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  • 1
    Publication Date: 2019-01-29
    Description: We consider an optimal control problem from hyperthermia treatment planning and its barrier regularization. We derive basic results, which lay the groundwork for the computation of optimal solutions via an interior point path-following method. Further, we report on a numerical implementation of such a method and its performance at an example problem.
    Keywords: ddc:510
    Language: English
    Type: reportzib , doc-type:preprint
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  • 2
    Publication Date: 2016-06-09
    Description: Optical technologies are ubiquitously used in hi-tech devices. As a common feature of such devices one finds structures with dimensions in the order of the wavelength of the used light. To design and produce such devices, the wave nature of light must be taken into account. Accordingly, robust simulation tools are required which are based on rigorously solving Maxwell's equations, the governing equations of light propagation within macroscopic media. This thesis contributes to the modeling and the numerical computation of light scattering problems: Light scattering problems are typically posed on the entire space. The Perfectly-Matched -Layer method (PML) is widely used to restrict the simulation problem onto a bounded computational domain. We propose an adaptive PML method which exhibits a good convergence even for critical problems where standard PML implementations fail. Besides the computation of the near field, that is the electromagnetic field within the computational domain, it is of major interest to evaluate the electromagnetic field in the exterior domain and to compute the far field. So far, this was numerically only possible for simple geometries such as homogeneous exterior domains or layered media. To deal with more complicated devices, for example with waveguide inhomogeneities, we develop an evaluation formula based on the PML solution which allows for an exterior domain field evaluation in a half space above the device. Finally, we generalize the PML method to problems with multiply structured exterior domains. The term “multiply structured exterior domain” is defined in this thesis and means that the exterior domain exhibits several half-infinite structures. Mathematically, this gives rise to various complications. For example, no analytical solutions to Maxwell's equations for standard light sources are available in the exterior domain, which are needed to describe the incoming field in a light scattering problem. To tackle this we propose a new light scattering problem formulation which fits well into the PML method framework and which may be regarded as an extension of classical contributions by Sommerfeld, Wiener and Hopf. An exterior domain evaluation formula for multiply structured exterior domains with an extended illumination is derived as well.
    Keywords: ddc:510
    Language: English
    Type: doctoralthesis , doc-type:doctoralThesis
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  • 3
    Publication Date: 2020-08-05
    Description: We introduce the coolest path problem, which is a mixture of two well-known problems from distinct mathematical fields. One of them is the shortest path problem from combinatorial optimization. The other is the heat conduction problem from the field of partial differential equations. Together, they make up a control problem, where some geometrical object traverses a digraph in an optimal way, with constraints on intermediate or the final state. We discuss some properties of the problem and present numerical solution techniques. We demonstrate that the problem can be formulated as a linear mixed-integer program. Numerical solutions can thus be achieved within one hour for instances with up to 70 nodes in the graph.
    Keywords: ddc:510
    Language: English
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  • 4
    Publication Date: 2021-08-05
    Description: Given a general mixed integer program (MIP), we automatically detect block structures in the constraint matrix together with the coupling by capacity constraints arising from multi-commodity-flow formulations. We identify the underlying graph and generate cutting planes based on cuts in the detected network. Our implementation adds a separator to the branch-and-cut libraries of SCIP and CPLEX. We make use of the complemented mixed integer rounding framework (cMIR) but provide a special purpose aggregation heuristic that exploits the network structure. Our separation scheme speeds-up the computation for a large set of MIPs coming from network design problems by a factor of two on average.
    Keywords: ddc:510
    Language: English
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  • 5
    Publication Date: 2022-03-14
    Description: Pseudo-Boolean problems lie on the border between satisfiability problems, constraint programming, and integer programming. In particular, nonlinear constraints in pseudo-Boolean optimization can be handled by methods arising in these different fields: One can either linearize them and work on a linear programming relaxation or one can treat them directly by propagation. In this paper, we investigate the individual strengths of these approaches and compare their computational performance. Furthermore, we integrate these techniques into a branch-and-cut-and-propagate framework, resulting in an efficient nonlinear pseudo-Boolean solver.
    Keywords: ddc:510
    Language: English
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  • 6
    Publication Date: 2020-08-05
    Description: Every day, millions of people are transported by buses, trains, and airplanes in Germany. Public transit (PT) is of major importance for the quality of life of individuals as well as the productivity of entire regions. Quality and efficiency of PT systems depend on the political framework (state-run, market oriented) and the suitability of the infrastructure (railway tracks, airport locations), the existing level of service (timetable, flight schedule), the use of adequate technologies (information, control, and booking systems), and the best possible deployment of equipment and resources (energy, vehicles, crews). The decision, planning, and optimization problems arising in this context are often gigantic and “scream” for mathematical support because of their complexity. This article sketches the state and the relevance of mathematics in planning and operating public transit, describes today’s challenges, and suggests a number of innovative actions. The current contribution of mathematics to public transit is — depending on the transportation mode — of varying depth. Air traffic is already well supported by mathematics. Bus traffic made significant advances in recent years, while rail traffic still bears significant opportunities for improvements. In all areas of public transit, the existing potentials are far from being exhausted. For some PT problems, such as vehicle and crew scheduling in bus and air traffic, excellent mathematical tools are not only available, but used in many places. In other areas, such as rolling stock rostering in rail traffic, the performance of the existing mathematical algorithms is not yet sufficient. Some topics are essentially untouched from a mathematical point of view; e.g., there are (except for air traffic) no network design or fare planning models of practical relevance. PT infrastructure construction is essentially devoid of mathematics, even though enormous capital investments are made in this area. These problems lead to questions that can only be tackled by engineers, economists, politicians, and mathematicians in a joint effort. Among other things, the authors propose to investigate two specific topics, which can be addressed at short notice, are of fundamental importance not only for the area of traffic planning, should lead to a significant improvement in the collaboration of all involved parties, and, if successful, will be of real value for companies and customers: • discrete optimal control: real-time re-planning of traffic systems in case of disruptions, • model integration: service design in bus and rail traffic. Work on these topics in interdisciplinary research projects could be funded by the German ministry of research and education (BMBF), the German ministry of economics (BMWi), or the German science foundation (DFG).
    Keywords: ddc:510
    Language: English
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  • 7
    Publication Date: 2020-08-05
    Description: The steel mill slab design problem from the CSPLib is a binpacking problem that is motivated by an application of the steel industry and that has been widely studied in the constraint programming community. Recently, several people proposed new models and methods to solve this problem. A steel mill slab library was created which contains 380 instances. A closely related binpacking problem called multiple knapsack problem with color constraints, originated from the same industrial problem, were discussed in the integer programming community. In particular, a simple integer programming for this problem has been given by Forrest et al. [3]. The aim of this paper is to bring these different studies together. Moreover, we adopt the model of [3] for the steel mill slab problem. Using a state of the art integer program solver, this model is capable to solve all instances of the steel mill slab library, mostly in less than one second, to optimality. We improved, thereby, the solution value of 76 instances.
    Keywords: ddc:510
    Language: English
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  • 8
    Publication Date: 2020-08-05
    Description: Nowadays most data networks use shortest path protocols such as OSPF or IS-IS to route traffic. Given administrative routing lengths for the links of a network, all data packets are sent along shortest paths with respect to these lengths from their source to their destination. One of the most fundamental problems in planning shortest path networks is to decide whether a given set of routing paths forms a valid routing and, if this is not the case, to find a small subset of the given paths that cannot be shortest paths simultaneously for any routing lengths. In this paper we show that it is NP-hard to approximate the size of the smallest shortest path conflict by a factor less than 7/6.
    Keywords: ddc:510
    Language: English
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  • 9
    Publication Date: 2020-08-05
    Description: The Vehicle Positioning Problem (VPP) consists of the assignment of vehicles (buses, trams or trains) of a public transport or railway company to parking positions in a depot and to timetabled trips. Such companies have many different types of vehicles, and each trip can be performed only by vehicles of some of these types. These assignments are non-trivial due to the topology of depots. The parking positions are organized in tracks, which work as one- or two-sided stacks or queues. If a required type of vehicle is not available in the front of any track, shunting movements must be performed in order to change vehicles' positions, which is undesirable and should be avoided. In this text we present integer linear and non-linear programming formulations for some versions of the problem and compare them from a theoretical and a computational point of view.
    Keywords: ddc:510
    Language: English
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  • 10
    Publication Date: 2020-03-11
    Description: The understanding of geometric structures and dynamical properties of molecular conformations gives insight into molecular long-term behavior. The identification of metastable conformations together with their life times and transition patterns is the intention of conformation dynamics. Conformation dynamics is a multi-scale approach that leads to a reduced description of the dynamical system in terms of a stochastic transition probability matrix. The present thesis deals with the error analysis of computed matrices and the resulting matrix functions. Since conformational membership vectors, as they are computed by the Robust Perron Cluster Analysis (PCCA+), form an invariant subspace of the transition matrix, subspace-based error estimators are of particular interest. The decomposition of the state space into basis functions and the approximation of integrals by Monte-Carlo quadrature give rise to row-wise correlated random matrices, for which stochastic norms are computed. Together with an appropriate statistical model for the distribution of matrix rows, this allows for the calculation of error bounds and error distributions of the invariant subspace and other variables of interest. Equilibration of errors among the basis functions can be achieved by enhanced sampling in regions where the trajectories are mixing slowly. Hierarchical refinement of such basis functions systematically improves the clustering into metastable conformations by reducing the error in the corresponding invariant subspace. These techniques allow for an evaluation of simulation results and pave the way for the analysis of larger molecules. Moreover, the extension of PCCA+ to non-reversible Markov chains, verified by the corresponding perturbation theory, and the modification of the objective function for the case of soft membership vectors represent a further generalization of the clustering method, thus continuing the development from PCCA over PCCA+ to PCCA++. The methods developed in this thesis are useful for but not limited to conformation dynamics. In fact, they are applicable to a broader class of problems which combine domain decomposition with Monte-Carlo quadrature. Possible application areas may include the chemical master equation or quantum dynamical systems.
