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  • Column liquid chromatography  (144)
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  • Chaotic behaviour
  • Handbook of geophysics
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  • 1995-1999  (264)
  • 1965-1969
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  • 1
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    OR spectrum 20 (1998), S. 101-107 
    ISSN: 1436-6304
    Keywords: Competitive location model ; Nash equilibria ; stability ; reachability ; Wettbewerbsmodelle in der Standorttheorie ; Nash Gleichgewicht ; Stabilität ; Erreichbarkeit
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mathematics , Economics
    Description / Table of Contents: Zusammenfassung In der Arbeit werden die Standorte von Duopolisten in einem Baum untersucht. Unter der Annahme festgesetzter Preise werden notwendige und hinreichende Bedingungen für Nash Gleichgewichte für Standorte auf Bäumen hergeleitet. Unter Verwendung dieser Bedingungen wird dann gezeigt, daß — angenommen Nash Gleichgewichte existieren — diese in einem wiederholt angewandten sequentiellen Standortfindungsprozeß, in dem beide Duopolisten als Zielfunktion kurzfristige Gewinnmaximierung haben, auch erreicht werden.
    Notes: Abstract This paper examines the location of duopolists on a tree. Given parametric prices, we first delineate necessary and sufficient conditions for locational Nash equilibria on trees. Given these conditions, we then show that Nash equilibria, provided they exist, can be reached in a repeated sequential relocation process in which both facilities follow short-term profit maximization objectives.
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  • 2
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    OR spectrum 20 (1998), S. 101-107 
    ISSN: 1436-6304
    Keywords: Key words: Competitive location model ; Nash equilibria ; stability ; reachability ; Schlüsselwörter: Wettbewerbsmodelle in der Standorttheorie ; Nash Gleichgewicht ; Stabilität ; Erreichbarkeit
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mathematics , Economics
    Description / Table of Contents: Zusammenfassung. In der Arbeit werden die Standorte von Duopolisten in einem Baum untersucht. Unter der Annahme festgesetzter Preise werden notwendige und hinreichende Bedingungen für Nash Gleichgewichte für Standorte auf Bäumen hergeleitet. Unter Verwendung dieser Bedingungen wird dann gezeigt, daß– angenommen Nash Gleichgewichte existieren – diese in einem wiederholt angewandten sequentiellen Standortfindungsprozeß, in dem beide Duopolisten als Zielfunktion kurzfristige Gewinnmaximierung haben, auch erreicht werden. “Equilibrium is a place in heaven, but how do we get there from here?”
    Notes: Abstract. This paper examines the location of duopolists on a tree. Given parametric prices, we first delineate necessary and sufficient conditions for locational Nash equilibria on trees. Given these conditions, we then show that Nash equilibria, provided they exist, can be reached in a repeated sequential relocation process in which both facilities follow short-term profit maximization objectives.
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  • 3
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    Empirical economics 23 (1998), S. 387-400 
    ISSN: 1435-8921
    Keywords: Key words: Money demand ; cointegration ; stability ; regime shift ; JEL classification: E41 ; C22
    Source: Springer Online Journal Archives 1860-2000
    Topics: Economics
    Notes: Abstract. Using several tests for structural stability in regressions with I(1) variables and for the existence of cointegration in models with regime shifts, the empirical evidence on the existence of a structural break in the Spanish long-run demand for broad money (ALP2) is analysed.  The results indicate that shifts affecting the demand for ALP2 in recent years have substantially altered its long-run properties. As to the cause of this structural break, emphasis is placed on the role played by the increasing openness of the Spanish financial system to international markets as obstacles to free capital movements have progressively disappeared.
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    Stochastic environmental research and risk assessment 12 (1998), S. 191-204 
    ISSN: 1436-3259
    Keywords: Keywords: groundwater flow ; inverse problems ; stability ; geostatistical interpolation ; kriging.
    Source: Springer Online Journal Archives 1860-2000
    Topics: Architecture, Civil Engineering, Surveying , Energy, Environment Protection, Nuclear Power Engineering , Geography , Geosciences
    Notes: Abstract The Differential System Method (DSM) permits identification of the physical parameters of finite-difference groundwater flow models in a confined aquifer when piezometric head and source terms are known at each point of the finite-difference lattice for at least two independent flow situations for which the hydraulic gradients are not parallel. Since piezometric head data are usually few and sparse, interpolation of the measured data onto a regular grid can be performed with geostatistical techniques. We apply kriging to the sparse data of a synthetic aquifer to evaluate the stability of the DSM with respect to uncorrelated measurement errors and interpolation errors. The numerical results show that the DSM is stable.
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  • 5
    ISSN: 1572-8358
    Keywords: Epidemiology ; sleeping sickness ; vector controls ; differential equations ; spacialization ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract A compartmental model is described for the spread of Gambian sleeping sickness in a spatially heterogeneous environment in which vector and human populations migrate between two "patches": the village and the plantations. The number of equilibrium points depends on two "summary parameters": gr the proportion removed among human infectives, and R0, the basic reproduction number. The origin is stable for R0 〈1 and unstable for R0 〉1. Control strategies are assessed by studying the mix of vector control between the two patches that bring R0 below 1. The results demonstrate the importance of vector control in the plantations. For example if 20 percent of flies are in the village and the blood meal rate in the village is 10 percent, then a 20 percent added vector mortality in the village must be combined with a 9 percent added mortality in the plantations in order to bring R0 below 1. The results are quite insentive to the blood meal rate in the village. Optimal strategies (that minimize the total number of flies trapped in both patches) are briefly discussed.
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    Journal of dynamics and differential equations 10 (1998), S. 151-188 
    ISSN: 1572-9222
    Keywords: Fourth-order solitary waves ; stability ; instability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mathematics
    Notes: Abstract We study ground-state traveling wave solutions of a fourth-order wave equation. We find conditions on the speed of the waves which imply stability and instability of the solitary waves. The analysis depends on the variational characterization of the ground states rather than information about the linearized operator.
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    ISSN: 1572-9281
    Keywords: asymptotic stability ; dichotomic maps ; retarded functional differential equation ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mathematics
    Notes: Abstract This paper deals with the study of the stability of nonautonomous retarded functional differential equations using the theory of dichotomic maps. After some preliminaries, we prove the theorems on simple and asymptotic stability. Some examples are given to illustrate the application of the method. Main results about asymptotic stability of the equation $$x'(t) = - b(t)x(t - r)$$ and of itsnonlinear generalization $$x'(t) = b(t)f(x(t - r))$$ are established.
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    Queueing systems 29 (1998), S. 55-73 
    ISSN: 1572-9443
    Keywords: multi‐server queue ; customer class ; state‐dependent routing ; stability ; Markov chain ; fluid limit
    Source: Springer Online Journal Archives 1860-2000
    Topics: Computer Science
    Notes: Abstract We consider a multi‐station queue with a multi‐class input process when any station is available for the service of only some (not all) customer classes. Upon arrival, any customer may choose one of its accessible stations according to some state‐dependent policy. We obtain simple stability criteria for this model in two particular cases when service rates are either station‐ or class‐independent. Then, we study a two‐station queue under general assumptions on service rates. Our proofs are based on the fluid approximation approach.
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    Queueing systems 28 (1998), S. 33-54 
    ISSN: 1572-9443
    Keywords: queueing networks ; throughput ; closed networks ; efficiency ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Computer Science
    Notes: Abstract A closed network is said to be “guaranteed efficient” if the throughput converges under all non-idling policies to the capacity of the bottlenecks in the network, as the number of trapped customers increases to infinity. We obtain a necessary condition for guaranteed efficiency of closed re-entrant lines. For balanced two-station systems, this necessary condition is almost sufficient, differing from it only by the strictness of an inequality. This near characterization is obtained by studying a special type of virtual station called “alternating visit virtual station”. These special virtual stations allow us to relate the necessary condition to certain indices arising in heavy traffic studies using a Brownian network approximation, as well as to certain policies proposed as being extremal with respect to the asymptotic loss in the throughput. Using the near characterization of guaranteed efficiency we also answer the often pondered question of whether an open network or its closed counterpart has greater throughput - the answer is that neither can assure a greater guaranteed throughput.
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    Queueing systems 29 (1998), S. 129-159 
    ISSN: 1572-9443
    Keywords: rate-based feedback control ; ATM networks ; stability ; optimal algorithms
    Source: Springer Online Journal Archives 1860-2000
    Topics: Computer Science
    Notes: Abstract Motivated by ABR class of service in ATM networks, we study a continuous time queueing system with a feedback control of the arrival rate of some of the sources. The feedback about the queue length or the total workload is provided at regular intervals (variations on it, especially the traffic management specification TM 4.0, are also considered). The propagation delays can be nonnegligible. For a general class of feedback algorithms, we obtain the stability of the system in the presence of one or more bottleneck nodes in the virtual circuit. Our system is general enough that it can be useful to study feedback control in other network protocols. We also obtain rates of convergence to the stationary distributions and finiteness of moments. For the single botterneck case, we provide algorithms to compute the stationary distributions and the moments of the sojourn times in different sets of states. We also show analytically (by showing continuity of stationary distributions and moments) that for small propagation delays, we can provide feedback algorithms which have higher mean throughput, lower probability of overflow and lower delay jitter than any open loop policy. Finally these results are supplemented by some computational results.
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    Advances in computational mathematics 9 (1998), S. 145-171 
    ISSN: 1572-9044
    Keywords: periodic pseudodifferential equations ; multiwavelets ; splines with multiple knots ; generalized Galerkin–Petrov schemes ; boundary element methods ; error analysis ; stability ; Strang–Fix condition ; 65J10 ; 65N30 ; 65N35 ; 65R20 ; 47G30 ; 45P05 ; 41A25 ; 41A30 ; 41A15
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mathematics
    Notes: Abstract We develop a stability and convergence analysis of Galerkin–Petrov schemes based on a general setting of multiresolution generated by several refinable functions for the numerical solution of pseudodifferential equations on smooth closed curves. Particular realizations of such a multiresolution analysis are trial spaces generated by biorthogonal wavelets or by splines with multiple knots. The main result presents necessary and sufficient conditions for the stability of the numerical method in terms of the principal symbol of the pseudodifferential operator and the Fourier transforms of the generating multiscaling functions as well as of the test functionals. Moreover, optimal convergence rates for the approximate solutions in a range of Sobolev spaces are established.
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    Celestial mechanics and dynamical astronomy 70 (1998), S. 41-58 
    ISSN: 1572-9478
    Keywords: three-body problem ; libration points ; stability ; normal forms.
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract In this paper we consider the problem of motion of an infinitesimal point mass in the gravity field of an uniformly rotating dumb-bell. The aim of our study is to investigate Liapunov stability of Lagrangian libration points of this problem. We analyze the stability of libration points in the whole range of parameters ω, μ of the problem. In particular, we consider all resonance cases when the order of resonance is not greater than five.
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    Monatshefte für Mathematik 126 (1998), S. 117-124 
    ISSN: 1436-5081
    Keywords: 52A20 ; 52A22 ; star bodies ; spherical integral transformations ; convex bodies ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mathematics
    Notes: Abstract LetK be ad-dimensional star body (with respect to the origino). It is known that the (d−1)-dimensional volume of the intersections ofK with the hyperplanes througho does not uniquely determineK. Uniqueness can only be achieved under additional assumptions, such as central symmetry. Here it is pointed out that if one uses, instead of intersections by hyperplanes, intersections by half-planes that containo on the boundary, then, without any additional assumptions, the volume of these intersections determinesK uniquely. This assertion, and more general results of this kind, together with stability estimates, are obtained from uniqueness results and estimates concerning a particular spherical integral transformation.
