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  • 2020-2024
  • 1990-1994  (2,154)
  • 1920-1924
  • 1905-1909
  • 1991  (2,154)
  • Analytical Chemistry and Spectroscopy  (1,511)
  • Chemical Engineering  (643)
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  • 2020-2024
  • 1990-1994  (2,154)
  • 1920-1924
  • 1905-1909
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  • 1
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 31 (1991), S. 110-115 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A new crystallization kinetic equation has been derived considering the decrease in growth rate. The average linear growth rate of spherulite was assumed to be proportional to the m-th order of the uncrystallized fraction of the crystallizing material. A modified Avrami equation, 1 - Vc = exp[-Kf(t)n], was used where f(t) is the integral of the growth function, (1 - Vc)m. The validity of the equation was tested by analyzing the isothermal crystallization kinetic data of poly(ethylene terephthalate) from the melt using differential scanning calorimetry.
    Additional Material: 8 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 31 (1991), S. 99-103 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Process changes aimed at improving printer engine performance must take into consideration not only the process variables (such as nip temperature and pressure and process time to), but also the melt rheological variables (such as the characteristic time scale of the toner Tc). The melt rheology relevant to the electrophotographic toner fusing process is discussed. One criterion for toner quality can be conveniently measured through the Deborah number De, which is the ratio of Tc to to. Modification of the melt rheology by matrix polymer composition and carbon black size and concentration has previously been explored. Here, the melt rheology of toners with a range of gel content was studied using a step shear test. The coupled relaxation model was employed to fit the stress relaxation data. The viscoelastic properties were calculated from the melt data with this model. These properties were then used to estimate the strain deformation of the toner as it passes through the nip with arbitrary residence time and nip pressure as a function of gel content. This method can be used to match the toner melt properties with the processing conditions.
    Additional Material: 3 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 31 (1991) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 31 (1991), S. 125-139 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The unified numerical simulation of the filling/postfilling stages of the injection-molding process described in Part I is compared in the present paper with experimental results obtained with instrumented test molds. Flush-mounted pressure traces in the delivery system as well as in the cavity are favorably compared with corresponding predictions for both an amorphous and a semicrystalline polymer. It is demonstrated that the present unified formulation is well suited to handle complicated molds where compressibility effects can become important even during the filling stage, as portions of the cavity fill and undergo a packing behavior even when other regions of the cavity are still only partially filled.
    Additional Material: 19 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 31 (1991), S. 116-124 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: This study employs a unified theoretical model to simulate the filling and postfilling stages of the injection-molding process. Implementation of such a model is based on a hybrid finite-element/finite-difference numerical solution of the generalized Hele-Shaw flow of a compressible viscous fluid under nonisothermal conditions. The shear viscosity of the polymeric material is represented by a Cross model for the shear-rate dependence and a WLF-type functional form for the temperature and pressure dependence, whereas the specific volume is modeled in terms of a double-domain Tait equation. The analysis also handles variable specific heat and thermal conductivity of the polymer as a function of temperature. Complex thin parts of variable thickness can be modeled and discretized by flat, triangular finite elements which may have arbitrary orientation in three-dimensional space, whereas runners and possible round pins or bosses in the part are represented as one-dimensional circular-tube elements. A control-volume scheme is employed that leads to automatic melt-front advancement during the cavity-filling stage.
    Additional Material: 4 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 31 (1991), S. 140-144 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The characteristic sigmoid compressive stress-strain relationships of sponges and their layered arrays are described by two kinds of mathematical models having three experimentally determined parameters. Since sponge compression is not accompanied by a significant cross-sectional area expansion, it was assumed that the stress in a multilayered array is the same in each layer. This enables prediction of the array's stress-strain relationship from the parameters of the individual layers and their known thickness. The applicability of the method is demonstrated with experimental data of two kinds of double-layered arrays of polyurethane sponges. It is shown that the arrays' compressive behavior can be satisfactorily predicted irrespective of the mathematical form of the model and whether the strain is expressed as engineering strain or Hencky's.
    Additional Material: 8 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 31 (1991), S. 145-152 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The gapwise density distributions of the injection molded specimens of two engineering thermoplastics, i.e., poly(phenylene ether) and poly(ether imide), were characterized employing the density gradient column technique. The samples were molded using a 40t Van Dorn injection molding machine. The effects of the thermal history on the density distribution of unconstrained quenched specimens were also investigated. In addition, various material properties, such as pressure-volume-temperature, isothermal contraction, and pressure induced densification behavior were characterized, for the two resins employed in this study. The moldings of the two resins exhibited different trends in their density distributions. These findings were explained in terms of the competing effects of cooling rate and the pressure history experienced by the engineering plastic resins during the molding cycle. The data collected were also used as input to mathematical modeling of density distributions in injection molded articles, which is reported in Part II of this article.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 31 (1991), S. 191-196 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The problem of steady solidification of a power law fluid flowing in a round tube was solved numerically. The fluid considered was a polymer with temperature dependent viscosity. The mathematical solution was obtained by using an implicit finite difference method. Results are presented to show the effects of the Peclet number, Nahme number, and the power law index on the profiles of the frozen layer. Melt temperature profiles at different axial locations are also presented.
    Additional Material: 6 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 31 (1991) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 31 (1991), S. 197-203 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Extensional flow of a bicomponent two-layer slot cast coextrusion process has been studied. A Newtonian and an upper-convected Maxwell fluid were considered to be the two layers, respectively, and the two-layer flow was assumed to be steady and isothermal. This choice was made as a simple model for a system which consists of two distinctly different fluids in terms of their extensional behaviors. Present study considered only the draw-down region where the film thickness changes slowly with the distance from the die exit. For this region, asymptotic solutions could be obtained for two limiting cases in which the elasticity effect of the Maxwell fluid layer is small and the applied tension at the take-off is large, respectively. When the elasticity effect is small, the melt thickness and the velocity profiles are exponential as in the case of a Newtonian single-layer flow. When the applied tension is large, on the other hand, the velocity profile is shown to be near linear. Furthermore, the viscoelasticity effect of the Maxwell fluid layer becomes so dominant that it dictates the mechanics of the coextrusion flow even when its flow rate and shear viscosity may be much smaller than those of the Newtonian layer.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 11
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 31 (1991) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
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  • 12
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 31 (1991), S. 353-364 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Optimal open loop control strategies are developed for a semibatch free radical copolymerization of methyl methacrylate and vinyl acetate using the multiobjective dynamic optimization method. A detailed kinetic model is validated through experimentation and used for the design of optimal controls. Both monomer feed rate and reactor temperature are varied to produce the copolymer of desired composition and molecular weight. The open loop control policies are implemented in a process control computer and tested on an experimental stirred tank polymerization system. Excellent agreement between the model predictions and the experimental data have been obtained.
    Additional Material: 9 Ill.
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  • 13
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 31 (1991), S. 333-352 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The dynamic behavior of two continuous stirred tank reactors in series has been investigated for free radical solution polymerization of styrene with a binary mixture of two initiators having different thermal decomposition activities. For a wide range of initiator feed composition, both reactors exhibit quite complex nonlinear steady state and transient behavior. When the reactor residence time is used as a bifurcation parameter, the second reactor can have up to five steady states. For certain range of reactor operating conditions, bifurcations to various types of periodic solutions have been observed, such as Hopf bifurcation, isolas, period doubling, period-doubling cascade, and homoclinics. The effects of other reactor variables, such as total initiator concentration, coolant temperature, and reactor volume ratio on the reactor dynamics, are illustrated to show the complex dynamic behavior of the two-reactor system catalyzed by a mixture of t-butyl perbenzoate and benzoyl peroxide.
    Additional Material: 15 Ill.
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  • 14
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 31 (1991), S. 365-375 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: This paper presents the development of a novel in-line extrusion rheometer based on the flow of polymer through a wedge (vertically tapered slit). This rheometer is suitable for measuring changes in rheological properties on-line during reactive extrusion, because it can be used to estimate the viscosity for a range of shear rates without the need to change the polymer flow rate (i.e., extruder throughput). Equations have been developed to estimate the parameters of the power-law equation, used to describe the viscosity-shear rate relationship, from measurements of pressure drops along the wedge. An experimental in-line wedge rheometer has been built and used to measure the viscosity for a series of polypropylenes prepared via reactive extrusion. Viscosity measurements from the experimental in-line wedge rheometer are compared with measurements from a capillary rheometer. Good agreement is found between the capillary and wedge rheometer measurements.