    Description: Das Verständnis von geometrischen Strukturen und dynamischen Eigenschaften molekularer Konformationen ist essentiell für die Vorhersage des Langzeitverhaltens von Molekülen. Die Identifikation metastabiler Konformationen sowie die Bestimmung von Übergangswahrscheinlichkeiten und Haltezeiten sind Bestandteil der Konformationdynamik. Dabei handelt es sich um eine Mehrskalenmethode, die auf eine reduzierte Beschreibung des Systems mittels einer stochastischen Übergangsmatrix führt. In der vorliegenden Dissertation wurde untersucht, wie man die Genauigkeit der Matrizen sowie der daraus berechneten Größen quantifizieren kann. Im Mittelpunkt stehen dabei Fehlerschätzer für den invarianten Unterraum, da die rechten Eigenvektoren als Grundlage der Robusten Perron Cluster Analyse (PCCA+) zur Identifizierung der metastabilen Konformationen dienen. Die Zerlegung des Zustandsraumes in Basisfunktionen sowie die Approximation der Matrixeinträge mittels Monte-Carlo-Quadratur führen zu zeilenweise korrelierten Zufallsmatrizen. Mit Hilfe einer stochastischen Norm sowie einem geeigneten statistischen Modell für die Verteilung der Matrixzeilen können u.a. Fehlerschranken und -verteilungen für den invarianten Unterraum brechnet werden. Eine Equilibrierung des Fehlers zwischen den Basisfunktionen kann durch erweitertes Sampling in solchen Regionen erreicht werden, in denen die Trajektorien nur langsam mischen.Eine hierarchische Zerlegung dieser Basisfunktionen verbessert systematisch die Zerlegung in metastabile Konformationen, indem sie den Fehler im invarianten Unterraum reduziert. Diese Techniken gestatten eine Evaluierung der Simulationsergebnisse und ebnen den Weg zur Behandlung komplexerer Moleküle. Desweiteren wurden Verallgemeinerungen der PCCA+ untersucht. Die Erweiterung der PCCA+ auf nicht-reversible Markov-Ketten sowie die Modifizierung der Zielfunktion für den Fall der weichen Clusterung setzen die Entwicklung von der PCCA über PCCA+ zu PCCA++ fort. Somit können neue Anwendungsfelder für dieses Cluster-Verfahren erschlossen werden. Die Methoden wurden zwar in Rahmen der Konformationsdynamik entwickelt, jedoch lassen sie sich auf eine weite Problemklasse anwenden, in der Gebietszerlegungsverfahren mit Monte-Carlo-Quadratur kombiniert werden. Mögliche Anwendungsgebiete umfassen die chemische Master-Gleichung oder quantenchemische Systeme.
    Keywords: ddc:510
    Language: English
    Type: doctoralthesis , doc-type:doctoralThesis
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  • 11
    Publication Date: 2020-08-05
    Description: The Vehicle Positioning Problem (VPP) is a classical combinatorial optimization problem in public transport planning. A number of models and approaches have been suggested in the literature, which work for small problems, but not for large ones. We propose in this article a novel set partitioning model and an associated column generation solution approach for the VPP. The model provides a tight linear description of the problem. The pricing problem, and hence the LP relaxation itself, can be solved in polynomial resp. pseudo-polynomial time for some versions of the problems.
    Keywords: ddc:510
    Language: English
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  • 12
    Publication Date: 2020-08-05
    Description: Since the initial application of mathematical optimisation methods to mine planning in 1965, the Lerchs-Grossmann algorithm for computing the ultimate pit limit, operations researchers have worked on a variety of challenging problems in the area of open pit mining. This thesis focuses on the open pit mining production scheduling problem: Given the discretisation of an orebody as a block model, determine the sequence in which the blocks should be removed from the pit, over the lifespan of the mine, such that the net present value of the mining operation is maximised. In practise, when some material has been removed from the pit, it must be processed further in order to extract the valuable elements contained therein. If the concentration of valuable elements is not sufficiently high, the material is discarded as waste or stockpiled. Realistically-sized block models can contain hundreds of thousands of blocks. A common approach to render these problem instances computationally tractable is the aggregation of blocks to larger scheduling units. The thrust of this thesis is the investigation of a new mixed-integer programming formulation for the open pit mining production scheduling problem, which allows for processing decisions to be made at block level, while the actual mining schedule is still computed at aggregate level. A drawback of this model in its full form is the large number of additional variables needed to model the processing decisions. One main result of this thesis shows how these processing variables can be aggregated efficiently to reduce the problem size significantly, while practically incurring no loss in net present value. The second focus is on the application of lagrangean relaxation to the resource constraints. Using a result of Möhring et al. (2003) for project scheduling, the lagrangean relaxation can be solved efficiently via minimum cut computations in a weighted digraph. Experiments with a bundle algorithm implementation by Helmberg showed how the lagrangean dual can be solved within a small fraction of the time required by standard linear programming algorithms, while yielding practically the same dual bound. Finally, several problem-specific heuristics are presented together with computational results: two greedy sub-MIP start heuristics and a large neighbourhood search heuristic. A combination of a lagrangean-based start heuristic followed by a large neighbourhood search proved to be effective in generating solutions with objective values within a 0.05% gap of the optimum.
    Keywords: ddc:510
    Language: English
    Type: masterthesis , doc-type:masterThesis
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  • 13
    Publication Date: 2019-01-29
    Description: In dieser Arbeit wird ein neuer Ansatz zur Modellierung von thermal signifikanten Gefäßsträngen im Hyperthermie-Kontext betrachtet. Ausgehend von einer Konvektions-Diffusions-Gleichung wird durch Reskalierung des Massenflussterms eine Reduktion des Adergebietes auf eine 1D-Struktur erreicht. Nach numerischen Vorbetrachtungen wird die Grenzgleichung innerhalb einer verallgemeinerten Sobolev-Algebra formuliert. Die Untersuchung der Lösungsfamilie in klassischen Funktionenräumen zeigt, dass deren schwacher Grenzwert die Lösung der korrespondierenden Diffusions-Gleichung ist. Die Diskretisierung einer formalen Grenzgleichung mit Linienstromanteil stellt jedoch eine gute Approximation an die Diskretisierung des ursprünglichen Problems dar, wenn man die lokale Maschenweite an die Gefäßradien koppelt und bei erhöhtem Genauigkeitsbedarf auf ein vollständiges 3D-Modell umschaltet.
    Keywords: ddc:510
    Language: German
    Type: masterthesis , doc-type:masterThesis
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  • 14
    Publication Date: 2022-03-14
    Description: We present Undercover, a primal heuristic for mixed-integer nonlinear programming (MINLP). The heuristic constructs a mixed-integer linear subproblem (sub-MIP) of a given MINLP by fixing a subset of the variables. We solve a set covering problem to identify a minimal set of variables which need to be fixed in order to linearise each constraint. Subsequently, these variables are fixed to approximate values, e.g. obtained from a linear outer approximation. The resulting sub-MIP is solved by a mixed-integer linear programming solver. Each feasible solution of the sub-MIP corresponds to a feasible solution of the original problem. Although general in nature, the heuristic seems most promising for mixed-integer quadratically constrained programmes (MIQCPs). We present computational results on a general test set of MIQCPs selected from the MINLPLib.
    Keywords: ddc:510
    Language: English
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  • 15
    Publication Date: 2020-08-05
    Description: We consider a system with Poisson arrivals and i.i.d. service times. The requests are served according to the state-dependent processor sharing discipline, where each request receives a service capacity which depends on the actual number of requests in the system. The linear systems of PDEs describing the residual and attained sojourn times coincide for this system, which provides time reversibility including sojourn times for this system, and their minimal non negative solution gives the LST of the sojourn time $V(\tau)$ of a request with required service time $\tau$. For the case that the service time distribution is exponential in a neighborhood of zero, we derive a linear system of ODEs, whose minimal non negative solution gives the LST of $V(\tau)$, and which yields linear systems of ODEs for the moments of $V(\tau)$ in the considered neighborhood of zero. Numerical results are presented for the variance of $V(\tau)$. In case of an M/GI/2-PS system, the LST of $V(\tau)$ is given in terms of the solution of a convolution equation in the considered neighborhood of zero. For bounded from below service times, surprisingly simple expressions for the LST and variance of $V(\tau)$ in this neighborhood of zero are derived, which yield in particular the LST and variance of $V(\tau)$ in M/D/2-PS.
