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  • Chemistry  (249)
  • Inorganic Chemistry  (15)
  • mass spectrometry  (6)
  • 1
    Digitale Medien
    Digitale Medien
    Springer
    The protein journal 9 (1990), S. 623-632 
    ISSN: 1573-4943
    Schlagwort(e): Pancreatic thread protein ; primary structure ; mass spectrometry
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Pancreatic thread protein (PTP) forms double helical threads in the neutralpH range after purification, undergoing freely reversible,pH-dependent globule-fibril transformation. The purified bovine PTP consists on SDS gels of two carbohydrate-free polypeptide chains (Grosset al., 1985). Plasma desorption mass spectrometry and amino acid sequence analysis now confirm that bovine PTP contains two disulfide-bonded polypeptides, an A chain of 101 amino acid residues with a molecular weight of 11,073 and a B chain of 35 residues with a molecular weight of 3970. The intact protein exhibits a molecular weight of 15,036, agreeing 〉99.9% with the molecular weight calculated from the sequence. The B chain sequence was determined by gas-phase Edman degradation of the intact polypeptide. The A chain sequence was determined from overlapping peptides generated by cleavage at lysyl, tryptophanyl, and aspartyl-prolyl residues. Based upon the bovine PTP cDNA structure, the two chains of the protein result from cleavage of a single polypeptide with removal of a dipeptide between the NH2-terminal A chain and COOH-terminal B chain. Comparison of bovine PTP with other proteins reveals significant structural relatedness with the single-chain homologues from human and rat pancreas and with the motif associated with Ca2+-dependent carbohydrate recognition domains. The physiological role of PTP has not yet been resolved. The protein is present in very high concentration in pancreatic secretion and it has been detected in brain lesions in Alzheimer's disease and Down syndrome and in regenerating rat pancreatic islets. The present results provide a firm protein base for ongoing molecular, physical-chemical, and structure-function studies of this unusual protein.
    Materialart: Digitale Medien
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  • 2
    ISSN: 1573-4986
    Schlagwort(e): N-terminal sequencing ; glycoprotein ; glycan analysis ; covalent immobilization ; mass spectrometry
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The characterization of site-specific glycosylation is traditionally dependent on the availability of suitable proteolytic cleavage sites between each glycosylated residue, so that peptides containing individual glycosylation sites are recovered. In the case of heavily glycosylated domains such as theO-glycosylated mucins, which have no available protease sites, this approach is not possible. Here we introduce a new method to gain site-specific compositional data on the oligosaccharides attached to a single amino acid. Using a model glycopeptide from a mutant human albumin Casebrook, glycosylated PTH-Asn was recovered after sequential solid-phase Edman degradation, subjected to acid hydrolysis and the sugars were identified by high performance anion exchange chromatography with pulsed amperometric detection. The PTH-Asn(Sac) derivative was further characterized by ionspray mass spectrometry. Comparison between an endoproteinase Glu-C glycopeptide and a tryptic glycopeptide showed that the oligosaccharide attached to Asn494 was stable after at least 10 cycles of Edman degradation.
    Materialart: Digitale Medien
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  • 3
    ISSN: 1573-904X
    Schlagwort(e): fluphenazine ; stable isotope ; deuterium labeled ; mass spectrometry ; schizophrenics ; pharmacokinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 4
    ISSN: 1573-1561
    Schlagwort(e): Alkaloids ; mass spectrometry ; infrared spectroscopy ; amphibians ; ants ; decahydroquinolines ; quinolizidines
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract Three alkaloids—two minor decahydroquinolines (DHQs) and a major quinolizidine—were detected in an extract of a Brazilian myrmicine ant (Solenopsis (Diplorhoptrum) sp. picea group). One DHQ (3) was identical to a known frog-skin alkaloid, cis-195A (cis-5-methyl-2-propyldecahydroquinoline), while the second DHQ, an isomer of 3, designated 195J, was assigned a tentative cis-2-methyl-5-propyldecahydroquinoline structure (2) based on mass and infrared spectra. The third alkaloid proved identical to the frog-skin alkaloid 195C, for which a structure had not been previously proposed. Mass and infrared spectral analysis, including chemical ionization tandem mass spectrometry, indicated a 4-methyl-6-propylquinolizidine structure (1) for 195C. The four possible diastereomers were synthesized and the (6Z,10E)-4-methyl-6-propylquinolizidine diastereomer (1b) was identical to the natural alkaloid. Skin extracts of a population of a Madagascan mantelline frog contained, among other alkaloids, minor amounts of the same alkaloid triad 1–3 with 1 again predominating. The common occurrence of alkaloids 1–3 in both ant and frog supports the hypothesis that ants are a likely dietary source for sequestered frog-skin alkaloids and brings to six, the alkaloid classes common to ant and frog.
