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  • 1
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 19 (1990), S. 27-31 
    ISSN: 1052-9306
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methodology is presented for convenient, reproducible and direct measurement of blood concentrations of ethyl carbamate, an experimental animal carcinogen. Extraction techniques requiring 20 μl of blood and selected ion monitoring using ethyl (13C, 15N)carbamate as internal standard enabled quantification of ethyl carbamate concentrations ranging from 50 ng ml-1 to 100 m̈g ml-1. Coefficients of variation at several representative concentrations averaged less than 4%. The method was used to determine the time course of elimination of ethyl carbamate from mice receiving doses of 125 m̈mol kg-1.
    Additional Material: 3 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 7 (1993), S. 828-836 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Conditions for the matrix-assisted laser desorption/ionization (MALDI) of oligodeoxyribonucleotides at 355 nm, developed using a 3-Tesla Fourier-transform ion cyclotron resonance mass spectrometer (FTMS), are reported. Efficient ion trapping and matrix selection are critical to the desorption and detection of oligonucleotides by FTMS. The achievable upper mass limit for the MALDI-FTMS of bio molecules on our 3-Tesla system has been extended from approximately 2 kDa to 6 kDa through the use of pulsed-trapping-plate ion deceleration techniques. By implementing the deceleration techniques, molecular ions for bovine insulin (MW = 5733.5), an oligodeoxythymidylic acid, pd[T]10 (MW = 3060.0), and a mixed-base 12-mer (MW = 3611.5) have been measured. For the analysis of oligonucleotides by FTMS, selection of an appropriate MALDI matrix is essential for the generation of [M—H]- ions. 3-Hydroxypicolinic acid provides a significant improvement over 2,5-dihydroxybenzoic acid for production of deprotonated molecules particularly for mixed-base oligomers. MALDI studies using FTMS have been duplicated using a newly constructed time-of-flight mass spectrometer (TOFMS) and oligonucleotide fragmentation on the TOFMS is reduced relative to that observed by FTMS. This may be a consequence of the longer times (milliseconds) required for FTMS detection.
    Additional Material: 10 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 9 (1995), S. 731-734 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A new interface for coupling electrospray (ES) ionization and Fourier transform ion cyclotron resonance (FTICR) mass spectrometry has been developed based on an electrostatic ion guide (EIG). In these initial studies, the EIG interface has been demonstrated to be a simple but effective means of transmitting ES ions generated outside the magnetic field to the FTICR cell. In the current system, the pressures in the EIG region and front FTICR cell are 10-5 and 10-6 Torr, respectively. Under these conditions, ions may be accumulated with low trapping voltages (0.5-0.75 V) and without a high pressure pulse of buffer gas. ES-FTICR spectra of picomole to femtomole quantities of several peptides, proteins, nucleotides and dinucleotides have been obtained. Modifications currently in progress should enhance performance with respect both to limits of detection and to mass resolution.