    Keywords: ddc:510
    Language: English
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  • 16
    Publication Date: 2020-12-11
    Description: Eigentlich war der erste Autor nur zu einem Grußwort zur Tagung „GML² 2009 - Grundfragen Multi¬medialen Lehrens und Lernens“ eingeladen. Daraus wurde ein E-Learning-bezogener Vortrag, der – basierend auf Erfahrungen im Fach Mathematik – einen kritischen Blick auf die E-Learning-Szene in Deutschland wirft und diese mit entsprechenden Aktivitäten weltweit vergleicht. Dies ist die in seinen mathematischen Teilen gekürzte, in den E-Learning-Anteilen ein wenig erweiterte schriftliche Fassung des Vortrags. Der Artikel stammt nicht von E-Learning-Spezialisten sondern von Personen, die sich seit fast zwanzig Jahren mit elektronischer Information und Kommunikation (kurz: IuK) – insbesondere in der Mathematik – beschäftigen. Nach einer Definition von Michael Kerres kennzeichnet der Begriff E-Learning (electronic learning – elektronisch unterstütztes Lernen) alle Formen von Lernen, bei denen digitale Medien für die Präsentation und Distribution von Lernmaterialien und/oder zur Unterstützung zwischenmenschlicher Kommunikation zum Einsatz kommen, siehe z.B. http://de.wikipedia.org/wiki/E-Learning. IuK und E-Learning haben nach dieser Begriffsbildung viele Berührungspunkte. Deswegen wagen wir es, unsere positiven und negativen Erfahrungen im Bereich IuK in diesem Eröffnungsvortrag zu berichten, einige Entwicklungslinien zu vergleichen und eine eigene Kurzversion der Definition von E-Learning (besser E-Teaching and -Learning) voranzustellen: „Lehren und Lernen mit Unterstützung elektronischer Hilfsmittel“.
    Keywords: ddc:510
    Language: German
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  • 17
    Publication Date: 2020-08-05
    Description: Telecommunication transport networks consist of a stack of technologically different subnetworks, so-called layers, which are strongly interdependent. For example, one layer may correspond to an Internet (IP) backbone network whose links are realized by lightpath connections in an underlying optical fiber layer. To ensure that the network can fulfill its task of routing all communication requests, the inter-layer dependencies have to be taken into account already in the planning phase of the network. This is particularly important with survivability constraints, where connections in one layer have to be protected against cable cuts or equipment failures in another layer. The traditional sequential planning approach where one layer is optimized after the other cannot properly take care of the inter-layer dependencies; this can only be achieved with an integrated planning of several network layers at the same time. This thesis provides mathematical models and algorithmic techniques for the integrated optimization of two network layers with survivability constraints. We describe a multi-layer network design problem which occurs in various technologies, and model it mathematically using mixed-integer programming (MIP) formulations. The presented models cover many important practical side constraints from different technological contexts. In contrast to previous models from the literature, they can be used to design large two-layer networks with survivability requirements. We discuss modeling alternatives for various aspects of a multi-layer network and compare different routing formulations under multi-layer survivability constraints. We solve our models using a branch-and-cut-and-price approach with various problemspecific enhancements. This includes a presolving technique based on linear programming to reduce the problem size, combinatorial and sub-MIP-based primal heuristics to compute feasible network configurations, cutting planes which take the multi-layer survivability constraints into account to improve the lower bound on the optimal network cost, and column generation to generate flow variables dynamically during the algorithm. We develop techniques to speed up computations in a Benders decomposition approach and compare this approach to the standard formulation with a single MIP. We use the developed techniques to design large survivable two-layer networks by means of linear and integer programming methods. On realistic test instances with up to 67 network nodes and survivability constraints, we investigate the algorithmic impact of our techniques and show how to use them to compute good network configurations with quality guarantees. Most of the smaller test instances with up to 17 nodes can be solved to near-optimality. Moreover, we can compute feasible solutions and dual bounds even for large networks with survivability constraints, which has not been possible before.
    Keywords: ddc:510
    Language: English
    Type: doctoralthesis , doc-type:doctoralThesis
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  • 18
    Publication Date: 2020-08-05
    Description: In the simplex algorithm, solving linear systems with the basis matrix and its transpose accounts for a large part of the total computation time. We investigate various methods from modern numerical linear algebra to improve the computation speed of the basis updates arising in LPs. The experiments are executed on a large real-world test set. The most widely used solution technique is sparse LU factorization, paired with an updating scheme that allows to use the factors over several iterations. Clearly, small number of fill-in elements in the LU factors is critical for the overall performance. Using a wide range of LPs we show numerically that after a simple permutation the non-triangular part of the basis matrix is so small, that the whole matrix can be factorized with (relative) fill-in close to the optimum. This permutation has been exploited by simplex practitioners for many years. But to our knowledge no systematic numerical study has been published that demonstrates the effective reduction to a surprisingly small non-triangular problem, even for large scale LPs. For the factorization of the non-triangular part most existing simplex codes use some variant of dynamic Markowitz pivoting, which originated in the late 1950s. We also show numerically that, in terms of fill-in and in the simplex context, dynamic Markowitz is quite consistently superior to other, more recently developed techniques.
    Keywords: ddc:510
    Language: English
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  • 19
    Publication Date: 2020-03-11
    Description: We compute expectation values for the solution of the nuclear Schrödinger equation. The proposed particle method consists of three steps: sampling of the initial Wigner function, classical transport of the sampling points, weighted phase space summation for the final computation of the expectation values. The Egorov theorem guarantees that the algorithm is second order accurate with respect to the semiclassical parameter. We present numerical experiments for a two-dimensional torsional potential with three different sets of initial data and for a six-dimensional Henon-Heiles potential. By construction, the computing times scale linearly with the number of initial sampling points and range between three seconds and one hour.
    Keywords: ddc:510
    Language: English
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  • 20
    Publication Date: 2022-03-14
    Description: This paper discusses how to build a solver for mixed integer quadratically constrained programs (MIQCPs) by extending a framework for constraint integer programming (CIP). The advantage of this approach is that we can utilize the full power of advanced MIP and CP technologies. In particular, this addresses the linear relaxation and the discrete components of the problem. For relaxation, we use an outer approximation generated by linearization of convex constraints and linear underestimation of nonconvex constraints. Further, we give an overview of the reformulation, separation, and propagation techniques that are used to handle the quadratic constraints efficiently. We implemented these methods in the branch-cut-and-price framework SCIP. Computational experiments indicates the potential of the approach.
    Keywords: ddc:510
    Language: English
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  • 21
    Publication Date: 2016-06-09
    Description: Supercomputers can simulate complex molecular systems. However, there is a very large gap between the fastest oscillations of covalent bonds of a molecule and the time-scale of the dominant processes. In order to extract the dominant time-scales and to identify the dominant processes, a clustering of information is needed. This thesis shows that only the subspace-based Robust Perron Cluster Analysis (PCCA+) can solve this problem correctly by the construction of a Markov State Model. PCCA+ allows for time-extrapolation in molecular kinetics. This thesis shows the difference between molecular dynamics and molecular kinetics. Only in the molecular kinetics framework a definition of transition rates is possible. In this context, the existence of an infinitesimal generator of the dynamical processes is discussed. If the existence is assumed, the Theorem of Gauß can be applied in order to compute transition rates efficiently. Molecular dynamics, however, is not able to provide a suitable statistical basis for the determination of the transition pattern.
    Keywords: ddc:510
    Language: English
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  • 22
    Publication Date: 2020-08-05
    Description: We consider a system with Poisson arrivals and general service times, where the requests are served according to the State-Dependent Processor Sharing (SDPS) discipline (Cohen's generalized processor sharing discipline), where each request receives a service capacity which depends on the actual number of requests in the system. For this system, denoted by $M/GI/SDPS$, we derive approximations for the squared coefficients of variation of the conditional sojourn time of a request given its service time and of the unconditional sojourn time by means of two-moment fittings of the service times. The approximations are given in terms of the squared coefficients of variation of the conditional and unconditional sojourn time in related $M/D/SDPS$ and $M/M/SDPS$ systems, respectively. The numerical results presented for $M/GI/m-PS$ systems illustrate that the proposed approximations work well.
    Keywords: ddc:510
    Language: English
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  • 23
    Publication Date: 2020-08-05
    Description: We consider a system with Poisson arrivals and i.i.d. service times and where the requests are served according to the state-dependent (Cohen's generalized) processor sharing discipline, where each request in the system receives a service capacity which depends on the actual number of requests in the system. For this system we derive asymptotically tight upper bounds for the moments of the conditional sojourn time of a request with given required service time. The bounds generalize corresponding results, recently given for the single-server processor sharing system by Cheung et al. and for the state-dependent processor sharing system with exponential service times by the authors. Analogous results hold for the waiting times.
    Keywords: ddc:510
    Language: English
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  • 24
    Publication Date: 2020-11-13
    Description: The Dynamic Multi-Period Routing Problem DMPRP introduced by Angelelli et al. gives a model for a two-stage online-offline routing problem. At the beginning of each time period a set of customers becomes known. The customers need to be served either in the current time period or in the following. Postponed customers have to be served in the next time period. The decision whether to postpone a customer has to be done online. At the end of each time period, an optimal tour for the customers assigned to this period has to be computed and this computation can be done offline. The objective of the problem is to minimize the distance traveled over all planning periods assuming optimal routes for the customers selected in each period. We provide the first randomized online algorithms for the DMPRP which beat the known lower bounds for deterministic algorithms. For the special case of two planning periods we provide lower bounds on the competitive ratio of any randomized online algorithm against the oblivious adversary. We identify a randomized algorithm that achieves the optimal competitive ratio of $\frac{1+\sqrt{2}}{2}$ for two time periods on the real line. For three time periods, we give a randomized algorithm that is strictly better than any deterministic algorithm.
