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  • Analytical Chemistry and Spectroscopy  (101)
  • modeling  (50)
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  • National Academy of Sciences
  • 2000-2004  (151)
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  • 2000  (151)
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  • Wiley-Blackwell  (101)
  • Springer  (50)
  • National Academy of Sciences
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  • 2000-2004  (151)
  • 1985-1989
  • 1960-1964
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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Adsorption 6 (2000), S. 93-104 
    ISSN: 1572-8757
    Keywords: adsorption refrigerator ; transient operation ; activated carbon ; methanol ; modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Adsorption refrigerators are a particular type of refrigerator in which compression is avoided, and in a sense replaced by adsorption. No mobile parts are needed; the energy input, instead of being mechanical, is thermal and is used to achieve desorption. Such machines have a cyclic operation, made of successive adsorption/evaporation and of desorption/condensation steps. The transient operation of adsorption refrigerators is a relatively recent subject of research. The modeling of the adsorber is the key point of such studies, because of the complex coupled heat and mass transfer phenomena that occur during the cycle. The present work therefore presents a study of an annular type adsorber which is intended to account for transient temperatures observed experimentally. The equipment in which the experiments were performed and which uses alcohol adsorption on activated carbon is briefly described, and its operating cycle described, along with typical experimental observations of pressure and temperature transients. A model of the adsorber unit is proposed which accounts for the coupling of adsorption and heat transfer, and describes mass-transfer in the annular adsorbent layer as a global diffusional mechanism with temperature dependent parameters. This model correctly predicts, qualitatively and semi-quantitatively, the observed trends of the temperature changes. Finally, various aspects of the performances are discussed.
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  • 2
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    Annals of operations research 94 (2000), S. 139-162 
    ISSN: 1572-9338
    Keywords: irrigated system ; modeling ; multi‐agent system ; simulation ; social networks ; coordination
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mathematics , Economics
    Notes: Abstract The viability of irrigated systems in the Senegal River Valley is being brought into question today due to their under‐utilization. We assume that their viability depends largely on the way their different components behave and interact. We therefore sought to examine in greater depth today's knowledge of the structure of these systems and activities performed within them. This led to the development of a multi‐agent system model, a kind of virtual irrigated system, with a special focus on rules in use for access to credit, water allocation and cropping season assessment as well as organization and coordination of farmers. The purpose of this paper is to show how this kind of tool is relevant to the study of irrigated systems' viability. As an example it is used to examine the influence of existing social networks on the viability of irrigated systems.
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  • 3
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    International journal of flexible manufacturing systems 12 (2000), S. 145-163 
    ISSN: 1572-9370
    Keywords: inventory ; modeling ; postponement ; supply chain management
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract This paper studies the impact of a reduction in hardware complexity on the supply-chain inventory against various customer on-time delivery alternatives and manufacturing environments. Different methods of reducing hardware complexity are proposed, and their impact on total supply-chain inventory and customer serviceability quantified. An analytical inventory optimization scheme taking into account multistage supply networks, product structure, forecast accuracy, lead-time variability, and supplier reliability is used to determine optimal inventory levels in a stochastic modeling environment. The analysis is based on a business case for an IBM midrange computer family consisting of more than 200 models and upgrades with hundreds of features. We investigate different hardware complexity reduction strategies, including low-usage feature reduction, low-volume feature reduction, and feature substitution, as well as quick response and postponement mechanisms. Our computational results show that, in a fabrication-fulfillment center environment, reducing hardware complexity results in significantly higher inventory savings than in an integrated manufacturing environment. The results presented in this paper were used to reduce hardware complexity in IBM's midrange computer division.
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  • 4
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    Topics in catalysis 13 (2000), S. 213-219 
    ISSN: 1572-9028
    Keywords: heterogeneous catalysis ; selectivity ; quantum chemistry ; modeling ; butadiene ; α–β unsaturated aldehydes ; enantioselectivity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Reaching high selectivities is an important concern for heterogeneous catalysis. Insights in the factors which control the reaction selectivity can be obtained from theoretical approaches, also a full computational description of the reaction is not yet possible, due to the great complexity of the molecules generally involved in fine chemical catalysis. Some theoritical works related to the interpretation of chemical selectivity are rewieved in this paper, with a focus on the various types of selectivity: chemoselectivity, regioselectivity and enantioselectivity.
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  • 5
    ISSN: 1572-9761
    Keywords: environmental change ; GIS ; landscape ecology ; modeling ; remote sensing ; riparian ; statistics ; wetland
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Ecotones are inherent features of landscapes, transitional zones, and play more than one functional role in ecosystem dynamics. The delineation of ecotones and environmental boundaries is therefore an important step in land-use management planning. The delineation of ecotones depends on the phenomenon of interest and the statistical methods used as well as the associated spatial and temporal resolution of the data available. In the context of delineating wetland and riparian ecosystems, various data types (field data, remotely sensed data) can be used to delineate ecotones. Methodological issues related to their detection need to be addressed, however, so that their management and monitoring can yield useful information about their dynamics and functional roles in ecosystems. The aim of this paper is to review boundary detection methods. Because the most appropriate methods to detect and characterize boundaries depend of the spatial resolution and the measurement type of the data, a wide range of approaches are presented: GIS, remote sensing and statistical ones.
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  • 6
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    Journal of thermal analysis and calorimetry 60 (2000), S. 333-343 
    ISSN: 1572-8943
    Keywords: base line ; DSC ; kinetics ; modeling ; thermodynamics ; TMDSC
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The application of non-linear heating program to a heat-flux DSC apparatus has attracted much attention. From thermodynamics viewpoint, it is shown that the variation of enthalpy of a sample changing with temperature change is due, to both the true heat capacity of the sample and the enthalpy of some transformations occurring in the sample, characterized by its degree of advance. Using the simple assumption that the rate of the transformation is proportional to the distance from the thermodynamic equilibrium, an electrical model of the thermal event is given. Using the coupled cell model of the DSC apparatus, we show how to obtain the rate of transformation of the sample and heat capacity, which is directly related to the base line of the experiment.
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  • 7
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    Journal of thermal analysis and calorimetry 59 (2000), S. 847-858 
    ISSN: 1572-8943
    Keywords: derivative thermogravimetry ; diffusion-induced stress ; modeling ; molybdenum ferrite ; oxidation kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract From a model for isothermal oxidation kinetics in nanosized ferrite spinels based on a diffusion-induced stress effect, the authors present a modeling of the DTG curves for the oxidation of Fe2+ and Mo3+ cations on octahedral sites of a molybdenum ferrite. This has been made by considering that the chemical diffusion coefficient is given by the relation $$\tilde D = D_o \exp \left( {\frac{{E'_{\text{a}} + pV_{\text{a}} }}{{RT}}} \right)$$ , when D o is a pre-exponential factor, E a ′ an activation energy and V a an activation energy induced by the oxidation.
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  • 8
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    Plasma chemistry and plasma processing 20 (2000), S. 65-86 
    ISSN: 1572-8986
    Keywords: thermal plasma ; waste processing ; fly-ash vitrification ; optical emission spectroscopy ; volatilization ; lead ; modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract Results are presented of optical emission spectroscopy (OES) application asa control tool to improve fly-ash plasma vitrification. A twin-torch plasmasystem has been used for the fly-ash processing, and a new OES method hasexamined metallic vapors above the melt. The method allows the study ofnonhomogeneous optically thin plasmas exhibiting a symmetry plane withoutsophisticated tomographic systems. The dc arc torches are mounted above acold crucible filled with a synthetic glass. The arc intensity is from200 to 400 Å. Argon is introduced into the torches along the cathodeand the anode, while argon, oxygen or hydrogen are injected through thelance between the torches. Local plasma temperatures above the melt havebeen evaluated using measured relative intensities of spectral lines ofthe plasma-forming gas. Metallic vapor concentration in the plasma isdeduced from the intensity ratio of the metal–gas spectral lines. Leadoxide has been used to study heavy-metal behavior at the fly-ash plasmavitrification. Distribution of the lead along the crucible surface,depending on the plasma-forming gas composition as well as the concentrationevolution with time, have been examined. The elemental analysis of theresultant glass has been measured by scanning electron microscopy (SEM)with energy-dispersive spectrometry (EDS). A predictive model has beenadapted to simulate the noncongruent vaporization of heavy metals from themelt. According to the data obtained, steep variations of the volatility ofthe elements depend strongly on reducing properties of gases controllingthe plasma composition near the melted surface. In addition, the melttemperature and the redox potential of the gas phase are found to be themost critical parameters.
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  • 9
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    Plasma chemistry and plasma processing 20 (2000), S. 521-553 
    ISSN: 1572-8986
    Keywords: thermal plasma ; transferred arc ; fumed silica ; modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract The volatilization of quartz in a transferred arc plasma followed byquench and recondensation is a promising route to the production offumed silica. In this work, an existing model of a transferred arcwas modified and combined with a newly developed model of a moltensilica anode to predict the behavior of a transferred arc evaporatoras a function of current and plasma gas flow rate. The model predictstemperature, current, and flow fields in both the plasma and anode aswell as evaporation rates. Although quantitative agreement withexperimental results was not possible because of insufficient propertydata for silica at high temperature, the results were within an orderof magnitude of those measured experimentally. The model developed isuseful for the design and scaleup of this type of reactor.
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  • 10
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    Journal of materials synthesis and processing 8 (2000), S. 139-144 
    ISSN: 1573-4870
    Keywords: TiO2 ; phase transformations ; mechanical alloying ; kinetics ; modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract A high-pressure and high-temperature phase of TiO2 : TiO2 II is formed transiently during room-temperature high-energy ball milling of anatase TiO2 : TiO2 anatase → TiO2 II → TiO2 rutile. Rutile is the only phase present after prolonged ball milling. The present paper focuses on the influences of physical and chemical processing conditions on the transformation kinetics. The effects of two milling parameters on the kinetics of phase transformation of anatase TiO2 were investigated: the nature of milling tools and the powder-to-ball weight ratio R. Granulometric characterizations and TEM observations have demonstrated that the transformation of TiO2 anatase into TiO2 II occurs without fracturing of particles and that TiO2 II nanograins form at the surface of anatase particles. The parameter R affects only the transformation rate. For a given R, the transformation rate is the largest with alumina grinding tools, intermediate with zirconia tools, and the smallest with steel tools. The parameters involved in current models of the mechanical alloying process do not suffice to explain the differences in transformation rates observed here. A parameter, which takes into account the influence of the mechanical properties of grinding materials, is considered.
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  • 11
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    Oxidation of metals 53 (2000), S. 49-75 
    ISSN: 1573-4889
    Keywords: FeCrAl ; α Al2O3 ; high-temperature resistance ; residual stresses ; thermal stresses ; X-ray diffraction ; relaxation ; modeling ; elasto-viscoplastic model
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The stresses generated in alumina scales during different oxidation stepscontrol the protective character of such scales and their lifetime. Laboratoryand industrial Fe–Cr–Al alloys, differing by their impuritycontent and preparation, and for which the oxidation kinetics werepreviously characterized, were studied here to experimentally determine ortheoretically calculate the stress level in the alumina scales. Theexperiments were performed by X-ray diffraction (XRD) at room temperature,using the sin2psi method. The oxide-stress level wascorrelated with many parameters, such as the scale microstructure andmorphology, the nature of the substrate, the substrate and oxide thickness,the oxide grain size, the cooling rate, etc. A numerical elasto-viscoplasticmodel was developed to calculate the thermal stresses and to point out theeffect of the relaxation phenomena either during cooling or duringisothermal treatment after oxidation. The results obtained by theelasto-viscoplastic model are in good agreement with the experimental ones.
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  • 12
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    Journal of nondestructive evaluation 19 (2000), S. 43-54 
    ISSN: 1573-4862
    Keywords: Ultrasonic testing ; modeling ; anisotropy ; shear horizontal wave ; field profile ; electromagnetic acoustic transducer
    Source: Springer Online Journal Archives 1860-2000
    Topics: Electrical Engineering, Measurement and Control Technology , Mathematics
    Notes: Abstract Based on the description of shear horizontal (SH) wave propagation in arbitrarily oriented transversely isotropic media, radiation characteristics of ultrasonic transducers for this wave type are determined. The radiated wavefields are obtained by point source superposition, making use of an analytical relationship for the wave propagation direction as a function of the spatial coordinates. Approximate formulae are given for the radiation characteristics of circular and rectangular transducers in the far-field, which are in a form similar to the isotropic material case. Focusing on transversely isotropic weld metal specimens and unidirectional composites, numerical evaluation is performed for normal-incidence probes as well as for electromagnetic acoustic transducers.
