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  • 1
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method has been developed for the quantitative determination of cholesterol and three of its major oxidative metabolites (the 5α,6α-epoxide, the 3β,5α,6β-triol, and the 5β,6β-epoxide) in a single sample of human breast fluid (2-50 μl), using gas chromatography/mass spectrometry with selected ion monitoring. High specificity and reliable quantification is achieved by the use of the inverse stable isotope dilution method, employing deuterium-labeled variants of the compounds as internal standards.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 426-430 
    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 foam rheometer has been developed based on the impulse theory of linear viscoelasticity. The rheometer is a large-volume parallel-plate device which operates under gap-loaded conditions, and is designed as an add-on fixture for the Materials Testing System Model 312. The rheometer provides characterization data of the pre-gel (via the zero-shear viscosity) or the post-gel (via the equilibrium modulus) properties of a foaming cellular polymer with a precision of better than ± 15%.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 33 (1993), S. 317-321 
    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: Sample size sensitivity of thermal gravimetric analysis (TGA) presents a serious handicap in the obtaining of reliable thermal stability data for high-temperature applications. For example, predictions of the apparent time for degradation during an isothermal experiment based on the results obtained using a 10 μm thick specimen can be off by an order of magnitude when applied to a product with a thickness of 10 cm. To address this effect, TGA experiments studying the thermal degradation of poly(methyl methacrylate) were conducted. Analysis of the experimental data resulted in the development of a relationship between the apparent time scale of the thermal degradation and the specimen thickness. Origins of the new dependence were traced to the change of the diffusivity resulting from material volatilization. Implications of the coupling between these two events for the analysis of thermal stability for new polymeric materials are discussed, and required changes in the current methodology are outlined.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 7 (1980), S. 381-384 
    ISSN: 1052-9306
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An improved analog four-channel selected ion recording system is described, in which major modifications permit a decrease in the dwell time to 33 ms per channel, thus minimizing the mass cycling error. Synchronization with a sinusoidal sweep voltage superimposed on the normal accelerating voltage (8 kV) enables two channels to be monitored simultaneously in real time and each mass to be recorded continuously. These improvements allow measurement of ion current ratios with a precision of 0.2% over a wide dynamic range, permitting accurate determination of isotopic enrichment in biomedical assays even when this enrichment is derived from a single label. Use of the system is illustrated by the analysis of palmitate turnover in dogs (using [1 - 13C] palmitic acid) with an average standard deviation corresponding to the detection of 0.04% excess of [1 - 13C] palmitate.
    Additional Material: 4 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 1 (1974), S. 418-422 
    ISSN: 1052-9306
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An analog multiple ion detection system has been developed for magnetic sector mass spectrometers based on accelerating voltage alternation in conjunction with the accurate maintenance of focusing by means of voltage sweeping, using a superimposed a.c. sine wave voltage. This multiple ion detector voltage sweep system is easily constructed, inexpensive and produces analytical data of much greater precision than that reported from conventional systems. The application of the multiple ion detector voltage sweep system to biomedical problems is illustrated by the development of a method for the determination of stable isotope enrichment in blood glucose and alanine in children infused with tetradeuterio-L-alanine and dideuterioglucose to study gluconeogenesis and glucose utilization in vivo.
    Additional Material: 5 Ill.
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  • 6
    ISSN: 1052-9306
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method for the quantitative determination of chlorpromazine and five of its major metabolites in a single sample of biological fluid in the ng/ml range has been developed utilizing gas chromatography/mass spectrometry with selected ion recording. The assay is highly specific and quantification is accomplished by an inverse stable isotope dilution technique, using deuterium-labeled variants of the compounds as internal standards. In this way the concentrations of chlorpromazine and five of its major metabolites (the sulfoxide, the N-oxide, the monodemethylated, the didemethylated, and the 7-hydroxylated compounds) can be determined in biological fluids. Levels in humans have been measured both in plasma and in red blood cells and are compared to those found in related in vitro studies.
    Additional Material: 2 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 10 (1983), S. 458-462 
    ISSN: 0306-042X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A stable isotope tracer method has been developed for studying lactate metabolism in humans. The method uses lactic acid triply labeled with 13C as the tracer. The stable isotope is infused to attain a level of approximately 1.5% of that of the circulating unlabeled lactate. Following the isolation of lactic acid from the blood, the percentage of triply labeled (13C)lactate is measured using gas chromatography mass spectrometry. We compared this method with tracer methodology using [14C]lactate and found comparable results.
    Additional Material: 4 Ill.
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  • 8
    ISSN: 0749-1581
    Keywords: Cobalt(III) porphyrins ; Conformations ; Azacyclooctane ; Azacycloheptane ; NMR ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel NMR shift reagent, cobalt(III) meso-tetraphenylporphyrin (CoTPP) was used to determine the conformations of azacycloheptane and azacyclooctane ligands complexed to the metalloporphyrin. Using the observed ring current shifts and a previously calibrated ring current model, the best agreement between the observed and calculated ring current shifts for azacycloheptane was obtained for a chair conformation, in agreement with previous theoretical and experimental studies on the conformational stability of seven-membered rings. The ring current shifts for azacyclooctane are best interpreted in terms of a mixture of many conformations. These results suggest that CoTPP may be useful as a probe of other conformationally mobile ligands.
    Additional Material: 3 Ill.
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  • 9
    ISSN: 0749-1581
    Keywords: Cobalt(III) porphyrin complexes ; ring currents ; ligand geometry ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The geometry of metalloporphyrin-ligand complexes [mono-(1:1) and bis-(1:2)] produced by cobalt(III) meso-tetraphenylporphyrin (CoTPP) with amine ligands has been investigated using the diamagnetic ring current shifts of the porphyrin on the ligand nuclei.The observed ring current shifts are corrected for complexation effects by the use of cobalt(III) dimethylglyoxime (DMG) complexes. Significant changes in ligand chemical shifts are observed on formation of a DMG complex, although saturated ligands only show changes at points close to the site of complexation.Crystallographic data and corrected ring current shifts for pyridine and N1-methylimidazole are used to parameterize a double-dipole model of the CoTPP ring current. For 4-methylpiperidine a geometry calculated from corrected ring current shifts is in reasonable agreement with that observed in the solid state. The geometry calculated for a cyclohexylamine CoTPP complex can be rationalized in terms of a minimization of steric interactions with the porphyrin.Corrected 13C ring current shifts are still in poor agreement with calculated values, although there is a considerable improvement compared with uncorrected values.
    Additional Material: 3 Ill.
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  • 10
    ISSN: 0749-1581
    Keywords: Phthalocyanine ; Porphyrin ; Ring current ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The change in ring current of octaethylporphyrin, meso-tetraphenylporphyrin and phthalocyanine cobalt(III) complexes with axial amine ligands was studied using a double dipole network model. The porphyrin ring current was found to be highest in octaethylporphyrin but decreased by 5% in meso-tetraphenylporphyrin and 29% in phthalocyanine. The ring current in the fused benzene rings of phthalocyanine was similar to that found in free benzene. An attempt was made to rationalize changes in the porphyrin ring current in terms of the porphyrin substituents.An existing ring current program, DIPCALC, was modified to allow the calculation of ring current shifts for phthalocyanines. The parameters required to calculate ring current shifts for all three porphyrins are presented.
    Additional Material: 2 Ill.
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