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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    The protein journal 9 (1990), S. 623-632 
    ISSN: 1573-4943
    Keywords: Pancreatic thread protein ; primary structure ; mass spectrometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1573-4986
    Keywords: N-terminal sequencing ; glycoprotein ; glycan analysis ; covalent immobilization ; mass spectrometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1573-904X
    Keywords: fluphenazine ; stable isotope ; deuterium labeled ; mass spectrometry ; schizophrenics ; pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 1573-1561
    Keywords: Alkaloids ; mass spectrometry ; infrared spectroscopy ; amphibians ; ants ; decahydroquinolines ; quinolizidines
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: 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.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 1573-904X
    Keywords: adinazolam mesylate ; gradient reversed-phase liquid chromatography ; mass spectrometry ; decomposition products assay
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A gradient high performance liquid chromatographic method was developed to determine degradation products of adinazolam mesylate in a sustained release tablet formulation. Sample preparations were chromatographed on a YMC-Basic column using a formate buffer/acetonitrile gradient with absorbance detection at 254 nm. Adinazolam mesylate was found to degrade at high relative humidity and temperature to form a major product, the 6-aminoquinoline analog, plus numerous other compounds. Five of these compounds were identified and their structures indicate that the solid-state degradation of adinazolam, in the presence of sufficient moisture, involves not only a hydrolytic mechanism, but also an oxidative mechanism. Potential process impurities were resolved from the drug and degradation products. Recovery was near 100% over the 0.5 to 10% range for the major degradate (6-aminoquinoline) and over the 0.5 to 1% range for the other analytes. The method was applied to tablet samples stressed at high relative humidity and temperature. The relative standard deviation of the assay for the 6-aminoquinoline was less than 2% and less than 13% for the minor components. Calculated mass balances (sum of adinazolam plus degradation products in the degraded tablet divided by the same sum in the undegraded tablet) were less than 100% and were dependent on the extent of degradation in the tablet. The average mass balance result obtained for samples that were an average of 9.5% degraded was 95.0 ± 1.5%. It is possible that the decrease in mass balance with increase in percent degradation may be explained by the formation of many components at trace levels due to degradation by various permutations of hydrolytic and oxidative reaction pathways.
    Type of Medium: Electronic Resource
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  • 6
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Mechanical properties were correlated with glass transition temperatures for a series of random copolymers of methyl methacrylate with comonomers selected from the higher n-alkyl acrylates and N-n-alkylacrylamides. The plasticizing comonomers were the n-butyl, 2-ethylhexyl, n-octadecyl, and oleyl acrylates, and the N-n-butyl-, N-n-octyl-, N-n-octadecyl-, and N-oleylacrylamides. The complete range of compositions was investigated. However, the bulk of the data was obtained on compositions in the glassy region below the onset of the vitreous transition. In this region it was found that the decrease in tensile and flexural moduli and strengths with increase in internal plasticizer for all of the systems was directly proportional to the decrease in Tg. It was concluded that the additive contribution to the free volume made by each side-chain methylene group was alone responsible for the magnitude of the rate of change of properties. However, polar contributions of the amide group to stiffening the main chain exceeded those of the ester, so that the amides were less efficient plasticizers. An empirical equation was derived which described, with fair accuracy, the decrease in the mechanical parameters with composition for the amorphous copolymers. It was reasonably successful in predicting properties even into the composition range where the ambient testing temperature corresponded to or exceeded the transition temperature. In this transition region an accelerated decrease in the magnitude of the physical properties was observed. All samples exhibited brittle fracture except those tested in the transition region. Here the strain was largely irrecoverable flow. Side-chain crystallinity did not interfere significantly with the mechanical properties because moduli and strengths had already decayed to small values near the compositions where crystallinity commenced. Non-random copolymers of vinyl stearate and methyl methacrylate showed no internal plasticization, apparently because of macrophase aggregation.