    Keywords: ddc:510
    Language: English
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  • 25
    Publication Date: 2021-08-05
    Description: This thesis introduces the novel paradigm of "constraint integer programming" (CIP), which integrates constraint programming (CP) and mixed integer programming (MIP) modeling and solving techniques. It is supplemented by the software SCIP, which is a solver and framework for constraint integer programming that also features SAT solving techniques. SCIP is freely available in source code for academic and non-commercial purposes. Our constraint integer programming approach is a generalization of MIP that allows for the inclusion of arbitrary constraints, as long as they turn into linear constraints on the continuous variables after all integer variables have been fixed. The constraints, may they be linear or more complex, are treated by any combination of CP and MIP techniques: the propagation of the domains by constraint specific algorithms, the generation of a linear relaxation and its solving by LP methods, and the strengthening of the LP by cutting plane separation. The current version of SCIP comes with all of the necessary components to solve mixed integer programs. In the thesis, we cover most of these ingredients and present extensive computational results to compare different variants for the individual building blocks of a MIP solver. We focus on the algorithms and their impact on the overall performance of the solver. In addition to mixed integer programming, the thesis deals with chip design verification, which is an important topic of electronic design automation. Chip manufacturers have to make sure that the logic design of a circuit conforms to the specification of the chip. Otherwise, the chip would show an erroneous behavior that may cause failures in the device where it is employed. An important subproblem of chip design verification is the property checking problem, which is to verify whether a circuit satisfies a specified property. We show how this problem can be modeled as constraint integer program and provide a number of problem-specific algorithms that exploit the structure of the individual constraints and the circuit as a whole. Another set of extensive computational benchmarks compares our CIP approach to the current state-of-the-art SAT methodology and documents the success of our method.
    Description: Diese Arbeit stellt einen integrierten Ansatz aus "Constraint Programming" (CP) und Gemischt-Ganzzahliger Programmierung ("Mixed Integer Programming", MIP) vor, den wir "Constraint Integer Programming" (CIP) nennen. Sowohl Modellierungs- als auch Lösungstechniken beider Felder fließen in den neuen integrierten Ansatz ein, um die unterschiedlichen Stärken der beiden Gebiete zu kombinieren. Als weiteren Beitrag stellen wir der wissenschaftlichen Gemeinschaft die Software SCIP zur Verfügung, die ein Framework für Constraint Integer Programming darstellt und zusätzlich Techniken des SAT-Lösens beinhaltet. SCIP ist im Source Code für akademische und nicht-kommerzielle Zwecke frei erhältlich. Unser Ansatz des Constraint Integer Programming ist eine Verallgemeinerung von MIP, die zusätzlich die Verwendung beliebiger Constraints erlaubt, solange sich diese durch lineare Bedingungen ausdrücken lassen falls alle ganzzahligen Variablen auf feste Werte eingestellt sind. Die Constraints werden von einer beliebigen Kombination aus CP- und MIP-Techniken behandelt. Dies beinhaltet insbesondere die "Domain Propagation", die Relaxierung der Constraints durch lineare Ungleichungen, sowie die Verstärkung der Relaxierung durch dynamisch generierte Schnittebenen. Die derzeitige Version von SCIP enthält alle Komponenten, die für das effiziente Lösen von Gemischt-Ganzzahligen Programmen benötigt werden. Die vorliegende Arbeit liefert eine ausführliche Beschreibung dieser Komponenten und bewertet verschiedene Varianten in Hinblick auf ihren Einfluß auf das Gesamt-Lösungsverhalten anhand von aufwendigen praktischen Experimenten. Dabei wird besonders auf die algorithmischen Aspekte eingegangen. Ein weiterer Hauptteil der Arbeit befasst sich mit der Chip-Design-Verifikation, die ein wichtiges Thema innerhalb des Fachgebiets der "Electronic Design Automation" darstellt. Chip-Hersteller müssen sicherstellen, dass der logische Entwurf einer Schaltung der gegebenen Spezifikation entspricht. Andernfalls würde der Chip fehlerhaftes Verhalten aufweisen, dass zu Fehlfunktionen innerhalb des Gerätes führen kann, in dem der Chip verwendet wird. Ein wichtiges Teilproblem in diesem Feld ist das Eigenschafts-Verifikations-Problem, bei dem geprüft wird, ob der gegebene Schaltkreisentwurf eine gewünschte Eigenschaft aufweist. Wir zeigen, wie dieses Problem als Constraint Integer Program modelliert werden kann und geben eine Reihe von problemspezifischen Algorithmen an, die die Struktur der einzelnen Constraints und der Gesamtschaltung ausnutzen. Testrechnungen auf Industrie-Beispielen vergleichen unseren Ansatz mit den bisher verwendeten SAT-Techniken und belegen den Erfolg unserer Methode.
    Keywords: ddc:510
    Language: English
    Type: doctoralthesis , doc-type:doctoralThesis
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  • 26
    Publication Date: 2020-08-05
    Description: In this paper we investigate the fare planning model for public transport, which consists in designing a system of fares maximizing the revenue. We discuss a discrete choice model in which passengers choose between different travel alternatives to express the demand as a function of fares. Furthermore, we give a computational example for the city of Potsdam and discuss some theoretical aspects.
    Keywords: ddc:510
    Language: English
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  • 27
    Publication Date: 2020-08-05
    Description: This extended abstract is about algorithms for controlling elevator systems employing destination hall calls, i.e. the passenger provides his destination floor when calling an elevator. We present the first exact algorithm for controlling a group of elevators and report on simulation results indicating that destination hall call systems outperform conventional systems.
    Keywords: ddc:510
    Language: English
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  • 28
    Publication Date: 2019-01-29
    Description: The paper proposes goal-oriented error estimation and mesh refinement for optimal control problems with elliptic PDE constraints using the value of the reduced cost functional as quantity of interest. Error representation, hierarchical error estimators, and greedy-style error indicators are derived and compared to their counterparts when using the all-at-once cost functional as quantity of interest. Finally, the efficiency of the error estimator and generated meshes are demonstrated on numerical examples.
    Keywords: ddc:510
    Language: English
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  • 29
    Publication Date: 2016-06-09
    Description: The paper considers the time integration of frictionless dynamical contact problems between viscoelastic bodies in the frame of the Signorini condition. Among the numerical integrators, interest focuses on the contact-stabilized Newmark method recently suggested by Deuflhard et al., which is compared to the classical Newmark method and an improved energy dissipative version due to Kane et al. In the absence of contact, any such variant is equivalent to the Störmer-Verlet scheme, which is well-known to have consistency order 2. In the presence of contact, however, the classical approach to discretization errors would not show consistency at all because of the discontinuity at the contact. Surprisingly, the question of consistency in the constrained situation has not been solved yet. The present paper fills this gap by means of a novel proof technique using specific norms based on earlier perturbation results due to the authors. The corresponding estimation of the local discretization error requires the bounded total variation of the solution. The results have consequences for the construction of an adaptive timestep control, which will be worked out subsequently in a forthcoming paper.
    Keywords: ddc:510
    Language: English
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  • 30
    Publication Date: 2020-08-05
    Description: The mathematical treatment of planning problems in public transit has made significant advances in the last decade. Among others, the classical problems of vehicle and crew scheduling can nowadays be solved on a routine basis using combinatorial optimization methods. This is not yet the case for problems that pertain to the design of public transit networks, and for the problems of operations control that address the implementation of a schedule in the presence of disturbances. The article gives a sketch of the state and important developments in these areas, and it addresses important challenges. The vision is that mathematical tools of computer aided scheduling (CAS) will soon play a similar role in the design and operation of public transport systems as CAD systems in manufacturing.
    Description: Die mathematische Behandlung von Planungsproblemen im öffentlichen Verkehr hat im letzten Jahrzehnt große Fortschritte gemacht. Klassische Probleme wie die Umlauf- und die Dienstplanung können heutzutage routinemäßig mit kombinatorischen Optimierungsmethoden gelöst werden. Die Behandlung von Problemen der Angebotsplanung und der Betriebssteuerung sind dagegen noch nicht ganz auf diesem Stand. Dieser Artikel gibt einen Überblick über den Stand der Forschung, über wichtige Entwicklungen und einige Herausforderungen in diesem Gebiet. Die Vision ist, dass mathematische Planungswerkzeuge im öffentlichen Verkehr (Computer Aided Scheduling, CAS) in Zukunft eine ähnliche Rolle spielen werden wie CAD-Systeme in der industriellen Fertigung.
    Keywords: ddc:510
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  • 31
    Publication Date: 2022-07-19
    Description: The reconstruction of geometric shapes plays an important role in many biomedical applications. One example is the patient-specific, computer-aided planning of complex interventions, which requires the generation of explicitly represented geometric models of anatomical structures from medical image data. Only solutions that require minimal interaction by medical personnel are likely to enter clinical routine. Another example is the planning of surgical corrections of deformities where the target shape is unknown. Surgeons are often forced to resort to subjective criteria. These applications still pose highly challenging reconstruction problems, which are addressed in this thesis. The fundamental hypothesis, pursued in this thesis, is that the problems can be solved by incorporating a-priori knowledge about shape and other application-specific characteristics. Here, we focus mainly on the aspect of geometric shape analysis. The basic idea is to capture the most essential variations of a certain class of geometric objects via statistical shape models, which model typical features contained in a given population, and restrict the outcome of a reconstruction algorithm (more or less) to the space spanned by such models. A fundamental prerequisite for performing statistical shape analysis on a set of different objects is the identification of corresponding points on their associated surfaces. This problem is particularly difficult to solve if the shapes stem from different individuals. The reason lies in the basic difficulty of defining suitable measures of similarity. In this thesis, we divide the correspondence problem into feature and non-feature matching. The feature part depends on the application, while the non-feature part can be characterized by a purely geometric description. We propose two different approaches. The first approach has proved useful in many applications. Yet, it suffers from some practical limitations and does not yield a measure of similarity. Our second, variational, approach is designed to overcome these limitations. In it, we propose to minimize an invariant stretching measure, constrained by previously computed features. An important property, which sets our method apart from previous work, is that it does not require the computation of a global surface parameterization.
