 2-pyrimidylnitrenium ion ; tetrazolo[1,5a]pyrimidine ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Photo-reactions of tetrazolo[1,5-a]pyrimidine (1) with benzene (2a) and substituted benzenes (2b-f) in the presence of trifluoroacetic acid (TFA) gave 2-(2-, 3- and 4-substituted anilino)pyrimidines (3-5) together with 2-aminopyridine (6) and biphenyl (7) or diarylmethanes (8b, 8c and 8e). From the effect of heavy-atom solvent on the reactions, it is reasonable to assume that 3-5 are formed via a singlet species, but 6-8 via a triplet species. The intermediacy of 2-pyrimidylnitrenium ion is consistent with the evidence derived by the above effect, by a Hammett plot with ρ = -2.9 and by effects of solvent nucleophilicity and counter-anions. The selective exocyclic N-arylation giving 3-5 is discussed. © 1998 John Wiley & Sons, Ltd.
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  • 98
    ISSN: 0894-3230
    Keywords: 3-methyl-2, 4-diphenyl-3-azabicyclo[3.3.1]nonan-9α-ol esters ; analgesics ; synthesis ; structure ; conformation ; pharmacological assays ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of esters derived from 3-methyl-2,4-diphenyl-3-azabicyclo[3.3.1]nonan-9α-ol (1) was synthesized and studied by 1H and 13C NMR spectroscopy, and the crystal structure of 3-methyl-2,4-diphenyl-9α-(3,5-dimethylbenzoyloxy)-3-azabicyclo[3.3.1]nonane (2) was determined by x-ray diffraction. The compounds studied display in CDCl3 a preferred flattened chair-chair conformation. This bicycle conformation is similar to that found for 2 in the crystal state. Pharmacological assays on mice were performed to evaluate drug-induced behavioral alteration, peripheral or central acute toxicity and analgesic activity. © 1998 John Wiley & Sons, Ltd.
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  • 99
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    Journal of Physical Organic Chemistry 11 (1998), S. 101-108 
    ISSN: 0894-3230
    Keywords: encounter complexes ; 1-cyanonaphthalene ; norbornadiene ; stereospecific ; nucleophilic trapping ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Photo-induced electron donor-acceptor reactions between 1-cyanonaphthalene (CNN) and norbornadiene (N) generate products of several structure types. Methanol adducts (1-3) formed in polar solvents are rationalized via the radical cation, N+·, and stereospecific (exo-) nucleophilic attack by methanol. In less polar solvents, CNN and N form [2 + 2]-cycloadducts, exclusively on the exo-face of N. In non-polar solvents containing methanol, CNN, N and methanol combine to form 1:1:1 adducts, containing the sensitizer on the endo- and the methoxy groups on the exo-face. The formation of these products is rationalized via the trapping of encounter complexes of different geometries. Any rearrangement of the norbornenyl system can be eliminated, since neither tricyclyl nor 7-methoxynorbornenyl structures are formed. Apparently, the alcohol captures an endo-encounter complex of CNN and N by attack from the exo-face, similar to the attack of methanol on N+·. © 1998 John Wiley & Sons, Ltd.
    Additional Material: 2 Ill.
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  • 100
    ISSN: 0894-3230
    Keywords: aromaticity ; Diels-Alder transition states ; Diels-Alder adducts ; reaction mechanism ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Semiempirical, ab initio and DFT investigations on the mechanism of the Diels-Alder reactions of a set of masked dienes (ring-fused dienes), viz. o-quinodimethane, anthracene and α-vinylnaphthalene, with ethylene, and reactions of α-vinylnaphthalene with maleic anhydride and p-benzoquinone were performed with a view to understanding the role of masking factors on the activation and reaction energies. The reactions were found to occur in a concerted fashion through synchronous transition states (TSs) in the first two reactions and through asynchronous TS in the other case. Of the compounds studied, o-quinodimethane is the most reactive diene both in a kinetic and a thermodynamic sense. α-Vinylnaphthalene reacts faster with maleic anhydride than p-benzoquinone, as expected, and two possible stereoselective TSs, one endo and the other exo, have been located for the reactions of α-vinylnaphthalene with the above dienophiles. Calculations show that the relative gain or loss of aromatic stabilization of the benzonoid ring in the transition state and in the product seems to play a major role in the kinetic and thermodynamic control of these reactions. © 1998 John Wiley & Sons, Ltd.
    Additional Material: 2 Ill.
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