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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 47 (1996), S. 695-700 
    ISSN: 0947-5117
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Oxidation und Sulfidierung von Eisenaluminiden bei hohen TemperaturenZur Beurteilung der Beständigkeit gegenüber Oxidation und Sulfidierung von mehreren neuartigen Eisenaluminiden mit 5 Gew.-% Cr, 0,2 Gew.-% Zr, 0 bis 0,3 Gew.-% Y und 8 bis 16 Gew.-% Al wurden Untersuchungen bei 500 bis 700°C durchgeführt. Die Testumgebungen waren H2/H2O/H2S Gasmischungen, die Sauerstoff- und Schwefelpartialdrücke im Bereich von 10-24 bis 10-31 atm bzw. 10-9 bis 10-11 atm ergaben. Der Einfluß einer Voroxidation auf die Korrosionsbeständigkeit wurde ebenfalls untersucht. Zum Vergleich wurden verschiedene Standard-Cr2O3- und Al2O3-bildende Legierungen in das Programm einbezogen.Allgemein waren die Al2O3-bildenden intermetallischen Phasen und Legierungen wesentlich beständiger gegenüber Schädigungen als die Cr2O3-bildenden Legierungen. Eine Voroxidaiton erhöhte in jedem Fall die Zeitspanne bis zum Auftreten von abplatzender Korrosion, die durch die Bildung und Wachstum von Sulfiden verursacht war. In Umgebungen, in denen die Cr2O3-bilddenen Legierungen dicken Sulfidzunder entwickelten, konnte festgestellt werden, daß die Eisenaluminide wirksamer schützenden Al2O3-reichen Zunder entwickelten und behielten als konventionelle Al2O3-bildende Legierungen. Bei den relativ niedrigen Temperaturen dieser Versuche war es schwieriger, den schützenden Zunder aufrechtzuerhalten als bei hohen Temperaturen, insbesondere bei Legierungen mit relativ niedriger Aluminiumkonzentration. So zeigte ein Eisenaluminid mit 16 Gew.-% Al eine gute Widerstandsfähigkeit bei allen Bedingungen während ein Aluminid mit 8 Gew.-% Al bei 500°C stärkere Sulfidbildung entwickelte als bei 700°C. Insgesamt nahm der Widerstand der intermetallischen Verbindungen gegenüber Schädigungen mit steigendem Aluminiumgehalt zu, wenn auch keine von ihnen eine übermäßige Sulfidierung in den 50 h Testprogrammen zeigte.
    Notes: An investigation has been carried out into the oxidation-sulphidation resistance of a series of novel iron aluminides, containing 5 wt% Cr, 0.2 wt% Zr, from 0 to 0.3 wt% Y and from 8 to 16 wt% Al, at 500°C to 700°C. The test environments were H2/H2O/H2S gas mixtures, giving oxygen and sulphur partial pressures in the ranges of 10-24 to 10-31 atm and 10-9 to 10-11 atm respectively. The effects of preoxidation on the degradation resistance have also been studied. For comparison, several standard Cr2O3-forming and Al2O3-forming alloys were included in the programme.In general, the Al2O3-forming intermetallics and alloys were much more resistant to degradation than the Cr2O3-forming alloys while, in all cases, preoxidation increased the time to the onset of breakaway-type corrosion resulting from the initiation and growth of sulphides. In environments in which the Cr2O3-forming alloys developed thick sulphide scales, it was found that the iron aluminides developed and retained protective Al2O3-rich scales more effectively than the conventional Al2O3-forming alloys. At the relatively low temperatures of these tests, it was more difficult to establish the protective scale than at high temperatures, particularly on the alloys of relatively low aluminium concentration. Thus, an iron aluminide containing 16 wt% Al showed good degradation resistance under all conditions while an aluminide containing 8 wt% Al developed more extensive sulphides at 500°C that at 700°C. Overall, the resistance of the intermetallics to degradation increased with increasing aluminium concentration, although none of them showed excessive sulphidation in the 50 h test programmes.
    Additional Material: 6 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 6 (1992), S. 257-264 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A fragmentation proccess observed for peptides that contain lysine, or other amino acids which possess a free amino group on their sidechain, is reported. The ions generated by this process are found 16 Da below the acylium-type B ions that result from fragmentation at the C-terminal side of lysine or other amine-containing residues in fast-atom bombardment (FAB) mass spectra. These ions, which are referred to as (B - 16) ions, permit differentiation between the isobaric amino acids lysine and glutamine in peptide mass spectra. High resolution measurements indicate that (B - 16) ions differ in composition from the corresponding B ions by the removal of one oxygen atom. Formation is believed to occur through a cyclization process initiated by nucleophilic attack by the free amino group of the lysine sidechain at the carbon of the acylium ion (B ion). A similar process initiated derectly from the protonated peptide may also occur. Analogous cyclization processes are restricted for glutamine because this residue is comparatively less nucleophilic than lysine (i.e., amide vs amine). Although (B - 16) ions have been detected under high energy collisionally induced dissociation, they are formed less readily than by FAB mass spectrometry. A mechanism consistent jwith this observation as well as other experimental evidence is presented to account for the formation of (B - 16) ions.