    Additional Material: 5 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Heteroatom Chemistry 1 (1990), S. 65-74 
    ISSN: 1042-7163
    Keywords: Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of pinanediol boronates with (1,1-dichloroethyl)lithium generated in situ at -78°C followed by rearrangement of the resulting borate complex 2S in the presence of zinc chloride at 25°C has resulted in chirally biased insertion of the 1-chloroethyl group into the carbon-boron bond. (s)-Pinanediol phenylboronate (7) produced (s)-pinanediol (1S)-(1-chloro-1-phenylethyl)boronate (8S) in 92% DE. Nonstererospecific reaction with ethylmagnesium bromide to form (s)-pinanediol (1S)-(1-phenyl-1-methylpropyl)boronate (5S) reduced the DE to 88%. Peroxidic deboronation yielded (R)-(+)-2-phenyl-2-butanol (6R) (84% EE). (s)-Pinanediol ethylboronate (4) with (1,1-dichloroethyl)lithium showed the opposite chiral preference, yielding (s)-pinanediol (1R)-(1-chloro-1-methylpropyl)boronate (3R) (89% DE), which was converted by phenylmagnesium bromide followed by hydrogen peroxide to 6R (76% EE). Diastereoselections were small in reactions of (1,1-dichloroethyl)-lithium with n-alkylboronates 9a and 13 and with cyclohexylboronate 9c. The 13 was converted to the enantiomer of the insect pheromone frontalin (17) (21% EE). Good diastereoselections were found with α-substituted alkylboronates 9b and 18, but the configurations of the products could not be determined. (s)-Pinanediol (1,1-dichloroethyl)boronate (1) reacts with Grignard reagents via an intermediate borate 2R with negligible diastereoselection.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 34 (1983), S. 446-450 
    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: Einfluß von Silicium und Yttrium auf die isothermische Verzunderung einer austenitischen FeCrNi-Legierung (IN 519) bei 1000 °CSowohl Silizium als auch Yttrium beeinflussen das Verzunderungsverhalten von austenitischen FeCrNi-Legierungen in Luft hoher Temperatur. Silizium fördert die Bildung und Erhaltung eines kontinuierlichen Chromoxidzunders, während Yttrium die Haftfestigkeit der Zunderschicht erhöht. Unter isothermischen Bedingungen wird bei 1000°C durch mindestens 0,8% Silizium die Verzunderungsgeschwindigkeit der Gießlegierung Fe 24Cr24Ni dadurch verringert, daß zusätzliche Zentren für die seitliche Ausbreitung der Chromoxidschicht geschaffen werden. Yttrium führt zur Bildung von Fe9Y-Teilchen, welche die Kontinuität der Chromoxidschicht unterbrechen. Der günstige Einfluß des Siliziums überwiegt bei den potentiell schädlichen Wirkungen des Yttriums in Legierungen, die beide Elemente enthalten.
    Notes: When present in austenitic Fe-Cr-Ni alloys, both silicon and yttrium influence scaling behaviour during oxidation tests in air at high temperatures. The former promotes the formation and maintenance of a continuous Cr2O3 scale and the latter improves scale adhesion. During the isothermal exposure of nominally Fe + 24%Cr + 24%Ni east alloys at 1000°C a silicon content above 0.8% reduces the rate of scaling by providing additional sites for the lateral growth of the Cr2 O3 layer. Yttrium gives rise to the formation of Fe9Y particles which disrupt the continuity of the Cr2O3 scale. The beneficial influence of silicon dominates the potentially detrimental effect of yttrium in alloys containing both silicon and yttrium.
    Additional Material: 6 Ill.
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  • 6
    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: Messung der mechanischen Eigenschaften von in oxydierender Umgebung entstehenden OberflächenfilmenDie mechanischen Eigenschaften von Oberflächenzunder auf Eisen und Nickel wurden mit Hilfe einer Vibrationstechnik schon früher bei hohen Temperaturen während des Wachstums bestimmt. Die Möglichkeit der Anwendung dieser Methode zur Untersuchung anderer Systeme wird erörtert und besonders die Anwendung auf Hochtemperaturlegierungen wird untersucht. Der Einfluß von Temperatur, Oxidationsgeschwindigkeit und Oxidstabilität auf die Ergebnisse werden erörtert und der E-Modul des Oxidzunders auf Nimonic 90 wurde in einem größeren Temperaturberich bestimmt.
    Notes: The mechanical properties of surface scales on iron and nickel have been previously measured, during growth at high temperatures, using a vibrational technique (1,2). The feasibility of using this technique to study other systems is discussed and, in particular, its application to high-temperature, oxidation rate and oxide stability on the results are considered and values of the Youngs modulus of the oxide scale on Nimonic 90 over a range of temperatures have been determined.