    Keywords: ddc:510
    Language: English
    Type: doctoralthesis , doc-type:doctoralThesis
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  • 32
    Publication Date: 2016-06-09
    Keywords: ddc:510
    Language: English
    Type: doctoralthesis , doc-type:doctoralThesis
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  • 33
    Publication Date: 2020-08-05
    Description: wird nachgereicht
    Keywords: ddc:510
    Language: English
    Type: doctoralthesis , doc-type:doctoralThesis
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  • 34
    ISSN: 1572-9729
    Keywords: community fingerprint ; polycyclic aromatic hydrocarbon ; 16S rRNA
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Energy, Environment Protection, Nuclear Power Engineering , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Microcosm experiments were conduced in which the surface of marine sediment was contaminated with naphthalene and subjected to either of three different bioremediation schemes, i.e., biostimulation (BS) by supplementing with slow-release nitrogen and phosphorus fertilizers, bioaugmentation (BA) by inoculating with Cycloclasticus sp. E2, an aromatics-degrading bacterium identified to play an important role for aromatic-hydrocarbon degradation in marine environments and combination (CB) of BS and BA. These three schemes were found to be similarly effective for removing naphthalene, while naphthalene disappearance in sediment without any treatment (WT) was slower than those in the treated sediments. Shifts in bacterial populations during and after bioremediation were analyzed by denaturing gradient gel electrophoresis (DGGE) of PCR-amplified 16S rRNA gene fragments. It was found that the Cycloclasticus rRNA type occurred as the strongest bands in the course of naphthalene degradation. Clustering analysis of DGGE profiles showed that bacterial populations in the WT, BS and CB sediments differed consistently from those in the uncontaminated control, while the profile for the BA sediment was finally included in the cluster for uncontaminated control sediments after a 150-day treatment. The results suggest that bioaugmentation with ecologically competent pollutant-degrading bacteria is an ecologically promising bioremediation scheme.
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  • 35
    ISSN: 1432-1432
    Keywords: 5S rRNA ; 16S rRNA ; Archaebacteria ; Cladistics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary The secondary structure of 5S rRNA has been elucidated by a cladistic analysis resulting in minimal models for eukaryotes, eubacteria, and halophilic-methanogenic archaebacteria, as well as for an ur-5S rRNA. This ancestor of all present-day 5S rRNA molecules is compared with an ur-tRNA and can be fitted into a tRNA-like structure allowing tertiary-structure interactions at the equivalent positions. A phylogenetic analysis of eukaryotic 5SrRNA and 16S rRNA sequences confirms particular monophyletic taxa: rhodophytes (red algae), chlorobionts (green algae and plants), metazoans (multicellular animals), euglenozoans (euglenids and trypanosomatids), a group of zygomycetes (excluding Kickxellales), a group of ascomycetes (excluding Protomycetales), two distinct groups of basidiomycetes, and a group consisting of phaeophyceans (brown algae) and oomycetes (water molds). The Euglenozoa show a distinct relation to the Eumycota (true fungi) and Metazoa. An analysis of archaebacterial sequences substantiates the paraphyletic nature of this third urkingdom defining the eubacteria as a sister group of the halophile-methanogens and defining the eukaryotes as a sister group of a particular lineage of the eocytes/sulfur-dependents. The latter fact implies that even the eocytes/sulfur-dependent archaebacteria are paraphyletic.
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  • 36
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Biomedical Chromatography 1 (1986), S. 1-6 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A fluorescence high performance liquid chromatographic method using an immobilized 3α-hydroxysteroid dehydrogenase column as a post-column enzymatic reactor was developed for the determination of corticosteroid metabolites in the urine of subjects with congenital adrenal hyperplasia. 3α-Hydroxysteroids, such as pregnanetriol, pregnanediol and pregnanetriolone, in the eluate from μ-Bondapak phenyl column (300 × 3.9 mm I.D.) using 0.05% ammonium phosphate buffer (pH 7.1)-acetonitrile-methanol (100: 55: 15) as the mobile phase was mixed with NAD+ solution in the enzyme column at 30 °C to generate NADH, which was monitored by a fluorophotometric detector. Each steroid was measured at the 2.5 μg/dl at the highest sensitivity of the detector. The mean recoveries and reproducibilities were 91.5-108.2% with 0.9-6.5% (CV%).
    Additional Material: 8 Ill.
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  • 37
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Biomedical Chromatography 1 (1986), S. 21-26 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A high-performance liquid chromatographic method with electrochemical detection (LC/EC) was developed to measure cystine and cysteinyl-penicillamine disulfide in the urine of patients screened or treated for cystinuria. Urine was acidified, centrifuged to remove urinary protein, diluted and injected. The disulfides were separated on a reversed-phase column, reduced at the upstream electrode of a dual electrochemical detector with gold-mercury amalgam (Au/Hg) electrodes and the resultant thiols measured at the downstream electrode. The sample preparation is simple, the analysis rapid, specimens can be easily batched and the specificity of the method is better than those of two other separative procedures with which it was compared. The coefficient of variation for cystine in cystinuric urine is 6.7%, 5.5% and 3.2% for levels of 0.09, 0.52 and 1.02 mmol/l respectively, and for cysteinyl-penicillamine disulfide 2.6% and 7.5% for levels of 0.45 and 0.98 mmol/l respectively. Urine for analysis of these disulfides should not be collected within 24 hours of administration of the radiopaque agent diatrizoate but no other interference to the assay has been noted. This method is suitable as a screen for cystinuria in patients with renal tract calculi, for ongoing monitoring of cystinuric patients and to check patient compliance with d-penicillamine therapy.
    Additional Material: 6 Ill.
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  • 38
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Biomedical Chromatography 1 (1986), S. 38-40 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The 190 nm high performance liquid chromatographic photodiode array profiling of the urinary carboxylic acids of the first urine of a newborn affected with isovaleric aciduria afforded an abnormal peak at 27.8 min. This peak was greatly increased in the carboxylic acid profiling of the 14 h urine sample from the same infant. Isolation of this peak by fraction collecting; solvent extraction of the eluent; trimethylsilyl derivatization of the residue and gas chromatographic/mass spectrometric analysis identified the compound as isovalerylglycine. Correlation of the 190 nm absorbance of isovalerylglycine (y) with concentration (x) afforded a least squares curve: y = 476.4x - 13.72 (r = 0.99) run-to-run variation 6.92%; day-to-day variation 8.88%; with a minimum detectable concentration of 25 μg/ml.
    Additional Material: 2 Ill.
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  • 39
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The trypsin-sensitive glycopeptides from cell surfaces of a multipotential murine haemopoietic cell line (DE) have been studied using serial lectin affinity chromatography on columns of immobilized lentil lectin (LCA), concanavalin A (Con A), and wheat-germ agglutinin (WGA). WGA-binding material consisted of glycopeptides that failed to bind to LCA and Con A. Step elution from the WGA-column with 0.01-, 0.1-, 0.5- and 1.0 M N-acetyl-D-glucosamine yielded four affinity classes of glycopeptide (WGA-W, WGA-I, WGA-S and WGA-SS respectively). WGA-W, WGA-I and WGA-S contained both alkali-stable (N-linked) and alkali-labile (O-linked) carbohydrate on high molecular weight glycopeptides. The WGA-SS fraction contained only N-linked carbohydrate. N-linked glycopeptides isolated from each WGA-binding class differed in molecular size, relative N-acetylneuraminic acid content and affinity for Ricinus communis 120 agglutinin. endo-β-Galactosidase digestion showed that these glycopeptides contained polylactosamine-type glycans. Gel filtration profiles of the enzyme treated materials were different for each WGA-binding population suggesting variation in branching patterns and/or substitution with fucose residues. Affinity chromatography has shown that the WGA binding molecules are the major glycopeptide group at DE cell surfaces.
    Additional Material: 5 Ill.
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  • 40
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Biomedical Chromatography 1 (1986), S. 64-77 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Additional Material: 21 Ill.
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  • 41
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Biomedical Chromatography 1 (1986), S. 93-94 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Additional Material: 1 Ill.
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  • 42
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Biomedical Chromatography 1 (1986), S. 95-100 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: In the clinical laboratory, paper chromatography is still the most useful, simple, inexpensive procedure for initial identification of abnormalities of amino acid excretion. The results of its use for more than 8000 paediatric and adult renal patients is surveyed. Nonspecific generalized aminoaciduria was the most frequent abnormality found, comprising some 70% of abnormal results, with cystine-lysinuria the next most common. The identification of the abnormal excretory pattern of amino acids as distinct from the normal was complicated by the effects of the New Zealand diet. In particular, valine, citrulline, hydroxyproline and glutamic acid are found in considerable amounts as part of the normal pattern. Their dietary origin is discussed. Varying mixtures of monosaccharides and disaccharides occurred in association with a range of amino acid patterns.
    Additional Material: 4 Tab.
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  • 43
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Biomedical Chromatography 1 (1986), S. 109-118 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Inherited purine and pyrimidine disorders may be associated with serious, sometimes life-threatening consequences. Early and accurate diagnosis is essential. Difficulties encountered when using existing high pressure liquid chromatographic (HPLC) methods led to the development of an improved method based on prior fractionation of urine. The advantages are as follows. 1. Production of fingerprints demonstrating altered urinary excretion patterns characteristic of any one of ten different disorders, in 30 minutes. 2. Positive identification and quantification by comparison with established methods (using conventional chromatography, electrophoresis and UV spectrophotometry) in addition to specific retention times and characteristic UV absorbance ratios at two separate wavelengths (245 and 280 nm) by HPLC. 3. Direct analysis of all the purines and pyrimidines normally found in human body fluids as well as identification of abnormal compounds. 4. Short time between successive analyses while maintaining excellent resolution between compounds of interest and column longevity. 5. Improved separation of the different adenine-based compounds encountered in some disorders, plus demonstration of potential interference by dietary or drug metabolites. 6. Applicability to the monitoring of therapy involving a variety of different purine and pyrimidine analogues.Particular attention should be paid to sample preparation. Plasma profiles will confirm the diagnosis in some, but not all, of these disorders.