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  • 13
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    Journal of materials synthesis and processing 8 (2000), S. 73-85 
    ISSN: 1573-4870
    Keywords: Chemical vapor deposition (CVD) ; diamond films ; modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The evolution of grain size, grain-size distribution, morphological and crystallographic texture, surface roughness, and the contribution of various surface facets to the growth of polycrystalline diamond films is performed by carrying out a series of two-dimensional computer simulations. The films are assumed to grow from a set of randomly oriented, {100}- and {111}-faceted nuclei by the motion of their vertices (the points where the adjoining facets of the same or neighboring grains meet). The vertex velocities are found to be a function of the orientation and the growth rate of the adjoining facets. To quantify the latter, a {100} to {111} growth-rate parameter is used. The results show that the evolution of the grain size and its distribution, surface roughness, morphological and crystallographic texture, and the portion of the film grown from different surface facets are all mutually linked and governed by the magnitude of the growth-rate parameter. The latter can be controlled by the CVD processing conditions, such as the substrate temperature, reactor pressure, mole fraction of carbon-source gas (e.g., CH4, C2H2).
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  • 14
    ISSN: 1573-4943
    Keywords: Serum transferrin ; modeling ; accessible surface area ; surface charge ; molecular recognition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In order to rationalize the physicochemical properties of human serum-transferrin (STf) and the STf-receptor (TfR) recognition process, we have tried to predict the 3D structures of apo- and iron-loaded STf using a homology modeling technique to study the changes in the structural characteristics that take place upon the uptake of iron by STf in solution. The crystal structures of both forms for ovotransferrin were used as templates for the STf modeling. The modeled structure of STf gave a satisfactory interpretation for the typical physicochemical properties such that (1) STf has a negative electrophoretic mobility and its value increases with iron uptake, and (2) the radius of gyration Rg of Tf decreases with iron uptake. It was found that upon iron binding, interdomain closures take place with large movements of the NII and CII subdomains comprising the N- and C-lobes in STf through a hinge-bending motion, accompanied by the opening of the bridge region with a displacement of more than 15 Å. Moreover, in view of the findings from our capillary electrophoresis experiments that the electrostatic interactions significantly contribute to a specific binding of Fe2-STf with TfR, it is inferred that the connecting (bridge) and its neighboring region associated with a surface exposure of negative charge play an important role in the STf-receptor recognition process.
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  • 15
    ISSN: 1871-4528
    Keywords: root-water uptake ; modeling ; SWACROP ; Ferralsols ; tropics ; Cuba ; Solanum tuberosum L.
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Summary The SWACROP root-water uptake function for potatoes was determined in the 1994–95 crop season on a Ferralsol in Havana province, west Cuba. The maximum pressure-heads under which water is optimally extracted by potato roots were very similar to the original Feddes function. Nevertheless, the anaerobiosis point and the wilting point pressure-head in both functions were not in agreement. However, the simulated values of soil water contents in the 0–40 cm soil depth by performing SWACROP runs in the 1995–96 potato crop season using both functions were very similar. The original Feddes function seems to be good enough for predicting soil water contents in the tropics and no specific other functions need to be developed for any particular soil or climate condition.
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  • 16
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    Biology and philosophy 15 (2000), S. 197-210 
    ISSN: 1572-8404
    Keywords: ecology ; Levins ; modeling ; provisionality ; sociality
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Philosophy
    Notes: Abstract This essay extends Levins' 1966 analysis of modelbuilding in ecology and evolutionary biology. Amodel, as the product of modeling, might bevalued according to its correspondence to reality. Yet Levins' emphasis on provisionality and changeredirects attention to the processes ofmodeling, through which scientists select and generatetheir problems, define their categories, collect theirdata, compare competing models, and present theirfindings. I identify several points where decisionsare required that are not determined by nature. Thisinvites examination of the social considerationsmodelers are reacting to at the “sites of sociality”.Modelers must weave “socio-ecological webs” so thatthe models can be seen to represent their subjectmatter at the same time as the modelers secure thesupport of colleagues, collaborators and institutions,and enjoin others to act upon their conclusions. Notonly do theory justification and theory generationmerge, but the joint project becomes simultaneouslyphilosophical and sociological.
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  • 17
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    Mathematical geology 32 (2000), S. 301-317 
    ISSN: 1573-8868
    Keywords: hydrogeology ; modeling ; atoll ; coral reef ; carbonate platform
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Mathematics
    Notes: Abstract Large-scale steady-state groundwater flow in atoll carbonate platforms results from temperature and salinity-induced density gradients. Atolls are built on top of a basaltic substrate that provides geothermal heating from beneath. Moreover, they are immersed in the tropical ocean where temperature decreases rapidly with depth. Groundwater circulation in these platforms has long been associated with the geothermal heat flux because it is capable of generating inward and upward flow of oceanic origin water by buoyancy effects. This study shows that hydraulic circulation occurs even in the absence of a geothermal flux because the combination of the cold subsurface ocean waters with the warm surface conditions is sufficient to maintain a convection cell within the carbonate platform. Using a one-dimensional analytical model, validated by more sophisticated two-dimensional simulations, we can investigate the interaction between these two driving forces. The flow rate inside the platform is, in fact, a function of the ratio of the geothermal flux to the temperature gradient in the ocean. It increases with the geothermal flux but decreases with the oceanic temperature gradient. This one-dimensional model also shows that taking salinity effects on density into account increases the flow rates transiting through the platform by a third.
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  • 18
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    Autonomous robots 8 (2000), S. 25-42 
    ISSN: 1573-7527
    Keywords: visual servoing ; robust control ; mobile robot ; vehicles ; modeling ; vision
    Source: Springer Online Journal Archives 1860-2000
    Topics: Computer Science , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract We have been interested in Automatic Guided Vehicles (AGV) for several years. In this paper, we synthesize controllers for AGV applications using monocular vision. In particular, we are interested in road following and direction change tasks, and in analyzing the influence of extrinsic camera parameter perturbations on vehicle behavior. We use the bicycle as the kinematic vehicle model, and we choose the position of the white band on the road as the sensor signal. We define an interaction between the camera, which is mounted inside the vehicle, and the white band detected in the image space. Using this kind of interaction, we present how to use a pole assignment technique to solve the servoing task. We show the simulation and experimental results (1/10 scale demonstrator) with and without perturbations. We then investigate the use of a robust controller to slow down the effect of perturbations on the behavior of the vehicle.
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  • 19
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    Natural resources research 9 (2000), S. 215-222 
    ISSN: 1573-8981
    Keywords: market ; electricity ; regression ; calibration ; modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences
    Notes: Abstract Hydro power schemes operating in a free electricity market seek to maximize profits by differing generation rates to take best advantage of fluctuating selling prices, subject to the constraints of keeping storage lakes within their operational bounds and avoiding spillage losses. Various computer algorithms can be used in place of manual scheme operation to aid this maximization process, so it is desirable to quantify any profit gained from a given algorithm. A standard approach involves applying the algorithm to a period of past river flow records to see how much additional scheme income might have been obtained. This process requires the use of a hydro power scheme model, which inevitably can only approximate operational details, so the anticipated income gains are likely to be biased estimates of actual income gained from implementation of the algorithm. In addition to preliminary algorithm evaluation, it is desirable that hydro scheme managers have methodology to confirm anticipated income gain. Such confirmation can be difficult because true income gains are typically in the order of a few percentage and may not be easily distinguishable from background noise. We develop an approach, which allows estimation of true income gain for the situation where a change is made from manual to computer control of hydro power scheme operations, or upgrading from one maximization algorithm to another. The method uses a regression model to describe the former period of scheme operation. Postimplementation residuals from the regression predictions then provide estimates of actual income gain. The method can be sensitive to small but consistent income gains. Also, there is no requirement to construct any hydro scheme simulation model so bias effects should be considerably reduced. The approach was developed in the context of evaluating an income-maximization algorithm applied to a small hydro power scheme in the Kaimai Ranges of New Zealand. However, the methodology seems sufficiently simple and general to be applicable, with modification, to other power schemes moving toward increasing income through operational changes.
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    Transport in porous media 41 (2000), S. 105-116 
    ISSN: 1573-1634
    Keywords: flow ; integration ; Gassmann ; acoustics ; reservoir ; characterization ; modeling ; simulation ; Newton–Raphson
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Technology
    Notes: Abstract Integrated flow modeling is the combination of a traditional flow simulator with a petrophysical model. By combining a petrophysical model with a traditional flow model, it is possible to perform calculations that improve our ability to monitor fluid movement in porous media. This paper outlines the formulation of an integrated flow model IFLO and its multi-variable, Newton–Raphson IMPES solution procedure. The benefits of integrated flow modeling and the underlying principles involved in the integration of a flow model with a petrophysical model are presented. Results from the IFLO model are used to illustrate the principles.
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  • 21
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    Higher education 40 (2000), S. 231-242 
    ISSN: 1573-174X
    Keywords: achievement ; attendance ; modeling ; motivation ; problem-based learning
    Source: Springer Online Journal Archives 1860-2000
    Topics: Nature of Science, Research, Systems of Higher Education, Museum Science
    Notes: Abstract Problem-based learning is a constructivist approach toprofessional education stressing the use of real lifeproblems in education. Several previous attempts tounderstand the intricacies of learning in theproblem-based context have led to a causal model,elements of which were tested in the present study.The focus of the investigation was on the students' motivation to committhemselves to studying in a problem-based healthsciences curriculum, expressed in term of levels ofattendance at tutorial meetings. Data were collectedregarding functioning of the tutorial group, tutorfunctioning, level of prior knowledge, quality of theinstructional problems, time spent on individualstudy, academic achievement and increased interest.These data were analyzed using a structural equationsmodeling approach. As hypothesized, commitment appears to bea potent determinant of achievement. In fact, itrepresents one of the strongest determinants oflearning in the model tested.
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  • 22
    ISSN: 1573-1634
    Keywords: NAPLs ; radon ; modeling ; monitoring ; partitioning ; tracer ; emanation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Technology
    Notes: Abstract The recently developed natural radon tracer method has potential as a rapid, low‐cost, nondestructive, and noninvasive method for quantifying NAPL contamination. In the subsurface, radon‐222 (radon) is produced by the decay of naturally occurring radium‐226 contained in the mineral fraction of aquifer solids. In groundwater radon occurs as a dissolved gas, with a half‐life of 3.83 days. In the absence of NAPL, the radon concentration in groundwater quickly reaches a maximum value that is determined by the mineral composition of the aquifer solids, which controls the rate of radon emanation. In the presence of NAPL, however, the radon concentration in the groundwater is substantially reduced due to the preferential partitioning of radon into the organic NAPL phase. A simple equilibrium model and supporting laboratory studies show the reduction in radon concentration can be quantitatively correlated with residual NAPL saturation. Thus, by measuring the spatial distribution in radon it may be possible to identify locations where residual NAPL is present and to quantify the NAPL saturation. When the basic processes of partitioning, radon emanation from the aquifer solids, and first‐order decay are incorporated into an advective/dispersive transport model, good agreement is obtained with the results of laboratory and field experiments. Model sensitivity analyses shows many factors can contribute to the radon concentration response, including the length of the NAPL zone, NAPL saturation, groundwater velocity, porosity, and radon emanation. Thus, care must be taken when applying the radon method to locate and quantify NAPL contamination in the subsurface.
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    Transport in porous media 41 (2000), S. 47-60 
    ISSN: 1573-1634
    Keywords: unsaturated flow ; peat ; filters ; septic ; modeling ; hydraulics ; soil moisture retention curve
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Technology
    Notes: Abstract Peat is an alternative filter medium for the treatment of various waste streams including septic tank effluent. The water holding capacity and adsorption capacity of peat make it a favorable filter medium over sand or gravel which are commonly used as the filter medium for the drainage field of septic systems. This paper presents the results of a field study to evaluate the hydraulics of a peat filter used to treat the septic tank effluent from a public school west of Ottawa, Canada. An experimental box was placed within the filter during its construction to provide access to the vertical profile of the peat layer. The filter is periodically pulsed with septic tank effluent, which is distributed over the top of the filter and flows vertically through the peat. The filter was instrumented with tensiometers and transducers to monitor the pore water pressures in response to a pulse of septic tank effluent. An in-depth study of the hydraulics of the system was completed. The soil moisture retention curve and the hydraulic conductivity as a function of density were determined in laboratory experiments. A one-dimensional unsaturated flow model was used to predict the pressure response due to a pulse. A comparison of the field and model results illustrates the impact of the density variations, and the corresponding hydraulic conductivity variations, on the model predictions. The compaction of the peat is an important design consideration for the filter since it directly impacts the flow characteristics and the hydraulic retention time within the filter.
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    Water resources management 14 (2000), S. 257-283 
    ISSN: 1573-1650
    Keywords: decision-making ; ecosystem management ; ecosystem protection ; ecosystem restoration ; modeling ; sustainable development
    Source: Springer Online Journal Archives 1860-2000
    Topics: Architecture, Civil Engineering, Surveying , Geography
    Notes: Abstract Ecosystem Management (EM) is a new holistic approach to the management of natural resources. It integrates the scientificknowledge on ecological interrelationships and the complex socioeconomic and political frame of values, aiming at the long-term sustainability of a region, i.e., the ecosystem. Itincludes the human, biological and natural dimensions, and canregulate the internal structures and functions of the ecosystem,and the inputs and outputs from it, so that solutions to development and protection problems can be achieved and be socially well-accepted. It has been given attention since 1991,mainly in the U.S.A., where the existing legal framework formeda basis for EM. The former experience of programs based on the traditional methods of management, the goal of sustainable development stated by many governmental, public or private agencies, and the advent of scientific knowledge, permitted the development of a theoretical basis for EM. Today, a significant number of EM programs have been established and are in progressin the U.S.A. Here the concept, general principles and methodology of EM are reviewed, and the EM program in the Stateof Florida in the U.S.A. is presented, which is considered a successful case study. In addition, the examples of managementof two very important ecosystems in Northern Greece are critically presented for comparison, in order to evaluate if they have EM characteristics.