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 853-865 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rate of adsorption of fractionated polyethylenimine (PEI) from water onto regenerated cellulose fibers was studied as a function of the polymer diffusion coefficient. Differences in polymer molecular weight, salt concentration, and pH were employed to vary the diffusion coefficient which was measured independently by a free-diffusion technique. The sorption rate was measured at the same conditions and found to increase with decreasing molecular weight, increasing polymer concentration, decreasing salt concentration, and increasing pH. A simplified rate equation based on diffusion control with Langmuirian adsorption in stirred solution was developed by utilizing the concept of a Nernst diffusional film. The equation was successful in predicting the relationship between adsorption rate and diffusion coefficient for most cases studied. It was found, however, that a very large barrier to mass transfer retards the adsorption rate. For the system studied it was concluded that this barrier is a result of diffusion into and subsequent adsorption onto the internal porous structure of the cellulose.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 29-43 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polyethyleneimine (PEI)-water-silica gel absorption system was used as a model system to investigate the relationship between diffusion into the porous structure, adsorption rate, and molecular weight of the polymer. Three silica gels, Porasil A, B, and and C having a range of characteristic porosity were used as adsorbents. Adsorption of PEI on Porasil C, which has the majority of its pores much larger than the dimensions of the adsorbate molecule, increased initially with increased molecular weight but became nearly constant at higher molecular weight. Little increase in adsorption occurred for this silica gel with increased ionic strength or with increased pH between 9.5 and 10.8. In contrast, adsorption increased sharply with increased ionic strength and for the same pH range on Porasil A. Molecular weight dependence was reversed. Adsorption decreased with increased molecular weight on Porasil A. In this case, the molecular size of PEI investigated was the same as the majority of pore apertures in the adsorbent. Solution environments (i.e., pH and ionic strength) that decrease the size of the PEI molecule and its affinity for the anionic silica gel surface, thus enabling it to more readily diffuse into the smaller porous regions of the adsorbent, are the apparent causes of the very large adsorption increase. Electrostatic repulsion between PEI molecules do not appear greatly to affect adsorption. Similar adsorption behavior has been reported in the literature for the PEI-cellulosic fiber adsorption system. Maximum adsorption on Porasil A occurred at pH 10.8, the same maximum generally reported for adsorption of PEI on cellulosic fibers. In this case, the silica gel (Porasil A) was found to have a pore size distribution and specific surface area of the same magnitude as cellulosic fibers prepared in the expanded state.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 3797-3810 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several N-vinylarylamines have been prepared by direct N-vinylation of arylamine salts with acetylene at atmospheric pressure. Nuclear magnetic resonance (NMR) spectra of the various N-vinylarylamines were recorded and chemical shift assignments were made for the first time. The vinyl protons of the enamines generally exhibit an ABX pattern. The electron-rich monomers are sensitive to acid-catalyzed hydrolysis in a wet solvent. Polymerizations of the monomers were carried out at low temperatures with phosphorous pentafluoride as an initiator. It was found that PF5 generated directly from thermal decomposition of p-chlorobenzenediazonium hexafluorophosphate is useful in the preparation of an extremely high-molecular-weight poly(N-vinylcarbazole) (Mw = 3 × 106) with a narrow molecular weight distribution (MWD = 2.1). The polymerizability of N-vinylarylamines appears to vary with the amine functional groups of the monomers. N-vinylarylamine containing a planar amine moiety such as carbazole forms a higher-molecular-weight polymer than the monomers with the nonplanar bulky amine groups.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2197-2215 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Seeded emulsion copolymerization of an azeotropic composition of styrene (St) and an acrylinitrile (AN) comonomer mixture in polystyrene (PS) seed at different polymerization temperature of 55-75°C were investigated. The kinetic data showed a transition temperature at 65°C, above which the activation energy of polymerization is low, 6.1 Kcal/mol, compared with 9.8 Kcal/mol below it. The particle-size results and thin layer chromatographic (TLC) data showed two types of particle of different composition and morphology in the final latex system: a smaller size of (St-AN) copolymer and a larger size of core-PS and (St-AN) copolymer shell, with a zone of PS grafted (St-AN) copolymer in between. Various polymerization parameters, that is emulsifier concentration, type of seed particle and its size, and monomer/polymer ratio, were studied and their effects on particle size and particle morphology were examined. The percent of grafted core-PS was 10% below a polymerization temperature of 65°C and 40% above that temperature. By adjusting the size and number of the seed particles, monomer-polymer ratio, and emulsifier concentration conditions were established in which a final copolymer latex with “perfect” core-shell morphology was achieved.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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