    Additional Material: 10 Ill.
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  • 44
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Biomedical Chromatography 1 (1986), S. 140-142 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A simple HPLC method for penbutolol and 4-hydroxypenbutolol assay has been developed. Plasma or serum (200 μl) is vortex-mixed (30 s) with Tris solution (2 M, pH 10.6) containing an internal standard (50 μl) and methyl t-butyl ether (200 μl). After centrifugation, the extract (100 μl) is analysed using an unmodified silica column (250 × 5 mm ID) and iso-octane-methanol-methyl t-butyl ether (55:25:20) containing ammonium perchlorate (10 mM, pH 5.7) as eluent and with fluorescence detection. No interference has been encountered and the limit of accurate measurement for both compounds is 5 μg/l.
    Additional Material: 1 Ill.
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  • 45
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A combination of gradient reversed-phase high performance liquid chromatography (RP/HPLC) with a radioreceptor assay detector that uses two ligands is used to obtain effectively the metabolic profile of endogenous receptoractive opioid peptides in the canine pituitary and in seven selected brain regions including the hypothalamus, caudate nucleus, mid-brain, amygdala, thalamus, pons-medulla, and the hippocampus. Gradient RP/HPLC separates a mixture of endogenous peptides over a wide range of hydrophobicities. A novel opioid preparation from canine limbic system synaptosomes is utilized in a radioreceptorassay screen; tritiated etorphine (ET) or D-2ala, D-5leu-leucine enkephalin (DADL) is used as the competitively displaced ligand. This receptor-rich preparation contains several receptor types, and thus serves well as a screen with the required low level of specificity. Subsequent analysis with other detectors of high specificity (MS, RIA) will follow this screen in other studies. Etorphine interacts with several of the opioid peptide-preferring receptors, whereas DADL is more specific towards the delta receptor that preferentially binds the smaller pentapeptides of the enkephalin family. The highest amount of peptide receptor activity found in this study is in the pituitary tissue, a smaller amount in the hypothalamus and caudate nucleus, and still lower amounts in the other five brain tissue extracts. This variation in peptide concentration most probably reflects three separate factors that operate in this biologic system: differential tissue-specific processing patterns of the large peptide precursors; distribution of the three opioid peptide systems; and the receptor preparation and the radioligand used in the assay. The structures of the receptoractive compounds in each RP/HPLC peak await mass spectrometric confirmation.
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  • 46
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Rat pituitary homogenates were subjected to two phase countercurrent partition in a poly(ethylene glycol)-dextran mixture using a simple apparatus with enhanced gravity to facilitate the phase separations. Assay of the fractions for organelle marker enzymes and prolactin after 17 transfers showed similar distributions for endoplasmic reticulum, lysosomes, prolactin granules and plasma membrane at the lowest dextran concentrations. Increasing the dextran concentrations had a differential effect on the various organelles. Excellent resolution of endoplasmic reticulum from the other organelles was obtained and marked organelle heterogeneity was demonstrated. Two-phase countercurrent partition thus offers an alternative approach to the subcellular fractionation of pituitary homogenates and should prove useful in separating endoplasmic reticulum from plasma membrane and other cell components.
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  • 47
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The simultaneous determination of amino acid composition including cysteine of egg albumin, a model protein containing a/s cysteine residue, is reported. All the thiol groups of the cysteine residue(s) of egg albumin were labelled with 4-(aminosulfonyl)-7-fluoro-2,1,3-benzoxadiazole, a fluorogenic reagent for thiol groups. The labeled egg albumin was hydrolyzed in 6N HCl at 110°C for 24 h. The hydrolysate was lyophilized, derivatized with 4-fluoro-7-nitro-2,1,3-benzoxadiazole, a fluorogenic reagent for amines, and subjected to HPLC. 18 derivatized amino acids including double labelled cysteine were separated within 90 min on a Nucleosil ODS column (150 mm × 4.6 mm i.d.; 5 μm), and detected at 530 nm (ex. 470 nm) in a range from 90 fmol (aspartic acid) to 1.3 pmol (cysteine) (S/N = 3). Composition ratios of amino acids of egg albumin were similar to theoretical values except for methionine, which would be destroyed under the present acid hydrolysis condition. Analytical methods for cysteine residues are reviewed, and the availability of fluorogenic reagents having the benzofurazan structure is also discussed.
    Additional Material: 4 Ill.
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  • 48
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The hypothesis tested was that a particular glycoconjugate(s) in the exposed cell-surface membrane of susceptible insect cells acts as a receptor and/or modulator for the specific interaction with the protoxin/activated toxin of the δ-endotoxin of Bacillus thuringiensis var. kurstaki. As candidates, the total neutral and acidic fraction glycolipids, and the isolated neutral glycosphingolipid components, were screened for binding activity by the thin layer chromatogram overlay technique. The main protoxin/activated toxin-binding glycolipid in the neutral fraction (5B) had the structure: Gal(α1-3)GalNAc(β1-4)GlcNAc(β1-3)Man(β1-4)Glc(β1-1)Cer. The main protoxin/activated toxin-binding glycolipid in the acidic fraction was designated band 1, the structure of which is at present unknown. The possibility that the component 5B carbohydrate sequence may also function as a toxin-binding site of relevant insect plasma membrane glycoproteins is discussed.
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  • 49
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    New York, NY : Wiley-Blackwell
    Biomedical Chromatography 1 (1986) 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Type of Medium: Electronic Resource
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  • 50
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    Biomedical Chromatography 1 (1986), S. 53-57 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A rapid, specific and sensitive method using reversed phase HPLC for the simultaneous determination of clozapine and its two metabolites in serum and urine has been developed. The mobile phase was a mixture of 67% (v/v) methanol in water containing 0.4% tetramethylethylenediamine and 0.32% acetic acid (pH 5.5). The influence of methanol content, the pH of the mobile phase and the effect of adding alkylammonium ions as peak tailing reducer in the mobile phase have been investigated. The solvent for extracting clozapine from serum and urine was ether. 50 μ1 of 0.25 M H2SO4 solution was used to redissolve the dry residue to eliminate the endogenous compounds which could otherwise be eluted together with clozapine from the HPLC column. The analysis of a single sample was accomplished within half an hour. The identities of the chromatographic peaks of clozapine and its N-demethyl metabolite collected from the patient urine sample were confirmed by mass spectrometry. The method is sufficiently sensitive (5 ng/ml) and reproducible (CV 2.9%-6.7%) for clinical and pharmacokinetic studies, and preliminary results in these respects are presented.
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  • 51
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    New York, NY : Wiley-Blackwell
    Biomedical Chromatography 1 (1986) 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
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  • 52
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Metabolites of 2,4,6-trinitrotoluene (TNT) were found in the urine of a group of TNT munition workers. The urine extracts were analysed by micro liquid chromatography/mass spectrometry. The metabolites found included 2-amino-4,6-dinitrotoluene, 4-amino-2,6-dinitrotoluene, 2,4-diamino-6-nitrotoluene, 2,6-diamino-4-nitrotoluene and untransformed TNT. The detection limit of the metabolites in urine was 0.1 ng/ml for 20 ml urine samples.
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  • 53
    Electronic Resource
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    New York, NY : Wiley-Blackwell
    Biomedical Chromatography 1 (1986) 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
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  • 54
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    Biomedical Chromatography 1 (1986), S. 143-146 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A high performance liquid chromatographic method is described for monitoring forphenicinol, a possible therapeutic drug for cancer and muscular dystrophy, in human plasma and erythrocytes. Forphenicinol in the deproteinized samples was separated from interfering biogenic substances on an aminopropyl-bonded silica (Unicil NH2) column within 10 minutes with isocratic elution, and determined with fluorescence detection. The detection limits for forphenicinol in plasma and erythrocytes are 65 pmol (12.8 ng)/ml and 160 pmol (31.5 ng)/ml, respectively, corresponding to 2 pmol each in a 100 μl injection volume. The method is very simple, and sensitive enough to permit the quantification of forphenicinol in the blood samples from man dosed with forphenicinol.
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  • 55
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    Biomedical Chromatography 1 (1986), S. 159-162 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A method for determining urine porphyrins by HPLC is described. In the preliminary step, porphyrins are purified in high yields and concentrated by low pressure reverse-phase chromatography on C18 (octadecylsilane bonded silica) cartridge. Porphyrins are stable for 10 days after adsorption on C18 cartridge. The separation of porphyrin esters is performed on an aminopropyl-bonded silica column with an eluting system containing n-heptane and ethyl acetate. The system enables rapid isocratic separation of porphyrin methyl esters with high selectivity. The simplicity and reproducibility of the whole procedure allows its application to the routine analysis of urinary porphyrins in the clinical laboratory.
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  • 56
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    Biomedical Chromatography 1 (1986), S. 155-158 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Endogenous opioid receptoractive peptides in the cerebrospinal fluid (CSF) of human controls and in those patients diagnosed as having senile dementia of the Alzheimer's type (SDAT) are measured with a radioreceptorassay following HPLC separation. [3H]Etorphine is the ligand used to detect in the HPLC fractions the presence of those endogenous peptides that preferentially interact with several opioid receptors. The RRA uses a receptor-rich P2 fraction extracted from a canine limbic system. The total opioid peptide content found in the HPLC fractions 6-20 (to avoid salts in fractions 1-5) of SDAT CSF (383 ± 187 pmol ME-equivalents per ml CSF) is significantly higher than the corresponding total from patients with no known neurological disorders (89.1 ± 46.3 pmol ME-equivalents per ml).
