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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 40 (1996), S. 257-264 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper is a personal recollection of some of the events and research that surrounded the amino acid sequence determination of the hypothalamic releasing factor, TRF (now known as TRH), by mass spectrometry (MS), and the development of reverse phase high performance liquid chromatography (RP-HPLC) MS and tandem MS (MS/MS) methods for the qualitative and quantitative analysis of native opioid neuropeptides in human pituitary tissue extracts. © 1996 John Wiley & Sons, Inc.
    Additional Material: 1 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 9 (1995), S. 264-275 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Five synthetic opioid peptides that were designed to have specific opioid receptor-binding properties were studied by low energy collision-induced dissociation (CID) tandem mass spectrometry (MS/MS). The MS/MS data are required for the analysis of those peptides in ovine plasma in a study to determine the placental transfer of the peptide to the fetus. The synthetic enkephalin-related peptides were: Tyr-D-Arg-Phe-Lys-NH2, (DALDA), N,N-diallyl-Tyr-Aib-Aib-Phe-Leu-OH, (ICI 174,864), Tyr-D-Thr-Gly-Phe-Leu-Thr, (DTLET), . Liquid secondary ion mass spectrometry (LSIMS) was used for sample desorption-ionization, and a hybrid (E1BE2qQ) tandem mass spectrometer was used to collect the product-ion spectra. A protonated molecule ion, [M + H]+, was observed for each peptide. Amino acid sequence-determining fragment ions were produced by CID and collected by MS/MS for the three linear peptides, and also for the two disulfide-bond-containing peptides in their unreduced and dithiothreitol (DTT)-reduced forms. The detection level for the [M + H]+ ion of DTLET was ca. 3 pmol; and the stabilities of the CTAP and ICI analogs in plasma were studied.
    Additional Material: 9 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 1 (1974), S. 20-28 
    ISSN: 1052-9306
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Complete mass spectra of the pertimethylsilylated derivatives of three high molecular weight polyene macrolide antibiotics are reported for the first time. The fragmentation pathways which are proposed have been corroborated by the stable isotope derivatives d9-TMS and d3-acetyl. Accurate mass measurements and metastable transitions confirm the proposed fragmentation mechanisms in the low mass range. Nystatin - the macrolide of highest molecular weight in this study - expels several TMSOH molecules and a TMS radical. Amphotericin B underwent extensive rearrangements preliminary to eliminating a series of TMSOH molecules. An apparent equilibrium between the keto and ketal forms of amphotericin B facilitated the rearrangements. Pimaricin fragmented in a manner parallel to that of the other two macrolides. The sugar portion of the molecules dominated the fragmentation in the low mass region in the spectra of all compounds. The transfer of a TMS group from the sugar amine to the glycosidic oxygen was observed when the amino sugar was eliminated from the intact molecule. The resulting sugar ion then expelled ammonia.
    Additional Material: 5 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 8 (1981), S. 565-568 
    ISSN: 1052-9306
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Field desorption production of protonated molecular ions from nanomole amounts of chemically underivatized penta-, tetra- and dipeptides, coupled with collision induced decomposition of [M + H]+ ions, yielded partial amino acid sequence information. Linked scanning of two of the three fields detected ions produced in the first field free region of a double focusing mass spectrometer.
    Additional Material: 3 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 17 (1988), S. 37-45 
    ISSN: 1052-9306
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A mass spectral characterization of a set of anthracyclines and anthracyclinones comprised of daunorubicin, adriamycin and their modified analogs was carried out by using negative and positive fast atom bombardment (FAB) ionization techniques. Addition of more than one hydrogen to the molecular ions of the anthracyclines was observed. The choice of the FAB matrix played an important role in the characterization of these compounds. The dominant ions in the molecular ion region were M-· (or M+·) and MH- (or MH2+·) when sulfolane and glycerol, respectively, were employed as the FAB solvents. The major fragmentation was cleavage of the glycosidic bond with the charge retention mainly on the aglycone moiety. Aromatization of the tetracyclic ring promoted further fragmentation of the aglycone moiety. The anthracyclinones could be characterized only by negative FAB ionization using sulfolane as the FAB matrix. The assigned fragmentation pathways were confirmed by acquiring metastable ion spectra using B/E linked-field scans.
