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  • 1985-1989  (13)
  • 1920-1924
  • Analytical Chemistry and Spectroscopy  (7)
  • Polymer and Materials Science  (6)
  • 1
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to determine the fraction of an intravenous bolus dose of ketamine which is metabolized in vivo to the corresponding N-desmethyl compound, norketamine, a novel stable isotope technique was developed and applied to a study in rats. Co-injection of equimoiar amounts of deuterium-labeled ketamine and unlabeled norketamine to four animals, followed by gas chromatographic/mass spectrometric analysis of both the administered compounds and deuterium-labeled norketamine in plasma yielded pharmacokinetic data from which the fraction of the parent drug subjected to N-demethylation (fm) was calculated from AUC data to be 36.8 ± 2.4%. It is concluded that this stable isotope co-administration technique represents a powerful approach to the determination of fm, in that the pharmacokinetics of the metabolite of interest, given as the preformed compound and generated in vivo, are determined simultaneously. This experimental design thus obviates the influence of time-dependent changes in metabolite clearance which may complicate the interpretation of studies performed using the classical cross-over design.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Alkoxycarbonyl derivatives of the cysteine-, N-acetylcysteine- and glutathione conjugates of acetaminophen have been prepared in aqueous buffer solutions and their chromatographic and mass spectrometric properties examined. Structurally informative fragmentation patterns of the cysteine- and N-acetylcysteine derivatives were obtained when their methyl esters were subjected to analysis by direct insertion chemical ionization (CH4) mass spectrometry, although field desorption and liquid secondary ion mass spectrometric techniques were required in order to obtain satisfactory spectral data for derivatives of the glutathione adduct. Treatment of ethoxycarbonyl derivatives of the three acetaminophen metabolites with N-methyltrifluoroacetamide-based silylating reagents led to the formation of a common volatile product which was ideally suited to analysis by gas chromatography/electron impact mass spectrometry. A mechanism is proposed for the formation of this novel derivative, which appears to possess a benzo-1,3-thioxalane structure, and its mass spectral characteristics are reported. Finally, the utility of alkoxycarbonyl derivatives for the analysis of drug - thioether conjugates in biological fluids is discussed in terms of their advantages for aqueous phase derivatization, purification by high-performance liquid chromatography and characterization by mass spectrometry.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 1 (1987), S. iv 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Fast-atom bombardment mass spectrometry of a synthetic renin substrate decapeptide (Pro-His-Pro-Phe-His-Leu-Val-Ile-His-D-Lys) indicated the presence of several of side-products, including a component 12 Da higher in mass. Low-energy collisionally activated decomposition analyses were performed using a hybrid tanden, instrument and demonstrated that the heavier side product had two components, in which the structural modification was either at the N- or the C-terminus. Additional analyses of the N-acetyl derivative indicated that for each component the strucutrual modification blcoked a site of N-acetylation. It is suggested that the formation of these side products is attributable to the generation of formaldehyde, during removal of the histidine protecting group (benzyloxymethyl), which reacts with the N-terminus of the peptide to give an imidazolidinone structure or with the D-lysine ε-amine group to yield an imine. While the precise genesis of the side-products remains speculative, it is clear that the combined strategy of derivatization and tandem mass spectrometry has allowed structural conclusions concerning individual components of an isobaric mixture.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 27 (1989), S. 993-1007 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The pressure-volume-temperature properties of poly(ether ether ketone) (PEEK) were studied experimentally at temperatures of 400°C and pressures to 200 MPa. Specific volume data were fitted successfully to the empirical Tait equation for T 〈 Tg and T 〉 Tm and to the theoretical Simha-Somcynsky equation of state for the melt. The pressure dependence of the glass-transition temperature is about 0.57-0.59°C/MPa and that of the melting point 0.483°C/MPa. The pressure dependence of the melting point, the specific volume of the melt at Tm, and the specific volume of the crystal at Tm determined from x-ray diffraction data at elevated temperatures were combined in the Clapeyron equation to calculate a heat of fusion of 161 ± 20 J/g for the PEEK crystal. This value is somewhat higher than the previously reported value of 130 J/g.