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  • 57
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    Biomedical Chromatography 1 (1986), S. 169-172 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A simple and accurate HPLC method for the determination of Orthophosphate in the presence of large amounts of organophosphates is described. The method is based on the formation and separation of the molybdenum Orthophosphate complex. In order to prevent the hydrolysis of organophosphates, the sample was deproteinized with silicotungstate in acetate buffer (pH 4.0) under ice-cooling and then treated with ammonium molybdate in maleate buffer (pH 7.0). The sample was injected onto Styragel 60 Å column (5 mm ID × 100 mm) with 38% (v/v) acetonitrile containing 0.3 M sulfuric acid as eluent. Detection was at 310 nm. The method was applied to the determination of Orthophosphate in liver, kidney, spleen and mouse blood.
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  • 58
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    Biomedical Chromatography 1 (1986), S. 177-179 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Trazodone, an anti-depressant medication, is found in serum in the 500-1000 ng/mL range in patients taking therapeutic doses. Because of this relatively high concentration, it has been possible to devise an HPLC assay system using the rapid, convenient microscale procedure described previously by Lam et al. (Clin. Chem. 26, 963 1980) to prepare the sample for chromatography. To 0.1 mL serum were added 0.1 mL acetonitrile and 10 μL of 10% zinc sulfate in water. The mixture was centrifuged and 50 μL of the clear supernatant was injected into a reversed-phase column which was eluted with 65% 0.05 M potassium phosphate-35% acetonitrile, with detection by ultraviolet absorbance at 210 nm. The trazodone elutes in 6 min, clearly resolved from endogenous interferences. The recovery of trazodone added to serum was better than 90%. Peak height was proportional to concentrations in the serum sample from 125 ng/mL to 3000 ng/mL.
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  • 59
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    New York, NY : Wiley-Blackwell
    Biomedical Chromatography 1 (1986) 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
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  • 60
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A sensitive HPLC method for the assay of UDP-GlcNAc:β-galactoside β1 → 3-N-acetylglucosaminyltransferase activity was developed. Using lactose as an acceptor, the formation of the product GlcNAcβ1 → 3Galβ1 → 4Glc can be determined without interference by substrates resulting from enzymatic and chemical breakdown of the donor substrate UDP-GlcNAc. The method is very specific since products of other transferase reactions, which potentially may be formed in the incubations in vitro, elute at positions different from that of GlcNAcβ1 → 3Galβ1 → 4Glc.By use of this assay method it could be demonstrated that normal and malignant hematopoietic cells and cell-lines, with the exception of erythrocytes and reticulocytes, contain β1 → 3-N-acetylglucosaminyltransferase activity.
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  • 61
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    Biomedical Chromatography 1 (1986), S. 151-154 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A high performance liquid chromatographic method with ultraviolet detection was developed for the determination of nivacortol (WIN 27914) in biological samples. The drug was isolated from human plasma by using a solid-phase extraction and eluted with ethanol. The solvent was evaporated and the residue dissolved in the chromatographic eluent. The sample was subjected to chromatography on a C8 silica column and eluted with a gradient of acetonitrile in 0.1 M sodium acetate buffer, pH 6.5. A single concentration of a structural analogue (WIN 31338) was used as internal standard for the quantitative determination of the analyte. The plasma concentrations were below that needed to suppress ACTH secretion by pituitary cells in culture and did not suppress plasma ACTH in Nelson's syndrome.
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  • 62
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    Journal of High Resolution Chromatography 9 (1986), S. 39-43 
    ISSN: 0935-6304
    Keywords: Gas chromatography, GC ; Fused silica capillary columns ; Parallel triple detection ; Diesel fuels ; Polyaromatic hydrocarbons ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Diesel fuels from different parts of the UK have been analyzed for polycyclic aromatic hydrocarbons (PAH), nitrogen-containing PAH, and sulfur-containing PAH using capillary column GC with simultaneous parallel triple detection. The concentrations of polyaromatic compounds (PAC) were high and showed considerable variability amongst the fuels. The PAH are mainly naphthalene, fluorene, and phenanthrene and their alkylated homologs; the PANH are mainly carbazole and its methyl derivatives; the PASH are mainly dibenzothiophene and its methyl derivatives.
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  • 63
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    Journal of High Resolution Chromatography 9 (1986), S. 240-241 
    ISSN: 0935-6304
    Keywords: Gas chromatography, GC ; Glass capillary columns ; Stationary phase immobilization ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 64
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    Journal of High Resolution Chromatography 9 (1986), S. 236-239 
    ISSN: 0935-6304
    Keywords: Liquid chromatography, LC ; Reversed phase ; Chemically bonded phases ; Mixed eluents ; Partition effects ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A simple linear relationship which enables the effect of the composition of a binary mobile phase on the retention of a solute to be assessed in reverse phase liquid chromatography using a bonded stationary phase has been derived. The equations have been tested using published experimental data.
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  • 65
    ISSN: 0935-6304
    Keywords: Supercritical fluid chromatography, SFC ; Chiral stationary phase, CSP ; Optical resolution ; α-Amino acid derivatives ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 66
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    Journal of High Resolution Chromatography 9 (1986) 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 67
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    Journal of High Resolution Chromatography 9 (1986), S. 213-217 
    ISSN: 0935-6304
    Keywords: Capillary supercritical fluid chromatography ; Injection system ; Polycyclic aromatic compounds ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A sample introduction system for capillary supercritical fluid chromatography, which allows the dissolution of the sample in the supercritical mobile phase before being introduced into the column, was constructed and evaluated. Supercritical n-pentane was shown to solvate high-molecular-weight polycyclic aromatic compounds that could not be solvated using typical liquid solvents. In addition, split injection of a supercritical fluid solution was found to be more reproducible than split injections of a liquid solution. The potential of such an injection system was demonstrated, although further developments are needed in order to make the technique of practically utility.
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  • 68
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    Journal of High Resolution Chromatography 9 (1986), S. 224-235 
    ISSN: 0935-6304
    Keywords: Thin-layer chromatography, HPTLC ; Biological matrices ; Fluorimetric detection ; Selenium ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The present determination of selenium in biological matrices by HPTLC with in situ fluorimetric detection is an accurate alternative method, comparable to other established methods such as photometry, polarography, neutron activation, or X-ray fluorescence analysis, gas chromatography, and atomic absorption spectrometry.The excellent sensitivity of this procedure is proved by the detection limit of 250 fg of selenium per spot (using purified 2,3,1-naphthoselenodiazole). The oxidation of organic matrices, applying a novel digestion procedure, may be carried out with little instrumental expenditure.Sample preparation steps, such as the oxidation of selenium to Se (VI) and subsequent reduction to Se (IV) do not lead to significant random or systematic errors, nor does the digestion step, if an optimized procedure is used.A recovery rate of 103% and nearly parallel calibration curves for digested selenocysteine standards compared with spiked human serum samples demonstrate the accurate quantitative preparation of a biological matrix. Any interfering metal ions can be masked by addition of chelate-forming reagents.
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  • 69
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    Journal of High Resolution Chromatography 9 (1986), S. 252-254 
    ISSN: 0935-6304
    Keywords: Liquid chromatography, HPLC ; Post-column derivatization reaction ; Fluorogenic reaction ; Haloperidol ; N1-Methylnicotinamide chloride ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 5 Ill.
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  • 70
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    Journal of High Resolution Chromatography 9 (1986), S. 260-260 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 71
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    Journal of High Resolution Chromatography 9 (1986) 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 72
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    Journal of High Resolution Chromatography 9 (1986), S. 289-290 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 73
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    Journal of High Resolution Chromatography 9 (1986), S. 295-297 
    ISSN: 0935-6304
    Keywords: Gas-liquid chromatography, GC ; Fused silica tubing ; Connector ; Coupling ; Press-fit ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 4 Ill.
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  • 74
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    Journal of High Resolution Chromatography 9 (1986), S. 304-305 
    ISSN: 0935-6304
    Keywords: HPLC ; Non-porous supports ; Tetra-ortho silicates ; Commercial supports ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 75
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    Journal of High Resolution Chromatography 9 (1986), S. 314-316 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 76
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    Journal of High Resolution Chromatography 9 (1986), S. 312-313 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Fused silica capillary micro-packed columns ; Open tubular columns ; Sample capacity ; Trace analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 77
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    Journal of High Resolution Chromatography 9 (1986), S. 320-327 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Electron capture detector, ECD ; Electron capture sensitization ; Polynuclear aromatic hydrocarbons ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electron capture detector (ECD) response to numerous aromatic hydrocarbons of low electron affinity (EA) is shown to be detrimentally affected by two processes which compete with and typically overwhelm the electron capture reactions of these molecules. It is shown that the effects of these two undesired reactions can be eliminated by the permanent addition of trimethylamine and one of several alkyl monochlorides to the detector make-up gas. These modifications of the detector gas result in greatly increased sensitivity, increased linearity, and increased reproducibility of response. A kinetic model for the ECD responses of low EA resonance capture molecules is developed which appears to explain these improvements.