    Additional Material: 6 Ill.
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  • 15
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 31 (1991), S. 391-391 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
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  • 16
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 31 (1991) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
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  • 17
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 31 (1991), S. 1-5 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Orbital space structures are required to be lightweight, have high specific stiffness, have near-zero coefficient of thermal expansion, exhibit low outgassing, and be cost-effective. Graphite-reinforced thermoplastics have the potential to satisfy the criteria noted. However, prior to committing the materials to specific projects, technology demonstration and risk reduction is necessary. In order to demonstrate the application of fiber-reinforced thermoplastic composites for truss structure applications, a graphite-reinforced poly(ether ether ketone) (PEEK) composite tetrahedron truss array was designed and manufactured. The resulting structure clearly demonstrated that fiber-reinforced thermoplastic composites are a viable alternative to epoxy composites for orbital structures.
    Additional Material: 7 Ill.
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  • 18
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The 371°C (700°F) properties of Celion 6000/N-phenylnadimide modified PMR-15 polyimide composites were investigated to determine the feasibility of using these materials at a 371°C (700°F) service temperature. The processing characteristics and physical and mechanical properties of the composite systems are presented. The results of the 371°C thermooxidative stability study suggest that the composite materials can be considered for short-term (at least 100 hours) application at 371°C.
    Additional Material: 8 Ill.
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  • 19
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 31 (1991), S. 6-13 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A series of graphite fiber/PMR-15 polyimide composites, isothermally aged at 316°C in flowing air (100 cc/min) for time periods up to 2000 h, were investigated for mechanical property changes, fiber/resin interface changes, overall dimensional changes, and weight loss. The mechanism of the degradation process is suggested based on shear and flexural property measurements at room temperature and 316°C, optical micrographs of composite cross sections, and SEM analysis of fractured surfaces. The fiber materials investigated in composite form were Celion 6000 unsized and epoxy sized. G40-700 unsized and epoxy sized, and T40R and IM6 both unsized.
    Additional Material: 6 Ill.
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  • 20
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 31 (1991), S. 28-33 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A high performance semi-interpenetrating polymer network (semi-IPN) has been synthesized from Thermid-600 and LARC-TPI. Notable improvements in resin fracture toughness and graphite fiber reinforced composite microcracking resistance over the unmodified Thermid-600 neat resin and composite have been realized. The chemistry, processing, physical and mechanical properties, and phase morphology of the neat resin and composite reinforced with graphite fibers are presented.
    Additional Material: 12 Ill.
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  • 21
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 31 (1991), S. 20-27 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Recently, we reported on the interpenetrating polyimide network (IPN) approach to develop tough and microcracking resistant high temperature matrix resins for use in aircraft/aerospace structural components. One such polymer developed is designated LaRC-RP40. This new simultaneous semi-IPN was prepared from easy-to-process but brittle crosslinking PMR-15 and tough but difficult-to-process linear NR-150B2. Significantly improved toughness, microcracking resistance, and glass transition temperature over PMR-15 were realized from the combination. These property improvements were achieved without compromising ease of processing, high temperature mechanical performance, and cost effectiveness compared to PMR-15. These results encouraged us to further explore this approach for the development of a wider range of polymers of basic technological and economic interest. In the present work, we combine crosslinking PMR-15 and linear LaRC-TPI to provide a new sequential semi-2-IPN called LaRC-RP41. The physical and mechanical properties of the neat resin and composite reinforced with graphite fibers are presented. The phase morphology and phase stability of the neat resin and composite studied by various techniques are also discussed.
    Additional Material: 15 Ill.
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  • 22
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 31 (1991), S. 40-46 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The mechanical properties of three dimensional stitched composites were compared against those of the traditional two dimensional laminates. An attempt was made to correlate the change in properties to the change in the third directional fiber density. Tests conducted were the impact, three-point bending, damage tolerance, end notched flexure, and bending fatigue test. The results of these tests show that the third directional fibers can effectively inhibit delamination by increasing the interlaminar shear strength. Three dimensional composites also possess better damage tolerance, fracture toughness, and fatigue life. However, a high stitching density can degrade the in-plane properties of the composites.
    Additional Material: 5 Ill.
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  • 23
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 31 (1991), S. 34-39 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Research has been conducted to investigate the water absorption in carbon fiber reinforced poly(ether ether ketone) (PEEK/CF) and poly(phenylene sulfide) composites (PPS/CF). Effect of humidity and temperature on tensile, flexural, and impact strength of these composites were also studied. Results indicated that the water absorbed in PPS/CF and PEEK/CF are 0.059 %wt, 0.130 %wt, 0.138 %wt, and 0.153 %wt at 80°C. 75 %RH and 85 %RH, respectively. The diffusion process is a classical Fickian diffusion in the temperature range investigated. The activation energies of diffusion are 667 cal/g-mole (for PPS/CF) and 8934 cal/g-mole (for PEEK/CF) at 80°C and 75 %RH. The retention of mechanical properties of these composites is very good under hot-wet conditions. These composite materials can be served as high performance materials even in the hostile environment. PEEK/CF composites shows excellent mechanical properties retention even at 80°C, 75 %RH, and 85 %RH.
    Additional Material: 16 Ill.
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  • 24
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 31 (1991), S. 47-55 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A feasibility study on the use of vibration spectrum analysis as a tool for nondestructive evaluation (NDE) of polymer composites was conducted. Material integrity of polymer composite samples was determined from the vibrational measurements by analyzing the resonant frequency and damping information. A number of important “states” in the composites tested could be characterized by this analysis. The vibration tehnique was found to be sensitive to physical flawing (fiber breakage, delamination, and matrix cracking). Vibrational NDE has many potential advantages that make it very attractive for composite applications. These include the ability to make global measurements of large structures in real-time, no geometry restrictions, and high sensitivity to a wide variety of damage states.
    Additional Material: 14 Ill.
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  • 25
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 31 (1991), S. 56-60 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Resin transfer molding (RTM) of advanced fiber architecture materials promises to be a cost effective process for obtaining composite parts with exceptional strength. However there are a larger number of material processing parameters that must be observed, known, and/or controlled during the resin transfer molding process. These include the viscosity both during impregnation and cure. In-situ sensors which can observe these processing properties within the RTM tool during the fabrication process are essential. This paper will discuss recent work on the use of frequency dependent electromagnetic sensing (FDMS) techniques to monitor these properties in the RTM tool. Our objective is to use these sensing techniques to address problems of RTM scaleup for large complex parts and to develop a closed loop, intelligent, sensor controlled RTM fabrication process.
    Additional Material: 9 Ill.
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  • 26
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Biomedical Chromatography 5 (1991) 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Type of Medium: Electronic Resource
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  • 27
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Biomedical Chromatography 5 (1991), S. 128-132 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Many drugs are recemic and therefore much effort has to be devoted towards the stereoselective synthesis of the most effective or less harmful component of a racemic mixture. High performance liquid chromatography will play an important role in the clinical analysis of racemic drugs in anticipation of regulations that are currently being discussed and are expected to be enforced by the end of this decade. In this review a number of methods for chiral resolution are outlined. These include the formation of diastereoisomers and the use of chiral stationary phases or chiral mobile phase additives.
    Additional Material: 3 Ill.
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  • 28
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    Electronic Resource
    New York, NY : Wiley-Blackwell
    Biomedical Chromatography 5 (1991), S. 141-141 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Type of Medium: Electronic Resource
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  • 29
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Biomedical Chromatography 5 (1991), S. 161-164 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Medium- and long-chain 3-hydroxymonocarboxylic acids represent intermediates in the β-oxidation of fatty acids: they accumulate in the plasma of patients with an inherited deficiency of long-chain 3-hydroxyacylcoenzyme A dehydrogenase. 3-Hydroxy acids with chain lengths varying from 6 to 16 were synthesized by a Reformatzky reaction. Capillary gas chromatography of the pertrimethylsilyl derivatives was performed on a CP-Sil 19 CB column, coupled to a quadrupole mass spectrometer in the electron impact mode. Calculation of the retention indices showed that the separation of the 3-hydroxy acids from the homologous straight-chain fatty acids may be troublesome, stressing the need for mass spectrometric identification.