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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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: Daughter ion spectra are reported for [M + H]+ ions generated by fast atom bombardment mass spectrometry of S-(N-methylcarbamoyl)glutathione (1) and a series of alkoxycarbonyl methyl ester derivatives thereof. Structurally informative, even-electron fragment ions, which serve to define the nature of both the xenobiotic and peptide components of the conjugate, are observed in the collisionally activated dissociation (CAD) spectra of 1 and its ethoxy- and benzyloxycarbonyl methyl esters. Studies with the t-butyloxycarbonyl (tBOC) methyl ester derivative, on the other hand, indicated that the tBOC group exerts a powerful directing influence on the CAD process, and that the major daughter ions in this case are associated with cleavage of the tBOC functionality itself and are of little diagnostic value. Of the derivatives examined, the benzyloxycarbonyl congener, which may be generated readily from 1 in aqueous media, is judged to be the most useful from the standpoints of ease of formation, desirable high-performance liquid chromatographic properties, and informative mass spectral fragmentation characteristics under CAD conditions.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 2 (1988), S. 195-195 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Type of Medium: Electronic Resource
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  • 8
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Liquid chromatography/thermospray mass spectrometry (LC/TSP-MS) has been used to identify and study the rates of formation of S-(N-methylcarbamoyl) cysteine and S-(N-methylcarbamoyl)glutathione as products of the in vitro reaction of cysteine and glutathione, respectively, with two monomethylcarbamate metabolites of the bronchodilator pro-drug bambuterol. The conjugates of interest afforded MH+ species and yielded abundant structurally informative fragment ions which were employed in the development of quantitative, selected-ion monitoring assays. It is concluded that LC/TSP-MS represents a rapid and convenient approach to the direct aqueous-phase analysis of the class of S-(N-alkylcarbamoyl) conjugates of cysteine and glutathione.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Biomedical Materials Research 19 (1985), S. 1101-1115 
    ISSN: 0021-9304
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine , Technology
    Notes: Macrophage adhesion to a wide variety of substrates has been measured, but no systematic study of the influence of specific substrate chemical properties on adhesion is available. These studies were conducted using two series of materials, copolymers of hydroxyethyl methacrylate (HEMA) and ethyl methacrylate (EMA) and copolymers of hydroxystyrene and styrene, to determine the effect of a single chemical property, polar character, on adhesion. Rat periotoneal macrophages were allowed to contact polymer substrates for periods ranging from 1 to 240 min before being subjected to a shear stress of 60-120 dynes/cm2 in a thin-channel flow cell. Percentage adhesion was calculated from the number of cells that remained adherent to the substrate after 30 s of applied shear stress. Macrophages remained adherent to 100% EMA and all hydroxystyrene-styrene copolymer surfaces after only 1 min of contact. In copolymers of the HEMA-EMA series, the time required to attain peak adhesion levels increased with increasing substrate hydrophilicity (increasing HEMA content). Cells did not attach to the 20% EMA/80% HEMA copolymer and the 100% HEMA polymer. The results demonstrate that there is a time delay between contact and adhesion of the cells to surfaces of increasing hydrophilicity within the HEMA-EMA series and no time delay with the hydroxystyrene-styrene series. The time delay is thought to be a function of the excluded volume provided by polymers that are able to undergo significant chain rotation and or swelling in the solvent, water. Small excluded volumes present in copolymers of high EMA content and all hydroxystyrene-styrene copolymers offer little or no resistance to formation of adhesive bonds by macrophages, whereas copolymers with large excluded volumes (high HEMA content) prevent contact and/or adhesion. A mechanism based on the net excluded volumes of both the cell and substrate surface macromolecule is proposed to explain this phenomenon.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Biomedical Materials Research 19 (1985), S. 1117-1133 
    ISSN: 0021-9304
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine , Technology
    Notes: The development of membranes that swell in response to glucose is reported. The membranes may prove to be useful in glucose monitoring or glucose-dependent insulin delivery. The polymers were synthesized by the radiation-induced polymerization of frozen solutions containing hydroxyethyl methacrylate, N,N-dimethylaminoethyl methacrylate, tetraethylene glycol dimethacrylate, ethylene glycol, water, and glucose oxidase. The polymers were hydrogels, with water contents in the range of 60-90%, depending on the pH or glucose concentration. Changes in swelling and permeability of the hydrogel were caused by exposure to glucose solutions. The gluconic acid formed by the glucose oxidase catalyzed oxidation of glucose in the membrane lowered the pH of the system and thus caused the changes in the membrane. The retention of enzyme activity by the membranes in vitro and in vivo is also reported. The large differences in properties among membranes made with different chemical formulations suggest that glucose-sensitive membranes with performance characteristics needed for an artificial pancreas may be an achievable goal.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
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