    Additional Material: 5 Ill.
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  • 3
    ISSN: 0306-042X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Fast atom bombardment (FAB) is useful for the characterization of all major metabolites of the analgesic acetaminophen (APAP). It is particularly useful for providing mass spectra of the polar glucuronide and sulfate conjugates which eluded identification by field desorption and other more conventional methods of ionization. A protocol is described for the use of FAB in the identification of urinary APAP metabolites isolated by reversed phase high-performance liquid chromatography (HPLC) following therapeutic dosages of the drug. A tentative set of recommendations for the off-line use of HPLC and FAB is directed towards solving problems encountered when using these two analytical techniques in concert. In addition, a method for calculating the signal to background ratio (S/B) for analyte peaks in FAB spectra from selected relative ion intensities is proposed. Examples are presented that show the potential of S/B as an empirical parameter for judging the quality of FAB spectra.
    Additional Material: 4 Ill.
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  • 4
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The use of high-performance liquid chromatography and fast atom bombardment mass spectrometry are shown to be an efficient combination for investigating protease-mediated digestion of synthetic analogs of the peptide hormone ANF (atrial natriuretic factor). As examples of the reported methodology, rANF5-23-NH2 and rANF7-23-NH2 were digested with the endopeptidase thermolysin. These truncated analogs were selected to investigate metabolism within the disulfide-linked core of ANF, particularly at the Cys7—Phe8 bond. While this position was the site of initial hydrolysis for rANF5-23-NH2 (t1/2 = 0.5 min), the Cys7—Phe8 bond remained intact for all observed degradation products of rANF7-23-NH2 (t1/2 = 16 min). These findings suggest that improved stability towards endopeptidase-mediated core hydrolysis may be conferred to analogs of ANF by removal of the first six residues from the N-terminus.
    Additional Material: 8 Ill.
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  • 5
    ISSN: 1052-9306
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ability to acquire structurally informative daughter ion spectra for individual peptides undergoing separation and analysis by continuous flow fast atom bombardment (CF FAB) is demonstrated. To illustrate the potential of this methodology, tryptic and chymotryptic digests of the 29-residue peptide glucagon were analyzed by CF FAB using mass specrromctric and tandem mass spectrometric detection in consecutive analyses. Daughter ion spectra were recorded using B/E linked scans for the major hydrolysis products observed by liquid chromatography/mass spectrometry. The peptide mixtures were separated by gradient capillary high-performance liquid chromatography with the FAB matrix being added post-column using a coaxial flow interface between the column and flow probe. The entire effluent (3 μl min-1) was sampled by the mass spectrometer. Results obtained using less than 300 pmol of digested glucagon indicated several advantages to tandem mass spectrometric detection including the ability to confirm identities for products of enzymatic digestion and the potential use of this method for tandem sequence analysis of peptide mixtures.
    Additional Material: 11 Ill.
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  • 6
    ISSN: 0449-2951
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A study has been carried out on the molecular weight distributions of polystyrene initiated by sodium naphthalene in tetrahydrofuran solution. Stringent high-vacuum techniques were used in order to minimize initiator destruction or chain termination. Molecular weights were measured by osmotic pressure, dilute solution viscosity, light scattering and sedimentation equilibrium. In general, the molecular weight distributions found were quite narrow, as predicted, and corresponded to a stoichiometry of one polymer chain for two initiator molecules. However, the breadth of the distribution was very sensitive to experimental conditions, the M̄w/M̄n values found ranging from 1.1 to 1.5. At the higher molecular weights, there was some indication of a chain transfer reaction, leading to a lower molecular weight than expected, as well as a broadening of the distribution. This transfer reaction did not appear to be due to any transfer step between the short-lived radical-anions and the solvent.
    Additional Material: 6 Ill.
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  • 7
    ISSN: 0749-1581
    Keywords: 13C NMR ; 2-Iodosobenzoic acids ; 2-Iodoxybenzoic acids ; Sodium 2-iodosobenzoates ; Sodium 2-iodoxybenzoates ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 13C NMR spectra for selected 2-iodosobenzoic acids, their sodium salts and the sodium salts of the corresponding iodoxybenzoic acids were measured and carbon assignments made using 2D and NOE experiments and relaxation times. Iodoso and iodoxy groups deshielded the ipso-carbon in these compounds by approximately 25 and 55 ppm, respectively, relative to the corresponding iodo compounds. The 13C NMR spectra of the 2-iodosobenzoate anions were almost identical with those of the corresponding free acids, both possessing cyclic structures. The iodoxybenzoic acids are either insoluble in, or oxidize, suitable NMR solvents (i.e. DMSO-d6, DMF-d7). The cyclic structure postulated for iodoxybenzoate anions is supported by their 13C chemical shifts.
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