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  • 30
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    Biomedical Chromatography 5 (1991), S. 153-160 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A new method is described for the analysis of vitamin D and its metabolites utilizing thermospray (TSP) mass spectrometry as an on-line detector for high performance liquid chromatogrpahy. Ionization conditions were optimized for use with isocratic reversed phase chromatography. TSP mass spectrometry was employed in series with a UV absorbance detector to facilitate comparisons between the two methods of detection. Positive ion TSP mass spectra were recorded for vitamin D2, vitamin D3, 25-hydroxyvitamin D3 (25(OH)D3), 1,25-dihydroxyvitamin D3 (1,25(OH)2D3) and 24,25-dihydroxyvitamin D3 (24,25(OH)2D3). The spectra contained protonated molecular ions, ammonium adduct ions and fragment ions due to the loss of one or more molecules of water. A comparison of quantitative precision was made by determining UV absorbance and TSP standard curves for vitamin D3 using two different methods: (1) External standard method with post-column (post UV detector) addition of ammonium acetate. (2) As (1) but using the method of internal standards with a closely eluting internal standard (vitamin D2). In each case the quantitative precision (correlation coefficient) for UV absorbance detection was superior owing to intrinsic instability of the TSP ion beam. A stable isotopically labelled internal standard was employed in the development of an assay for 1,25(OH)2D3. The assay was used to quantify in vitro enzymic conversion of 25(OH)D3 to 1,25(OH)2D3 in guinea pig and sheep renal mitochondrial incubations. TSP LC/MS was also applied to analysis of an extract of human blood plasma in which D3 and each of its principal metabolites were identified in a single analysis.
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  • 31
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    Biomedical Chromatography 5 (1991), S. 113-121 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Chromatography has played a pivotal role in the advances made during the last 30 years in our knowledge of inborn errors of metabolism. This review discusses the application of some of these techniques to the analysis of organic acids and acylcarnitines. The separation of organic acids needed a comprehensive approach that would permit all of the many organic acids present in urine or other complex mixtures to be extracted, analysed and identified in a single run. This required analytical methods of great resolving power, wide linear range and universal detectors such as gas chromatography (GC), or GC coupled with mass spectrometry. Sample preparation was another problem that has been tackled by a variety of approaches. Organic solvents have been employed widely for the extraction of organic acids from physiological fluids. Unfortunately, recoveries of the different organic acids by this method are sometimes less than quantitative and variable depending on the compound. Other methods, such as the use of DEAE-Sephadex columns, have the advantage of resulting in close to 100% recoveries, but are more tedious. Liquid partition chromatography on short silicic acid columns has also been recommended as a useful clean-up step prior to GC, permitting both the identification and quantitation of organic acids in urine, plasma or amniotic fluid. Although many derivatization procedures have been used to prepare organic acids for gas chromatography, the most common is trimethylsilylation. Oxo acids are usually reacted with one of several commonly used reagents to form oximes. GC analysis of organic acids was initially done using packed columns with methylsilicone-based, non-polar stationary phases. In recent years most laboratories have switched to the commercially available, bonded-phase capillary columns. Some authors have recommended the use of two columns of slightly differing polarities to improve the reliability of identification without mass spectrometry. Carnitine and acylcarnitines are substances whose measurement may yield useful diagnostic information about inborn errors and about the basic biochemical mechanisms of disease. While free carnitine is usually measured by a radioenzymatic assay, the separation of acylcarnitines requires paper chromatography or high performance liquid chromatography. The identification of various acylcarnitines following separation has been accomplished by mass spectrometric methods. Another technique relies on gas chromatographic identification of the acyl groups liberated following alkaline hydrolysis. Recently, liquid chromatography/mass spectrometry has also been utilized to separate and identify the various acylcarnitines present in urine and other biological samples.
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  • 32
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    Biomedical Chromatography 5 (1991), S. 180-183 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A sensitive and selective, reasonably fast method for the determination of glucose content has been developed. A glucose oxidase immobilized column was coupled to a small-size anion exchange column/borate buffer chromatograph. The hydrogen peroxide produced in the enzyme reaction was detected directly by an amperometric detector using a platinum working electrode. The detection limit was 0.03 ppm (1.5 × 10-7 M, 3 pmol/injection). The linear dynamic range was three orders of magnitude at least. The system was stable and reproducible both in short-and long-term operation. The proposed method is suitable for analysis of complicated matrices of biological samples because of its good selectivity and sensitivity.
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  • 33
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    New York, NY : Wiley-Blackwell
    Biomedical Chromatography 5 (1991) 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
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  • 34
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    Biomedical Chromatography 5 (1991), S. 198-201 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Plasma B-6 vitamer and plasma and urinary 4-pyridoxic acid concentrations of 21 young white women, 21-27 years, having radiomonitored pyridoxal 5′-phosphate and coenzyme stimulation of erythrocyte alanine amino-transferase activities indicative of adequate vitamin B-6 status were determined in an effort to establish normal ranges for plasma B-6 vitamers. B-6 vitamers and 4-pyridoxic acid were quantitated using reversed phase high performance liquid chromatography with fluorometric and ultraviolet detection. Pyridoxal phosphate values obtained by radioenzymatic and chromatographic, fluorometric and ultraviolet, assays were highly correlated as were pyridoxine phosphate values determined using both detectors. The B-6 vitamer and 4-pyridoxic acid values of these subjects should be of use in the establishment of normal ranges of these congeners in women.
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  • 35
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: We have compared anion exchange chromatography on APS-Hypersil (4.6 × 100 mm) eluted with a phosphate gradient with reversed phase chromatography on ODS-Hypersil (4.6 × 100 mm) in the presence of either tetrabutylammonium (TBA) or triethylammonium (TEA) ions with a methanol gradient. The systems have been compared both for ease of operation and for their resolving power with standard mixtures and acid extracts of both normal red cells (RBC) and ischaemic tissues. The two chromatographic modes exhibited similar separating efficiencies for standard mixtures of nucleotides but retention times were most stable using reversed phase liquid chromatography (RPLC) with TEA. Anion exchange columns slowly lost ion exchange capacity but selectivity was unchanged. RPLC in the presence of TBA gave reproducibile capacity factors only when operated isocratically due to irreversible changes to the silica surface. For RBCs the RPLC with TEA and anion exchange sysems resolved 17 and 15 peaks, respectively, and for the ischaemic samples 22 and 14 peaks, respectively. However, nucleosides and bases were also resolved by the ODS column causing chromatographic crowding and uncertain peak identification.
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  • 36
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    Biomedical Chromatography 5 (1991), S. 229-230 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The effect of peroxidizing herbicides on the liver porphyrin content of experimental animals was examined. Mice treated with the herbicide oxadiazon accumulated uroporphyrin and protoporphyrin in the liver. Fomesafen-treated mice accumulated uroporphyrin and heptacarboxylic porphyrin.
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  • 37
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    Biomedical Chromatography 5 (1991), S. 235-239 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The measurement of the nucleoside deaminases - cytidine deaminase, guanosine deaminase and adenosine deaminase - by reversed phase high performance liquid chromatography is reviewed. The clinical value of assaying the enzyme activity is discussed for each of these enzymes. Both cytidine deaminase and adenosine deaminase measurements have proven clinical value, although the use of the assay of cytidine deaminase in the diagnosis of pre-eclampsia is probably not helpful.
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  • 38
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The optical purity of scopolamine derived from Datura sanguinea was determined using coupled column chromatography. A C18 column was used to separate scopolamine from the additional alkaloids and other biological material present in the vegetal extract. The C18 column was coupled through a six-port switching valve to two β-cyclodextrin columns in series which were used to resolve the scopolamine enantiomers. A single acetylated β-cyclodextrin column gives equivalent results to the native cyclodextrin columns because of slightly higher enantioselectivity for scopolamine. A multistep extraction procedure is used to isolate scopolamine from the vegetal material. 4-6% of the scopolamine in the final extract was found to be the d enantiomer. Sample extracts as well as commercial scopolamine hydrobromide were treated under various conditions commonly encountered during typical commercial extraction procedures and analyzed in order to determine if the d enantiomer was present in the original material or if it was produced during the extraction process and, if so, determine which step and conditions contribute to acemization. Both the salt and the extract were found to be susceptible to racemization under basic conditions (≥pH 9) although the extract appeared to be more susceptible than the salt. Tropic acid formed from the hydrolysis of scopolamine seemed to be completely racemized even though the remaining scopolamine was only partially racemized. Within experimental error, no d enantiomer was found in the original fresh plant material.