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    Catalysis letters 53 (1998), S. 97-101 
    ISSN: 1572-879X
    Keywords: ethene hydroformylation ; heterogeneous catalysts ; cobalt catalysts ; gas‐phase deposition ; dispersion ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The results from ethene hydroformylation at 173°C showed that a Co(acac)3/SiO2 catalyst prepared from Co(acac)3 precursor by gas‐phase deposition was three times as active as a catalyst prepared by impregnation from cobalt nitrate, but oxo‐selectivities were similar. The high propanal selectivities on the Co(acac)3/SiO2 seem to be related to the presence of highly dispersed active sites favouring CO insertion. As dispersion is decreased from 23 to 8% due to increasing metal content (from 5 to 16 wt%), oxo‐selectivity decreased from 39 to 25%. The activity of Co(acac)3/SiO2 remained unchanged during 68 h on stream. The gas‐phase deposition technique described here is a promising method for the preparation of active, selective and stable heterogeneous hydroformylation catalysts.
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    ISSN: 1572-879X
    Keywords: nanolithography ; model catalyst ; palladium ; copper ; stability ; spin-coating ; SEM ; AFM ; XPS
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Metal clusters arranged on nanostructured oxidized silicon wafers are presented as new model catalyst systems. A photoresist layer spun on top of a wafer was patterned by laser interference exposure. The grid obtained after removing the exposed parts of the resist is used as an etching mask. Hollows with diameters of 300 nm and depths between 50 and 60 nm were etched into the oxide layer using wet chemical methods. Two methods were applied to deposit metal clusters (Pd or Cu) in a defined way within the hollows. The particles ranged from 10 to 50 nm in height and from 80 to 200 nm in diameter. The model catalyst systems were characterized by atomic force microscopy and X-ray photoelectron spectroscopy. The method presented here allows us to produce 4 inch wafers that are covered completely by nanometer-sized structures in a reasonable period of time.
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    Journal of intelligent and robotic systems 23 (1998), S. 27-43 
    ISSN: 1573-0409
    Keywords: autonomous control ; actuator delays ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Computer Science , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract In this paper, we consider the control design problem of vehicle following systems with actuator delays. An upper bound for the time delays is first constructed to guarantee the vehicle stability. Second, sufficient conditions are presented to avoid slinky-effects in the vehicle following. Next, zero steady state achieved by the proposed controller is proven. Finally, simulations are given to examine our claims.
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    Journal of statistical physics 91 (1998), S. 285-305 
    ISSN: 1572-9613
    Keywords: Chapman–Enskog expansion ; Burnett equation ; Boltzmann equation ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract This paper continues the author's study of procedures for rewriting the well-known Chapman–Enskog expansion used in the kinetic theory of gases. The usual Chapman–Enskog expansion, when used in isothermal fluid motion, will introduce nonlinear instability at super-Burnett order O(ε3) truncation. The procedure given here eliminates the truncation instability and produces the desired dissipation inequality.
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    Journal of intelligent and robotic systems 22 (1998), S. 23-38 
    ISSN: 1573-0409
    Keywords: robot dynamic model ; stiffness matrix ; constant disturbance ; integrator backstepping ; Liapunov functions ; Barbalat lemma ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Computer Science , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract A robust regulator for flexible-joint robots is proposed, which yields constant torque disturbance rejection acting on the links. The design uses the integrator backstepping technique [4,5] to cancel nonlinearities and disturbance not in the range space of the control. Stability of the closed loop system is shown using iterative Liapunov functions.
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    Environmental and resource economics 11 (1998), S. 503-520 
    ISSN: 1573-1502
    Keywords: biodiversity ; dynamics ; resilience ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering , Economics
    Notes: Abstract The ecological concept of resilience has begun to inform analysis of change in economy-environment systems. The linkages between resilience and the stability of dynamical systems are discussed, along with its role in understanding of the evolution of such systems. Particular linkages discussed include those between resilience, biodiversity and the sustainability of alternative states. Recent developments in modelling the resilience of joint economy-environment systems suggest the advantages of analysing change in the system as a Markov process, the transition probabilities between states offering a natural measure of the resilience of the system in such states. It is argued that this ‘emergent property’ of the collaboration between ecology and economics has far-reaching implications for the way we think about, model and manage the environmental sustainability of economic development.
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    Acta mechanica Sinica 14 (1998), S. 274-282 
    ISSN: 1614-3116
    Keywords: time delay ; stability ; frozen time approach ; retarded dynamic systems
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract By means of the frozen time approach and the Kronecker product, two criteria of asymptotic stability are derived for the linear, time variant dynamic systems with either short time delays or with weak feedback involving arbitrary time delays, respectively. It is found that the asymptotic stability of these retarded dynamic systems is governed by the maximal and minimal singular values of the coefficient matrices and their time derivatives.
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    Acta mechanica Sinica 14 (1998), S. 226-233 
    ISSN: 1614-3116
    Keywords: jet ; stability ; dispersion equation ; swirling gas
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract Based on the linear analysis of stability, a dispersion equation is deduced which delineates the evolution of a general 3-dimensional disturbance on the free surface of an incompressible viscous liquid jet injected into a gas with swirl. Here, the dimensionless parameterJ e is again introduced, in the meantime, another dimensionless parameterE called as circulation is also introduced to represent the relative swirling intensity. With respect to the spatial growing disturbance mode, the numerical results obtained from solving the dispersion equation reveal the following facts. First, at the same value ofE, in pace with the changing ofJ e , the variation of disturbance and the critical disturbance mode still keep the same characters. Second, the present results are the same as that of S.P. Lin whenJ e 〉1; but in the range ofJ e 〈1, it's no more the case, the swirl decreases the axisymmetric disturbance, yet increases the asymmetric disturbance, furthermore the swirl may make the character of the most unstable disturbance mode changed (axisymmetric or asymmetric); the above action of the swirl becomes much stronger whenJ e ≪1.
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    Biology and philosophy 13 (1998), S. 541-554 
    ISSN: 1572-8404
    Keywords: complex natural system ; stability ; evolvability ; decomposable hierarchy ; genetic network ; Random NK Boolean Network
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Philosophy
    Notes: Abstract I criticize Herbert Simon's argument for the claim that complex natural systems must constitute decomposable, mereological or functional hierarchies. The argument depends on certain assumptions about the requirements for the successful evolution of complex systems, most importantly, the existence of stable, intermediate stages in evolution. Simon offers an abstract model of any process that succeeds in meeting these requirements. This model necessarily involves construction through a decomposable hierarchy, and thus suggests that any complex, natural, i.e., evolved, system is constituted by a decomposable hierarchy. I argue that Stuart Kauffman's recent models of genetic regulatory networks succeed in specifying processes that could meet Simon's requirements for evolvability without requiring construction through a decomposable hierarchy. Since Kauffman's models are at least as plausible as Simon's model, Simon's argument that complex natural systems must constitute decomposable, mereological or functional hierarchies does not succeed.
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  • 23
    ISSN: 1573-0646
    Keywords: Antagonist G ([Arg6, D-Trp7,9,,MePhe 8 ]-Substance P {6-11}) ; analytical characterization ; parenteral formulation ; stability ; oxidative degradation products
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Abstract The aim of this study was to develop a stable parenteral dosage form for the investigational cytotoxic drug [Arg6, D-Trp7,9, MePhe8]-Substance P {6-11} (Substance P Antagonist G; Antagonist G). Antagonist G bulk drug was structurally and analytically characterized. The drug exhibits excellent aqueous solubility, although relatively poor aqueous stability characteristics. Lyophilization was, therefore, selected as the manufacturing process. Differential scanning calorimetry studies were conducted to determine the freeze-drying cycle parameters which resulted in a stable, lyophilized formulation of Antagonist G. The prototype, containing 50 mg Antagonist G per vial, was found to be the optimal formulation in terms of solubility, length of the freeze-drying cycle, stability, and dosage requirements in the planned phase I clinical trials. Quality control of the freeze-dried formulation showed that the manufacturing process does not change the integrity of Antagonist G. Shelf life studies demonstrated that the formulation is stable for at least 3 years, when stored at 2–8°C in a dark environment. Oxidative degradation products of Antagonist G were isolated and structurally characterized by mass spectrometry, nuclear magnetic resonance spectroscopy, and infrared spectroscopy.
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    Applied mathematics and mechanics 19 (1998), S. 163-168 
    ISSN: 1573-2754
    Keywords: nonlinear equation ; stability ; Newton's method ; auto-adjustable damping method ; the vector of damping factors
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Mathematics , Physics
    Notes: Abstract The general approach for solving the nonlinear equations is linearizing the equations and forming various iterative procedures, then executing the numerical simulation. For the strongly nonlinear problems, the solution obtained in the iterative process is always difficult, even divergent due to the numerical instability. It can not fulfill the engineering requirements. Newton's method and its variants can not settle this problem. As a result, the application of numerical simulation for the strongly nonlinear problems is limited. An auto-adjustable damping method has been presented in this paper. This is a further improvement of Newton's method with damping factor. A set of vector of damping factor is introduced. This set of vector can be adjusted continuously during the iterative process in accordance with the judgement and adjustment. An effective convergence coefficient and quichening coefficient are employed to relax the restricted requirements for the initial values and to shorten the iterative process. Then, the numerical stability will be ensured for the solution of complicated strongly nonlinear equations. Using this method, some complicated strongly nonlinear heat transfer problems in airplanes and aeroengines have been numerically simulated successfully. It can be used for the numerical simulation of strongly nonlinear problems in engineering such as nonlinear hydrodynamics and aerodynamics, heat transfer and structural dynamic response etc.
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    Applied mathematics and mechanics 19 (1998), S. 861-867 
    ISSN: 1573-2754
    Keywords: rotating fluids ; motion of body ; small disturbances ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Mathematics , Physics
    Notes: Abstract In this paper, the disturbances to a uniformly rotating ideal fluid with a sphere moving steadily along the axis of rotation are analysed by using linearization theory, the equations of disturbance, pressure and disturbance stream function governing the stability of motion are derived based on the assumption that the flow is rotational symmetric. The equation of disturbance stream function is analysed with the method of normal modes, and the constraints on wave number and wave velocity of the nontrivial neutral disturbances are established and the exact expression of the neutral disturbances are obtained. The conclusion is drawn that three are three kinds of possible forms of neutral disturbances.
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    Studia geophysica et geodaetica 42 (1998), S. 320-327 
    ISSN: 1573-1626
    Keywords: MHD ; stability ; bifurcations
    Source: Springer Online Journal Archives 1860-2000
    Topics: Architecture, Civil Engineering, Surveying , Geosciences , Physics
    Notes: Abstract A series of numerical studies on the behaviour of magnetic fields and motions in a spherical body of an electrically conducting incompressible fluid have been carried out. The magnetic field was assumed to be maintained by a given electromotive force inside the body and to continue as a potential field in outer space. In view of the motion an external forcing was taken into account, and boundary conditions were considered which correspond to a stress-free surface. The stability of several steady states has been studied as well as the evolutions starting from unstable states. In this paper a configuration with a poloidal magnetic field and a differential rotation, both symmetric about the same axis, is considered. This configuration is stable only for sufficiently small Hartmann numbers but evolves, if disturbed, in the case of larger Hartmann numbers toward a non-axisymmetric state. In this case the well-known symmetrization effect of differential rotation in magnetic fields is destroyed.