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    Water quality and ecosystem modeling 1 (2000), S. 193-222 
    ISSN: 1573-1669
    Keywords: Sediment transport ; modeling ; Upper Hudson River
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract Two-dimensional, vertically-averaged hydrodynamic and sediment transport models were developed and applied as part of a PCB fate and transport modeling study of Thompson Island Pool (TIP), Upper Hudson River. Mechanistic formulations were used to simulate cohesive and non-cohesive suspended load transport; site-specific data were extensively used to determine model inputs. This modeling approach is compared and contrasted to non-mechanistic solids transport sub-models used in other contaminant fate studies. A minimum number of model parameters were adjusted to calibrate the sediment transport model using data collected during the 1994 spring flood. The model was validated during the 1997 spring flood and for a 22-year (1977–1998) period. Successful calibration and validation of the model showed that: (1) deposition and resuspension processes were realistically and accurately formulated in the model; (2) the model is an effective diagnostic tool for quantitatively evaluating net deposition and erosion from various areas of TIP; and (3) sediment transport results can be coupled with a PCB fate model with a high degree of confidence.
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    Water quality and ecosystem modeling 1 (2000), S. 271-309 
    ISSN: 1573-1669
    Keywords: zebra mussels ; modeling ; water quality ; Seneca River ; dissolved oxygen
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract The development, testing and application of a dynamic two-dimensional (longitudinal-vertical) mass balance model for dissolved oxygen (DO) and chlorophyll (Chl) for rivers is documented that for the first time accommodates both the oxygen demand and filtering effects of zebra mussels. The test system is a phytoplankton-rich section (∼ 15 km long) of the Seneca River, NY, that is believed to represent an upper bound of the impact of this exotic invader. Changes in common measures of water quality of the river brought about by the zebra mussel invasion are reviewed and related longitudinal patterns in DO, Chl, and Secchi disc transparency are documented. Model testing is supported by comprehensive measurements of DO, Chl, and various forcing conditions over a three-month period, and independent determinations of several model coefficients. Wide variations in the areal consumption rate of DO (ZOD; g·m−2·d−1) and filtering rate (m3·m−2·d−1) of zebra mussels, as determined through model calibration, occurred over the study period. Values of ZOD in areas with dense zebra mussel populations at times (e.g., 〉 50 g·m−2·d−1) were an order of magnitude greater than the sediment oxygen demand associated with organically enriched deposits. The value of determinations of these fluxes from model calibration procedures is evaluated within the context of the limitations of protocols presently available to support independent specification of these rates. Model analyses are conducted to evaluate the relative magnitude of source and sink processes for DO and Chl, the potential operation and implications of feedback from low DO levels on oxygen consumption by zebra mussels, and the sensitivity of model simulations to selected sources of uncertainty and variability. Model projections of oxygen resources of the river are presented in a probabilistic format in evaluating reductions in zebra mussel biomass that would be necessary to eliminate violations of standards and regain assimilative capacity.
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    European journal of plant pathology 106 (2000), S. 401-413 
    ISSN: 1573-8469
    Keywords: inoculum density–disease incidence ; biological control agents ; pathogen detection and quantification with molecular and serological techniques ; polymerase chain reaction ; marker and reporter genes ; modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Understanding the dynamics between a pathogen and a biocontrol agent (BCA) in soil or in an infection court such as the rhizosphere is crucial for predicting the success of biological control. This is especially true for biological control using the strategy of reduction of initial inoculum prior to infection. By studying the population density fluxes over time, one can observe how the BCA and pathogen influence each other's population and life cycles, and how the biological and physical environment influence this relationship. Methods for quantifying fungi and bacteria in soil, including classical (dilution plating, baiting, bioassays), immunological (ELISA, IFC, immunomagnetic) and molecular (DNA hybridization, PCR, marker and reporter genes) methods, are discussed and critiqued. Finally, the value of mathematical modeling of population dynamics as a means of providing important information about the tripartite relationship between the pathogen, BCA, and host plant is reviewed.
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    Journal of electroceramics 5 (2000), S. 153-182 
    ISSN: 1573-8663
    Keywords: modeling ; SOFC ; internal reforming ; cermet
    Source: Springer Online Journal Archives 1860-2000
    Topics: Electrical Engineering, Measurement and Control Technology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Approaches to models and computer simulations of conductivity, polarization resistance, and impedance of composite electrodes in solid oxide fuel cells (SOFC) are reviewed with respect to the more important experimental findings. The approaches are classified according to how they model the highly disordered structure of composite SOFC electrodes: As corrugated layers of electrode material covered by a thin film of electrolyte or vice versa (thin film model), as a random packing of particles (Monte Carlo calculations), or using a macroscopic, averaged description of the disordered electrode structure (macroscopic porous-electrode model). Thin film models appear to be useful rationalizations of some experimental measurements of polarization resistance, but in the stricter sense fail to predict a number of important electrode characteristics. The Monte Carlo method, on the other hand, apparently meets with most of the more prominent experimental results reported so far, although some issues concerning parameter choices, among other things, remain to be resolved. The macroscopic porous-electrode theory may serve as a useful simplification of the Monte Carlo method, but with a more limited scope. Modeling of composite electrodes for SOFC thus appears to have reached a level where it can be used for practical engineering applications. As an example of this, the rate of methane reforming at Ni-YSZ cermet anodes under current load is calculated using the framework of the macroscopic porous-electrode theory, modified to include non-linear kinetics and gas-phase diffusion. The reforming reaction is quite evenly distributed in the anode, and its overall rate is therefore strongly dependent on thickness. However, most of the electrochemical reaction is likely to occur in a region closer than 10 μm to the bulk electrolyte. For an anode thickness larger than this, the current-collector potential at a given current is by and large independent of thickness. The ratio between the rates of the reforming and the electrochemical reactions can therefore be balanced to a certain degree by optimizing thickness, without significant loss in cell power. In addition, cermet porosity, volume fraction of Ni and Ni-particle size, appears to have a moderate effect in controlling the rate balance, which will have to be manipulated within the constraints set by the requirement of percolation in the gas-phase and the Ni- and YSZ-networks.
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    Pharmaceutical research 17 (2000), S. 589-592 
    ISSN: 1573-904X
    Keywords: modeling ; stochastic ; Log-normal ; distributions ; pharmacodynamics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. To develop a mathematical model for therapeutic drugmonitoring and to assess the kinetic relationships between the intensity ofcorrective action and the approach of drug concentrations to targetvalues. Methods. A mathematical model that succinctly accounts for thecorrective actions and the variability inherent in the pharmacokineticswas used. Results. The validity of the variability term was tested usingexperimental data for steady state concentrations of the drug procainamide.The approach of the monitored process to the target value followedexponential kinetics and an analytical expression for dependence thevariance with time and various dosing parameters was derived. Thevariance of the drug concentration depends critically on a singlenon-dimensional parameter containing the rate constant for the therapeuticcorrective actions and a coefficient describing the variance rate. Whenthe rate constant for the therapeutic corrective actions was less thanthis critical value, the variance increased indefinitely. Conclusions. From a dosing standpoint, large variances in drugconcentrations are undesirable because some patients will be overdosedor underdosed. Since deterministic models cannot provide analyticalsolutions for the moments of drug concentration distribution functions,stochastic models can be used to provide useful insights into the designof therapeutic regimens.
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    ISSN: 1573-904X
    Keywords: controlled release ; diffusion ; hydrophilic matrix ; hydroxypropyl methylcellulose (HPMC) ; modeling ; swelling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. The aims of this study were (i) to elucidate the transport mechanisms involved in drug release from hydrophilic matrices; and (ii) to develop an improved mathematical model allowing quantitative predictions of the resulting release kinetics. Methods. Our previously presented model has been substantially modified, by adding: (i) inhomogeneous swelling; (ii) poorly water-soluble drugs; and (iii) high initial drug loadings. The validity of the improved model has been tested experimentally using hydroxypropyl methylcellulose (HPMC)-matrices, containing either a poorly or a freely water-soluble drug (theophylline or chlorpheniramine maleate) at various initial loadings in phosphate buffer pH 7.4 and 0.1 N HCl, respectively. Results. By overcoming the assumption of homogeneous swelling we show that the agreement between theory and experiment could be significantly improved. Among others, the model could describe quantitatively even the very complex effect on the resulting relative release rates (first slowing down, then accelerating drug release) observed when increasing the initial loading of poorly water-soluble drugs. Conclusions. The practical benefit of this work is an improved design model that can be used to predict accurately the required composition and dimensions of drug-loaded hydrophilic matrices in order to achieve desired release profiles, thus facilitating the development of new pharmaceutical products.
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    ISSN: 1573-904X
    Keywords: glycyrrhizic acid ; modeling ; enterohepatic cycling ; PBPK ; pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. To analyze the role of the kinetics of glycyrrhizic acid (GD) in its toxicity. A physiologically-based pharmacokinetic (PBPK) model that has been developed for humans. Methods. The kinetics of GD, which is absorbed as glycyrrhetic acid (GA), were described by a human PBPK model, which is based on a rat model. After rat to human extrapolation, the model was validated on plasma concentration data after ingestion of GA and GD solutions or licorice confectionery, and an additional data derived from the literature. Observed interindividual variability in kinetics was quantified by deriving an optimal set of parameters for each individual. Results. The a-priori defined model successfully forecasted GA kinetics in humans, which is characterized by a second absorption peak in the terminal elimination phase. This peak is subscribed to enterohepatic cycling of GA metabolites. The optimized model explained most of the interindividual variance, observed in the clinical study, and adequately described data from the literature. Conclusions. Preclinical information on GD kinetics could be incorporated in the human PBPK model. Model simulations demonstrate that especially in subjects with prolonged gastrointestinal residence times, GA may accumulate after repeated licorice consumption, thus increasing the health risk of this specific subgroup of individuals.
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    ISSN: 1573-6873
    Keywords: neural networks ; modeling ; population density ; orientation tuning ; visual cortex
    Source: Springer Online Journal Archives 1860-2000
    Topics: Computer Science , Medicine , Physics
    Notes: Abstract We explore a computationally efficient method of simulating realistic networks of neurons introduced by Knight, Manin, and Sirovich (1996) in which integrate-and-fire neurons are grouped into large populations of similar neurons. For each population, we form a probability density that represents the distribution of neurons over all possible states. The populations are coupled via stochastic synapses in which the conductance of a neuron is modulated according to the firing rates of its presynaptic populations. The evolution equation for each of these probability densities is a partial differential-integral equation, which we solve numerically. Results obtained for several example networks are tested against conventional computations for groups of individual neurons. We apply this approach to modeling orientation tuning in the visual cortex. Our population density model is based on the recurrent feedback model of a hypercolumn in cat visual cortex of Somers et al. (1995). We simulate the response to oriented flashed bars. As in the Somers model, a weak orientation bias provided by feed-forward lateral geniculate input is transformed by intracortical circuitry into sharper orientation tuning that is independent of stimulus contrast. The population density approach appears to be a viable method for simulating large neural networks. Its computational efficiency overcomes some of the restrictions imposed by computation time in individual neuron simulations, allowing one to build more complex networks and to explore parameter space more easily. The method produces smooth rate functions with one pass of the stimulus and does not require signal averaging. At the same time, this model captures the dynamics of single-neuron activity that are missed in simple firing-rate models.
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    Analog integrated circuits and signal processing 25 (2000), S. 157-169 
    ISSN: 1573-1979
    Keywords: microwave measurements ; SOI technology ; small-signal parameters ; modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: Abstract SOI devices are frequently used nowadays in the RF and HF field. Design of complex SOI integrated circuits involves a prior detailed analog simulation, that can only be performed through accurate SOI active components models. We are interested here in linear operation modeling; we test new methods for small-signal parameters determination, suitable for a conventional MOSFET high-frequency model and somewhat inspired from methods applied to MESFET technology. In this paper, we deal mainly with extrinsic parameters, for which we obtain reliable estimation on a large frequency range. Our finally adopted extraction procedure takes closely into account the model topology, which reflects the device electrical behavior. We completely describe the procedure, from measurements to the extracted equivalent circuit simulation, without having to optimize parameters and with a straightforward extrinsic elements extraction.