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  • 39
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Racemic phenylpropanolamine was resolved on a high performance liquid chromatographic (HPLC) chiral stationary phase (CSP) as the 3,5-dinitrophenyl ureide derivative. The CSP was prepared by a simple in situ procedure in which (R)-(1-naphthyl)ethyl isocyanate was bound to aminopropyl silanized silica through a urea linkage. The enantiomeric ureides were prepared by a room-temperature, 60-second procedure, accomplishing simultaneous extraction and derivatization and utilizing achiral 3,5-dinitrophenyl isocyanate as reagent. Baseline resolution was readily achieved under normal phase conditions, with a separation factor (α) of 1.16 and a resolution factor (Rs) of 2.2. Elution was complete within 10 min. A limit of detection, by UV at 235 nm, of 250 pg per isomer was established. Feasibility of the procedure for plasma determinations was demonstrated by assay of samples from a canine subject.
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  • 40
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    Biomedical Chromatography 5 (1991), S. 47-52 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Peroxyoxalate chemiluminescence may be used for sensitive postcolumn detection of phenothiazine analytes separated by high performance liquid chromatography with appropriate optimization of measurement conditions such as solvent, pH and oxalate ester. Detectability of fluorescent analytes by chemical excitation varies greatly, but analytes with low oxidation potentials are generally more readily detected at low levels, as demonstrated for phenothiazines, an important class of fluorescent drugs. Some improvement in detection limits is observed for fluphenazine when chemiluminescence detection is compared to conventional fluorescence detection. Because of the specificity of chemical excitation, fewer interferences from fluorescent impurities in a urine matrix are observed.
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  • 41
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Sensitive and specific methods for the simultaneous determination of gemfibrozil (Lopid®), a lipid-lowering agent, and its metabolites in plasma and urine are described. The methods are based on a fully automated high performance liquid chromatographic (HPLC) system with fluorescence detection. Urine samples, diluted with acetonitrile, were directly analysed by HPLC using a flow and eluent programming method. In the case of plasma, gemfibrozil and its main metabolites were extracted from acidified samples and the resulting extracts injected into the chromatographic system. The sensitivity was approximately 100 ng/mL for gemfibrozil and its four metabolites using 0.5 mL plasma or urine. An acyl glucuronide of gemfibrozil excreted in human urine after oral administration of the drug was isolated and its structure and stability examined.
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  • 42
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    Biomedical Chromatography 5 (1991), S. 83-85 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A simple and sensitive high performance liquid chromatographic method for the analysis of tocopherols (α, β, γ and δ) in serum with UV detection is described. In normal phase mode excellent separation of positional isomers (β and γ) was achieved by adjusting the proportion of isopropanol in the mobile phase. Detection limits for both β and γ were 0.62 mg/L and 0.42 and 1.2 mg/L for α and δ isomers, respectively. Measurement of all the tocopoherol structural isomers (α, β, γ and δ) in a sample required only 400 μL of serum and each run was completed in less than 22 min.
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  • 43
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    Biomedical Chromatography 5 (1991), S. 1-1 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
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  • 44
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    Biomedical Chromatography 5 (1991), S. 38-42 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A high performance liquid chromatographic (HPLC) technique for the determination of three metabolites of theophylline, 3-methylxanthine (3-MX), 1-methylxanthine (1-MX) and 1,3-dimethyluric acid (1,3-DMU) in human liver microsomes is described. The analytes were extracted from human liver microsomes with methylene chloride/isopropanol and stepwise gradient elution was employed for the resolution of peaks. The limits of quantitation were 15 ng/mL for 3-MX, 20 ng/mL for 1-MX and 20 ng/mL for 1,3-DMU. The calibration range was linear for the three metabolites and the calibration ranges were 15-250 ng/mL for 3-MX, 20-250 ng/mL for 1-MX and 250-4000 ng/mL for 1,3-DMU. The absolute recovery ranged from 63-84% for 3-MX, 65-79% for 1-MX and 77-89% for 1,3-DMU over the calibration curve range. Accuracy for all three metabolites was within ± 10% and adequate seletivity was demonstrated by the lack of interfering peaks in blank chromatograms. The within-run and interday precision were within 10% RSD for all three metabolites tested at two concentrations. The advantage of this method over previous methods is that the use of quaternary ammonium ion pair reagents in the mobile phase has been obviated. Also, unlike a previous radiometric HPLC method, the need for radiolabelled theophylline has also been eliminated. The method was used to characterize theophylline metasbolism in human liver microsomes for immunoinhibition studies and to investigate the interaction of theophylline with selected quinolone antibiotitics.
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  • 45
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A new porphyrin, peroxyacetic acid uroporphyrin I, has been isolated from the urine of patients with congenital erythropoietic porphyria by reversed phase high performance liquid chromatography. The porphyrin was characterized by high resolution mass spectrometry and by typical chemical reactions of a peroxyacid.
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  • 46
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A direct, isocratic, sensitive and precise liquid chromatographic method is presented for the enantiomeric separation of aminoglutethimide (AG) and its acetylated metabolite (AcAG) using cellulose tris-3,5-dimethyl phenyl carbamate (Chiralcel OD) and cellulose tris(4-methylphenyl benzoate) ester (Chiralcel OJ) columns in series. The enantiomeric elution order is determined by separate chromatography of the racemate AG and racemate AcAG and of their separate enantiomers under similar conditions. This method has been used to determine and identify the enantiomers of AG and AcAG in the urine sample collected from a metastatic breast cancer patient after administration of AG for 24 h. Large amounts of (+)-R-AG are excreted unchanged in the urine together with smaller quantities of (+)-R-AcAG, while most of the (-)-S-AG is metabolically converted into (-)-S-AcAG.
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  • 47
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A high performance liquid chromatographic (HPLC) system is described for determination of the unsaturated disaccharide (ΔDi-HA) derived from hyaluronic acid (HA) in human urine by digestion with hyaluronidase SD. The effects of eluents on the separation of ΔDi-HA and ΔDi-OS, which is derived from the reaction of chondroitin with the enzyme, have been studied. The established chromatographic conditions were as follows-column: a stainless steel tube (4 mm i.d. × 250 mm) packed with TSKgel NH2-60; eluent: a mixture of acetonitrile and 0.1 M Tris-HCI buffer containing 0.1 M boric acid and 10 mM sodium sulphate, pH 7.0 (64:36, v/v). The strong fluorescence of unsaturated disaccharide after the reaction with 2-cyanoacetamide in alkaline medium was used for post-column detection. The calibration curve for ΔDi-HA was linear in the range 5 pmol-5 nmol with a practical detection limit of 2 pmol. The assay coefficients of variation (n = 5) at 200 pmol for ΔDi-HA and ΔDi-OS were 1.7 and 1.5%, respectively. This HPLC system has been applied to the determination of HA in human urine.
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  • 48
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    Biomedical Chromatography 5 (1991), S. 193-197 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A rapid, reproducible and sensitive high performance liquid chromatography (HPLC) method for the determination and purification of metallothionein-I (MT-I) and metallothionein-II (MT-II) in mouse and rabbit livers has been developed. Methallothioneins (MTs) were separated by an HPLC anion exchange column, eluted through a linear gradient of Tris buffer and the peak containing MTs was determined by atomic absorption spectrophotometry. Furthermore, the content of MT-I or MT-II was calculated by protein peak area in a short time (about 20 min). The sample to be tested was homogenized, centrifuged and saturated by cadmium. MT-I and MT-II were eluted at 15.9 and 19.3 min, respectively. The following mouse liver cytosols were tested: controls, Cd-injected samples and 60Co-irradiated samples. A detection limit of 5 μg/g liver was established for this method. We have analysed more than 100 biological samples and obtained satisfactory results.