    Materialart: Digitale Medien
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  • 5
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Biopolymers 25 (1986), S. 1875-1893 
    ISSN: 0006-3525
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The heat denaturation of pepsinized bovine nonfibrillar and fibrillar collagen was studied by differential scanning calorimetry. For fibrillar preparations that had been rapidly precipitated with stirring at low ionic strength, then resuspended at physiological ionic strength, multiple denaturational transitions were observed. At heating rates of 10°C/min, melting endotherms occurred at about 44, 50, 53, and 57°C. Fibrillar collagen that was slowly gelled without stirring at physiological ionic strength exhibited a similar series of endotherms, but the lower melting transitions were less conspicuous. In contrast, nonfibrillar bovine collagen in acidic solution showed only a single denaturational transition at 40°C. Nonfibrillar solutions at pH 7, to which inhibitors of fibrillogenesis were added, showed a major endotherm as high as 46°C. These results suggest that reconstituted fibrillar collagen contains a heterogeneous fibril population, possibly including molecules in a nonfibrillar state. It was proposed that the multiple melting endotherms of such preparations were due to sequential melting of molecular and fibril classes, each with a distinct melting temperature. The fibrillar classes may represent three or more types of banded and nonbanded species that differ from each other in packing order, collagen concentration, and possibly also in fibril width and level of cross-linking.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 6
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Biopolymers 27 (1988), S. 1143-1157 
    ISSN: 0006-3525
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The effects of pH and temperature on the 300-MHz 1H-nmr spectra of three cardioactive polypeptides from sea anemones, anthopleurin-A from Anthopleura xanthogrammica (AP-A) and Anemonia sulcata toxins I and II (ATX I and II), are described. AP-A and ATX II exhibit major spectral heterogeneity. Evidence from the pH and temperature studies and from high performance liquid chromatography indicates that this heterogeneity is conformational rather than chemical in origin. By contrast, purified isotoxins of ATX I show no evidence of conformational heterogeneity. The pKa values of most of the ionizable groups in these polypeptides are not strongly perturbed by interactions in the tertiary structure, with the exception of one of the Asp carboxylates, which has a pKa of ≲ 2 in AP-A and ATX II and 3.0 in ATX I. Protonation of this carboxylate, suggested to be Asp-9, leads to a conformational change in all three molecules. All three polypeptides are thermally stable, showing some conformational changes but not major unfolding at elevated temperatures.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 7
    ISSN: 0006-3525
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Fluorescence, CD, absorption, and 1H-nmr studies are reported for complexes of 7-amino-actinomycin D with deoxydinucleotides, deoxytetranucleotides, and poly(dG-dC)· poly(dG-dC). The optical spectra for the 7-amino-actinomycin D complex with pdG-dC, pdG-dC-dG-dC and pdC-dG-dC-dG are similar in shape to the 7-amino-actinomycin D complex with either DNA or poly(dG-dC). The changes in the 1H chemical shifts of the 7-amino-actinomycin D and the pdG-dC resonances that accompany complex formation show that 7-amino-actinomycin D forms a minature intercalated complex with two pdG-dC molecules. The magnitudes of the induced chemical shifts for the 7-amino-actinomycin D complex formation with pdG-dC are similar to, but slightly different from, the induced chemical shifts which are obtained when actinomycin D forms a minature intercalated complex with two pdG-dC molecules. The pdN-dG dinucleotides (N = C, A, or T) form stacked complexes with 7-amino-actinomycin D. The presence of the 7-amino-group results in a larger dimerization constant (in aqueous solution) for 7-amino-actinomycin D [KD(6°C) = 4.4 × 103M-1], as compared to actinomycin D [KD(6°C) = 1.7 × 103M-1]; the chemical shifts which accompany dimer formation indicate that the chromophores stack in an inverted manner. Intercalation of 7-amino-actinomycin D into minature double helices, as well as into calf thymus DNA, poly(dG-dC)·poly(dG-dC), and poly(dA-dC)·poly(dG-dT), results in an enhancement of the relative fluorescence intensity and a shift in both the absorbance and corrected emission spectra.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 8