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    Applied mathematics and mechanics 19 (1998), S. 457-462 
    ISSN: 1573-2754
    Keywords: neural networks ; equilibrium ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Mathematics , Physics
    Notes: Abstract In this paper, some sufficient conditions are obtained for the global asymptotic stability of the equilibrium of neural networks with interneuronal transmission delays of the type $$x'_i (t) = - b_i x_i (t) + \sum\limits_{j = 1}^n {\omega _{\ddot y} f_j (x_j (t - \tau _j )) + p_i (t 〉 0;i = 1,2, \cdots ,n)} $$
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    Discrete event dynamic systems 8 (1998), S. 137-173 
    ISSN: 1573-7594
    Keywords: hybrid systems ; switched systems ; timed Petri nets ; stability ; supervisory control
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mathematics
    Notes: Abstract In this paper, timed Petri nets are used to model and control hybrid systems. Petri nets are used instead of finite automata primarily because of the advantages they offer in dealing with concurrency and complexity issues. A brief overview of existing results on hybrid systems that are based on Petri nets is first presented. A class of timed Petri nets named programmable timed Petri nets (PTPN) is then used to model hybrid systems. Using the PTPN, the stability and supervisory control of hybrid systems are addressed and efficient algorithms are introduced. In particular, we present sufficient conditions for the uniform ultimate boundness of hybrid systems composed of multiple linear time invariant plants which are switched between using a logical rule described by a Petri net. This paper also examines the supervisory control of a hybrid system in which the continuous state is transfered to a region of the state space in a way that respects safety specifications on the plant's discrete and continuous dynamics.
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    Journal of scientific computing 13 (1998), S. 173-183 
    ISSN: 1573-7691
    Keywords: Modified conjugate gradient method ; conjugate gradient method ; Krylov space ; convergence rate ; stability
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    Topics: Computer Science
    Notes: Abstract In this note, we examine a modified conjugate gradient procedure for solving $$A\underset{\raise0.3em\hbox{$\smash{\scriptscriptstyle-}$}}{x} = \underset{\raise0.3em\hbox{$\smash{\scriptscriptstyle-}$}}{b}$$ in which the approximation space is based upon the Krylov space ( $$A\underset{\raise0.3em\hbox{$\smash{\scriptscriptstyle-}$}}{x} = \underset{\raise0.3em\hbox{$\smash{\scriptscriptstyle-}$}}{b}$$ ) associated with $$\sqrt A$$ and $$\underset{\raise0.3em\hbox{$\smash{\scriptscriptstyle-}$}}{b}$$ . We show that, given initial vectors $$\underset{\raise0.3em\hbox{$\smash{\scriptscriptstyle-}$}}{b}$$ and $$\sqrt A \underset{\raise0.3em\hbox{$\smash{\scriptscriptstyle-}$}}{b}$$ (possibly computed at some expense), the best fit solution in $$K^k \sqrt A ,\underset{\raise0.3em\hbox{$\smash{\scriptscriptstyle-}$}}{b}$$ can be computed using a finite-term recurrence requiring only one multiplication by A per iteration. The initial convergence rate appears, as expected, to be twice as fast as that of the standard conjugate gradient method, but stability problems cause the convergence to be degraded.
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  • 30
    ISSN: 1573-773X
    Keywords: constrained learning ; factorization ; feedforward networks ; IIR filters ; polynomials ; stability
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    Topics: Computer Science
    Notes: Abstract Adaptive artificial neural network techniques are introduced and applied to the factorization of 2-D second order polynomials. The proposed neural network is trained using a constrained learning algorithm that achieves minimization of the usual mean square error criterion along with simultaneous satisfaction of multiple equality and inequality constraints between the polynomial coefficients. Using this method, we are able to obtain good approximate solutions for non-factorable polynomials. By incorporating stability constraints into the formalism, our method can be successfully used for the realization of stable 2-D second order IIR filters in cascade form.
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    Journal of dynamical and control systems 4 (1998), S. 457-519 
    ISSN: 1573-8698
    Keywords: Boundary control ; nonlinear distributed parameter system ; center manifold theorem ; stability ; local attractors
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    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: Abstract In this paper we consider a boundary control problem for a forced Burgers' equation in a Hilbert state space consisting of square integrable functions on a finite interval. Our first main result consists in proving the global in time existence of solutions of the closed loop boundary control system for arbitrary L 2 initial data and quite general forcing terms (disturbances). For the unforced problem, our main interest is in stability of equilibria, while for the forced problem we are interested in steady state behavior of solutions. We note that the uncontrolled (open loop), unforced problem is not asymptotically stable on L 2. However, for positive gains we show that the unforced closed loop system is globally Lyapunov stable and locally exponentially stable. In addition, for nonzero stationary forcing, we show that there is a local absorbing ball and that the corresponding nonlinear semigroup is compact for all t 〉 0. Using this fact, we are able to deduce several consequences regarding the existence and properties of local attractors. Our method of proof is based on a systematic investigation of the smoothing properties of the controlled dynamics. In particular we establish various regularity results for the dynamics of the closed loop system.
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    Dynamics and control 8 (1998), S. 83-106 
    ISSN: 1573-8450
    Keywords: fuzzy modeling ; robust control ; stability
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    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: Abstract Robust control designs for a discrete Takagi and Sugeno (T-S) fuzzy model are proposed. The T-S fuzzy model contains (possibly fast) time-varying uncertainty. First, a switching-type robust control is shown to stabilize the T-S fuzzy model asymptotically. Second, a saturation-type robust control is shown to render the T-S model practically stable. In both designs, only the bound of uncertainty is needed. The effectiveness of proposed designs is analyzed rigorously and illustrated by simulations.
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    Mathematical notes 63 (1998), S. 396-400 
    ISSN: 1573-8876
    Keywords: ordinary differential equations ; fast and slow time ; periodic solutions ; existence ; stability
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    Topics: Mathematics
    Notes: Abstract We consider a system of ordinary first-order differential equations. The right-hand sides of the system are proportional to a small parameter and depend almost periodically on fast time and periodically on slow time. With this system, we associate the system averaged over fast time. We assume that the averaged system has a structurally unstable periodic solution. We prove a theorem on the existence and stability of almost periodic solutions of the original system.
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  • 34
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    Pharmaceutical research 15 (1998), S. 1702-1707 
    ISSN: 1573-904X
    Keywords: stability ; isothermal ; nonisothermal ; thymopentin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. The degradation kinetics of thymopentin (RKDVY) and its analogs (RKDVW and RPDVY) in aqueous solution was studied by isothermal and nonisothermal methods. Methods. The isothermal decomposition of thymopentin and its analogs was investigated as a function of pH (2−10), temperature (37, 57, and 80°C) and ionic strength (μ = 0.02 to 1). Nonisothermal decomposition studies were performed using a linear temperature programmer. The temperature increasing rate was set to 0.25°C per hour and the temperature interval varied from 40 to 88°C. Results. The decomposition of thymopentin and its analogs followed first order kinetics. The dependence of the rate constant on temperature followed a linear Arrhenius plot. This indicated that the degradation mechanism of thymopentin and its analogs might be the same within the temperature range studied. The energies of activation were found to be in close agreement for the isothermal and nonisothermal studies, suggesting that the nonisothermal studies may save considerable amount of time in the early stages of drug development. The logK-pH profile of thymopentin suggests that maximum stability is achieved in the pH range of 6−8. Conclusions. These results indicate that the nonisothermal methodology provides an attractive alternative to isothermal methods, as it requires a much lower amount of both material and time, to determine the peptide stability and to estimate the shelf-life for peptide pharmaceutical preparations.
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  • 35
    ISSN: 1573-5060
    Keywords: Triticum turgidum ; farmers' varieties ; genetic diversity ; composite ; stability ; durum wheat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The Ethiopian peasant farms are characterized by highly varied micro-environments differing in characteristics such as topography, soil type, water, temperature and fertility. The bulk of the durum wheat planting material currently in use on these farms is largely represented by traditional farmers' varieties/landraces. These traditional farmers' varieties/landraces generally, are stable but low yielding, and often fail to adequately meet the level of productivity essential for production beyond subsistence level, unless they are enhanced to improve their competitiveness with modern varieties in respect to yield. Improving the productivity of landraces, while maintaining an appreciable level of genetic diversity is crucial to yield stability. This could be achieved by developing composites that are formed by bulking together three or more potentially high yielding spikes (agrotypes) that vary for various morphologic and agronomic characteristics, but due to their similarity in plant height, maturity, glume color and seed color give the composite a uniform field appearance like a modern variety.
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  • 36
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    Environmental biology of fishes 53 (1998), S. 365-371 
    ISSN: 1573-5133
    Keywords: Carassius auratus ; Metynnis hypsauchen ; Pterophyllum scalare ; goldfish ; angelfish ; silver dollar ; swimming ; stability
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    Topics: Biology
    Notes: Abstract Goldfish, Carassius auratus, silver dollar, Metynnis hypsauchen, and angelfish, Pterophyllum scalare were induced to swim through narrow vertical and horizontal tubes ranging in length from 0 to 20 cm (approximately 0 to 3 times total fish length, FL). The ability to stabilize the body while negotiating these confined spaces was quantified as (1) the minimum width of vertical (wv) and horizontal (wh) tubes traversed, where width is the smaller cross-sectional dimension of the tube, (2) the ratio wv/wh, and (3) transit speed through the tubes. Tube width was expressed as relative width, obtained by dividing tube width by fish length. Minimum relative widths traversed increased from 0.15 to 0.19 in the order silver dollar 〉 angelfish 〉 goldfish for vertical tubes and from 0.17 to 0.18 in the order goldfish=silver dollar 〉 angelfish for horizontal tubes. wv/wh increased from 0.91 to 1.10 in the order silver dollar=angelfish 〉 goldfish. Minimum tube widths generally increased with tube length for vertical tubes. Although significant differences in relative minimum widths among species were found, these were small. In contrast, for horizontal tubes, there was no significant effect of tube length on minimum tube width for any species. Large differences were found in transit speed. Transit speed generally decreased as the tube length increased. The slope of the relationship between transit speed and tube length varied among species generally increasing from − 0.41 to − 1.16 for horizontal tubes in the order goldfish 〉 silver dollar 〉 angelfish and from − 0.42 to − 1.07 in the order silver dollar 〉 goldfish 〉 angelfish for vertical tubes. As a result, goldfish usually took longest to traverse tubes of zero length but the shortest time to traverse the longest tubes. In contrast, angelfish traversed short tubes in the least time and long tubes in the greatest time. Deeper bodied angelfish swam slowly and traversed tubes with difficulty because they required experience during each trial to replace median and paired fin with body and caudal fin swimming. According to our data, goldfish were best able to swim in confined spaces.
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  • 37
    ISSN: 1435-1536
    Keywords: Key words Heterophase polymerization ; emulsion ; polymer particle ; stability ; styrene conversion
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract  Heterophase polymerization of styrene in the presence of di-p-tolyl-o-carbalkoxyphenylcarbinol (DTC) soluble in monomer and insoluble in water, as stabilizer, was investigated. The factors affecting polymer particle diameter, their size distribution and stability were investigated. It was suggested that polymer particles are formed from monomer droplets. The polystyrene suspension with narrow particle size distribution synthesized in the presence of DTC, was used for immunochemical research.