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  • 49
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    Biomedical Chromatography 5 (1991), S. 202-206 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A high performance liquid chromatography (HPLC) method was developed for the determination of seven short-chain fatty acids in equine caecal liquor. Samples were cleaned up on a Sep-pak (C18) cartridge, and the analyte was eluted from the extraction cartridge and filtered through a 0.45 μm cellulose nitrate filter. The analyte was chromatographed by ion exchange HPLC. Detection was by UV at 210 nm. Recovery from phosphate buffer (0.05 M, pH 7.0) and equine caecal liquor was 76.95% (lactic), 76.76% (acetic), 84.40% (propionic), 89.35% (isobutyric), 88.73% (butyric), 80.33% (isovaleric) and 72.61% (valeric). The limit of detection of the short-chain fatty acids in phosphate buffer was 0.00006 M (lactic), 0.0001 M (acetic), 0.0002 M (propionic), 0.0001 M (isobutyric), 0.0002 M (butyric), 0.0002 M (isovaleric) and 0.0003 M (valeric). The specificity and sensitivity of this method was sufficiently high to allow the characterization of the pattern of these short-chain fatty acids in equine caecal liquor following intravenous administration of oxytetracycline at the recommended dose rate in a pony.
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  • 50
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    Biomedical Chromatography 5 (1991), S. 273-273 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
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  • 51
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A gas - liquid chromatographic method for the determination of pentoxifylline and its secondary alcohol metabolite in serum has been developed. The method is based on the combination of solid phase extraction, capillary column separation and nitrogen - phosphorus detection of the analytes. Optimization of the solid phase extraction conditions permitted a low concentration determination, with limits of determination of 2 n/mL and 10 n/mL for pentoxifylline and its metabolite, respectively. The simplicity and rapidity of the extraction step was preserved.
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  • 52
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    Biomedical Chromatography 5 (1991), S. 269-272 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: REMEDi (Rapid EMErgency Drug identification; Bio-Rad) is an automated high performance liquid chromatographic (HPLC) system designed to detect, identify and measure a range of basic and neutral drugs in 0.5-1.0 mL of urine or plasm/serum. We have evaluated REMEDi in the analysis of the antiarrhythmic drug disopyramide in patient samples. The specimens were also analysed by a conventional HPLC method, based on solvent extraction and UV detection (254 nm), and by EMIT. There were good correlations between the results obtained with each method (r = 0.91 or greater). REMEDi gave a lower mean result than EMIT [means±SD (m/L): REMEDi 2.64±1.10, EMIT 3.14±1.51; t = 4.0, p〈0.01; n = 25], but there were no other significant differences in mean results. The principal disopyramide metabolite, mono-N-desalkyldisopyramide, did not interfere in any method. Clearly REMEDi can be used for therapeutic drug monitoring of disopyramide provided enough sample is available.
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  • 53
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: In this study we report the levels of 3-methoxy-4-hydroxyphenylglycol, 3,4-dihydroxyphenylacetic acid, homovallinic acid, tryptophan, 5-hydroxyindole-3-acetic acid and serotonin in lumbar cerebrospinal fluid (CSF) from patients with multiple sclerosis, cerebrovascular disease and muscular tension headache the latter, as healthy controls. The separation of these substances was performed on a reversed phase column by ion pair high performance liquid chromatography and detection was made by a glassy carbon electrode set at +900 mV vs Ag+/AgCI. The whole separation was achieved within 25 min. Concentrations of all substances (10-1000 pmole/L) were linearly proportional to areas obtained. The system is sensitive, stable and reproducible. The significance of CSF levels of these metabolites from patient groups compared with healthy controls are discussed.
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  • 54
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    Biomedical Chromatography 5 (1991), S. 133-138 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Samples of biomedical interest which have been analysed by field-flow fractionation techniques are surveyed. The list begins with whole cells and microorganisms, going through viruses, nucleic acids, cell fragments and organelles, down to proteins and their aggregates. The principles of separation in the normal and steric mode of retention are illustrated, and instrumentation and techniques are described. The review concentrates mainly on the two systems of choice for biomedical applications: sedimentation and flow field-flow fractionation.
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  • 55
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    Biomedical Chromatography 5 (1991), S. 14-18 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The liquid chromatographic analysis of drugs in urine through direct injection without any sample pretreatment was extended to micellar chromatography with nonionic surfactants, the Pinkerton™ ISRP column and the shelded hydrophobic phase (Hisep™) column. The feasibility of using each was demonstrated through the determination of the diuretic, hydrochlorothiazide, in urine. Good separation, recovery, precision and linearity, and adequate limits of detection were obtained for this analysis with all three techniques. The advantages and limitations of the mobile phase approach of micellar chromatography and the two stationary phase approaches are discussed for the direct injection of urine as well as other biological fluids.
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  • 56
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    Biomedical Chromatography 5 (1991), S. 32-37 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A method for determining Picumast, an antiallergic drug, in plasma by HPLC and column switching has been developed. The system consisted of two precolumns, an analytical column, three pumps, an autosampler and a fluorescence detector. The precolumns (17 × 4.6 mm i.d.) were packed with LiChroprep RPR (a moderately polar reversed phase) and the analytical column with Nucleosil ODS (RP 18, 5 μm). The columns were connected according to the alternating precolumn technique. The mobile phase consisted of 30% CH3CN/70% 0.05M KH2PO4, pH 2.5, with a flow gradient. Detection wavelengths were 333 nm for excitation and 383 nm for emission. The retention times of Picumast, M1 and M2 were 12, 3.6 and 4.0 min, respectively. Total run time was 15 min. The limit of detection was 3 ng/mL for M1 and 1 ng/mL for M2 and Picumast using an injection volume of 150 μL. The recoveries vary between 89% and 97% with standard deviations between 2.4 and 3.3%.
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  • 57
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    Biomedical Chromatography 5 (1991) 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
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  • 58
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    Biomedical Chromatography 5 (1991), S. 62-67 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: High performance hydrophobic interaction chromatography has been used to separate progestin receptors (PRs) from human uterus and from the T47D human breast cancer cell line. Reproducible separations of high resolution were achieved using a TSK Phenyl-5PW column and a reverse salt gradient of 400 mM to 0 mM sodium sulfate in phosphate buffer, pH 7.4. Peaks of radioactivity exhibiting hydrophobic behaviour were isolated, as well as a smaller proportion of specific bound receptors located in the void volume fraction. No differences in retention times were observed between uterine and breast cell line samples. When the technique was used in conjunction with rapid vertical tube sucrose density gradient centrifugation, the 8S sedimenting PR from fresh, low-salt cytosol always eluted with a retention time of 24 min. The natural 4S receptor chromatographed as a single peak at 29 min while the 4S receptor species from high-salt cytosol appeared as two distinct peaks of radioactivity with retention times of 29 and 33 min. While specific binding was shown to occur in the void volume of the column, the origin of these receptors were indeterminate. These results would suggest that under these conditions the 8S receptor occurs as a single hydrophobic class of protein, whereas the data provides evidence that transformed 4S receptor may be proportioned into two unequal entities as a function of exposure to salt.
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  • 59
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A procedure for the preparative separation of proteins was developed by using consecutively sodium dodecyl sulfate (SDS)-polyacrylamide gel electrophoresis (SDS-PAGE) and reversed phase high performance liquid chromatography (HPLC). The proteins were separated by SDS-PAGE and afterwards extracted from the gel. The extracted proteins were separated from SDS and other small molecular weight contaminants on a Fractogel TSK HW-40 (F) column in acidic aqueous acetonitrile. The proteins eluted from the Fractogel column were fractionated by HPLC. The identity and purity of the recovered proteins was confirmed by SDS-PAGE analysis.
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  • 60
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    Biomedical Chromatography 5 (1991), S. 99-99 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
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  • 61
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    Biomedical Chromatography 5 (1991), S. 122-127 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Reversed phase ion pair chromatography is a highly selective separation technique for the determination of free porphyrin carboxylic acids from human materials. Isocratic and gradient elution methods can be used to analyse porphyrin isomers and to establish porphyrin profiles for the biochemical diagnosis of porphyrias. Ion pair high performance liquid chromatography led to the discovery of the atypical isomers II and IV of uroporphyrin and coproporphyrin in human urine. Advantages and limitations of the ion pair technique are discussed.