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    Flow, turbulence and combustion 63 (2000), S. 1-21 
    ISSN: 1573-1987
    Keywords: turbulence ; RANS ; modeling ; length-scale
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract We derive an equation for the average length-scale in a turbulent flow from a simple physical model. This is a tensorial length-scale. We use as a model the evolution of a blob of turbulent kinetic energy under the influence of production, dissipation, and transport, as well as distortion by the mean motion. A single length-scale is defined which is biased toward the smallest of the scales in the various directions. Constants are estimated by consideration of homogeneous decay. Preliminary computations are carried out in a mixing layer and a two-dimensional jet, using the new length-scale equation and the equation for the turbulent kinetic energy. The results are compared with data and with the predictions of the classical k-epsilon equations; the new results are quite satisfactory. In particular, the plane jet/round jet anomaly is approximately resolved.
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    Mitigation and adaptation strategies for global change 5 (2000), S. 123-142 
    ISSN: 1573-1596
    Keywords: Kyoto Protocol ; GHG ; mitigation strategies ; economiccosts ; modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering , Geography
    Notes: Abstract The Kyoto Protocol requires the U.S.to reduce the rate of emissions of six greenhousegases (GHG) to 93% of their 1990 rate and to achievethis target by the 2008 to 2012 commitment period. This study assesses the magnitude of change needed inthe U.S. economy and, specifically, in the U.S. energysector, to achieve and maintain the target establishedby the Kyoto Protocol. A simple carbon (C)emissions-energy model is explained in this analysisusing four key variables. Current and future trendsin C emissions are explained by: the carbon/energy(C/E) ratio, Gross Domestic Product growth, energyprices and an energy trend variable. Potential GHGmitigation policy actions affect C emissionsindirectly by affecting at least one of these keyvariables. The analysis concludes that reducingfossil energy use in the U.S. to meet the Kyoto GHGemissions reduction target would be very costly. Technological progress that reduces C emissions wouldnot be fully sufficient without prematurely abandoningproductive capital equipment. Energy price increasesof about 14% per year, or declines in economic growthof almost 5% per year, could reduce energy demand andassociated C emissions enough to achieve the terms ofthe Kyoto Protocol.
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    Nutrient cycling in agroecosystems 58 (2000), S. 259-276 
    ISSN: 1573-0867
    Keywords: agroecosystem ; trace gas ; modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract A computer simulation model was developed for predicting trace gas emissions from agricultural ecosystems. The denitrification-decomposition (DNDC) model consists of two components. The first component, consisting of the soil climate, crop growth, and decomposition submodels, predicts soil temperature, moisture, pH, Eh, and substrate concentration profiles based on ecological drivers (e.g., climate, soil, vegetation, and anthropogenic activity). The second component, consisting of the nitrification, denitrification, and fermentation submodels, predicts NH3, NO, N2O, and CH4 fluxes based on the soil environmental variables. Classical laws of physics, chemistry, or biology or empirical equations generated from laboratory observations were used in the model to parameterize each specific reaction. The entire model links trace gas emissions to basic ecological drivers. Through validation against data sets of NO, N2O, CH4, and NH3 emissions measured at four agricultural sites, the model showed its ability to capture patterns and magnitudes of trace gas emissions.
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    Irrigation and drainage systems 14 (2000), S. 281-299 
    ISSN: 1573-0654
    Keywords: drainage design ; modeling ; steady-state criteria ; subsurface drainage
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract This paper presents the results of modelsimulations to evaluate drainage designparameters for the Fourth Drainage Project(FDP), Punjab, Pakistan. The SWAP model wasapplied to compute the effects of landdrainage (12 combinations of drain depthand spacing) on soil moisture conditions inthe root zone and their effect on cropyield and soil salinization. For theconditions considered, the selection ofdrain depth is found to be more criticalthan that of drain spacing. Deeper drainsperform technically better in relation tocrop growth and soil salinization. Theoptimum drain depth for the multiplecropping system of the FDP-area was foundto be 2.2 m. This drain depth will producereasonably good crop yields at rather lowdrainage intensity while keeping the rootzone salinity within acceptable limits.This drainage design also maintained thegroundwater table depth below the root zonethroughout the growing season. The outcomeof this study reveals that the drainagedesign criteria applied for the FDP israther conservative with high drainageintensity. The FDP-area can effectively bedrained with a 25 percent lower drainageintensity (q drain/Δh)provided no operational or maintenanceconstraints are present. However, the finaldecision on the optimum combination ofdrain depth and drain spacing would requirea thorough economical analysis. Thenon-steady state approach proved successfulin analyzing the complex interactionsbetween irrigation and drainage components.It is a valuable tool to optimize thedesign of drainage systems against cropyields and soil salinization.
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    Earth, moon and planets 89 (2000), S. 135-160 
    ISSN: 1573-0794
    Keywords: C/1995 O1 (Hale-Bopp) ; 19P/Borrelly ; 46P/Wirtanen ; comets ; modeling ; nucleus ; observations ; rotation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract We review several techniques used to retrieve rotational parameters from observations. The spin period of a dozen of comets retrieved with these techniques are summarized. We describe how the spin period of comet Hale-Bopp (C/1995 O1) has been calculated with a high accuracy (11.30–11.34 h). Although several authors converged to a spin axis orientation at (α,δ) = (275 ± 15°, -55 ± 5°), detailed studies indicate that the dust jets morphology in 1996–1997 may be incompatible with this orientation. Comet 19P/Borrelly has been recently observed by the Deep Space 1 spacecraft. At the same time, its spin axis orientation and period have been determined by several authors to be respectively (α,δ) = (225 ± 15°, -10 ± 10°)and 26h. These two comets are likely to be in (or close to) a principal axis spin state. We discuss new modeling of the spin state of comet 46P/Wirtanen, the target of the Rosetta mission. The model involves a three-dimensional shape and thermal model, from which the torque of the non gravitational force is calculated at each time step. The moments of inertia are computed for each irregular shape. The results from numerical integrations show that this comet can remain in a principal axis spin state during more than 10 orbits if the spin period does not get above∼6 h. If the spin period increases, its nucleus gets rapidly into excited spin states. It shows that even small and very active short-period comets are not necessarily in non principal axis spin states. In the last section, the consequences of recent observations and modeling of the rotational parameters of comet nuclei are discussed, and unsolved problems are presented.
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    ISSN: 1573-1839
    Keywords: virtual reality ; modeling ; constructionism ; astronomy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Natural Sciences in General , Technology
    Notes: Abstract In this manuscript we describe an introductory astronomy course for undergraduate students in which we moved from the large-lecture format to one in which students were immersed in a technologically-rich, inquiry-based, participatory learning environment. Specifically, undergraduate students used 3-D modeling tools to construct virtual reality models of the solar system, and in the process, build rich understandings of various astronomical phenomena. For this study, primarily naturalistic inquiry was used to gain a holistic view of this semester-long course. These data are presented as two case studies focusing on: (1) the role of the teacher in this participatory learning environment; (2) the particular dynamics that formed in each group; (3) the modeling process; (4) the resources used, specifically student-developed inscriptions; and (5) the role of technology and whether learning the technology interfered with learning astronomy. Results indicated that VR can be used effectively in regular undergraduate university courses as a tool through which students can develop rich understandings of various astronomical phenomena.
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    Photosynthesis research 66 (2000), S. 199-224 
    ISSN: 1573-5079
    Keywords: C4 photosynthesis ; modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract A computer model comprising light reactions in PS II and PS I, electron-proton transport reactions in mesophyll and bundle sheath chloroplasts, all enzymatic reactions and most of the known regulatory functions of NADP-ME type C4 photosynthesis has been developed as a system of differential budget equations for intermediate compounds. Rate-equations were designed on principles of multisubstrate-multiproduct enzyme kinetics. Some of the 275 constants needed (ΔG0′ and K m values) were available from literature and others (V m) were estimated from reported rates and pool sizes. The model provided good simulations for rates of photosynthesis and pool sizes of intermediates under varying light, CO2 and O2. A basic novelty of the model is coupling of NADPH production via NADP-ME with ATP production and regulation of the C3 cycle in bundle sheath chloroplasts. The functional range of the ATP/NADPH ratio in bundle sheath chloroplasts extends from 1.5 to 2.1, being energetically most efficient around 2. In the presence of such stoichiometry, the CO2 concentrating function can be explained on the basis of two processes: (a) extra ATP consumption for starch and protein synthesis in bundle sheath leads to a faster NADPH and CO2 import compared with CO2 fixation in bundle sheath, and (b) the residual photorespiratory activity consumes RuBP by oxygenation, NADPH and ATP and causes the imported CO2 to accumulate in bundle sheath cells. As a wider application, the model may be used for predicting results of genetic engineering of plants.
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    Plant growth regulation 31 (2000), S. 1-16 
    ISSN: 1573-5087
    Keywords: apple ; application methods ; caustic sprays ; economics ; flowering ; growth regulators ; Malus xdomestics Borkh. ; modeling ; photosynthesis ; review
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The history of fruit thinning is reviewed, beginning with hand removalof fruits, the effects upon subsequent flowering, and current attemptsto develop mechanical methods of fruit removal. Early experiments withcaustic compounds and growth regulators and their subsequent developmentas commercial practices are discussed, as well as the modes of action ofgrowth regulators. Brief reviews of methods of application, factorsaffecting response, modeling to improve efficiency, and the economicvalue of thinning to the grower are also included.
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    Journal of aquatic ecosystem stress and recovery 8 (2000), S. 39-51 
    ISSN: 1573-5141
    Keywords: broad spectrum analysis ; contaminants ; distribution ; fate ; metals ; modeling ; persistent organic pollutants ; pulp-mill effluents
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Northern river ecosystems worldwide are under increasing environmental stress from degrading developments that influence water quality and associated ecological integrity. In particular, contaminant-related threats to these systems are rising from enhanced industrial and municipal effluent discharges along with elevated non-point source inputs related to land-use activities such as forestry, agriculture, mining and long-range atmospheric transport. In this regard, the contaminants program of the Northern River Basins Study (NRBS) in western Canada identified key contaminant sources to the Athabasca, Slave and Peace river basins (particularly related to pulp-mill developments) and assessed their environmental fate and distribution in water and sediments. The study also developed and employed new analytical approaches and generated improved models to predict contaminant transport and fate in the aquatic environment and related food webs. Consequently the study focused on those contaminant families identified in characterization studies as arising from key point- and non-point sources within the basins or as being of greatest toxicological significance. These included resin acids, polychlorinated dioxins and furans, polychlorinated biphenyls, chlorinated phenolics, polyaromatic hydrocarbons and selected heavy metals such as mercury. Low or non-detectable concentrations of a number of contaminant groups were found in the ambient water phase including chlorinated phenolics, some chlorinated dioxins and furans and some resin acids. For both suspended and depositional sediments, significant declines were observed over the study period for the major chlorinated contaminant groups tested, correlating directly with the implementation of improved effluent treatment in many of the pulp mills located in the basins. In general, the environmental levels of chlorinated organic and metal contaminants in water or sediments were low and within Canadian health or environmental guidelines. It is hoped that the approaches used and lessons learned from the NRBS will be of use to others assessing contaminant and multiple stressor issues in other large river ecosystems.
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    ISSN: 1573-2959
    Keywords: modeling ; New York City ; risk assessment ; watershed monitoring
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract The International Life SciencesInstitute (ILSI) Risk Science Institute (RSI) convenedan expert panel of scientists to developrecommendations for a comprehensive monitoring programfor the Croton and Catskill/Delaware watersheds, whichprovide drinking water to New York City's residents. This effort was conducted as part of efforts topreserve and enhance the quality of New York City'sreservoir system through a watershed protectionprogram. The panel developed recommendations for astrategic framework on which to construct a monitoringprogram. As part of this activity, the paneldetermined whether existing monitoring activities weredeficient and, where activities were deficient, thepanel developed recommendations for additionalinformation that should be collected.The panel recommended the development and use of anintegrated approach to watershed monitoring, whichdraws on modeling, risk-based planning and analysis,statistical sampling and design, and basic compliancemonitoring. The approach should be designed toprovide an assessment of natural and anthropogenicsources of stress to the system as well as anassessment of water quality trends in response tostresses acting in concert, both over the long termand over the five-year New York City Memorandum ofAgreement (MOA) assessment time frame. It should alsoprovide an assessment of the human health andenvironmental risks posed by a variety of stressors,and the impact of management actions implemented toameliorate stressors.
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    Water, air & soil pollution 120 (2000), S. 139-167 
    ISSN: 1573-2932
    Keywords: base saturation ; clay soils ; loess soils ; modeling ; nutrient uptake ; soil acidification ; weathering
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract To assess the impact of acid deposition on forestedloess and clay soils in the Netherlands, changes inbase saturation and soil solution concentrations weresimulated with the dynamic soil acidification modelReSAM for 38 loess soils and 16 clay soils. Theselected locations represent the range in geographicalposition and diversity in parent material occurring inforested loess and clay soils in the Netherlands. Twodeposition scenarios were used for the period1992–2050: a business as usual scenario (BAU) and ascenario in which deposition was reduced according topresent Dutch policy plans (MV-3). A comparison ofsimulated and measured soil solution concentrationsand base saturation in 1992/1993 showed that the modelsimulated concentrations and base saturation in theloess soils quite good. However, the model tended tooverestimate acidification in the top (0–10 cm) of theclay soils. Despite the reasonable agreement betweenmeasured and simulated data some uncertainty in thevalidity of the model predictions remains because timetrends to validate the model were not available. Themodel predicted a small but ongoing acidificationduring the BAU scenario in the loess soils asindicated by a decline in median base saturation andpH in the topsoil in 2050. Present policy plans (MV-3)lead to a slight recovery of the base saturation in2050 and a decline in Al concentrations. In the claysoils a strong decline in base saturation is simulatedin the topsoil, whereas an increase in base saturationis predicted for the subsoil.