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Biopolymers 33 (1993), S. 1481-1503 
    ISSN: 0006-3525
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A winter flounder antifreeze polypeptide (HPLC-6) has been studied in vacuo and in aqueous solution using molecular dynamics computer simulation techniques. The helical conformation of this polypeptide was found to be stable both in vacuum and in solution. The major stabilizing interactions were found to be the main-chain hydrogen bonds, a salt-bridge interaction, and solute-solvent hydrogen bonds. A significant bending in the middle of the polypeptide chain was observed both in vacuo and in solvent at 300 K. Possible causes of the bending are discussed. From simulations of mutant polypeptide molecules in vacuo, it is concluded that the bend in the native polypeptide was caused by side chain to backbone hydrogen bond competition involving the Thr 24 side chain and facilitated by strains on the helix resulting from the Lys 18-Glu 22 salt bridge. © 1993 John Wiley & Sons, Inc.
    Zusätzliches Material: 15 Ill.
    Materialart: Digitale Medien
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  • 9
    ISSN: 0006-3525
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The small-angle x-ray scattering (SAXS) technique has been applied to investigate solution and gel structures of alginate in the absence and presence of two divalent cations: Ca(II) and Cu(II). We have observed a broad maximum in the scattering curve, a characteristic of polyelectrolyte, for the purified alginate sample. The scattering maximum disappears in excess of added simple salt and shifts toward the higher angle region with increasing alginate concentration. Concentration dependence of the position and intensity of the maximum follows power law relations with exponents close to those predicted by theory. Data analysis shows an increase in correlation length ξ and cross-sectional diameter d0, of polymer chains upon gelation and suggests that a dimeric structure is adopted in the junction zone, consistent with the “egg-box” model previously proposed. In the Ca(II)-alginate system, the molecular parameters ξ and d0 are found to have good correlation with the macroscopic properties of gelation, such as gel point determined by viscosity measurements. However, for the Cu(II)-alginate system there is no clearly transitional behavior observed in ξ and d0, implying that the junction zone may be replaced by a more uniformly distributed site binding of Cu(II) ions to the carboxyl groups of both mannuronate and guluronate residues, in confirmation of previous 13C-nmr results. © 1995 John Wiley & Sons, Inc.
    Zusätzliches Material: 14 Ill.
    Materialart: Digitale Medien
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  • 10
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 99 (1966), S. 3503-3523 
    ISSN: 0009-2940
    Schlagwort(e): Chemistry ; Inorganic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Verschiedene N-8-substituierte Lumazine werden synthetisch erhalten und durch ihre pK-Werte und UV-Absorptionsspektren charakterisiert. Die Neutralmoleküle und Monokationen zeigen übereinstimmende Strukturen, wogegen im alkalischen pH-Bereich unter normalen Bedingungen wenig übereinstimmende physikalische Daten erhalten werden. Kovalente Hydratation an das konjugierte System in 1.7-Stellung führt zu Gleichgewichtsgemischen verschiedener Molekülformen. Zur Klärung der Verhältnisse werden mit Hilfe einer Schnell-bestimmungsmethode die wahren pK-Werte und UV-Spektren der zum Teil instabilen Molekülformen bestimmt. Durch kinetische Messungen am 6.7.8-Trimethyl-lumazin (16) wird gezeigt, daß sich bei 6.7-Dimethyl-8-alkyl-lumazinen an die Wasseraddition noch eine reversible Ringöffnung des Pyrazinringes anschließt.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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