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  • 62
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    Biomedical Chromatography 5 (1991), S. 175-179 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Samples of pregnant urine were treated with three diatomaceous earth columns to fractionate organic solvent-soluble components. The first column was pre-injected with the urine sample. The second and the third columns were pre-injected with sodium bicarbonate and sodium hydroxide solutions, respectively; these played an important role in capturing acidic components in the urine extract from the first column. Neutral components could be eluted out from the columns with the organic solvent, while the basic components were retained in the first column. Once strongly and weakly acidic components were captured on the alkaline columns, they were separately treated with an acidic mobile phase and recovered. The digoxin-like activities of each fraction were examined for cross-reactivity to antidigoxin antibody and inhibitory effects on dog kidney Na+, K+-ATPase. Both types of reactivity were found in all three fractions and decreased in the following order: strongly acidic, neutral and weakly acidic. The neutral fraction of pregnant urine showed significantly greater cross-reactivity than that of the non-pregnant urine. Following hydrolysis of the pregnant urine with β-D-glucuronidase, the cross-reactivity of the neutral fraction increased significantly. High performance liquid chromatographic analysis showed that several components in the neutral fraction had apparently increased after the hydrolysis, showing the possible presence of unknown digoxin-like components in the pregnant urine.
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  • 63
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Wide porous glass (WPG) chemically coated with a poly-N-(2-hydroxyethyl)acrylamide layer is proposed as a carrier of biospecific ligands in affinity chromatography. The method of WPG chemical modification includes synthesis of the γ-aminopropyl derivative followed by chemical adsorption of poly(p-nitrophenyl acrylate). Ester groups of the polyacrylate-coated WPG can be used for coupling the ligands bearing primary amino groups. Condensation of esters with ethanolamine yields a poly-N-(2-hydroxyethyl)acrylamide-coated support with non-specific adsorption properties resembling those of Sepharose 4B. Human IgG immobilized on the polyacrylate support was used for isolation of the first complement component from human serum and for its separation into subcomponents C1r, C1s and C1q by a one-step method. An unbound part of serum may be used as the R1 reagent for determining haemolytic C1 activity. The stepwise elution of C1r, C1s and C1q from the column reflects the course of C1 breakdown after its activation on immune complex formation.
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  • 64
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    Biomedical Chromatography 5 (1991), S. 101-107 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Chromatographic techniques for the determination of trace amounts of neurotransmitters were reviewed. The two techniques found to be most useful were GC-MS and the reversed-phase mode of HPLC with an electrochemical or fluorescent detector. For structure determination or unequivocal peak identification, GC-MS is the method of choice. In addition the limits of detection of GC-MS were better than those obtained by HPLC. However for routine analyses, HPLC is now being used in studies of mental illness and other diseases. Good resolution, reproducibility and sensitivity can be obtained without the derivatisation steps required for GC-MS, and catecholamines, serotonin, and their acidic metabolites can be concomitantly determined in one analysis.
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  • 65
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    Biomedical Chromatography 5 (1991), S. 139-140 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
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  • 66
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    Biomedical Chromatography 5 (1991) 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
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  • 67
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A rapid, sensitive and simple-to-operate high performance liquid chromatographic method for the simultaneous determination of oxcarbazepine, 10-hydroxycarbazepine and 10,11-dihydro-10,11-trans-dihydroxy-carbamazepine in plasma is described. The drug and its metabolites were extracted from plasma using commercially available reversed phase octadecylsilane bonded-silica columns (Bond Elut C18, 1 mL capacity). Chromatographic separation of oxcarbazepine and its metabolites was achieved using a mobile phase consisting of acetonitrile/methanol/water (13:25:62 by volume) at a flow rate of 1.2 mL/min in conjunction with a Waters Associates Nova-Pak C18 column. The analytical column, in Radial-Pak cartridge form, was used in combination with a LiChrospher 5 μm C18 guard column. By measuring the UV absorbance at 214 nm, plasma levels in the region of 50-100 ng/mL for the drug and its metabolites can be detected with only 100 μL of plasma. The method has been applied to pharmacokinetic studies of oxcarbazepine and its metabolites in children with epilepsy; preliminary pharmacokinetic findings in two patients at steady-state are presented.
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  • 68
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 69
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    Biomedical Chromatography 5 (1991) 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 70
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A high performance liquid chromatographic post-column fluorescent ion pair extraction system was developed for the analysis of quaternary ammonium and amine drugs in serum. A new fluorescent ion pair reagent, sodium α-(3,4-dimethoxyphenyl) cinnamonitrile-2′-sulfonate (DPS), was synthesized and characterized. The post-column extraction system consisted of a three-dimensional knitted teflon mixing coil and a membrane phase separator which was modified from an original literature design. Physostigmine and its metabolite eseroline were used as model cations. A solid phase extraction procedure using octadecylsilane columns was developed to extract the compounds and neostigmine bromide (internal standard) from human serum. The compounds were chromatographed on a diol column using a 80:20 aqueous phosphate buffer pH 4 absolute methanol mobile phase at a flow rate of 1 mL/min. Methylene chloride was used as the on-line extraction solvent for the DPS ion pairs formed. Fluorescence of the extracted ion pairs was measured using an excitation of 243 nm and an emission cut-off filter at 418 nm. Linearity was in the 2-100 ng/mL and 5-100 ng/mL ranges for physostigmine and eseroline, respectively. Detection limits based on a signal-to-noise ratio of 2, were 2 and 5 ng/mL, respectively. Precision of the method was found to be in the 1.5-3% range and percentage error in the 1.5-7% range for both compounds.
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  • 71
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    Biomedical Chromatography 5 (1991), S. 232-232 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
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  • 72
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    Biomedical Chromatography 5 (1991), S. 240-247 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Chemical derivatization by phenylgyoxal (PGX) was applied to the identification of arginine in the neuropeptides dynorphin A (1-6) and substance P. The obtained products were separated on a short reversed phase C18 column and analysed on-line with the photodiode array UV technique. The selective attachment of a chromogenic molecule into the arginine residue resulted in significant change in the absorbance spectra around 250 nm, depending on the number of PGX molecules attracted. Further analysis employed fast atom bombardment mass spectrometry (FAB MS) and C-terminal sequencing for detailed verification of the derivatives formed during modification with PGX. The results clearly demonstrated that the photodiode array technique, when combined with chemical modification of certain amino acids, provides new possibilities for the analysis of peptide structures.
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  • 73
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    Biomedical Chromatography 5 (1991), S. 262-264 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: The first high performance liquid chromatographic method for determination of the plasma concentration of 2-chloro-2′-deoxyadenosine (CdA) in patients, which is significantly more sensitive than the previously used RIA method, is presented. CdA is a purine analogue with useful clinical activity against lymphoproliferative disorders and it has recently been found to be the single most active agent in the treatment of hairy cell leukaemia. Guaneran (6-nitroimidazol-6-thioguanine) was added to 1 mL plasma as the internal standard and CdA was extracted using ethyl acetate. A Perkin-Elmer C18, 3 μ, 8 cm column was used for the separation of CdA and the internal standard from endogenous compounds in the sample with a mixture of sodium phosphate buffer 10 mM, methanol and acetonitrile (85:10:5, pH = 3.0) as the mobile phase. The sensitivity of the method (1 nM) allows the determination of CdA in plasma 24 h after the administration of 0.14 m/kg as a 2 h infusion.
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  • 74
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    Biomedical Chromatography 5 (1991), S. 143-147 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Lipids from hydrolysed extracts of Harderian glands from the rabbit were examined as trimethylsilyl, acetonide, nicotinate and picolinyl esters and shown to consist mainly of acylated glycerol ethers and acylated hydroxyglycerol ethers. Constitutents amounting to 98.8% of the recovered secretion were identified. Fatty acids were mainly normal, saturated compounds with chain legths from 12 to 24 carbon atoms; n-16:0 and n-18:0 accounted for about 40% of the identified acids. Small concentrations of iso-17:0 and unsaturated acids with 18-carbon chains were also identified. Fatty alcohols were again mainly normal-unsaturated compounds; the chains varied from C18 to C25 with 20:0-OH and 22:0-OH being the most abundant. Three types of 1-alkyl glycerols were found. The major constituents had normal, saturated chains with from 14 to 23 carbon atoms with the even carbon chains predominating. These were accompanied by hydroxylated derivatives of the 16- and 18-carbon glycerol ethers with hydroxy groups in the 10, 11 and 12 positions. Branched-chain glycerol ethers were of low concentration and contained predominently iso chains. Many of these compounds have not been reported before in this secretion. Low concentrations of the previously reported hydroxy acids with n-C14, -C15 and -C16 chains were also found. Nicotinate derivatives were applied to the structural determination of glycerol ethers for the first time and shown to reveal the position of methyl branch points in an analogous manner to that previously shown for mono- and di-hydric alcohols. Acids were identified as picolinyl esters.