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  • 45
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    Applied mathematics and mechanics 21 (2000), S. 19-26 
    ISSN: 1573-2754
    Keywords: structure ; optimization ; topology optimization ; modeling ; dual programming ; O223 ; TU323
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Mathematics , Physics
    Notes: Abstract Topology optimization design of continuum structures that can take account of stress and displacement constraints simultaneously is difficult to solve at present. The main obstacle lies in that, the explicit function expressions between topological variables and stress or displacement constraints can not be obtained using homogenization method or variable density method. Furthermore, large quantities of design variables in the problem make it hard to deal with by the formal mathematical programming approach. In this paper, a smooth model of topology optimization for continuum structures is established which has weight objective considering stress and displacement constraints based on the independent-continuous topological variable concept and mapping transformation method proposed by Sui Yunkang and Yang Deqing. Moreover, the approximate, explicit expressions are given between topological variables and stress or displacement constraints. The problem is well solved by using dual programming approach, and the proposed element deletion criterion implements the inversion of topology variables from the discrete to the continuous. Numerical examples verify the validity of proposed method.
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  • 46
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    Pharmaceutical research 17 (2000), S. 252-256 
    ISSN: 1573-904X
    Keywords: Monte Carlo ; computer assisted trial design ; modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Clinical trial simulation is the application of old technologies, e.g., Monte Carlo simulation, to a newproblem, that problem being how to maximize the information content obtained during the drugdevelopment process with an intent to have the greatest chance of “success” in a clinical trial. When the informationcontent of the drug is high, then simulation provides a method to synthesize that information into acoherent package that indicates the sponsor has good control over the pharmacology of the drug. Froma purely financial point of view, what simulation offers pharmaceutical companies is the possibility ofreducing the number of required studies, maximizing the chances for success in a clinical trial, andpossibly shortening development time; all outcomes which will reduce drug development costs. Thepurpose of this paper is to introduce clinical trial simulation to the reader by discussing its potential indrug development, to briefly review the literature, and to make recommendations and caveats regardingits use.
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  • 47
    ISSN: 1573-2932
    Keywords: adsorption ; arsenic ; chromium ; copper ; iron-oxide-coated sand ; modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract The adsorption of copper, chromate, and arsenate (CCA)onto iron-oxide-coated sand (IOCS) was examined insingle-metal and mixed-metal systems. Copper andarsenate were strongly adsorbed or formed inner-spheresurface complexes with the IOCS surface while chromatewas weakly adsorbed or formed an outer-sphere surfacecomplex with the IOCS surface. Copper adsorption byIOCS slightly increased in the presence of arsenatebut was not affected by the presence of chromate. Arsenate adsorption was not affected by the presenceof copper and/or chromate. Chromate adsorptionincreased in the presence of copper by the combinationof electrostatic effects and possiblesurface-copper-chromate ternary complex formation. The presence of arsenate significantly decreasedchromate adsorption due to competition for adsorptionsites and electrostatic effects. Using inner-spheresurface complexation constants for copper and arsenateand outer-sphere surface complexation constants forchromate, the triple-layer model (TLM) was successfulin describing adsorption of copper, chromate, andarsenate in single-solute systems. The modelindicated that each metal uses a different number ofadsorption sites. For CCA metals-IOCS systems, theequilibrium constants determined from single-solutesystems were not able to predict adsorption frommulti-solute systems. The TLM does not currentlyaccount for the heterogeneity of oxide surface sitesand the formation of ternary complexes and/or solidphases that do not exist in single-solute systems.
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  • 48
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    Journal of chemical ecology 26 (2000), S. 303-313 
    ISSN: 1573-1561
    Keywords: Eucalyptol ; essential oils ; cineole ; monoterpenes ; chlorophyll fluorescence ; Echinochloa crusgalli ; Cassia obtusifolia ; natural products ; modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract The volatile monoterpene analogs, 1,4-cineole and 1,8-cineole, have been identified as components of many plant essential oils, but relatively little is known about their biological activities. We compared the effects of 1,4- and 1,8-cineole on two weedy plant species by monitoring germination, mitosis, root and shoot growth, chlorophyll content, and photosynthetic efficiency. 1,4-Cineole severely inhibited growth of roots and shoots, causing cork-screw shaped morphological distortion, whereas 1,8-cineole caused a decrease in root growth and germination rates. Chlorophyll fluorescence data (yield and F v / F m) indicated that 1,4-cineole caused significantly higher stress (P ≤ 0.001) to photosynthesis when compared to controls. Mitotic index data showed that 1,8-cineole severely decreased (P ≤ 0.001) all stages of mitosis when compared with controls, while 1,4-cineole only caused a decrease in the prophase stage (P ≤ 0.05). Although superficially similar in structure, these two cineoles appear to have different modes of action.
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  • 49
    ISSN: 1573-1111
    Keywords: Calixarene-crown ether ; Cs+ complexation ; solvent extraction ; SXLSQI ; equilibrium constants ; partition ratio ; modeling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The extraction of CsNO3 by the highly lipophilic calixarene-crown ether calix[4]arene-bis(t-octylbenzo-crown-6) (CABOBC6) in 1,2-dichloroethane (1,2-DCE) at 25 °C has been shown to be consistent with the formation of both 1 : 1 and 2 : 1 metal : ligand species. Variation of the aqueous-phase CsNO concentration up to 1.0 M and variation of the organic-phase calixarene concentration up to 0.10∼M was modeled by the program SXLSQI. Formation of the organic-phase species CsBNO3 (B = calixarene) was confirmed as well as the organic-phase dissociation products CsB+ and NO3 -. Good evidence for the 2 : 1 metal : ligand organic-phase species Cs2B(NO3)2 was also found, although the dissociation of nitrate from this complex was not observed. Binding of the second Cs+ cation by the ligand is approximately two orders of magnitude weaker than binding of the first Cs+ cation. The logarithm of the apparent partition ratio (log PB) of the calixarene between water and 1,2-DCE was found by 1H-NMR techniques to be 〉 5.1.
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  • 50
    ISSN: 0935-6304
    Keywords: Capillary HPLC ; gradient elution ; temperature programming ; phenolic compounds ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---This paper describes a liquid chromatographic method using a reversed phase capillary column coupled to an UV detector for the quantitation of thirteen pollutant phenols. Chromatographic separation was carried out with gradient elution at 25.0 ± 0.1°C. The two major anisocratic elution modes (gradient elution and temperature programming) were evaluated. The detection limit range was 10-81 pg (100 nL injected). The chromatographic method combined with liquid-liquid extraction was applied to analysis of these compounds in river water. Recoveries of 75-103% were achieved for most of them.
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    Journal of High Resolution Chromatography 23 (2000), S. 389-392 
    ISSN: 0935-6304
    Keywords: Capillary SFC ; zinc dialkyldithiophosphates ; lubricating oils ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract
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    Journal of High Resolution Chromatography 23 (2000), S. 393-396 
    ISSN: 0935-6304
    Keywords: Supercritical fluid chromatography (SFC) ; micropacked capillary columns ; waxes ; restoring ; objects of art ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract
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  • 53
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    Journal of High Resolution Chromatography 23 (2000), S. 379-385 
    ISSN: 0935-6304
    Keywords: Aroma ; “lulo del Chocó” ; Solanum topiro ; volatiles ; glycosidically bound volatiles ; glycoside TFA derivatives ; enantioselective gas chromatography ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The volatile constituents of lulo del Chocó (Solanum topiro) fruit pulp obtained by liquid-liquid extraction were analyzed by capillary GC and capillary GC-MS. In total, 30 components were identified with methyl salicylate, hexadecanoic acid, hexanal, guaiacol, ethyl butanoate, and ethyl acetate being the major components. Chirospecific MDGC analysis revealed the predominance of (R)-ethyl-3-hydroxybutanoate (ee 40%) and the presence of racemic mixtures both of δ-octalactone and of δ-decalactone. For γ-hexalactone, γ-octalactone, and γ-decalactone enantiomeric distributions of 22.4 : 77.6, 22.9 : 77.1, and 20.0 : 80.0, (R) : (S), respectively, were determined. Glycosidically bound aroma compounds were identified by capillary GC and capillary GC-MS after isolation of the glycosidic fraction obtained by Amberlite XAD-2 adsorption and methanol elution followed by hydrolysis with a commercial pectinase enzyme. In total 13 bound aroma compounds (aglycones) were identified. These aglycones mainly consisted of compounds exhibiting aromatic structures. Additionally, with the aid of capillary GC and capillary GC-MS (EI and NCI) of trifluoroacetylated derivatives we identified eight glucosides: the novel 3,6-epoxy-7-megastigmen-5,9-diol β-D-glucopyranoside and the hexyl, benzyl, linalyl oxide (furanic), 2-phenylethyl, vomifolyl (isomer 1), (6S,9R)-vomifolyl, and scopoletin β-D-glucopyranosides.
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    Journal of High Resolution Chromatography 23 (2000), S. 409-412 
    ISSN: 0935-6304
    Keywords: Cyclodextrin ; capillary electrophoresis ; system peak ; CHES 1 ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using a running buffer containing cyclodextrins (CDs) and 2-[N-cyclohexylamino]-ethanesulfonic acid (CHES), positive system peaks were observed in the analysis of a ganglioside mixture by CE-UV. These system peaks were related to CDs in the running buffer because these peaks were also detected when a plug of solution devoid of CDs but having the same CHES concentration and pH as the running buffer was injected. Neutral CDs were separated owing to the formation of inclusion complexes with the anionic CHES ion. One possible explanation for the positive system peaks is that the anionic CD-CHES inclusion complex is displaced by co-ions with higher UV absorptivity.
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  • 55
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    Journal of High Resolution Chromatography 23 (2000), S. 565-566 
    ISSN: 0935-6304
    Keywords: Liquid chromatography ; zinc dithiocarbamate ; vulcanization accelerator ; rubber gloves ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract
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  • 56
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    Journal of High Resolution Chromatography 23 (2000), S. 603-608 
    ISSN: 0935-6304
    Keywords: Solvation parameter model ; ystem constants for poly(dimethyldiphenylsiloxane) HP-5 and poly(ethylene glycol) HP-INNOWax stationary phases ; temperature ; molecular interaction ; retention models ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---No abstract
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    Journal of High Resolution Chromatography 23 (2000), S. 561-564 
    ISSN: 0935-6304
    Keywords: Retention factors ; Cinnamomi ramulus ; high-performance liquid chromatography ; capillary electrophoresis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---No abstract
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    Journal of High Resolution Chromatography 23 (2000), S. 590-594 
    ISSN: 0935-6304
    Keywords: Ion chromatography ; graphitic carbon stationary phases ; anions ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Inorganic anions could be separated on porous graphitic carbon stationary phases in ion chromatography. Ion exchange between eluent anions and sample anions on the stationary phase was confirmed by the retention behavior and the possibility of indirect photometric detection. The elution order of anions was different from that observed for commercially available anion exchangers. Chloride, nitrate, and sulfate contained in tap water could be determined in 7 min.
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    Journal of High Resolution Chromatography 23 (2000), S. 485-488 
    ISSN: 0935-6304
    Keywords: Pyrethroids ; solid-phase microextraction ; water analysis ; temperature ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Synthetic pyrethroids are increasingly being used for insect control on field crops because of their advantageous environmental properties such as short field life, broad spectrum of insecticide activity, and relatively low mammalian toxicity. In the present work, experimental conditions were optimized for trace analysis of pyrethroids in water by using solid-phase microextraction followed by capillary gas chromatography. Effects of temperature, SPME-fiber diameter, and matrix were studied. SPME used off-line with a gas chromatograph electron-capture detection (GC-ECD) showed a linear response over a wide concentration range. Our results showed a strong temperature effect on pyrethroid extraction yield. The detection limit after 5 min of SPME-fiber exposure to the samples changed from 1 ppb (at 30°C) to 0.1 ppt (at 90°C), which is a 10000 increase in pyrethroid detection. The standard deviations of the analyte peak area ratios were typically in the range of 1-7% at 30°C and of 3 to 15% at 90°C. Best conditions for pyrethroids analysis were achieved using high temperature solution and a 100 μm polydimethylsiloxane fiber. No matrix (river water) influence was observed on detection of the investigated pyrethroids.