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    Empirical economics 23 (1998), S. 387-400 
    ISSN: 1435-8921
    Keywords: Money demand ; cointegration ; stability ; regime shift ; E41 ; C22
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    Topics: Economics
    Notes: Abstract Using several tests for structural stability in regressions with I(1) variables and for the existence of cointegration in models with regime shifts, the empirical evidence on the existence of a structural break in the Spanish long-run demand for broad money (ALP2) is analysed. The results indicate that shifts affecting the demand for ALP2 in recent years have substantially altered its long-run properties. As to the cause of this structural break, emphasis is placed on the role played by the increasing openness of the Spanish financial system to international markets as obstacles to free capital movements have progressively disappeared.
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  • 39
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    International journal of thermophysics 19 (1998), S. 461-470 
    ISSN: 1572-9567
    Keywords: small-angle neutron scattering ; stability ; vesicles
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    Topics: Physics
    Notes: Abstract Small-angle neutron scattering (SANS) was used to investigate the structure of mixed colloids of egg yolk phosphatidylcholine (EYPC) with the bile salt, cholylglycine (CG), in D2O as a function of pressure (P) and temperature (T). At atmospheric pressure, the system forms an isotropic phase of mixed, single-bilayer vesicles (SLVs). Increasing the external hydrostatic pressure brought about significant changes in particle morphology. At T=25°C, application of a pressure of 3.5 MPa resulted in collapse of the SLVs. A further increase in P, up to 51.8 MPa, resulted in a transition from a phase of ordered (stacked), collapsed vesicles to one of stacked, ribbon-like particles. A similar collapse of the vesicles was observed at a higher temperature (T=37°C) with increasing P, but at this temperature, no ribbon phase was found at the highest pressure explored.
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    International journal of infrared and millimeter waves 19 (1998), S. 1721-1734 
    ISSN: 1572-9559
    Keywords: optical phase-locked loop ; stability ; phase jitter ; four-wave mixing ; semiconductor laser amplifier
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract In this paper, the properties of the optical phase-locked loop(PLL) based on the four-wave mixing in the semiconductor laser amplifiers (SLAs) are discussed. The components that achieve the function of detecting the bit phase of the input optical signal are concerned and discussed in detail together as a function module named as the optical bit phase detector referred to the general electronic PLL. Therefore, most of the properties of the optical PLL can be analyzed by applying the general phase-locked theory. Here the stability of the optical PLL is discussed. It's shown that the variance of input signal power in the practical application will cause optical PLL system unstable because of its long loop delay. The influence on the output phase jitter of the optical PLL is also investigated.
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    Euphytica 102 (1998), S. 151-161 
    ISSN: 1573-5060
    Keywords: Oryza sativa ; head rice ; seeding date ; rice ; rough rice yield ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The rice (Oryza sativa L.) crop in Arkansas is seeded from late March through early June each year. Farmers need new rice cultivars that not only produce both high rough rice yields and high head rice across this range of seeding dates but do so consistently. Thus, a seeding date study was conducted during 1994 and 1995 at Stuttgart, Arkansas, to study seeding date effects on rough rice yield and head rice and selection for stability. Fourteen rice cultivars were seeded at five dates ranging from late March through mid-June. Kang's yield-stability statistic was used to select cultivars for both high rough rice yields and high head rice as well as stability for both traits. Plant stands from March seedings of each year were significantly lower than for the later seeding dates. Maturity (days to 50 percent heading) was extended at the early seeding dates. Some rice cultivars, such as ‘LaGrue’, had lower and more variable head rice when seeded early. In the June seeding dates each year, ‘Kaybonnet’ produced rough rice yields that were more consistent with yields when planted at the earlier planting dates. ‘Bengal’, ‘Cypress’, ‘Kaybonnet’, and ‘Newbonnet’ were cultivars selected by Kang's stability statistic, which was targeted to select cultivars with stable, high rough rice yields and stable, high head rice. The validity of using Kang's yield-stability statistic for cultivar selection is also evident empirically by the adaptation and wide use of these four cultivars by southern U.S. rice producers. These results indicate that seeding date studies and stability analyses would be useful tools for rice breeders to identify cultivars that will be readily adapted and grown by rice producers.
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    Euphytica 100 (1998), S. 15-18 
    ISSN: 1573-5060
    Keywords: biparental mating ; stability ; Triticum durum
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Three populations of an intervarietal durum wheat cross IWP5308/PDW208, F5, F5BIP1 (population derived after intermating in F2) and F5BIP2 (population derived after intermating in BIPF1), were evaluated under three different agronomic environments for mean performance and stability of genotypes for grain yield, yield components and protein content. Though the biparental progenies indicated a higher mean performance, they did not differ significantly from progenies of the pedigree method for almost all characters. The biparental progenies, however, produced a higher number of stable genotypes for grain yield per plant, grains per ear and protein content. The F5 population had a higher number of stable genotypes for 1000 grain weight and number of tillers per plant. The BIP progenies also had a higher number of genotypes with above average mean performance, and many were significantly higher than the checks WH896 and WH542, compared with F5 progenies. Hence, in spite of high G x E interactions, the use of cycles of biparental mating and selection of top yielding lines on the basis of yield components can enable selection of stable genotypes with high protein content. Number of tillers per plant and 1000 grain weight were the yield component characters which made maximum contribution to phenotypic stability of the genotypes.
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  • 43
    ISSN: 1573-5060
    Keywords: adaptation ; correlations ; genotype-environment interaction ; landraces ; performance ; stability ; tetraploid wheat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Plant breeding has always been concerned with genotype-environment interaction. Normally high and stable performance are desirable attributes of cultivars. However, this is practically difficult to achieve where environmental variations are high and unpredictable and significant genotype-environment interactions occur. Stability of performance of 13 landraces evaluated at 4 different locations for 3 years in the highlands of Ethiopia was investigated. The testing locations have different climatic and edaphic conditions providing the conditions necessary for the assessment of stability. Stability parameters like b, s2d, s2, r2 and cv which are in common use were employed. Grain yield and 1000-kernel weight were the agronomic traits considered for the stability analysis. There were differences in the ranks of genotypes across the locations. Significant main environmental as well as interaction effects were observed showing the importance of genotype-environment interaction in both traits. Many of the landraces evaluated are rated as stable for these traits within the environmental conditions prevailing in these highland locations. Genotypes with specific adaptation to poor and favourable conditions were also identified. Certain genotypes showed similar manners of adaptation and stability for both of the traits. Grain yield showed low correlations with the stability parameters showing the possibility of attaining high yield and stability. Correlations between the stability parameters were mainly positive and significant for grain yield. Only a few of these correlations were found to be significant for kernel weight. The good adaptability of landraces should be exploited in the improvement of their yield potential.
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  • 44
    ISSN: 1573-5117
    Keywords: hypoxia ; anoxic hypolimnion ; volcanic crater lake ; stratification ; productivity ; heat budget ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract This paper quantifies the temporal pattern of thermal stratification and deoxygenation in Lake Nkuruba, a small (3 ha), deep (maximum depth = 38 m) crater lake in western Uganda. Dissolved oxygen penetrated to an average depth of 9 m and a maximum depth of 15 m below which the lake was permanently anoxic over the 2 years of study. Although surface oxygen levels were correlated with both surface water temperature and rainfall, seasonal cycles of dissolved oxygen were not well-defined and may have been obscured by the high frequency of short-term fluctuations and by inter-annual variations caused by shifts in rainfall. Surface water temperature averaged 23.3±0.7 °C (S.D.) and varied directly with air temperature. Both diurnal changes and top-bottom temperature differentials were small averaging 1.7±0.7 °C and 1.6±0.8 °C, respectively. Thermal stability ranged from 101.3 to 499.9 g-cm cm-2 and was positively related to surface water temperature suggesting that this small protected lake responds rapidly to short-term meteorological changes. Because contribution to the annual heat exchange cycle was confined to upper waters, the lake's annual heat budget was low, 1,073.8 cal cm-2 yr-1. However, net primary productivity was relatively high averaging 1.3 g C m-2d-1. The region where Lake Nkuruba is situated experienced a very strong earthquake (6.2 on the Richter scale) on 4 February, 1994. Subsequently, water levels dropped markedly in the lake, falling 3.14 m over a 5-month period.
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  • 45
    ISSN: 1573-5117
    Keywords: hypoxia ; anoxic hypolimnion ; volcanic crater lake ; stratification ; productivity ; heat budget ; stability
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    Topics: Biology
    Notes: Abstract This paper quantifies the temporal pattern of thermal stratification and deoxygenation in Lake Nkuruba, a small (3 ha), deep (maximum depth = 38 m) crater lake in western Uganda. Dissolved oxygen penetrated to an average depth of 9 m and a maximum depth of 15 m below which the lake was permanently anoxic over the 2 years of study. Although surface oxygen levels were correlated with both surface water temperature and rainfall, seasonal cycles of dissolved oxygen were not well-defined and may have been obscured by the high frequency of short-term fluctuations and by inter-annual variations caused by shifts in rainfall. Surface water temperature averaged 23.3±0.7 °C (S.D.) and varied directly with air temperature. Both diurnal changes and top-bottom temperature differentials were small averaging 1.7±0.7 °C and 1.6±0.8 °C, respectively. Thermal stability ranged from 101.3 to 499.9 g-cm cm-2 and was positively related to surface water temperature suggesting that this small protected lake responds rapidly to short-term meteorological changes. Because contribution to the annual heat exchange cycle was confined to upper waters, the lake's annual heat budget was low, 1,073.8 cal cm-2 yr-1. However, net primary productivity was relatively high averaging 1.3 g C m-2d-1. The region where Lake Nkuruba is situated experienced a very strong earthquake (6.2 on the Richter scale) on 4 February, 1994. Subsequently, water levels dropped markedly in the lake, falling 3.14 m over a 5-month period.
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  • 46
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    Journal of optimization theory and applications 97 (1998), S. 707-729 
    ISSN: 1573-2878
    Keywords: Nonlinear integral equations ; optimal control in L p-spaces ; relaxation ; existence ; stability ; nonconcentration ; optimality conditions ; Pontryagin maximum principle
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mathematics
    Notes: Abstract Optimal control problems with nonlinear equations usually do not possess optimal solutions, so that their natural (i.e., continuous) extension (relaxation) must be done. The relaxed problem may also serve to derive first-order necessary optimality condition in the form of the Pontryagin maximum principle. This is done here for nonlinear Fredholm integral equations and problems coercive in an L p-space of controls with p〈+∞. Results about a continuous extension of the Uryson operator play a key role.
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    Applied mathematics and mechanics 19 (1998), S. 135-146 
    ISSN: 1573-2754
    Keywords: nonholonomic system ; Lagrange's theorem ; manifold ; stability ; Liapunov's direct method
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Mathematics , Physics
    Notes: Abstract The stability problem for the manifold of equilibrium positions of a class of nonholonomic systems is studied in this paper. Based on Liapunov's direct method and the definition of stability. Lagrange's theorem of holonomic systems is extended to a class of nonholonomic conservative systems and dissipative systems, and a new expression is made to the relation between asymptotic stability for the manifold of equilibrium positions of this class of nonholonomic systems and dissipative forces. Two examples are finally given to illustrate the application of the theorems.
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    Journal of logic, language and information 7 (1998), S. 143-163 
    ISSN: 1572-9583
    Keywords: Belief revision ; consolidation ; coherence ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Linguistics and Literary Studies , Computer Science
    Notes: Abstract The notion of epistemic coherence is interpreted as involving not only consistency but also stability. The problem how to consolidate a belief system, i.e., revise it so that it becomes coherent, is studied axiomatically as well as in terms of set-theoretical constructions. Representation theorems are given for subtractive consolidation (where coherence is obtained by deleting beliefs) and additive consolidation (where coherence is obtained by adding beliefs).