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  • 75
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A novel method for measuring AMP-deaminase activity in human erythrocytes is presented, based on the determination of the reaction product, IMP, using high performance liquid chromatography. IMP formation was found to be proportional both to the incubation time and the amount of haemolysate over a wide range. The minimal detectable AMP-deaminase activity was more than 1000 times lower than the mean activity found in healthy controls (1083 nmol/h/mg Hb). No marked difference of activity was found in the patients with the following inherited purine disorders: familial juvenile gouty nephropathy and deficiencies of adenosine deaminase, hypoxanthine-guanine phosphoribosyltransferase or adenine phosphoribosyltransferase. The activity in the erythrocytes of patients with chronic renal failure was also similar to controls. The existence of subjects with low erythrocyte AMP-deaminase activity in the population has been confirmed.
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  • 76
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    Biomedical Chromatography 5 (1991), S. 187-187 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
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  • 77
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    Biomedical Chromatography 5 (1991), S. 221-225 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A rapid procedure of isoelectric focusing (IEF) of proteins in polyacrylamide rod gels (i.d., 1.1 mm; lenght, 7.5 cm) is described. The time required for IEF can be reduced to 0.5 h by using high voltages up to 3000 V in the presence or absence of urea in the gels. When used as the first dimension of a two-dimensional technique for IEF sodium dodecyl sulphate electrophoresis, high voltage IEF gives smaller protein spots on the second dimension gel, associated with an increase in resolution. The method has been tested by a two-dimensional separation of an eye sample of the goodeid fish Xenotoca eiseni.
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  • 78
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    Biomedical Chromatography 5 (1991), S. 226-228 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Automated cation exchange microcolumn chromatography of haemoglobins has been modified for the analysis of haemoglobin A2. It provides the quantitative data of sufficient precision and specificity for the investigation of potential heterozygotes for β-thalassaemia. Results have been compared with an established method of electrophoresis followed by densitometry of the eluted bands.
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  • 79
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    Biomedical Chromatography 5 (1991), S. 233-233 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
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  • 80
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    Biomedical Chromatography 5 (1991), S. 248-250 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: A routine high performance liquid chromatographic method for the rapid determination of flecaïnide (Flecaine®), using a novel internal standard, N-methylflecaïnide, has been developed. After deproteinization of spiked samples, flecaïnide was totally recovered at neutral pH. Flecaïnide and the internal standard were separated on a reversed phase XL 3 μm ODS column using 10 mM phosphate buffer, pH 3.0: acetonitrile (70:30) as mobile phase, in less than 10 min. With spectrofluorometric detection, the limit of quantitation for flecaïnide was 10 n/mL. Intra- and inter-assay precision variations were 0.24% and 1.4%.
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  • 81
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    Biomedical Chromatography 5 (1991), S. 265-268 
    ISSN: 0269-3879
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine
    Notes: Quantitative determination of tetroxoprim and sulphadiazine in serum and urine was performed using reversed phase high performance liquid chromatography. Protein precipitation using 10% perchloric acid was utilized for purification of serum samples while urine samples were diluted prior to analysis. The mobile phase consisted of triethylammonium acetate buffer (85%), acetonitrile (12%) and methanol (3%), with a final pH of 4.2. The eluent was monitored at 280 nm. Benzoic acid was used as an internal standard. Standardization, validation and application of the method is described.
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  • 82
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    Journal of Chemometrics 5 (1991), S. 545-545 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 83
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 84
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    Journal of Chemometrics 5 (1991), S. 129-145 
    ISSN: 0886-9383
    Keywords: Multivariate calibration ; Biased regression ; Partial least squares (PLS) ; Principal component regression (PCR) ; Model validation ; Non-linear calibration ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: With the goal of understanding global chemical processes, environmental chemists have some of the most complex sample analysis problems. Multivariate calibration is a tool that can be applied successfully in many situations where traditional univariate analyses cannot. The purpose of this paper is to review multivariate calibration, with an emphasis being placed on the developments in recent years. The inverse and classical models are discussed briefly, with the main emphasis on the biased calibration methods. Principal component regression (PCR) and partial least squares (PLS) are discussed, along with methods for quantitative and qualitative validation of the calibration models. Non-linear PCR, non-linear PLS and locally weighted regression are presented as calibration methods for non-linear data. Finally, calibration techniques using a matrix of data per sample (second-order calibration) are discussed briefly.
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  • 85
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    Journal of Chemometrics 5 (1991), S. 147-161 
    ISSN: 0886-9383
    Keywords: Digital filtering ; Real-time analysis ; Kalman filtering ; Infrared spectroscopy ; Principal components regression ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Real-time monitoring of pollutant levels from a mobile measuring platform requires fast, flexible data analysis methods. This paper reports a method for rapid analysis of passive remotely sensed infrared data with the aid of a Kalman filter. The background spectra produced by emission from the atmosphere are modelled at the start of the data collection sequence with a simple principal components model obtained by eigenanalysis of the initial ‘blank’ data taken with the spectrometer. The species of interest are included in the state space model by a separate measurement of their infrared spectra. It is demonstrated that for best filter performance in detecting the simulated pollutant species SF6 in the atmosphere, a filter model with two principal components describing the emission background works best. The filter ‘maps’ of SF6 closely follow the integrated spectral intensities measured after removal of suitable backgrounds.
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  • 86
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    Journal of Chemometrics 5 (1991), S. 163-179 
    ISSN: 0886-9383
    Keywords: Principal component analysis ; Factor analysis ; Chemometrics ; Exploratory data analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Principal component analysis is used to examine large multivariate databases. The graphical approach to exploratory data analysis is described and illustrated with a single example of chemical composition data obtained on environmental dust particles. While the graphical approach to exploratory data analysis has certain advantages over the numerical procedures, the empirical approach described here should be viewed as complementary to the more robust treatments that statistical methodologies afford.
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  • 87
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    Journal of Chemometrics 5 (1991), S. 227-239 
    ISSN: 0886-9383
    Keywords: Unit-sum constraint ; Mixing proportions ; Ratio data ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The statistical analysis of compositional data is of fundamental importance to practitioners in general and to chemists in particular. The existing methodology is principally due to Aitchison, who effectively uses two transformations, a ratio followed by the logarithmic, to create a useful, coherent theory that in principle allows the plethora of normal-based multivariate techniques to be used on the transformed data. This paper suggests that the well-known class of Box-Cox transformations can be employed in place of the logarithmic to significantly improve the existing methodology. This is supported in part by showing that one of the most basic problems that Aitchison managed to overcome, namely the specification of an interpretable covariance structure for compositional data, can be resolved, or nearly resolved, once the ratio transformation has been applied. Hence the resolution is not directly dependent on the logarithmic transformation. It is then verified that access to the general Box-Cox family will allow a more accurate use of the normal-based multivariate techniques, simply because better fits to normality can be achieved. Finally, maximum likelihood estimation and some associated asymptotics are employed to construct confidence intervals for ratios of the true, unknown compositional constituents. Heretofore this had not been done even in the context of the logarithmic transformation. Applications to real data are presented.
    Additional Material: 3 Ill.
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  • 88
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    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 5 (1991), S. 241-248 
    ISSN: 0886-9383
    Keywords: Multivariate kurtosis ; Generalized distance ; Multivariate outliers ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Multivariate outliers in environmental data sets are often caused by atypical measurement error in a single variable. From a quality assurance perspective it is important to identify these variables efficiently so that corrective actions may be performed. We demonstrate a procedure for using two multivariate tests to identify which variable ‘caused’ each outlier. The procedure is tested with simulated data sets have have the same correlation structure as selected water chemistry variables from a survey of lakes in the Western United States. The success rates are evaluated for three of the variables for sample sizes of 50 and 100, significance levels of 0.01 and 0.05 and various amounts of mean shift. The procedure works best for highly correlated variables.
    Additional Material: 2 Ill.