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    Journal of High Resolution Chromatography 23 (2000), S. 19-26 
    ISSN: 0935-6304
    Keywords: Microfabrication ; monolith ; electrochromatography ; peptides ; reactive ion etching ; reversed phase ; nanocolumns ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Monolith columns are generally fabricated by polymerization of monomers within a column. This paper reviews an alternative strategy in which the bed is microfabricated in an inorganic material by ablation. Channels of 1.5 μm width and 10 μm depth were sculpted in quartz by deep reaction ion etching. Using this approach chromatographic beds were constructed in which cubic support structures were created and arranged in rows to mimic particles in a conventional column. Beds ranging from hundreds of thousands to millions of “particles” with volumes of 15 nL to 15 μL were produced. Columns that had been derivatized with an octadecyl silane stationary phase were used to separate both low molecular weight analytes and peptides in the CEC mode. Plate height in the CEC mode was 1.2 μm at maximum efficiency.
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    Journal of High Resolution Chromatography 23 (2000), S. 39-43 
    ISSN: 0935-6304
    Keywords: Monoliths ; CIM® monolithic column ; dynamic binding capacity ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The characterization of CIM® DEAE monolithic columns in terms of dynamic binding capacity is presented in this paper. Breakthrough experiments were performed for capacity determination. Bovine serum albumin (BSA) was used as a model protein. It is shown that CIM® monolithic columns have good batch-to-batch reproducibility as well as long-term stability. The experiments performed under different linear velocities demonstrated that the dynamic capacity is unaffected at least up to a linear velocity of 2450 cm/h. Furthermore, the breakthrough curve slope is constant, indicating that the capacity would remain constant at even higher linear velocities. The adsorption isotherm of BSA dissolved in 20 mM Tris-HCl buffer shows a constant capacity of around 30 mg/mL of support down to a concentration of 20 μg/mL. The capacity is substantially influenced by the ionic strength; however, 20% of the maximal capacity is still preserved at 0.3 M NaCl.
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  • 62
    ISSN: 0935-6304
    Keywords: Monolith ; factor VIII ; affinity chromatography ; combinatorial peptide library ; peptide synthesis ; recombinant proteins ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: FVIII is a very complex molecule of great therapeutic significance. It is purified by a sequence of chromatographic steps including immunoaffinity chromatography. A peptide affinity chromatography method has been developed using peptides derived from a combinatorial library. Spot technology using cellulose sheets has been applied for this purpose. The dual positional scanning strategy was used for identification of the amino acids in random positions. Approximately 5000 possible candidates found in the first screening round were reduced to a panel of 36. Six candidates have been selected empirically. Five peptides seem to be directed against the light chain of FVIII, one peptide seems to be directed against the heavy chain. The peptides have been immobilized on conventional beaded material and CIM polymethacrylate monoliths. Much better performance with respect to capacity and selectivity has been observed with the monolithic material. Exposure of the ligand and its ensuing accessibility are responsible for these properties.
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    Journal of High Resolution Chromatography 23 (2000), S. 67-72 
    ISSN: 0935-6304
    Keywords: Capillary electrochromatography ; monolithic column ; electroosmotic flow ; retention mechanism ; aromatic compound ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new kind of monolithic capillary electrochromatography column with poly(styrene-co-divinylbenzene-co-methacrylic acid) as the stationary phase has been developed. The stationary phase was found to be porous by scanning electron microscopy and the composition of the continuous bed was proved by IR spectroscopy to be the ternary polymer of styrene, divinylbenzene, and methacrylic acid. The effects of operating parameters, such as voltage, electrolyte, and organic modifier concentration in the mobile phase on electroosmotic flow were studied systematically. The retention mechanism of neutral solutes on such a column proved to be similar to that of reversed-phase high performance liquid chromatography. In addition, fast analyses of phenols, chlorobenzenes, anilines, isomeric compounds of phenylenediamine and alkylbenzenes within 4.5 min were achieved.
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    Journal of High Resolution Chromatography 23 (2000), S. 73-80 
    ISSN: 0935-6304
    Keywords: Continuous-bed ; sol-gel ; octadecylsilica ; mixed-mode stationary phase ; large-pore ; column technology ; capillary electrochromatography ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Sol-gel bonded packing materials in continuous-bed columns have been prepared for capillary electrochromatography (CEC). Three packing materials were investigated: small-pore Spherisorb ODS1 (3 μm, 80 Å) with octadecyl as stationary phase, small-pore mixed-mode Spherisorb ODS/SCX (3 μm, 80 Å) with octadecyl and propyl sulfonic acid as stationary phases, and large-pore Nucleosil ODS (7 μm, 1 400 Å) with octadecyl as stationary phase. The characteristics of these columns were compared in terms of electroosmotic flow, efficiency, inertness, and retention factors. In contrast to columns containing sol-gel bonded ODS, columns containing sol-gel bonded mixed-mode ODS/SCX generated nearly pH independent electroosmotic flow (EOF) over pH 2-9. Columns containing sol-gel bonded large-pore ODS produced nearly three times lower reduced plate height than those containing small-pore ODS. Efficiencies of 220,000 plates per meter and 175,000 plates per meter were obtained from columns containing sol-gel bonded 7 μm, 1 400 Å ODS and columns containing sol-gel bonded 3 μm, 80 Å ODS, respectively, which are among the highest reported efficiencies for continuous-bed columns. In CEC, over one million plates per meter and pH independent EOF are expected from continuous-bed columns containing sol-gel bonded 1.5 μm particles with large pores and mixed-mode stationary phases.
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    Journal of High Resolution Chromatography 23 (2000), S. 81-88 
    ISSN: 0935-6304
    Keywords: Monolithic chromatography columns ; capillary electrochromatography (CEC) ; micro high performance liquid chromatography ; sol-gel based columns for chromatography ; fritless capillary chromatography columns ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Particle-loaded (3 μm, octadecylsilica) monolithic sol-gel columns have been prepared and selected characteristics measured. Several electrical properties may be calculated from simple current measurements in the column as a whole. Resistivity in the packed segment is approximately three times that in open segments, resulting in a 60% increase in field strength in the packed regions compared to the capillary with no packing. The surprisingly high specific permeability of these sol-gel columns is characteristic of 8-μm particles, which allows their operation in the microLC mode at pressures as low as 69 kPa where their efficiency is about 50,000 plates per meter and in the CEC mode where efficiency is about 106,000 plates per meter at 5 kV. There is a relatively rapid loss of efficiency with increasing linear velocity beyond 0.2 mm/s in microLC mode, which may be due to additional diffusion processes in the inter-particulate voids. A rapid loss of efficiency above 0.5 mm/s is also observed in the CEC mode, for the same reasons. Chromatographic retention behavior in either separation mode is characteristic of conventional octadecylsilica particles, indicating that analytes have significant access to the surface within the pores of the immobilized bonded phase.
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    Journal of High Resolution Chromatography 23 (2000), S. 89-92 
    ISSN: 0935-6304
    Keywords: Capillary electrochromatography ; packed columns ; fritless columns ; stationary phases ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Fritless packed silica gel columns were prepared using sol-gel technology. A part of a 75 μm i.d. fused silica capillary was filled with a mixture of tetramethoxysilane and poly(ethylene glycol). After gelling at 40°C and heating at 300°C, the resultant silica gel was derivatized with dimethyloctadecylchlorosilane. A scanning electron micrograph of a cross-section of the capillary column showed that the gel took the form of a spherical particle aggregate and adhered to the column inner wall. The column performance was evaluated for electrochromatography using acetonitrile-50 mM HEPES buffer (pH 6.6) (60/40 or 40/60, v/v) as the mobile phase. An electroosmotic flow of 1.0 mm/s was generated with (60/40, v/v) acetonitrile/HEPES buffer at a field strength of 546 V/cm. Using a sol-gel-derived packed column at an electroosmotic flow of 0.5 mm/s, efficiencies of up to 1.1×105 plates/m were obtained for retained solutes.
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    Journal of High Resolution Chromatography 23 (2000), S. 93-99 
    ISSN: 0935-6304
    Keywords: HPLC ; monolithic column ; silica rod column ; fast separations ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The application of a new silica-based, monolithic-type HPLC-column for fast separations is presented. The column is prepared according to a new sol-gel process, which is based on the hydrolysis and polycondensation of alkoxysilanes in the presence of water soluble polymers. The method leads to “rods” made of a single piece of porous silica with a defined pore structure, i. e. macro- and mesopores. The main feature of silica rod columns is a higher total porosity, about 15% higher than of conventional particulate HPLC columns. The resulting column pressure drop is therefore much lower, allowing operation at higher flow rates including flow gradients. Consequently, HPLC analysis can be performed much faster, as it is demonstrated by various applications.
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    Journal of High Resolution Chromatography 23 (2000), S. 3-18 
    ISSN: 0935-6304
    Keywords: Capillary electrochromatography ; monolithic columns ; synthetic polymers ; stationary phase ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Monolithic materials have quickly become a well-established stationary phase format in the field of capillary electrochromatography (CEC). Both the simplicity of their in situ preparation method and the large variety of readily available chemistries make the monolithic separation media an attractive alternative to capillary columns packed with particulate materials. This review summarizes the contributions of numerous groups working in this rapidly growing area, with a focus on monolithic capillary columns prepared from synthetic polymers. Various approaches employed for the preparation of the monoliths are detailed, and where available, the material properties of the resulting monolithic capillary columns are shown. Their chromatographic performance is demonstrated by numerous separations of different analyte mixtures in variety of modes. Although detailed studies of the effect of polymer properties on the analytical performance of monolithic capillaries remain scarce at this early stage of their development, this review also discusses some important relationships such as the effect of pore size on the separation performance in more detail.
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    Journal of High Resolution Chromatography 23 (2000), S. 100-105 
    ISSN: 0935-6304
    Keywords: Preparative chromatography ; silica monoliths ; PrepROD™ ; productivity ; SMB-chromatography ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The use of monolithic silica sorbents for the isolation of substances by preparative liquid chromatography is demonstrated. Preparative liquid chromatography is recognized as a valuable technique for the isolation and purification of substances in the pharmaceutical and fine chemicals industry. The system technology has meanwhile reached a high standard, and the greatest future improvements are expected to arise from new and improved adsorbents. Monolithic silica sorbents offer some unique features for preparative liquid chromatography. They exhibit high efficiencies even at high flow rates due to their fast convective mass transfer and can therefore be used at very high mobile phase velocities, leading to high productivity and hence to maximum process economy. The benefits of this new type of adsorbent are illustrated for an example in batch-chromatographic mode and an example using the continuous simulated moving bed (SMB) technology.
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  • 70
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    Journal of High Resolution Chromatography 23 (2000), S. 106-110 
    ISSN: 0935-6304
    Keywords: Silica ; monolithic column ; aging ; mesopores ; pore size distribution ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Mesopore formation in silica gels having continuous macropores has been investigated. The macroporous wet silica gel prepared by the sol-gel process including phase separation was aged in a basic solvent making use of hydrolysis of urea in a closed condition. The mesopore structure was finally obtained by subsequent evaporation drying of solvent and heat-treatment at 600°C for 2 h. The dissolution-reprecipitation kinetics at the interfaces between wet gel skeletons and an external solvent affected the size and volume of pores formed within the skeletons. Below 120°C, mesopores suitable for various chromatographic applications have been formed typically within 24 h. On the other hand, at 200°C, the pore size attained the macropore dimensions (〉50 nm), and the whole macroporous morphology was significantly modified.
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  • 71
    ISSN: 0935-6304
    Keywords: Monolithic column ; silica monolith ; HPLC ; capillary liquid chromatography ; capillary electrochromatography ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Two types of monolithic silica columns derivatized to form an ODS phase, one prepared in a fused silica capillary (SR-FS) and the other prepared in a mold and clad with an engineering plastic (poly-ether-ether-ketone) (SR-PEEK), were evaluated. The column efficiency and pressure drop were compared with those of a column packed with 5-μm ODS-silica particles and of an ODS-silica monolith prepared in a mold and wrapped with PTFE tubing (SR-PTFE). SR-FS gave a lower pressure drop than a column packed with 5-μm particles by a factor of 20, and a plate height of 20 μm at a linear velocity below 1 mm/s. SR-PEEK showed higher flow-resistance than the other monolithic silica columns, but they still showed a minimum plate height of 8-10 μm and a lower pressure drop than popular commercial columns packed with 5-μm particles. The evaluation of SR-FS columns in a CEC mode showed much higher efficiency than in a pressure-driven mode.
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  • 72
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    Journal of High Resolution Chromatography 23 (2000), S. 119-126 
    ISSN: 0935-6304
    Keywords: Gas chromatography ; retention volume ; real gas carrier ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The problem of the calculation and interpretation of the net retention volume with a real gas as carrier is revisited. The properties of the carrier are described by a first order virial equation of state. The net retention volume of a solute is related to the mean flow rate of the carrier, therefore determination of the mean flow rate of a real gas carrier is reviewed. It is shown that the mean flow rate cannot be calculated from the mean column pressure. With a real gas carrier the local capacity factor depends on the local pressure of the real gas. The basic relationship between the net retention volume and the function describing this pressure dependence is also reviewed. Precise formulae as well as practical approximations are presented for the calculation of the mean flow rate, of the mean column pressure, and of a representative pressure related to the mean capacity factor.