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    Chromatographia 47 (1998), S. 25-34 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Solid Phase Extraction ; RP-HPLC gradient analysis ; Taxus Cell Cultures ; Taxol and Taxanes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Solid phase extraction (SPE) methods are studied for the sample pretreatment for HPLC analysis ofTaxus cell suspension cultures. Various types of SPE materials were tested for the extraction of both the taxane standards and samples of various origin. Comparison between the different cartridges and the different elution solvents are made in terms of extraction recovery and sample clean-up. Selective elution of the taxanes is achieved by a gradient elution scheme.
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    Chromatographia 47 (1998), S. 77-80 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Ion chromatography ; Stability constants ; Ionic strength ; Heavy metals ; Tartaric acid
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Ion chromatography and potentiometry were used for the determination of the stability constants Pb, Zn, Co, Ni, Mn tartrate complexes at different ionic strengths. An extrapolation function based on the Debye-Hückel equation was applied to obtain the thermodynamic stability constants.
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  • 51
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Ion-pair LC ; Plasma ; 2,4-Toluendiamine ; 2,6-Toluendiamine
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    Topics: Chemistry and Pharmacology
    Notes: Summary An ion-pair HPLC method is presented for the determination in plasma of 2,4- and 2,6-toluendiamine (TDA), known carcinogens. The chromatographic conditions consisted in isocratic elution on a reversed phase C18 column with 5 mM octanesulfonic acid in methanol-water, 45∶55, as mobile phase. UV detection was performed at 235 nm. Samples were analyzed after a simple single step liquid-liquid extraction and the method was validated by measurement of precision (interassay and intraassay), sensitivity, specificity, linearity, and recovery. The detection limit for both TDAs in plasma was 20 ng mL−1. The correlation coefficients based on the intrassay calibration curve were 0.998 and 0.997 for 2,6- and 2,4-TDA, respectively. The intraassay accuracy, expressed in terms of recovery, was found to be up to 89.91% and 97.05% for 2,6- and 2,4-TDA, respectively.
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  • 52
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Enantiomer separation ; Voriconazole (UK-109,496) ; Effect of organic mobile-phase modifier
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    Topics: Chemistry and Pharmacology
    Notes: Summary Coupled achiral-chiral high-performance liquid chromatography (HPLC) with an achiral amino-based column coupled with a chiral amylose-based column has been used for qualitative and quantitative determination of the potential chiral and achiral impurities of Voriconazole (UK-109,496), a new antifungal agent with two stereogenic centres. The effect of the organic mobile-phase modifier, ethanol, was studied. The assay response was linearly dependent on concentration over the range 1.2–40.4 μg for Voriconazole and 2.5–104.0 ng for the impurities. The limit of detection was 2.5 ng for each analyte.
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  • 53
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Ion chromatography ; Titania packings ; Inorganic anions and cations
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The ion-exchange retention behavior of titania synthesized in our laboratory was investigated by ion chromatography of inorganic anions and cations. Dilute acetic acid-sodium acetate and bicine-sodium hydroxide buffers were used as mobile phases with no use of suppresor. We observed that the titania, although poor at separating monovalent anions expcept nitrite ion in this experiment, was both an anion and a cation exchanger, and selectively retained fluoride and carbonate ions. We concluded that because of its specific retention properties there were possibilites of using this amphoteric exchanger for simultaneous analysis of anions and cations, and of using it as a selective packing material for ion chromatography.
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  • 54
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Porous graphitic carbon ; Optimization ; Morphine and metabolites
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The chromatographic behaviour of a series of morphine-based opiates has been investigated using a porous graphitic carbon packing material at acid and alkaline pH. The effects of mobile phase pH, mobile phase organic percentage, column temperature and ionpairing agents were studied. All six opiates were separated within a close retention window despite large differences in measured lipophilicities of the individual opiates. The retention order was not related to the log P values of the opiates and strong retention of the fully ionised compounds was observed, particularly those with acidic functional groups. The effect of pH on the retention of the compounds indicated that the degree of ionisation of the individual compounds was important in the separation mechanism, suggesting that hydrophobic interactions were present in addition to the polar retentive effects observed above. The strong retention of the ionised glucuronide and sulphate conjugates of morphine is a particularly useful feature of the porous graphitic carbon packing material which has general applicability to the analysis of polar or ionised drug metabolites.
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  • 55
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Amperometric detection ; Solid-phase extraction ; Plasma ; Clozapine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A sensitive and selective high-performance liquid chromatographic method has been developed for monitoring clozapine levels in human plasma. Chromatography was performed on a reversed-phase column (C8, 150 mm×4.6 mm i.d., 5 μm) with acetonitrile-aqueous sodium acetate solution, 88∶12 (v/v), as mobile phase; the flow rate was 1 mL min−1. Clozapine oxidation at +800 mV was detected amperometrically. Response was linearly dependent on concentration over the range 50–1500 ng mL−1 clozapine in plasma. Sample preparation by solid-phase extraction before HPLC analysis gave high extraction yield (94%). The accuracy and precision of the method were both very good (recovery: 97%;RSD〈3.3%).
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  • 56
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    Chromatographia 47 (1998), S. 299-304 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Plasma samples ; Direct injection ; Restricted-access media ; Column-switching
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A new restricted access media (RAM) type of precolumn, Bio Trap 500 C18, for direct injection of plasma samples in column-switching systems was evaluated with respect to the elution of plasma proteins in different mobile phases, the loading capacity of plasma samples, the chromatographic behavior during plasma injections and protein contamination of the packing and sealings. More than 95% of plasma proteins could be excluded from the precolumn within three minutes for all selected mobile phases. Quantitative analyte recoveries could be obtained by injecting plasma samples ranging from 5 to 500 μL with the analyte mass〉150 ng onto a BioTrap 500 C18 column (20×4 mm I.D.). One precolumn tolerated about 15 mL of plasma injection without out noticeable change in retention and pressure. Clogging of the precolumn was encountered (≥45 mL of plasma) due mainly to the adsorption of proteins on the packing. The performance of the analytical column (Kromasil C18) was also examined. The column efficiency decreased by 60% after processing 45 mL plasma in total.
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  • 57
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    Chromatographia 47 (1998), S. 373-382 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Polyaromatic hydrocarbons ; Pitch
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A new high performance liquid chromatography method for the characterisation of toluene-soluble fractions of pitches has been developed. Although a chromatographic system typical of size exclusion chromatography was used, results indicate that, for these structurally complex samples, separation does not follow the usual discrimination by molecular size. A differentiation between several classes of polyaromatic hydrocarbons is achieved instead. Data are reported on the analysis of individual standard polyaromatic hydrocarbons, showing that four different elution ranges can be observed: three ofcata-condensed compounds (Cata1, Cata2 and Cata3) and one ofperi-condensed compounds (Peri). Results are reported proving the capacity of this high performance liquid chromatography method to distinguish between pitches of different origin and nature. It is also effective for the study of the chemical reactions occurring during heat treatment.
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  • 58
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Opium alkaloids ; Papaver somniferum L.
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    Topics: Chemistry and Pharmacology
    Notes: Summary A reversed phase HPLC method for the separation of the five major alkaloids fromPapaver somniferum L., morphine, codeine, thebaine, papaverine and noscapine, has been developed and validated. By use of a basedeactivated silica-based stationary phase excellent peak shape was achieved for each substance. The five alkaloids were quantified by internal standardization within 20 min and with good precision. The method is applicable to opium and to poppy straw.
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  • 59
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Carbofuran pesticides ; On-line analysis of milk
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    Topics: Chemistry and Pharmacology
    Notes: Summary A method has been developed for extraction and determination of carbofuran in milk. The method involved direct injection of raw milk on to a human serum albumin dimethyloctyl-silica gel (HSA-C8) column and the use of 80:20 (v/v) 0.01 M phosphate buffer pH 5.5-acetonitrile as mobile phase. UV spectrophotometric detection was performed at 220 nm. Identification was based on retention time. Quantification was performed by automatic peak-area determination and was calibrated by use of an external standard.
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  • 60
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    Chromatographia 48 (1998), S. 17-19 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Dibromomannitol in plasma ; Pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Myelobromol 1,6-dibromo-1,6-dideoxy-D-mannitol (dibromomannitol, DBM) is a bifunctional alkylating agent that has been in clinical use since 1963. It is currently included at high dose in preconditioning regimen for bone marrow transplantation (BMT) and is a main-stay of treatment for polycythaemia vera. A high-performance liquid chromatographic method was developed for the determination of DBM in the plasma. The basis of the assay is a derivatization with sodium-diethyldithiocarbamate at 42°C in the presence of 1-bromo-1-deoxy-3,6-anhydro-galactitol as internal standard (IS). The analysis was carried out on a 250×4mm Hypersil 5 CPS column equipped with a 20×4 mm Hypersil 10 CPS precolumn. The eluent consisted of heptane:isopropyl-alcohol: glacial acetic acid=600:76:80 w/w. The flow rate was 1.2 mL min−1. UV detection was performed at 254 nm. The calibration graph was linear in the concentration range of 2.5–260 μM of DBM in plasma. The limit of detection was 1.0 μM. The precision and accuracy of the method was between the good laboratory practice (GLP) required limits.
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  • 61
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    Chromatographia 48 (1998), S. 37-42 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Biologically active amines ; Polyamines ; Cereal and Cereal products
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Biologically active amines (putreanine sulphate, N-acetyl putrescine, putrescine, cadaverine, histamine, agmatine, N-acetyl spermidine, spermidine, spermine) were separated and quantified in cereal flour and cereal products by a liquid chromatographic method. The method consists of the separation of ion pairs formed between biologically active amines and octanesulphonic acid on a reversed-phase column, postcolumn derivatization with o-phtalaldehyde-2-mercapthoethanol and spectrofluorometric detection. Results of the reliability study were satisfactory. The method was linear for each amine at 1–10 mg L−1. Putrescine and spermidine were the only amines always detected in cereal flour and cereal products, ranging from 2.45 to 47.83 mg kg−1 for putrescine and 3.27 to 37.14 mg kg−1 for spermidine. The most important differences among types of samples were found in polyamine derivatives.
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  • 62
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Normal- and reversed-phase LC ; Fumagillin in fish samples
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    Topics: Chemistry and Pharmacology
    Notes: Summary Fumagillin is an antibiotic agent mostly used in the veterinary profession. A normal-phase liquid chromatographic method was developed for the determination of this drug in fish matrices. A hexane-dichloromethanedioxan-2-PrOH-acetic acid (43:43:9:5:0.1 v/v %) eluent was used on a Perkin Elmer silica gel column. For validation of the process a reversed-phase HPLC method was also developed (eluent: acetonitrile-water-bicyclohyxylamine 70:30:0.05 v/v %, with Spherisorb ODS, as stationary phase). Recovery is about 100% and the limit of detection is 5 ng g−1 for meat samples.
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  • 63
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Buckminsterfullerene ; Hydrogenation ; Separation technique
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    Topics: Chemistry and Pharmacology
    Notes: Summary The effect of composition and flow rate of the mobile phase on the HPLC separation of hydrogenated buckminsterfullerene (C60Hn n=2–38) was investigated on BuckySep column. Toluene was used as the basic solvent and hexane, heptane, cyclohexane, THF, acetonitrile, acetone, ethanol and 2-propanol as co-solvents. The fraction of co-solvents was varied 10–80%, and the flow rate 1–0.1 mL min−1. Toluene-acetonitrile 65∶35 and toluene-acetone 50∶50 provided the best separation. Under the best conditions complete separation of C60H2 and almost complete separation of the four most abundant isomers of C60H4 were achieved. Separation of derivatives with higher hydrogen content was very poor.