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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: In a study to test the hypothesis that defects in the metabolism of neuropeptides might be a contributing factor to human anterior pituitary tumor formation, the proenkephalin A, proopiomelanocortin (POMC), and tachykinin systems, which produce methionine enkephalin (ME), β-endorphin (BE), and substance P (SP), respectively, were measured in patients who had a wide variety of pituitary tumors. Mass spectrometry was used to optimize the level of molecular specificity of the ME and BE analytical measurements, and radioimmunoassay was used to measure SP-like immunoreactivity (SP-li). Compared to data obtained from pituitaries from post-mortem controls, the non-secreting tumors contained a significantly lower amount of the POMC neuropeptide, BE. The lower ME level was not significant. However, two adrenocorticotrophic hormone (ACTH)-secreting tumors contained ME, BE, and SP-li amounts that were much higher than both the controls and nonsecreting tumors. These data suggest that a hypometabolism of the POMC precursor may be operating in non-secreting tumors, and that a hypermetabolism of the proenkephalin A, POMC, and tachykinin precursors may be operating in two ACTH-secreting tumors. These data demonstrate that mass spectrometry plays a critical role in the study of human pituitary tumors.
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 8 (1994), S. 715-719 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The introduction of 18-crown-6 into the liquid sheath during the electrospray ionization mass spectrometry (ESI-MS) of peptides leads to the formation of crown ether/peptide complexes. The nominal mass spacing of the peaks from these complexes allows an unambiguous determination of the charge state of the ions and thus of their actual mass. The 264 Da mass shift is much larger than what is achieved by either Na+ or Cu2+ adduction, and is thus potentially more useful for the determination of charge states, especially for multiply charged high-molecular-weight species. The addition of an uncharged crown ether does not appear to interfere with the ESI process. Because the crown ether is added to the liquid sheath and not to the original solution, the method should be particularly amenable to chromatographic or electrophoretic techniques because it is essentially a post-column noncovalent derivatization procedure. Finally, because the complex formation constants are relatively large, the peptide/crown ether complex yields high intensity ions, normally the base peak in the spectrum when analyzing pure peptide samples. Finally, as the crown ether is neutral and noncovalently complexed, a constant-neutral-loss scan of their collision-induced dissociation spectra yields a simplified spectrum that is free of chemical noise.
    Additional Material: 4 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 20 (1991), S. 130-138 
    ISSN: 1052-9306
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Fast atom bombardment (FAB) mass spectrometry and multiple reaction monitoring (MRM) in the B/E linkedfield scan mode were used to quantify endogenous β-endorphin (BE) in individual human pituitary extracts. The experimental protocol includes the addition of a stable isotope-labeled internal standard ((2H4-Ile22)BE1-31, human) to the tissue homogenate before extraction, purification of the native BE by a combination of Sep-Pak chromatography and gradient high-performance liquid chromatography (HPLC), trypsin digestion to cleave BE into smaller peptides, and separation of the tryptic fragment BE20-24 (NAIIK) by isocratic reversed-phase HPLC. Mass spectrometric quantification is based upon recording either (a) the [M + H]+ ions of NAIIK and its deuterated analog ((2H4)NAIIK), or (b) the transitions {[NAIIK + H]+ → [NAI]+} and {[(2H4)NAIIK + H]+ → [(2H4)NAI]+} using the B/E linked-field scan. Linear calibration curves were obtained using these two mass spectrometric techniques from standard solutions containing 1.25-20 μg of BE; each standard solution also contained 10 μg of (2H4)BE. The amounts (x̄ ± s.d.) of endogenous BE in five separate human pituitaries were found to be 156 ± 84 ([M + H]+ method) and 169 ± 99 pmol mg-1 protein (MRM method).
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 1 (1987), S. 77-79 
    ISSN: 0951-4198
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Additional Material: 2 Tab.
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  • 10
    ISSN: 1076-5174
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The molecular ion of intact β-endorphinbovine, 1-31 (BE), which was extracted from bovine pituitary, was determined by electrospray ionization mass spectrometry. Liquid secondary ion mass spectrometry determined the molecular masses of three peptides produced by trypsin digestion of BE, and tandem mass spectrometry was used to determine the amino acid sequence of the tryptic peptide BE20-24. These data, in combination, were used to characterize BE in bovine pituitary.
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