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  • 73
    ISSN: 0935-6304
    Keywords: Chemiluminescence ; diol compound ; oxalate ; post-column reaction ; ruthenium complex ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---In this paper we propose a new post-column detection method for polyols containing 1,2-diol, 1,3-diol, and saccharides. The polyols are oxidized in a photochemical reactor to yield oxalate with subsequent chemiluminescence detection using [Ru(III)(bpy)3]3+. A mixing solution of eluate and oxidizing reagent is delivered to a reaction coil, which is then irradiated with ultraviolet light to promote the oxidation reaction. The detection limits for 1,2-ethanediol (ethylene glycol) and 1,3-propanediol were 38 pmol and 23 pmol, respectively.
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  • 74
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    Journal of High Resolution Chromatography 23 (2000), S. 131-137 
    ISSN: 0935-6304
    Keywords: On-line coupled LC-GC ; nitrogen selective detection ; NPD ; carbazoles ; PANH ; personal exposure measurement ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A coupled LC-GC method for the analysis of carbazole-type PANH has been developed and evaluated. Group separation and isolation of carbazoles from interfering acridines in a complex sample matrix was accomplished by using a back-flush technique and an in situ end-capped dimethylaminopropyl silica column in the HPLC part of the system. On-line injection of the carbazole fraction into the GC column was performed with a loop-type interface utilizing concurrent solvent evaporation technique. An LOD of 1-3 pg of individual carbazole compounds was achieved by nitrogen selective detection using an NPD. The method is shown to be robust and is demonstrated by application to personal exposure measurement in an aluminum reduction plant.
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  • 75
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    Journal of High Resolution Chromatography 23 (2000), S. 138-142 
    ISSN: 0935-6304
    Keywords: Capillary electrochromatography ; nucleosides ; short-end injection ; phenyl-bonded silica ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The influence of several experimental parameters (pH, ionic strength, organic modifier content of hydro-organic buffer) upon EOF, migration time, and retention factor has been studied in CEC with a phenyl-bonded silica column on a model mixture of five nucleosides. This paper illustrates the current interest in CEC as a method of resolving complex mixtures of neutral and ionic solutes and demonstrates the potential of the short-end injection method as a means of reducing analysis time.
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  • 76
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    Journal of High Resolution Chromatography 23 (2000), S. 143-148 
    ISSN: 0935-6304
    Keywords: Analysis of anthraquinones ; capillary electrophoresis ; high-performance liquid chromatography ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The separation and determination of twelve anthraquinones, viz. anthraquinone 1, chrysphanol 2, aloe-emodin 3, alizarin 4, anthraquinone-2-carboxylic acid 5, purpurin 6, sennoside B 7, sennoside A 8, emodin 9, quinalizarin 10, rhein 11, and anthraflavic acid 12, were achieved by capillary electrophoresis (CE) and high-performance liquid chromatography (HPLC). Detection at 260 nm with a buffer solution containing 30 mM sodium borate (adjusted to pH = 10.56 with 0.05N NaOH) and acetonitrile (9 : 1) in CE or with a linear gradient elution containing 20 mM KH2PO4 with 0.05% phosphoric acid (pH = 2.91) and methanol in HPLC was found to be the most suitable approach for this separation. Contents of six components (2, 3, 7, 8, 9, 11) in crude Rhei Rhizoma extract could easily be determined within 39 min by CE or 63 min by HPLC. The effects of buffers on this separation and the validation of the two methods were studied.
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  • 77
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    Journal of High Resolution Chromatography 23 (2000), S. 156-157 
    ISSN: 0935-6304
    Keywords: Capillary gas chromatography ; trichlorophenols ; ammonia ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---No abstract
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  • 78
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    Journal of High Resolution Chromatography 23 (2000), S. 149-155 
    ISSN: 0935-6304
    Keywords: Capillary GC ; fast GC ; on-column injection ; narrow-bore column ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---In this work a fast gas chromatography set-up with on-column injection was optimized and evaluated with a model mixture of C8-C28 n-alkanes. Usual injection volumes when using narrow-bore (e. g., 0.1 mm i.d.) analytical columns are ca. 0.1 μL. The presented configuration allows introduction of 10-30-fold larger sample volumes without any distortion of peak shapes. In the set-up a normal-bore retention gap (1 m×0.32 mm i. d.) was coupled to a narrow-bore (4.8 m×0.1 mm i. d.×0.4 μm film thickness) analytical column using a low dead volume column connector. The effects of the experimental conditions such as inlet pressure, sample volume, initial injection temperature, and oven temperature on a peak focusing are discussed. H-u curves for helium and hydrogen are used to compare their suitability for high speed gas chromatography and to show the dependence of separation efficiency on the carrier gas velocity at high inlet pressures. In the fast gas chromatography system a baseline separation of C10-C28 n-alkanes was achieved in less than 3 minutes.
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  • 79
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    Journal of High Resolution Chromatography 23 (2000), S. 182-188 
    ISSN: 0935-6304
    Keywords: Comprehensive two-dimensional gas chromatography ; GC×GC ; thermal modulation ; oil analysis ; petroleum analysis ; analysis of middle-distillate oil fractions ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Comprehensive two-dimensional gas chromatography (GC×GC) is an utterly suitable separation technique for the analysis of complex samples, such as oil fractions. Once the two columns and the operating conditions are properly tuned, the technique is able to provide a detailed characterization of such materials. Some considerations applying to the tuning of a GC×GC system for a specific separation are presented and discussed. The authors present a number of different column sets and conditions which allow the separation of a non-aromatic hydrocarbon solvent, a kerosene, the light end of a crude oil, and an olefinic fraction, respectively. The highly structured GC×GC chromatograms, together with chemical knowledge about the samples, provide a much more comprehensive characterization of the samples than hitherto possible.
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  • 80
    ISSN: 0935-6304
    Keywords: Comprehensive two-dimensional gas chromatography ; thermal desorption modulator ; temperature programming ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---In comprehensive two-dimensional gas chromatography, two individual separations are coupled by means of a rotating thermal desorption modulator interface. The injection pulse introduced via the interface onto the second column should be as short as possible. Parameters affecting the modulator operation are studied. In the set-up used in this study, the temperature of the second column can be programmed independently from that of the first column. Optimization of the second-dimension separation to minimize peak broadening and maximize resolution is discussed and an elegant approach to determine second-dimension retention times using a non-constant modulation frequency is demonstrated. The high separation power of the comprehensive system is demonstrated by the analysis of technical and biota samples containing chlorinated biphenyls and toxaphene.
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  • 81
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    Journal of High Resolution Chromatography 23 (2000), S. 197-201 
    ISSN: 0935-6304
    Keywords: Multidimensional gas chromatography ; comprehensive two-dimensional gas chromatography ; GC×GC ; oxygenates ; MTBE ; reformulated gasoline ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Comprehensive two-dimensional gas chromatography (GC×GC) has been applied to the quantitation of oxygenates in reformulated gasoline. Target oxygenates were C1-C4 alcohols, tert-pentanol, methyl tert-butyl ether (MTBE), diisopropyl ether (DIPE), ethyl tert-butyl ether (ETBE), and tert-amyl methyl ether (TAME). These were separated from the gasoline matrix using a volatility-based selectivity in the first chromatographic dimension, followed by a mixed-phase polarity/shape selectivity in the second dimension. The high resolving power of this stationary phase combination completely separated all oxygenates except DIPE, ETBE, and TAME, which exhibited coelution with other nonpolar gasoline components. Oxygenates quantitation was achieved with the use of an internal standard, an FID detector, and calibration curves. Quantitation results are in good agreement with ASTM and EPA standard methods. When coupled with our previous method for BTEX and aromatics, a single GC×GC method can now quantitate MTBE, alcohols, BTEX, and aromatics in a one-hour analysis.
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  • 82
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    Journal of High Resolution Chromatography 23 (2000), S. 474-478 
    ISSN: 0935-6304
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Solid-phase extraction, on-line derivatization, and measurement by ion trap mass spectrometry (ITD-MS) were used to investigate the biological degradation of pharmaceutical residues (clofibric acid, ibuprofen, diclofenac). The results of the single steps of sample pretreatment and analytical determination are reported. MS/MS measurements were performed on an ITD-MS by selecting collision induced dissociation of the molecular ions (M+) as parent ions to defined daughter ions. A pilot sewage plant and biofilm reactors operating under oxic and anoxic conditions were run as model systems with synthetic sewage water containing 10 to 50 mg/L dissolved organic carbon (DOC) and pharmaceuticals in concentrations of 10 μg/L. Clofibric acid displayed its persistent character in all cases. The pilot sewage plant and the oxic biofilm reactor showed comparable results for diclofenac and ibuprofen, which both were partly degraded. These results can explain the occurrence of these substances in sewage effluents and in the aquatic environment. A high degree of degradation was found especially for ibuprofen in the oxic biofilm reactor, which was attributed to adaptation of the biofilm to the residue. Two metabolites of ibuprofen could be identified on the basis of their mass spectra and comparison with literature data, viz. hydroxyibuprofen and carboxyibuprofen.
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  • 83
    ISSN: 0935-6304
    Keywords: Silicone oil ; supercritical fluid chromatography (SFC) ; micropacked columns ; MALDI-TOF ; GC/MS ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---No abstract
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  • 84
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    Journal of High Resolution Chromatography 23 (2000), S. 511-514 
    ISSN: 0935-6304
    Keywords: CZE ; indirect UV detection ; metal ions ; ecological samples ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---No abstract
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  • 85
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    Journal of High Resolution Chromatography 23 (2000), S. 297-303 
    ISSN: 0935-6304
    Keywords: Sample preparation ; gas extraction techniques ; membrane-type techniques ; water analysis ; soil analysis ; gas chromatography ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---This review focuses on the role of so-called solventless methods of sample preparation in contemporary environmental analysis. The basic classification of this group of methods as well as the principal features and advantages of the techniques in current use are discussed.
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  • 86
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    Journal of High Resolution Chromatography 23 (2000), S. 253-258 
    ISSN: 0935-6304
    Keywords: Comprehensive gas chromatography ; cryogenic modulation ; semi-volatile aromatics ; thermal sweeper ; peak widths ; peak asymmetries ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The two current technologies for achieving comprehensive gas chromatography (GC×GC) - the thermal sweeper and the cryogenic modulator - are compared in an interlaboratory study using a multicomponent semi-volatile aromatic compound sample. The same column set (phases, film thickness, dimensions of columns) and conditions of oven temperature program were used. Carrier gas flow settings however were different for the data reported here. The thermal sweeper has a longer overall length due to the extra ca. 30 cm length of narrow bore tubing used for the modulator/accumulator section. Data reveal that the two methods behave in an analogous manner in respect of delivering GC×GC results, with key peak parameters of peak widths and symmetry measures showing good correlation. Retention time dissimilarity on the first dimension columns in the two systems arises from different flow rates used, however the second column retention is similar, and this is due to the resulting different elution temperatures that peaks elute on the first dimension in each system. Overall, the two approaches to GC×GC appear to produce equivalent results within the scope of the application studied. Each system does have its experimental limitations; the thermal sweeper has what may be called a ‘thick film effect’, where at high temperature it can be difficult to sufficiently trap the migrating bands in the accumulator column, and the pulsing of solutes in the cryogenic system may suffer from a ‘thick wall effect’ if a column with too thick a wall dimension is used at low oven temperature.
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  • 87
    ISSN: 0935-6304
    Keywords: Proteomics ; protein analysis ; multidimensional HPLC ; ion-exchange chromatography ; reversed phase chromatography ; comprehensive HPLC ; two-dimensional HPLC ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The interactive modes of High Performance Liquid Chromatography (HPLC) of proteins provide a platform for the construction of a multidimensional HPLC system coupled to mass spectrometry. We present a system composed of both anion and cation exchanger columns, in the first dimension, and n-octadecyl bonded 1.5 μm nonporous silica columns in the second dimension. Both columns are operated under gradient conditions. A system suitability test with standard proteins showed that the total analysis can be performed within about 20 minutes. The fractions taken from the ion exchanger column are directly analyzed within one minute on the reversed phase column at a high flow rate. Two reversed phase columns are applied and operated alternatively: while the first column performs the separation within one minute, the analytes leaving the first dimension are enriched in an on-column focusing mode on top of the second column. The sample clean-up and enrichment is performed on a novel type of restricted access cation exchanger column with internal sulfonic acid groups and external diol groups. The columns exhibit a molecular weight exclusion limit for globular proteins of about 15 kDa. Our next studies will be directed towards the analysis of proteins and peptides from extracts of fibroblasts.