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  • 64
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    Chromatographia 47 (1998), S. 440-442 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Preparative scale separations ; Chiral stationary phase ; Enantiomer separation ; Morphanthridine analog
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The preparative chromatographic enantioseparation of a chiral morphoanthridine analog has been performed on an analytical column using amylose-tris(3,5-dimethylphenylcarbamate) as chiral stationary phase. The racemate (100 mg) was resolved to baseline within 15 min. This paper describes the development of the method, estimation of the capacity of the chiral stationary phase and discussed the potential of the chromatography if performed under preparative conditions. From the results and calculations presented it seems likely that the resolution of 70 tons year−1 could easily be achieved on 30 kg of stationary phase with a mobile-phase consumption of only 720 L day−1.
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  • 65
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    Chromatographia 47 (1998), S. 449-450 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Chitin stationary phase ; Marrubiin ; Analgesic activity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Marrubiin is the main active compound isolated fromM. vulgare, a medicinal plant used in folk medicine to cure several diseases. The present study shows that chitin, an abundant natural polymer, may be successfully in chromatography column to separate marrubiin from complex mixtures. The experimental procedure described here represents an efficient and rapid method to obtain such compound in high yield.
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  • 66
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Affinity chromatography ; Molecular imprinting ; Molecular recognition ; Combinatorial libraries
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    Topics: Chemistry and Pharmacology
    Notes: Summary Molecular imprinting is an attractive method for producing highly selective adsorbents, and several new and potentially useful applications based on molecularly imprinted polymers (MIPs) have been described in recent years. In this article, we highlight some of the areas where these materials have found application, and also describe some new fields of application where the selectivities of imprinted materials can be gainfully employed, for example as binding matrices in the screening of combinatorial libraries, and as auxiliary agents in enzymatic syntheses.
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  • 67
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Fermentation ; Microdialysis sampling ; Monosaccharides and ethanol ; On-line monitoring ; Biosensors
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Two amperometric biosensors were used as detection units in liquid chromatography for on-line monitoring of the production of fuel ethanol during a fermentation. Sampling was performed with a microdialysis probe, and the dialysate was introduced into a liquid chromatographic system providing separation of the substrates and the product: three monosaccharides and ethanol. The analytes were detected by two carbon paste electrodes based on pyranose oxidase and alcohol oxidase, respectively, co-immobilised with horseradish peroxidase, operating in parallel at −50 mVvs. Ag/AgCl. The measured linear ranges of the biosensors by direct injection into the LC system were for glucose 0.3–2.5 g L−1, xylose 0.5–6.7 g L−1, galactose 0.5–6.7 g L−1, and ethanol 1.6–11.7 g L−1, respectively. Injection of standard solutions were required to monitor the stability of the biosensors. Due to the strict selectivity of the biosensors, no interference from other compounds in the broth was encountered from other compounds in the broth was encountered in the quantification. The fermentation process was monitored for 16 h. The on-line results were compared with off-line measurements.
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  • 68
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Cisapride in plasma ; Pharmacokinetics
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    Topics: Chemistry and Pharmacology
    Notes: Summary An HPLC method has been developed for the quantification of cisapride in plasma for pharmacokinetic studies. Clebopride was used as internal standard. Plasma samples were extracted at alkaline pH withtert-butyl methyl ether. The organic phase was then extracted with sulphuric acid to eliminate endogenous interferences, and cisapride and the internal standard were then extracted at alkaline pH intotert-butyl methyl ether. After evaporation oftert-butyl methyl ether, the residue was analysed by HPLC. Chromatography was performed at 20°C on a 250mm×4mm i.d. reversed-phase column selective for basic compounds. The isocratic mobile phase was 48∶52 (v/v) acetonitrile-water containing 0.05 M potassium dihydrogen phosphate and 0.04 M triethylamine, adjusted to pH 5.5; the flow rate was 1 mL min−1. Cisapride and the internal standard were detected by ultraviolet monitoring at 276 nm. The calibration graph was linear for quantities of cisapride from 1 to 200 ng mL−1. Intra- and inter-day precision (CV) did not exceed 13.98%. The limit of quantitation (LOQ) was 0.68 ng mL−1 for human plasma. The applicability of the method has been demonstrated in a pharmacokinetic study of normal volunteers who received 10 mg cisapride orally.
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  • 69
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    Chromatographia 47 (1998), S. 285-290 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Enantiomeric separation ; β-Cyclodextrins ; Methylenedioxylated amphetamines ; Ecstasy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Native and derivatized β-cyclodextrins such as chiral stationary phases (CSP) were used for the simultaneous enantiomeric separation of four methylenedioxylated amphetamines (MDA, MDMA, MDEA and MBDB) by liquid chromatography. Fluorimetric detection was used in order to enhance sensitivity and selectivity. The mobile phase was, optimised by studying the influence of pH, triethylamine concentration, organic solvent type, column temperature and flow rate of the mobile phase. This method was validated by determining linearity, precision, accuracy, limits of detection and quantification, and was applied to the stereoselective analysis of illicit tablets (23 samples) and of human whole blood samples (spiked samples and two post-mortem cases). Whereas no significant deviation from a racemic ratio was observed in the tablets contents, the analysis of blood samples showed an enantioselective metabolism of MDMA.
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  • 70
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Aminopropyl-silica sorbent ; Continuous cleanup/preconcentration ; Hydroxyvitamin D3 metabolites ; Flow injection analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A new procedure for continuous cleanup and concentration of hydroxyvitamin D3 metabolites prior to their separation by HPLC and UV-detection is reported. The process is based on the use of aminopropyl-silica as solid-phase sorbent as an alternative to the use of nonpolar sorbents. The improvement thus achieved has been tested by comparing the results with those obtained using octadecyl-C18 as non-polar sorbent. The comparison has been based on the calibration graphs (linear range, detection and quantitation limits), precision and multiple standard addition method.
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  • 71
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Coulometric detection ; Mandelic acids ; Phenylglycols ; Urine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A method has been developed for the quantification of urinary 3,4-dihydroxymandelic acid (DOMA), 4-hydroxy-3-methoxymandelic acid (VMA), 3,4-dihydroxyphenylglycol (DHPG), and 4-hydroxy-3-methoxyphenyglycol (MHPG). Separation and determination of these compounds in biological samples was previously thought to be very difficult. In this work the separation has been achieved by reversed-phase high-performance liquid chromatography with step-wise gradient elution with three mobile phases. The conditions for coulometric detection have been optimized for effective determination of these compounds. In analysis of a sample of human urine, after a simple deproteinization proceudre, DOMA, VMA, DHPG, and MHPG were separated from interferences and quantified successfully; the average levels of these compounds in six different samples were 33.87±1.03, 1202±41.3, 31.3±1.92, and 80.6±2.15 μg (24 h)−1, respectively. Their precursors E, MN, DOPA, DA, NE, DOPAC, HVA, 3MT, and NMN, and the indolamine 5HT and its metabolite 5HIAA (a list of abbreviations is given at the end of the paper) can also be determined simultaneously in the same chromatographic run. The overlapping peak of DHPG was resolved by deconvolution.
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  • 72
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Optimization ; Mixture design ; Special cubic polynomial model ; Pareto-optimality ; Overlapping resolution mapping (ORM)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A systematic approach, using a mixture-design statistical technique, has been developed for selecting the optimum mobile phase for the separation of fat-soluble vitamins in reversed-phase high-performance liquid chromatography. A quaternary mixture of methanol, acetonitrile, tetrahydrofuran and water was used as mobile phase. Retention time and peak width were recorded in ten runs augmented with five replicates and the data were subsequently fitted to special cubic polynomial models. The resulting mathematical equations enabled prediction of resolution over the entire parameter space. Contour plots of minimum effective resolution and maximum retention time as a function of mobile phase composition are presented and discussed. Visual inspection of these plots provides an overview of the quality of the separation and the analysis time required for each possible mobile-phase composition with n the parameter space. It is demonstrated that the methodology followed was an important tool which enabled the taking of informed decisions necessary for selection of the optimum mobile phase for a chromatographic separation. A combination ofR S minimum andt R maximum as optimization criteria in a multicriteria decision-making plot using pareto-optimality concept is discussed. This combination enabled visual demonstration of the compromise between separation quality and the economics of analysis time. Our methodology has been compared with the common used technique of ‘overlapping resolution mapping’.
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  • 73
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    Chromatographia 47 (1998), S. 457-464 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Imprinted polymer ; Non-covalent imprinting ; Selectivity and capacity ; Association constant
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Imprinted polymers as stationary phases for HPLC separations have been the subject of extensive investigations in recent years. In order to aid the rational design of synthetic protocols for the preparation of imprinted polymers, a series of calculations were made to assess the equilibrium concentration of templatemonomer complexes as a function of association constant (K) for the functional groups involved in the interactions and initial concentrations of reactants. This data was then used to predict the selectivity of polymers prepared under different reaction conditions and the model was tested using an experimentally determined value ofK and separation factors taken from the literature.
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  • 74
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; N-(dansyl)-dl-amino acids ; Human serum albumin ; Chiral discrimination ; Optimization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The effect of perchlorate anion as mobile phase modifier on the separation factor, α, forN-(dansyl)-dl-norvaline andN-(dansyl)-dl-tryptophan on a human serum albumin (HSA) column was studied by varying the concentration,c, of the chaotropic agent and the column temperatureT. Gibbs-Helmholtz parameters Δ(ΔH) and Δ(ΔS) between thed andl enantiomers were determined from linear van't Hoff plots of lnα against 1/T. Thermodynamic results indicated that the enhancement of the separation factor observed asc was increased was enthalpically controlled owing to stereoselective H-bonding interactions. Such behavior was used to optimize the chromatographic conditions for separation ofN-(dansyl)-amino acids on HSA.
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  • 75
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Solid phase extraction ; Sample treatment optimisation ; Taguchi method ; Albendazole metabolites ; Milk samples
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Reversed phase HPLC methods for the determination of two metabolites of albendazole in cow's milk are described. Albendazole is an anthelmintic agent used both in veterinary and human practice. Its main metabolites are albendazole-sulfoxide and albendazole-sulfone. The separation of the two metabolites was performed on a μ-Bondapak C-18 column using an acetonitrile/methanol/phosphate buffer as mobile phase, with detection at 290 nm. For the sample preparation of the milk samples we used solid phase extraction. A new sample treatment optimisation procedure is also presented for the sample preparation method. Since sample preparation is a critical step in the analysis of residues in biological samples, the second part of our publication describes an optimisation using Taguchi's methodology that increased recovery, accuracy and reliability. After optimisation of the sample preparation, the limit of detection was 10 ng mL−1 milk and the recovery was 70–80% in the concentration range of 30–1000 ng mL−1 milk for both metabolities.