    Additional Material: 7 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 35 (1984), S. 266-272 
    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: Einfluß von Silicium und Yttrium auf die Verzunderung austenitischer FeCrNi-Legierungen bei thermischer WechselbeanspruchungMit Hilfe von thermogravimetrisch und aufgrund der Resonanzfrequenz erhaltenen Ergebnissen sowie der Gefügeanalyse wird der Einfluß von Silicium- und/oder Yttrium-Zusätzen zu Fe 24 Cr 24 Ni auf das Oxidationsverhalten bei thermischer Wechselbeanspruchung untersucht. Silicium begünstigt danach die Bildung eines schützenden Chromoxidzunders, jedoch kann die Ansammlung einer mechanisch schwachen, siliciumreichen Oxidschicht an der Zunder/Metall-Grenzfläche zum Abplatzen des Zunders führen. Yttrium allein beeinflußt das Oxidationsverhalten nur geringfügig; zusammen mit Silicium verhindert es jedoch die Bildung der genannten siliciumreichen Zwischenoxidschicht. Die Temperaturänderung, die erforderlich ist, um den Zunder zum Abplatzen zu bringen und die schützende Wirkung aufzuheben, dient als Maß für die mechanische Integrität der entstandenen Zunderschicht. Die Fähigkeit von Legierungen, auch bei häufigem Temperaturwechsel rasch schützende Zunderschichten zu bilden und Schäden der Zunderschicht im Laufe längerer isothermischer Behandlung zum Ausheilen zu bringen, werden getrennt untersucht.
    Notes: Data obtained using thermogravimetric and resonant frequency techniques and the results of structural analysis are used to evaluate the effects on oxidation of silicon and/or yttrium additions to an Fe-24% Cr-24% Ni alloy tested under thermal cycling conditions. Silicon promotes the formation of a protective chromia scale, but the accumulation of a mechanically weak, silicon-rich oxide at the scale-metal interface eventually leads to scale spalling. Yttrium alone is found to have little influence on the rate of alloy degradation, but in alloys containing silicon its presence prevents the accumulation of the interfacial silicon-rich oxide layer. The temperature change required to cause scale failure and loss of protection to the substrate material is used as a measure of the mechanical integrity of the scales formed. The ability of alloys to form scales rapidly under conditions of frequent thermal cycling and to repair damage caused to a scale grown over a prolonged period of isothermal exposure are separately examined.
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  • 8
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 45 (1960), S. 195-204 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The reaction between Et3Al and TiCl4 is discussed, with emphasis on the effect of temperature, concentration, stoichiometry, and order of component addition on the ability of products to catalyze the isotactic polymerization of styrene. A well-defined peak in relative catalyst activity becomes apparent when the interaction of these variables is followed by measuring the average oxidation state of titanium. Experimentally, the polymerization is first-order with respect to styrene and titanium, although efficiency of Ti use is small. The mode of polymerization is characterized by a lower activation energy for active site generation and a higher activation energy for termination than is typical of free-radical polymerization. A convenient procedure for laboratory preparation of isotactic polystyrene employing the Et3Al/TiCl4 catalyst is given.
    Additional Material: 8 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 44 (1960), S. 272-275 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Ill.
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  • 10
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the acridine orange-dermatan sulfate system, free and bound dye can be distinguished from each other spectroscopically. This permits the use of fluorometric methods to study the binding of acridine orange to the acid mucopolysaccharide dermatan sulfate. Experiments were conducted at 24°C in 10-3 M citrate/phosphate buffer at pH = 7.0. The binding of the dye is highly cooperative, as evidenced by considerable interaction between adjacent bound dye molecules. Analysis of the data indicates that dermatan sulfate binds 2.3 ± 0.3 mol of acridine orange per dermatan sulfate uronic acid residue with a cooperative binding constant, Kq ranging from 4.9 to 6.0 × 105 M-1 which corresponds to a free energy of 7.74 ≤ ΔG° ≤ 7.86. The cooperativity parameter q apparently increases with increasing polymer-to-dye ratio.
    Additional Material: 4 Ill.
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