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  • 78
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    Journal of High Resolution Chromatography 9 (1986), S. 328-334 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; GC/MS ; Fused silica (capillary) columns ; Retention index data ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Retention indices of standard organic compounds of environmental interest were determined by gas chromatography/mass spectrometry, using a DB-5 fused-silica capillary column. Retention indices are useful references for tentative compound identification by gas chromatography, or confirmation by gas chromatography/mass spectrometry. They provide elution order for isomers that might be indistinguishable based on mass spectra. Modified Kovats and Lee retention indices are given for polycyclic aromatic hydrocarbons; sulfur heterocycles; nitrogen heterocycles; aromatic amines; oxygen heterocycles; phenols; alcohols; ketones; alkanes; nitriles; and methylesters of fatty, dicarboxylic, and aromatic acids for comparison and reference. Retention index values for heterocycles by gas chromatography/mass spectrometry are comparable with gas chromatography values previously reported.
    Additional Material: 1 Tab.
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  • 79
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Capillary columns, glass ; OV-240-H, 33% cyanopropyl ; Immobilization by condensation ; Crosslinker, dimethyltetramethoxysiloxane ; in situ methylation, diazomethane ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Coating intensely leached glass capillaries with OV-240-OH, the most polar commercially available OH-terminated polysiloxane phase at the present time, is described. Beside chemical bonding of the phase via condensation with silanol groups of the support, additional immobilization using dimethyltetramethoxysiloxane as a crosslinker is carried out. After in situ methylation of the immobilized coating, and transformation of acidic impurities of the cyanopropyl substituted phase into the respective methyl esters, increased inertness of the column was observed. Working instructions are given, and processes involved are discussed.
    Additional Material: 3 Ill.
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  • 80
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    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 9 (1986), S. 366-372 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 81
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 9 (1986), S. 383-387 
    ISSN: 0935-6304
    Keywords: Gas chromatography, GC ; Dual capillary gas chromatography ; Alcohols ; MTBE ; Gasolines ; Additives ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A gas chromatographic method has been developed for the identification and direct determination of alcohols and methyl tert-butyl ether (MTBE) in gasolines. The technique involves simultaneous injection of the gasoline without any sample preparation onto two fused silica capillary columns of differing polarities. The method permits simultaneous determinations of methanol, ethanol, 2-propanol, tert-butanol, 1-propanol, sec-butanol, 1-butanol, and MTBE. By using an automatic sampler in combination with electronic pressure programming and BASIC programming, the determinations were performed automatically and reproducibly with a relatively short analysis time.
    Additional Material: 6 Ill.
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  • 82
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 9 (1986), S. 409-410 
    ISSN: 0935-6304
    Keywords: Liquid chromatography, HPLC ; Reversed phase ; MAPS phase ; Explosives ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 83
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 9 (1986), S. 417-419 
    ISSN: 0935-6304
    Keywords: Liquid chromatography, HPLC ; Normal phase ; Bonded phases ; Mercaptopropyl silica gels ; Donor-acceptor complexes ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 84
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 9 (1986), S. 561-565 
    ISSN: 0935-6304
    Keywords: Liquid chromatography, HPLC ; Pharmacokinetics ; Quantification in human plasma ; Bronchosecretolyticum ; Separation from metabolites ; Ambroxol ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The bronchosecretolytic drug ambroxol can be reliably quantified in human plasma by high performance liquid chromatography. Plasma is buffered alkaline, extracted with ether, and the organic solvent back-extracted with diluted acid. An automatically sampled aliquot is separated by reversed phase HPLC; the analyte is well separated from two metabolites that interfered strongly in earlier methods. UV detection at 230 nm enables a lower limit of quantitation of 5 ng/ml. Internal standardization with propranolol allows accurate and precise quantification. Evaluation of the optimized combination of mobile and stationary phase is described, and application of the method to experimental and clinical pharmacokinetic studies is illustrated.
    Additional Material: 4 Ill.
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  • 85
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 9 (1986), S. 122-124 
    ISSN: 0935-6304
    Keywords: Liquid chromatography, HPLC ; Nonsuppressed ion exchange ; Conductivity ; Detectability ; Inorganic anions ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 86
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 9 (1986), S. 127-128 
    ISSN: 0935-6304
    Keywords: Liquid chromatography, HPLC ; Reversed-phase HPLC ; Metal chelates ; 8-Hydroxyquinolinates ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 87
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 9 (1986), S. 595-595 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; Connection device ; Micro packed columns ; Macrobore capillaries ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 88
    ISSN: 0935-6304
    Keywords: Preparative planar chromatography, PPC ; Centrifugal planar-column chromatography, CPCC ; Circular development ; On-line observation and detection ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 89
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 9 (1986), S. 613-617 
    ISSN: 0935-6304
    Keywords: Fused silica capillary tube isotachophoresis ; Multichannel photodiode array detector ; Cationic dye analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Isotachophoresis carried out in a 0.25 mm i.d. fused-silica capillary tube yielded high resolution, compared with that in a fluorinated ethylene-propylene polymer tube. The use of an ultraviolet-visible multichannel spectrophotometer with photodiode array as detector together with a cross flow cell (volume 0.01 μl) was investigated. The system was successfully applied to the analysis of cationic dyes such as neutral red, bismarck brown, and basic fuchsine.
    Additional Material: 6 Ill.
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  • 90
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    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 9 (1986), S. 535-537 
    ISSN: 0935-6304
    Keywords: Liquid chromatography ; Fused silica capillary columns ; Reverse-phase ; Nanoliter flow cell ; Column packing ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 91
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 9 (1986) 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 92
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 9 (1986), S. 306-307 
    ISSN: 0935-6304
    Keywords: Liquid chromatography ; Fluorometric determination ; Postcolumn reaction ; o-Phthaldehyde ; Saliva bradykinin ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 93
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    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 9 (1986), S. 335-340 
    ISSN: 0935-6304
    Keywords: Capillary gas-liquid chromatography ; Stationary-phase focusing ; Swelling ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Sample introduction using the solvent effect can lead to significant swelling of the stationary phase. The phenomenon has been studied theoretically and experimentally. The longitudinal profile of the swollen phase has been established. Swelling can affect the retention time of solutes, the shape of solute bands emerging from the inlet, and the maximum permissible sample size.
    Additional Material: 8 Ill.
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  • 94
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    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 9 (1986), S. 345-349 
    ISSN: 0935-6304
    Keywords: Isothermal vs programmed indices ; Coefficient of index increase ; Equivalent isothermal temperature ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A systematic approach was utilized to deduce the relation between the programmed and isothermal retention indices in chromatography. The relation was given in the form of a chart from which the equivalent isothermal temperature Te is plotted vs ΔT′ with IP as the parameter. ΔT′ is a function of both the inlet and outlet temperatures during the temperature programmed run and Te is the temperature at which the isothermal index is equal to the programmed index IP.
    Additional Material: 2 Ill.
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  • 95
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    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 9 (1986), S. 362-363 
    ISSN: 0935-6304
    Keywords: Back fat of pigs ; Skatole ; Indole ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 96
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    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 9 (1986), S. 388-391 
    ISSN: 0935-6304
    Keywords: Gas chromatography, GC ; Cryogenic GC ; Capillary, fused silica ; Sulfur gases ; Water alterations of phase polarity ; Reverse solvent effect ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Data are presented to illustrate putative water effects on the retention times and peak shapes for seven sulfur-containing compounds when determined by sub-ambient FSOT capillary GC/FPD. The observations are consistent with explanations based upon reported “phase soaking” and “reverse solvent effect” phenomena.
    Additional Material: 3 Ill.
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  • 97
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    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 9 (1986), S. 405-407 
    ISSN: 0935-6304
    Keywords: Capillary GC ; Solvent effects ; Solvent trapping ; Phase soaking ; Large sample volumes ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 98
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    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 9 (1986), S. 397-399 
    ISSN: 0935-6304
    Keywords: Gas chromatography, GC ; Capillary columns ; Nifedipine ; Determination in human plasma ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A rapid, sensitive, and reliable method for the determination of nifedipine in human plasma is described. Using a single-step solvent extraction and capillary gas chromatography combined with electron capture detection, an assay sensitivity of 2 ng/ml is achieved routinely using 0.5 ml of plasma. Intact nifedipine is quantitated and separated from its nitroso- and nitropyridine-derivatives. The suitability of the assay for pharmacokinetic studies is illustrated.
    Additional Material: 3 Ill.
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  • 99
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    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 9 (1986), S. 30-34 
    ISSN: 0935-6304
    Keywords: Gas chromatography, GC ; Nickel capillary columns ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Electroformed nickel tubing was deactivated by chemical vapor deposition of silicon from silane gas and subsequent treatment with cyclooctamethyltetrasiloxane (D4). Standard activity tests performed on the uncoated tube and also on columns coated with crosslinked and uncrosslinked, nonpolar stationary phase, show that good quality flexible columns can be prepared from nickel tubing. The inner surface of the silicon coated tube was characterized by Auger depth profile analysis.
    Additional Material: 6 Ill.
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  • 100
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    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 9 (1986), S. 102-105 
    ISSN: 0935-6304
    Keywords: Liquid chromatography, HPLC ; Pharmacokinetics ; Quantitation in human serum ; Antidiabeticum ; Glibenclamide ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The antidiabetic drug glibenclamide can be reliably quantitated in human serum with high performance liquid chromatography. The serum is buffered and extracted with toluene. The organic solvent is evaporated, the residue dissolved in the mobile phase and an aliquot sampled automatically and chromatographed. UV-detection at 229 m allows a lower limit of quantitation of 5 ng/ml. Precise handling of exact volumes facilitates external calibration. Statistical data for imprecision and inaccuracy are given and illustrate reliable quantification. Application of the method to experimental and clinical pharmacokinetic studies with specific problems is illustrated.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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