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  • 76
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Ketotifen analysis ; Stability indicating analysis ; Aqueous and oil-based formulations
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A simple and specific high-performance liquid chromatographic (HPLC) method for the analysis of ketotifen in aqueous solutions and silicon oil suspensions is described. The HPLC system is based on a reversed phase μBondapak C18 (30×0.39 cm) column with a mobile phase of phosphate buffer (0.001 M, pH 7.4):methanol: acetonitrile: trimethylamine (29.8:45:25:0.2, by volume) at a flow-rate of 1 mL min−1. The eluent was monitored by UV absorption at 299 nm. Silicon oil-based samples were extracted with HCl (0.05 M) using imipramine as internal standard. The recovery of ketotifen and imipramine was greater than 80%. The calibration curves for both assays were linear over the ranges examined, yielding correlation coefficients greater than 0.997. The assay was shown to be stability indicating by subjecting solutions of ketotifen in phosphate buffer to heat, oxidative stress and irradiation with ultraviolet light (254 and 369 nm)for up to 8 h. The methodology was also shown to be applicable for the analysis of ketotifen in simple aqueous based formulations, in suspension in silicon oil and for the analysis of samples derived fromin vitro skin transfer experiments.
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  • 77
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    Chromatographia 48 (1998), S. 43-47 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Vitamin C analysis ; Ascorbate-2-phosphate and sulphate esters ; Enzyme shifting
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A method was devised to assay four forms of vitamin C: L-ascorbic acid (AA), dehydroascorbic acid (DHA), ascorbate-2-mono- and polyphosphate (AMP, APP), as well as ascorbate-2-monosulphate (AMS), in sample series of different fish tissues and feed. Direct and indirect detection were combined. Sample extractions were carried out with 0.2 mol L−1 sodium acetate buffer (pH 4.8) and extracts were deproteinized after different chemical or enzymatic reactions, with perchloric acid. The DHA was reduced to AA with dithioerythritol (DTE). Ascorbate oxidase enzyme was used for the detection of background and an acidic phosphatase enzyme for the hydrolysis of different phosphate esters. Ascorbate-2-sulphate was detected directly with help of coinjection of the compound. Chromatographic analysis was carried out with a single column isocratic reverse phase method. The mobile phase was an aqueous buffer of 0.04 M sodium-acetate, 0.05 mM EDTA, 0.5 mM tetrabutylammonium dihydrogen phosphate (TBA) adjusted to pH 3.76 with 85% H3PO4 and with 24 mL methanol added to 1000 mL. C-18 columns were used with 0.6 mL min−1 flow rate at 23°C. The vitamin C forms were detected by UV absorption at 250 nm. The determination limit was 1.0–5.0 μg g−1 in AA equivalent. The standard deviations were between 1–6% and depended on the concentrations of vitamin C forms and tissues. Recoveries were between 90–96% in samples.
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  • 78
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Multicomponent mixtures ; Separation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Coupling of full adsorption-desorption and size-exclusion chromatography (FAD-SEC) has been applied to the separation and molecular characterization of three- and four-component polymer blends. The method is based on the full adsorption of alln orn−1 components of the polymer blend in a specially designed FAD minicolumn. By appropriate eluent switching the adsorbed polymers are desorbed stepwise from the FAD minicolumn into an on-line SEC column for molecular characterization. It is shown that the desorption isotherms of particular blend components give valuable information about the appropriate displacer composition. The exact position of the desorption isotherms depends, however, both on the amount of polymer adsorbed and in the presence of other, chemically different, polymers within FAD column. The nature and composition of the displacer must, therfore, be adjusted if the intervals between the desorption of particular blend components are to be large enough to prevent displacement overlap.
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    Chromatographia 48 (1998), S. 360-364 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Acylated anthocyanins ; Rudbeckia hirta L. ; In vitro cultures
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Conditions were determined for the separation of a complex set of anthocyanins (free aglycones, mono- and multiglycosides and esterified forms) by HPLC. The optimised gradient elution method was then used to carry out qualitative and quantitative analysis of anthocyanin compounds present in the callus tissue ofRudbeckia hirta L. and the tubular flowers of the soil-based plant. The summary content of anthocyanin pigments and the content of the main pigment was identified in the analysed biomass. The method developed is useful for the purposes of monitoring the process of biosynthesis of anthocyanins in tissues obtained through in vitro cultures. The advantages of the method for anthocyanins and its application to other anthocyanin-rich materials are also discussed.
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  • 80
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Basic drug compounds ; Amino additives ; Cyanoalkyl columns
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The separation of basic antidepressant and antipsychotic drugs on a cyanoalkyl-bonded silica column has been studied to determine the effects on peak retention, symmetry, efficiency, and resolution of six different amine mobile-phase additives. The amines—ammonia,n-butylamine, triethylamine,N,N-diisopropylethylamine,N,N-dimethylbutylamine andN,N-dimethyloctylamine—were, except forN,N-diisopropylethylamine, chosen because of their widespread use for improvement of peak symmetry in chromatographic methods;N,N-diisopropylethylamine was included as an example of a sterically hindered amine to see if the stereochemistry around the nitrogen atom is an important consideration in the selection of an additive. This study shows that a gain in symmetry and efficiency is accompanied by loss of resolution. The results obtained also indicate that one type of amine additive should be used when symmetry and efficiency are most important and another when resolution is paramount.
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  • 81
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Amphotericin B ; Oil-water lecithin-based microemulsions ; Extraction of drug from microemulsion ; Reversed-phase HPLC
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A method employing extraction then reproducible reversed-phase high-performance liquid chromatography (RPHPLC) with monitoring of the drug by absorbance at 405 nm has been developed and validated for the determination of amphotericin B in oil-water lecithin-based microemulsions. The precision and accuracy of the method are excellent (SD 2.4% and 4.2%, respectively). The established linearity range was 10–60 μg mL−1 (r 2=0.9967). The recovery of amphotericin B from spiked placebo was 〉90% over the linear range. The extraction procedure was simple and the HPLC conditions were able to separate the drug from its degradation products and excipients. The method has been used successfully for determining the amphotericin B content of microemulsions and for evaluating the chemical stability of amphotericin B-loaded microemulsions.
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  • 82
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    Chromatographia 48 (1998), S. 183-189 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Polymeric phases ; Shape selectivity ; PAH selectivity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Stationary phases with octadecyl groups have been prepared with different carbon content without and in the presence of water and characterized for their selectivity for the shape of various polyaromatic hydrocarbons. It is shown that both a high hydrocarbon content and a good accessibility of the bonded groups within the pores is required to achieve shape recognition for PAH. High carbon content alone is not sufficient. The two tests for shape selectivity proposed by Sander and Wise as well as by Tanaka are compared. In most cases the results are similar: A low selectivity with the Sander and Wise test (α TBN/BaP〈1) corresponds to a high value with the Tanaka test (α TRI/o-TER〉3). However, not in all cases the tests give corresponding answers. Further studies on molecular recognition are required.
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  • 83
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    Chromatographia 48 (1998), S. 197-202 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Molecular imprinting ; Molecular recognition ; Chiral recognition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Molecularly imprinted polymers were prepared using 2-vinylpyridine and/or methacrylic acid as functional monomers in a self-assembly imprinting protocol. The resulting polymers were analyzed in aqueous media, and the effects from the pH of the mobile phase and the degree of added organic solvent were investigated. The results are indicative of the importance of ionic bonds in conjunction with hydrophobic interactions in the formation of the complexes between the analyte and the polymers.
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  • 84
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    Chromatographia 48 (1998), S. 190-196 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Ion-interaction chromatography ; Dye-coated reversed phase ; Retention model ; Experimental design
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The separation of inorganic anions (NO3 −, NO2 −, Cl−, Br−, I−, SO4 2−, S2O3 2−) by ion-interaction chromatography mediated with a specific dye has been investigated. Chromatography was performed on a LiChrospher RP-18 colum dynamically coated with crystal violet, using acetonitrile-water buffered with phthalate as the mobile phase. The presence of the dye in the eluent enabled indirect spectrophotometric detection of the analytes, which have no significant UV absorption. Retention data were collected for the different anions by varying the composition of the mobile phase according to a full factorial experimental design. A theoretical model for the retention of singly- and doubly-charged analytes, on the basis of the two main processes of ion-exchange and ion-pair formation, has been proposed and validated with the experimental data.
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  • 85
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    Chromatographia 48 (1998), S. 209-214 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Covalent chromatography ; Thiophilic and hydrophobic ligands ; Wheat β-amylase ; Salt promoted adsorption
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The behaviour of wheat β-amylase from crude extracts in chromatography on agarose gels substituted with different ligand types was investigated. The enzyme displayed high salt promoted adsorption onto thiophilic gels provided with sulfone-thioether and 2-thiopyridine ligands. Quantitative recovery of the enzyme was easily accomplished by elution with buffer in the absence of Na2SO4. The 3-(2-pyridylthio)-2-hydroxypropylagarose (PyS-gel) also allowed elimination of pigments present in the wheat extract. These pigments showed no adsorption onto the gel, thus regeneration is easily achieved, allowing its re-use. The enzyme also displayed strong salt-dependent adsorption onto adsorbents provided with pyridyldisulfide moieties, but in this case enzyme binding was due to its thiol content since elution was achieved mainly through reduction with DTT. When the enzyme was chromatographed on a series of hydrophobic alkyl ligands in the presence of 0.5 M sodium sulphate, it was partially adsorbed on pentylagarose and quantitatively adsorbed on hexyl-agarose, elution being easily performed by sodium sulphate-free buffer. This behaviour was markedly different from that towards phenyl-Sepharose, to which the enzyme was strongly adsorbed and which required much more drastic elution conditions.
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  • 86
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Chromatographic behavior ; pH optimization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The effects of pH on both the solute retention and the peak shape of ionogenic compounds are studied in order to propose accurate models for pH optimization purposes. Several mathematical models (theoretical and empirical) for describing the variation of the retention factor versus pH are compared within different pH ranges. Limits of such models used for optimizing the pH by requiring only 3 preliminary experimental runs, are discussed in terms of deviations (≤±5%) of predicted retention times from experimental retention times. An original procedure is developed for selecting the most convenient retention model, from a given set of three retention data. This set is also applied to modeling the variation of both peak width and peak asymmetry with mobile phase pH conditions. Such a procedure is demonstrated as helpful for the separation of ionogenic solutes by considering mobile phase pH as an additional variable that can be useful during optimization procedures.
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  • 87
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Retention mechanism ; Donor-acceptor complex ; Molecular interactions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Charge-transfer interactions are often assumed to be dominant among the noncovalent interactions that govern the solute retention in electron donor-acceptor chromatography. This popular view, however, has been called into question by recent studies that suggest an important role for electrostatic interactions in the formation of donor-acceptor complexes. We reported here an experimental investigation concerning the question as to whether charge-transfer or electrostatic interactions are the driving force for solute retention in donor-acceptor chromatography. Using three chromatographic systems composed of a dinitrobenzene derived stationary phase and a hexane based mobile phase, we determined retention factors for a range of aliphatic and aromatic hydrocarbons and correlated them with molecular properties that describe the solute's dispersion, charge-transfer, and electrostatic characteristics. It was found that the molecular polarizability and ionization potential give either very poor or no correlation with solute retention whereas the molecular quadrupole moment is a linear function of the logarithmic retention factor. These results were interpreted as showing that electrostatic, rather than charge-transfer or dispersion, interactions play a major role in determining solute retention. The dominance of the electrostatic interactions over the other noncovalent interactions was discussed in terms of distance dependency of the interaction energy.
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  • 88
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    Chromatographia 48 (1998), S. 584-588 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Circular dichroism detection ; Multiscan detection ; Peak purity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A method has been developed to detect inhomogeneity of apparently homogeneous peaks of very similar analytes. The method utilizes the rapid scan feature of state-of-the-art spectrometers/detectors that allow the recording of up to 30 spectra in a single chromatographic peak. Sensitivity and selectivity are enhanced by chiroptical/optical detection. Thus, identification of “front” and “rear” components of the peak can be carried out. The method is exemplified by mixtures of codeine, hydrocodone and oxycodone as analytes.