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  • 88
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    Journal of High Resolution Chromatography 23 (2000), S. 343-347 
    ISSN: 0935-6304
    Keywords: SPME ; desorption ; fiber conditioning ; field sampling ; sample preparation ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No abstract
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  • 89
    ISSN: 0935-6304
    Keywords: Silver ion high-performance liquid chromatography (Ag-HPLC) ; conjugated linoleic acid (CLA) ; p-methoxyphenacyl derivatives ; single-column Ag-HPLC ; fatty acid analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---No abstract
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  • 90
    ISSN: 0935-6304
    Keywords: Artemisia palustris ; Asterothamnus centrali-asiaticus ; capillary gas liquid chromatography ; Compositae (Asteraceae) ; Heteropappus hispidus ; seed oil ; silver ion thin layer chromatography ; trans-fatty acids ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Seed oils from the Compositae plant family are known to contain a variety of unusual fatty acids. Subsequent to the recent discovery of γ-linolenic acid in Saussurea and Youngia, further Mongolian Compositae species were investigated for their seed oil fatty acid composition. A number of δ3trans-fatty acids (16 : 1δ3t, 18 : 1δ3t and 18 : 3δ3t, 9c, 12c) were found in the seed oils of Heteropappus hispidus and Asterothamnus centrali-asiaticus. The latter fatty acid, but not the trans-monoenes, was also found in one species of Artemisia. These unusual fatty acid isomers were characterized by capillary gas-liquid chromatographic (GLC) separations in combination with other chromatographic techniques (analytical thin layer chromatography, TLC and preparative argentation TLC), and infrared spectrocsopy (IR). Their identity was further confirmed by co-chromatography with other seed oils known to contain these trans-fatty acids. The fact that within the Compositae plant family there are apparently two or three distinct groups of genera containing δ3trans-fatty acids is discussed.
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  • 91
    ISSN: 0935-6304
    Keywords: 2H/1H ratio analysis ; HRGC-P-IRMS ; stable isotopes ; benzaldehyde ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Isotope ratio monitoring gas chromatography-mass spectrometry of the 2H/1H ratio by pyrolysis isotope ratio mass spectrometry (P-IRMS) was used to analyze benzaldehyde originating from various sources. Based on the δ2HSMOW value of an authentic reference sample determined with an elemental analyzer (EA), the range of reproducibility and linearity was checked. Correct (EA related) and reproducible data were obtained for sample amounts 〉0.6 μg benzaldehyde (on column). In another series of experiments, the influence of sample preparation, i. e. simultaneous distillation-extraction (SDE) was found to be negligible. The following ranges of δ2HSMOW values were determined for benzaldehyde using five types of samples, i. e. (i) synthetic (δ2HSMOW -78 to -85‰, ex benzal chloride; +420 to +668‰, ex toluene) and ‘natural’ (including ‘ex-cassia’) references (δ2HSMOW -83 to -144‰); (ii) bitter almond oils (δ2HSMOW -113 to -148‰); (iii) fruits (δ2HSMOW -111 to -146‰); (iv) kernels (δ2HSMOW -115 to -188‰); and (v) leaves (δ2HSMOW -165 to -189‰).
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  • 92
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    Journal of High Resolution Chromatography 23 (2000), S. 373-378 
    ISSN: 0935-6304
    Keywords: Open tubular columns ; capillary electrochromatography ; column efficiency ; injected volume ; applied voltage ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of some instrumental parameters on column efficiency in open tubular capillary electrochromatography (OTCEC) has been evaluated. First, it was investigated whether band broadening due to the sample injection process is within a tolerable range when an open tubular column (OTC) of about 10 μm i. d. is used. As a result of the small injection profile factor (K2 = 1.3), injected volumes must be sufficiently small (less than 10 pL) to avoid a significant efficiency loss (〉5%) when hydrodynamic injection by siphoning is employed. Secondly, the kinetic performance of OTCs in a CEC system was estimated from the variation of the reduced plate height (h) with the reduced linear velocity (ν) which was controlled by the voltage applied. Reasonable agreement was obtained between the theoretical h versus ν curve and the experimental values for a group of polycyclic aromatic hydrocarbons used as test compounds. Values of 0.25 for minimum h at an optimum ν of 16 are estimated, which permit separations with around 400,000 plates per meter to be obtained in less than 5 min. Finally, the possibility of estimating the diffusion coefficients of the solutes in the mobile phase from the plot of the height of a theoretical plate versus electroosmotic flow velocity is shown.
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  • 93
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    Journal of High Resolution Chromatography 23 (2000), S. 413-429 
    ISSN: 0935-6304
    Keywords: Capillary electrophoresis ; enantiomer separation ; chiral drugs ; TM-γ-cyclodextrin ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---High-throughput screening is a promising new approach in analytical chemistry. Within the framework of an extended screening program (The German-Chinese Drug Screening Program), the enantioseparation of 86 drugs was investigated by capillary zone electrophoresis in the presence of the chiral solvating agent (CSA) octakis-(2,3,6-tri-O-methyl)-γ-cyclodextrin (TM-γ-CD). By this means, 15 drugs could be separated into enantiomeric pairs. Approximate measures for the degree of interaction (migration retardation factor, Rm) and for the degree of enantiomer recognition (migration separation factors, αm) revealed intriguing patterns that were compared with those found for native γ-cyclodextrin (γ-CD). Although there is a distinct influence of the analyte structure on the electrophoretic data, interpretation remains difficult. Most remarkably, permethylation of γ-CD leads neither to a higher affinity nor to better chiral recognition, in contrast to the findings with α-CD.
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    Journal of High Resolution Chromatography 23 (2000), S. 445-448 
    ISSN: 0935-6304
    Keywords: O-Aryl,O-(1-methylthioethylideneamino)phosphates ; retention prediction ; quantitative structure-retention relationship (QSRR) ; reversed-phase HPLC ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Using factor analysis and stepwise linear regression methods, two parameters - CMR and ECCR - were selected from eight solute-related structure parameters as the most retention-influencing parameters. The relationships between the retention data (k ´) and the two structure parameters were established for 13 O-aryl,O-(1-methylthioethylideneamino)phosphate compounds under a wide range of experimental conditions. The retention data (k ´) of another seven compounds with similar structures were predicted using these QSRR equations. Good agreement was obtained between the experimental k ´ values and predicted ones.
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    Journal of High Resolution Chromatography 23 (2000), S. 525-530 
    ISSN: 0935-6304
    Keywords: Packed capillary liquid chromatography ; temperature programming ; Fourier-transform infrared spectroscopy ; polymer additives ; pneumatic nebulization ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Temperature-programmed packed capillary liquid chromatography has been coupled off-line to Fourier-transform infrared spectroscopy, utilizing a commercially available interface with a pneumatic nebulizer rebuilt to handle low flow rates at elevated temperatures. The modified interface showed excellent performance with regard to non-aqueous reversed phase separations of polymer additives, resulting in constructed Gram-Schmidt chromatograms comparable to chromatograms obtained using UV detection. The spray of the in-house constructed nebulizer was not influenced by temperature changes of the column effluent, and hence temperature-programmed gradient separations could be used successfully. The relative standard deviation of peak height was 4.4% (n = 5) and the mass limit of detection was determined to be about 40 ng, using a polymer antioxidant as model compound. The present instrumental coupling has been used for characterization of the antioxidant Irgafos P-EPQ.
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  • 96
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    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 23 (2000), S. 531-538 
    ISSN: 0935-6304
    Keywords: Capillary isotachophoresis ; capillary electrophoresis ; column-coupling electrophoresis ; enantiomers ; chiral ; amino acids ; tryptophan ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The ability of capillary zone electrophoresis (CZE) coupled on-line with capillary isotachophoresis (ITP) sample pretreatment in the column-coupling capillary electrophoresis equipment to separate trace enantiomers present in samples of complex ionic matrices and enantiomers present in their mixtures at significantly differing concentrations has been studied. Enantiomers of 2,4-dinitrophenyl labeled norleucine (DNP-Nleu) and tryptophan enantiomers were employed as model analytes in this work while urine and mixtures of tryptophan enantiomers of differing concentrations served as model samples. Experiments performed with urine samples spiked with the DNP-Nleu racemate at sub-μmol/L concentrations demonstrated excellent sample pretreatment capabilities of ITP (concentration of the analytes, in-column and post-column sample clean up) when coupled on-line with chiral CZE separations. In the CZE separations of enantiomers present in the samples at trace concentrations the sample pretreatment could be performed in both achiral and chiral ITP electrolyte systems. The use of a chiral electrolyte system was found to be essential in the ITP pretreatment of the samples containing the enantiomers at very differing concentrations. For example, a 2×10-7 mol/L concentration of L-tryptophan could be detected in the CZE separation stage of the ITP-CZE combination in samples containing about a 104 excess of D-tryptophan only when the ITP pretreatment was carried out in the electrolyte system providing the resolution of enantiomers (α-cyclodextrin served for this purpose in the present work). A post-column ITP sample clean up was found effective in enhancing the destacking rate of the trace enantiomer in the CZE stage when the migration configuration of the enantiomers was less favorable (the trace constituent migrating behind the major enantiomer).
    Additional Material: 8 Ill.
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  • 97
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    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 23 (2000), S. 554-560 
    ISSN: 0935-6304
    Keywords: Comprehensive gas chromatography ; multidimensional gas chromatography ; essential oils ; coupled column analysis ; high resolution analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---The essential oils from French lavender (Lavandula angustifolia) and tea tree (Melaleuca alternifolia) were separated by the two-dimensional GC technique of comprehensive gas chromatography. A coupled column combination of non-polar (5% phenyl equivalent) and polyethylene glycol phase columns was used to provide the desired resolution performance. By using a range of known standards, some of the peaks in lavender oil can be assigned. Some of these also occur in tea tree oil; however, from our knowledge of the major constituents in this oil and their relative retention behaviour, most of the major peaks may be tentatively assigned within the 2-dimensional separation space. There appear to be elution patterns within the 2-D space which should be useful in correlating retention with chemical and structural properties of the components, although this will require further evaluation. A range of coeluting peaks, which may not be so readily separated by using a single column capillary GC analysis, are resolved in the experiment described.
    Additional Material: 10 Ill.
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  • 98
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    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 23 (2000), S. 619-627 
    ISSN: 0935-6304
    Keywords: Enantiomer separation ; mixed chiral selectors ; modified cyclodextrins ; gas chromatography ; PCB ; o,p´-DDD ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Columns containing different types of cyclodextrin derivatives have been evaluated for chiral gas chromatographic separation of atropisomeric PCBs, o,p´-DDT and o,p´-DDD. Separation was attempted on columns containing mixed chiral selectors, and the performance of two closely related selectors was also examined. The cyclodextrins were: permethylated-β-CD (PM-β-CD), heptakis(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl)-β-CD (2,3-M-6-TBDMS-β-CD), heptakis(2,3-di-O-methyl-6-O-tert-hexyldimethylsilyl)-β-CD (2,3-M-6-THDMS-β-CD), and heptakis(2,3-di-O-ethyl-6-O-tert-hexyldimethylsilyl)-β-cyclodextrin (2,3-E-6-THDMS-β-CD). The cyclodextrins were dissolved in OV-1701 or in a dimethylsiloxane/silarylene copolymer containing 5% phenyl in the backbone. The application of mixed chiral selectors led to improved separations, however; at most eleven PCB congeners were separated on a single column. Chiral resolution of o,p´-DDD was achieved. The use of a dimethylsiloxane/silarylene copolymer as a matrix for the cyclodextrins is a promising approach. With such a matrix, blocking of the CD cavities by silicone substituent groups can be avoided, and a reasonable CD solubility can be provided. The selectivity of heptakis(2,3-di-O-ethyl-6-O-tert-hexyldimethylsilyl)-β-CD and heptakis(2,3-di-O-methyl-6-O-tert-hexyldimethylsilyl)-β-CD was quite different, the former selector could separate four congeners, while the latter separated ten congeners.
    Additional Material: 5 Ill.
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  • 99
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    Electronic Resource
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 23 (2000), S. 576-582 
    ISSN: 0935-6304
    Keywords: Gas chromatography-mass spectrometry ; amino acid enantiomers ; D-amino acids ; physiological fluids ; mammals ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---Quantities of D-amino acids were determined in body fluids (urine, blood plasma and blood serum, milk) of mammals (hamster, horse, bovine, sheep, pig, and dog). Amino acids were isolated using a cation exchanger and converted into their N(O)-pentafluoropropionyl (or trifluoroacetyl) amino acid 2-propyl esters. Enantiomers were separated and quantified on a Chirasil-L-Val capillary column with mass spectrometric detection using selected ion monitoring. D-Enantiomers of most protein L-amino acids were detected. Largest absolute and relative amounts in most cases were determined for D-Ser and D-Ala in urine. Stereoisomers of 2,6-diaminopimelic acid were also measured in bovine, ovine, and porcine urine. Since D-amino acids were detected in all representative classes of the major orders of Mammalia, namely Artiodactyla, Perissodactyla, Rodentia, and Carnivora, and taking reports in the literature into account, it is postulated that D-amino acids occur in all mammals.
    Additional Material: 5 Ill.
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  • 100
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    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 23 (2000), S. 595-599 
    ISSN: 0935-6304
    Keywords: GC-MS/MS ; PCDDs ; PCDFs ; human tissue ; fish tissue ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ---This paper outlines the possibilities of selectivity and sensitivity enhancement in measuring PCDD/F congeners using an ion trap GC-MS/MS. The pressure of the collision gas and the collision energy were optimized. The modified GC-MS/MS method was applied to the determination of PCDDs and PCDFs in human and fish tissues. Limits of quantification were about 1 pg/g of fat for all seventeen 2378 PCDD/Fs tested (starting amount of fat, 2 g).
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