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  • 89
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    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 5 (1991), S. 249-261 
    ISSN: 0886-9383
    Keywords: Asymptotic power ; Clean-up standard ; Gamma distribution ; Likelihood ratio test ; Uniformly most powerful unbiased test ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The object of this paper is to develop a suitable statistical procedure to evaluate clean-up standards at hazardous waste sites. Under the assumptions that contaminant masses at a site follow a gamma distribution and that the data from the pre-remediation baseline sample as well as from the interim or final sample taken after a certain period of operation are both distributed as gamma with the same shape parameter but different scale parameters, we derive a uniformly most powerful unbiased test of the hypothesis that a specified percentage of contaminant mass has been reduced. A large-sample approximation of the exact test procedure and a comparison with the likelihood ratio test are provided.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 90
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 5 (1991), S. 263-271 
    ISSN: 0886-9383
    Keywords: Mean ; Variance ; Lognormal ; Optimal estimators ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Theoretical and simulation results are employed to evaluate mean and variance estimates for normal data when a lognormal distribution is assumed and for lognormal data when a normal distribution is assumed. Misspecifying the distribution leads to the use of suboptimal estimation methods. However, the results show that the suboptimal methods still produce estimators of good quality (low bias and variance) relative to the minimum variance unbiased estimators for each distribution, at least when practical efficiency is considered.
    Additional Material: 2 Tab.
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  • 91
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 5 (1991), S. 273-290 
    ISSN: 0886-9383
    Keywords: Correspondence analysis ; Eastern Lake Survey - Phase I data ; Acidic deposition ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Correspondence analysis (CA) was applied to lakewater data in order to study the effects of acidic deposition on the geochemical composition of lakes in the Adirondacks. The lake chemistry data analyzed were taken from the Eastern Lake Survey - Phase I (ELS-I) conducted by the U.S. Environmental Protection Agency. CA was used to identify ‘outlying’ lake samples as well as ‘superflous’ and ‘unresolved’ analytes. Correlational relationship among analytes were also examined.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 92
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 5 (1991), S. 291-298 
    ISSN: 0886-9383
    Keywords: Absorbance ratio ; Statistical confidence ; Quality control ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ratio measurements are commonly used to address a variety of analytical problems in environmental, forensic and pharmaceutical laboratories. In absorbance ratioing techniques, analytical chemists rely on the spectral features of the analyte(s) of interest. The absorbances at two wavelengths are monitored and the ratio of these two absorbances is computed. This ratio is then used to confirm the identity of the analyte(s) of interest, the purity of a product of the overlap of chromatographic peaks. These decisions often have far-reaching consequences (e.g. the identification of the source, biogenic or petrogenic, of hydrocarbons in biological tissues or water). Given the cost and the liabilities associated with such decisions, it is unfortunate that these ratios are seldom reported with any statistical confidence. The purpose of this study is to delineate the parameters that affect absorbance ratio measurements. The models that can be used to estimate the statistical confidence in these measurements are derived and evaluated experimentally. The results show that these models can estimate the relative standard deviations in absorbance ratios accurately. They can also estimate the effect of signal-to-noise ratio and the choice of wavelengths on the precision of absorbance ratios.
    Additional Material: 2 Ill.
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  • 93
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    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 5 (1991), S. 299-308 
    ISSN: 0886-9383
    Keywords: Errors in variables ; Orthogonal regression ; Latent variables ; Acid rain ; Acidic deposition ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Techniques for testing for and estimating relative bias between two laboratories are developed and applied to a survey of the chemistry of streams in the United States. The design of the quality assurance program allows estimation of linear corrections for bias as well as testing of the hypothesis of linearity. Designs of this type are useful, but improvements are suggested.
    Additional Material: 3 Ill.
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  • 94
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    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 5 (1991), S. 309-319 
    ISSN: 0886-9383
    Keywords: Confidence intervals ; Products of normal random variables ; Risk/exposure modeling ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In many environmental applications, such as exposure assessment and risk modelling, the desired estimate is a random variable computed as the product of three independently distributed random variables. These variables may not necessarily have the same mean and variance. The method for finding the 100(1 - α)% confidence interval for the mean of the product random variable has been proposed by some practitioners as the product of the 100(1 - α)% confidence interval of the three means. In this paper we show that the distribution of the product of three independent normal variables is not normal. We find the mean and variance of the product distribution. Further, we show that although the mean of the product is equal to the product of the means, the product of the three confidence intervals is not a good approximation of the confidence intervals for the mean of the product variable. The confidence interval of the mean of the product variable may be estimated by computer simulation. An algorithm for estimating the confidence interval for the mean of the product random variable is given. The program implementing this algorithm is given as an appendix.
    Type of Medium: Electronic Resource
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  • 95
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    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 5 (1991), S. 321-331 
    ISSN: 0886-9383
    Keywords: Screening ; Ground-water quality ; Monitoring ; Volatile organic compounds (VOCs) ; Optimization ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is shown that the presence of 31-35 commonly measured volatile organic compounds (VOCs) in ground water can be detected with small error rates by using screening methods which analyze for a subset of such VOCs. A study of selected data sets indicates that analytical determinations of only from two to eight VOCs will suffice to detect 95% of all VOC hits. It is also shown that a serially optimal algorithm for selecting the VOCs for screening is very nearly as accurate as a globally optimal algorithm and much easier to implement. These conclusions are supported by empirical evidence from two drinking-water data sets and one hazardous waste site data set. Additional research areas are also outlined.
    Additional Material: 4 Ill.
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  • 96
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 5 (1991) 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 97
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 5 (1991), S. i 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 98
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 5 (1991), S. 333-343 
    ISSN: 0886-9383
    Keywords: Rank estimation ; Bootstrap resampling ; Canonical correlation ; Excitation-emission matrix ; Singular value decomposition ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rank estimation by canonical correlation analysis in multivariate statistics has been proposed as an alternative approach for estimating the number of components in a multicomponent mixture. A methodological turning point of this new approach is that it focuses on the difference in structure rather than in magnitude in characterizing the difference between the signal and the noise. This structural difference is quantified through the analysis of canonical correlation, which is a well-established data reduction technique in multivariate statistics. Unfortunately, there is a price to be paid for having this structural difference: at least two replicate data matrices are needed to carry out the analysis.In this paper we continue to explore the potential and to extend the scope of the canonical correlation technique. In particular, we propose a bootstrap resampling method which makes it possible to perform the canonical correlation analysis on a single data matrix. Since a robust estimator is introduced to make inference about the rank, the procedure may be applied to a wide range of data without any restriction on the noise distribution. Results from real as well as simulated mixture samples indicate that when used in conjunction with this resampling method, canonical correlation analysis of a single data matrix is equally efficient as of replicate data matrices.
    Additional Material: 3 Ill.
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  • 99
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    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 5 (1991), S. 345-360 
    ISSN: 0886-9383
    Keywords: Three-way PCA ; Three-way PLS ; PARAFAC ; Trilinear ; Unfolding ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: For the calibration of chromatographic systems, different methods can be used. One class of methods utilizes three-way approaches. The calibration problem is stated in such a way that the decomposition of a three-way array can serve for the prediction of retention on new stationary phases.Two three-way approaches are presented: the Unfold-PCA and PARAFAC models. The theory of both methods is presented and the differences are highlighted, the main difference being that PARAFAC is a trilinear decomposition whereas Unfold-PCA is not. Both three-way methods are evaluated on a small data set consisting of retention measurements of eight solutes at six mobile phase compositions on six stationary phases. The differences in performance of the two models are minor.For calibration purposes, two variants of the methods are discussed: three-way PLS and an extension of PARAFAC. Again the theory and differences between the two methods are explained. The predictive performance of the two methods is compared using the same data set as earlier. The differences in predictive performance, however, are minor. Both methods are capable of predicting 98% of the variation in the test sets. Yet, there are other considerations when comparing methods than predictive performance, e.g. the quality of the predictions.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
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  • 100
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    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 5 (1991), S. 361-374 
    ISSN: 0886-9383
    Keywords: Closure ; Normalization ; Multivariate trimming ; Minimum distance ; Bootstrap ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Compositional data arise naturally in several branches of science, including chemistry, geology, biology, medicine, ecology and manufacturing design. In chemistry, these constrained data seem to occur typically when raw data are normalized or when output is obtained from a constrained estimation procedure, such as might be used in a source apportionment problem. It is important not only for chemists to be aware that the usual multivariate statistical techniques are not applicable to constrained data, but also to have access to appropriate techniques as they become available. The currently available methodology is due principally to Aitchison and is based on log-normal models. This paper suggests new parametric and non-parametric approaches to significantly improve the existing methodology. In the parametric setting, some recent work of Rayens and Srinivasan is extended and a practical regression model is proposed. In the development of the non-parametric approach, minimum distance methods coupled with multivariate bootstrap techniques are used to obtain point and region estimators.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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