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  • 89
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    Chromatographia 48 (1998), S. 589-590 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Berberine in plasma ; Ischemic heart failure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Berberine absorption by patients with ischemic heart failure (IHF) after oral administration and the relationship between clinical effect and plasma berberine concentration are studied. Plasma samples were pretreated by chloroform extraction. Berberine was determined on a μBondapak column with acetonitrile-phosphoric acid mobile phase and UV detection. The limit for berberine in plasma was 8 ng mL−1 for an injection volume of 50 μL. Average berberine recovery was 96.5%. Results showed that improvements in symptoms were more significant for patients with plasma berberine concentration〉0.1 mg L−1 than for those with〈0.1 mg L−1. Plasma berberine monitoring may be helpful in the treatment of patients with IHF.
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  • 90
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Micellar liquid chromatography ; Diethyldithiocarbamates ; Metal complexes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary This paper presents the, chromatographic retention of Co(II), Ni(II) and Cu(II) as diethyldithiocarbamate complexes in the presence of hexadecyltrimethylammonium bromide/ethanol/water systems, as mobile phase, by reversed phase high performance liquid chromatography. The presence of an organic modifier reduces the retention times and improves the efficiency. In order to evaluate the interaction between the metal complexes and the mixed micellar system the values of solute binding constants are calculated in, two ways: a) Arunyanart and Cline-Love's treatment and b) multiple regression analysis taking account of the ethanol percentages.
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  • 91
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Homocysteine ; Human plasma ; Routine analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Elevated plasma homocysteine is, a known risk factor in arteriosclerotic vascular disease. To measure homocysteine in a large number of samples, we have developed a rapid, simple, robust and inexpensive reversed-phase HPLC method for routine analysis. Mercaptopro-pionylglycine was used as the internal standard and an external calibration in plasma was performed. Improvement was achieved by the use of gradient elution (using a sodium acetate buffer and methanol) resulting in a higher number of samples analyzed per day. Plasma samples were reduced with tributylphosphine and the proteins were precipitated with perchloric acid before addition of internal standard. The analytes were derivatized by use of 7-fluorobenzofurazone-4-sulfonic acid ammonium salt. For calibration human plasma was spiked with nine different concentrations of homocysteine (range 2–50 μmol L−1). The inter-assay precision of replicate (n=29) analysis of the concentration of homocysteine in a sample of pooled plasma was 3.0%. The limit of detection, defined as three times the signal-to-noise ratio, was 0.25 μmol L−1. The linearity of the assay was confirmed for a plasma concentration range of 2–2000 μmol L−1. The variation of duplicate analyses of 842 plasma samples was 2.6±1.7%.
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  • 92
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Tramadol andO-demethyl tramadol in plasma ; Pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A sensitive liquid chromatographic assay for the quantitative determination of the opioid analgesic tramadol and its active metabolite is described. Fluconazole was used as internal standard. The assay involved a singletert-butyl methyl ether extraction and LC analysis with fluorescence detection. Chromatography was at 30°C pumping an isocratic mobile phase of acetonitrile-water (19∶81, v/v) containing 0.06M NaH2PO4 and 0.05M triethylamine, adjusted to pH 7.90, at 1 mL min−1 through a reversed-phase, 250×4 mm base-stable column. The limit of quantitation of tramadol and its active metabolite was 1 ng mL−1, only 0.5 mL plasma sample was required for the determination. The calibration curve was linear from 1–1000 ng mL−1. Intra and inter-day precision (C.V.) did not exceed 10%. Mean recoveries of 96.38% for tramadol and 96.62% forO-demethyltramadol with CVs of 0.43% and 1.46% were obtained. Applicability of the method was demonstrated by a pharmacokinetic study on normal volunteers who received 100 mg tramadol intravenously.
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  • 93
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    Chromatographia 48 (1998), S. 561-568 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Planar chromatography ; S-Carboxymethyl-L-cysteine ; Metabolic studies
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The analysis of 08:00–16:00 (0–8) hour urine collections following oral S-carboxymethyl-L-cysteine administration of 750 mg to 30 individuals identified S-carboxymethyl-L-cysteine, S-carboxymethyl-L-cysteine S-oxide, S-methyl-L-cysteine and S-methyl-L-cysteine S-oxide as the major urinary drug related compounds. No S-(carboxymethylthio)-L-cysteine mixed disulphide metabolite was found in the 08:00–16:00 hour urine collection but the metabolite was detected in the 16:00–00:00 (8–16) hour urune collection by paper chromatography, TLC and HPLC. The production of the S-oxide metabolites 08:00–16:00 hour urine collection) and the mixed disulphide metabolite (16:00–00:00 hour urine collection) were both shown to be biomodally distributed. A significant linear correlation of the S-oxides recovered following 08:00–16:00 hour urine collection as analysed by paper chromatography, TLC and HPLC is reported.
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  • 94
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Normal phase gradient elution ; Polyester resins
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Polymers can be characterized by gradient elution techniques in order to obtain information on their chemical composition and molar mass. In this paper, features and applications of Normal Phase Gradient Polymer Elution Chromatography (NP-GPEC) for the characterization of (co)polyesters are investigated. Two polyesters were characterized, using various stationary and mobile phases. Separation was shown to be dominated by end groups in most cases, and to a lesser extent by molar mass. A distinct influence of both column type and mobile phase type was observed. A polymer based polyamine (PA) column povided the best results, although no complete separation between the mono- and di-acid fractions could be obtained. In all cases, separation was governed by sorption rather than by precipitation/redissolution. NP-GPEC was shown to be a potentially interesting technique for the characterization of copolyesters according to the chemical composition of the backbone, independent of end groups.
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  • 95
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Enantiospecific analysis ; N-Ethyl-N-methylaniline ; N-Oxidation ; N-Dealkylation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A robust, sensitive reverse-phase high-performance liquid chromatographic (HPLC) method for the quantification of the majorin vitro oxidative microsomal metabolites of the prochiral tertiary amineN-ethyl-N-methyllaniline (EMA) is described. The analytes were resolved on a Spherisorb 5 ODS1 HPLC column using an acetonitrile/phosphate buffer system under isocratic conditions. Use of solid-phase extraction (SPE) and ultraviolet (UV) detection at low wavelength (210 nm) enabled the detection of EMAN-oxide simultaneously with the majorN-dealkylated metabolites,N-ethyl andN-methylaniline. Previous chromatographic methods described for the quantification ofN,N-dialkylarylamineN-oxides have generally required sample pretreatment to reduce theN-oxide to its parent tertiary amine prior to analysis. The above method, in combination with a previously reported chromatographic resolution based on the Chiralcel OD chiral stationary phase (CSP), allows accurate and precise determination of both the quantity and stereochemical composition of metabolically derived EMAN-oxide.
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  • 96
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Chlorophyllc ; Marine phytoplankton ; Octylsilica phases ; Photosynthetic pigments
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The separation of mono- and divinyl chlorophyllc forms was estudied employing several octylsilica and octadecylsilica columns under isocratic conditions. In this paper we show that, using the adequate mobile phases, the monomeric C8 columns can separate the mentioned chlorophylls. A comparison between C8 and C18 columns reveals that monomeric OS phases provide always higher resolution of the MV- and DV chlorophyllc pairs. Such a result could be explained in terms of differences in column polarity. When adequate gradient profiles and injection conditions are used the separation is accomplished together with that of other chlorophylls and carotenoids.
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  • 97
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    Chromatographia 47 (1998), S. 637-642 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Ligand-exchange chromatography ; Chiral stationary phases ; Enantiomer separation ; Amino acids
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Chiral stationary phases (CSPs) were synthesized by reaction of aminopropylsilica (APS) with chiral monochloro-s-triazines (MCTs). MCTs were obtained by reaction of 2,4,6-trichloro-s-triazine (cyanuric chloride) with one equivalent of methanol and, subsequently, with one equivalent of L-prolinetert butyl ester (H-Pro-OtBu) orN-tert butyloxycarbonyl-L-lysinetert butyl ester (Boc-Lys-OtBu). End-capping of unreacted amino groups of APS with acetic anhydride, followed by trifluoroacetolytic cleavage of the protecting groups of amino acids (AAs), afforded two chiral stationary phases bearing either L-proline (CSP-3) or L-lysine (CSP-4) as chiral selector. Using ligand-exchange chromatography matography with addition of Cu2+ to the mobile phase, enantiomers of free DL-AAs and a fewN-(2,4-dinitrophenyl)-DL-AAs were separated on CSP-3, whereasN-(dansyl)-DL-AAs were separated on CSP-4.
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  • 98
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Atmopheric Pressure Chemical Ionization (APCI) mass ; spectrometry ; Glucuronide-conjugates ; Toxicological compounds
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A new chromatographic method for the direct determination of metabolites (glucuronide-conjugates) of molecules of toxicological relevance in biological media with the minimum sample pre-treatment has been developed. A high performance liquid chromatographyatmospheric pressure chemical ionization-mass spectrometry (LC-APCI-MS) system was used for this purpose. The separation of four glucuronides Aminophenylglucuronide (APhG), Phenylglucuronide (PhG),p-Nitrophenylglucuronide (NPhG) and α-Naphthylglucuronide (NG) was obtained under ion-suppressed reversed-phase chromatography conditions, by using high-speed (3 cm, 3 μm) columns and formic acid (2 mM) as the acid modifier in the mobile phase. Different C-18 stationary phases (partially endcapped and non-endcapped) were evaluated in order to obtain retention for these very polar, water soluble molecules. The ionization of the analytes was obtained in negativeion (NI) mode. Detection limits were in the range 1–5 mg L−1 and calibration curves were linear over two order of magnitude. Intra-day and inter-day precision were in the range 2.9–10.6% for all the compounds. The method was successfully applied for the determination of PhG in a urine sample of a European Quality Assurance Programme for Organic Solvent Metabolites.
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  • 99
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Column liquid chromatography ; Solid-phase microextraction ; Local anaesthetic lidocaine ; Optimisation of extraction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Solid-phase microextraction (SPME) has been combined with gas chromatography (GC) and liquid chromatography (LC) for the determination of lidocaine in human urine. A polydimethylsiloxane (PDMS) coated fibre was directly immersed into buffered urine. Extraction conditions such as time, pH, ionic strength, temperature, and agitation were optimised. The extracted lidocaine was thermally desorbed in a split/splitless injector for analysis with a GC-FID system or desorbed with liquid in a specially designed SPME-LC interface for analysis with an LC-UV system. After optimisation the method developed was evaluated and validated. Extraction yields of 22% were obtained in about 45 min. The reproducibility of the method is 〈5% (relative standard deviation). For five-times diluted urine, linear ranges were found from 5–1000 and 25–1000 ng·mL−1 for SPME-GC and SPME-LC, with detection limits of 5 ng·mL−1 for SPME-GC and 25 ng·mL−1 for SPME-LC. SPME can be used as a simple sample pretreatment method for the determination of lidocaine in urine by GC and LC.
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  • 100
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Vitamin A in flour and milk powder ; Method validation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary An experimental and statistical approach is presented which enables, with a minimum of determinations, the validation of a high-performance liquid chromatographic (HPLC) method for the determination of vitamin A in milk powder and flour for children. The principal aspects of method validation are examined and discussed.
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