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  • 1
    Digitale Medien
    Digitale Medien
    Springer
    Journal of solution chemistry 25 (1996), S. 179-189 
    ISSN: 1572-8927
    Schlagwort(e): Intramolecular hydrogen bond ; solvent effect ; dipole moment ; IR ; UV ; NMR
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Solvent effect on intramolecular hydrogen bond in 8-quinolinol N-oxide has been studied by IR, UV,1H NMR and13C NMR spectroscopy, dipole moment measurements and quantum-mechanical calculations. The solute-solvent interactions are of local character and they vary considerably over the range of solvent under study. The results suggest that formation complexes with solvent molecules weaken the intramolecular hydrogen bond in 8-quinolinol N-oxide.
    Materialart: Digitale Medien
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  • 2
    Digitale Medien
    Digitale Medien
    Springer
    Journal of inorganic and organometallic polymers and materials 5 (1995), S. 217-236 
    ISSN: 1572-8870
    Schlagwort(e): Polysilane ; NMR ; pyrolysis ; randomization
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Bimodal molecular weight distributions of alternating copolymers of the type (Me2Si−R2Si−SiMe2) n , where R=hexyl and butyl, were obtained by polymerization of BrSiMe2−R2Si−Me2SiBr, using the Wurtz coupling method. Analysis of the samples by pyrolysis GC MS and solution29Si NMR indicated that some randomization occurred, due to cleavage of the original Si−Si bonds in the monomer. The extent of randomization was significantly greater in the high molecular weight fractions. Based on the nature of the rings from the py MGC/MS traces and the number on nonads found in the29Si spectra, two types of randomization processes have been proposed, involving backbiting followed by (1) ring expulsion or (2) redistribution.
    Materialart: Digitale Medien
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  • 3
    ISSN: 1572-8927
    Schlagwort(e): Hydrogen-1 ; carbon-13 ; nitrogen-15 ; NMR ; magnesiumisothiocyanate complexes
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract A hydrogen-1, carbon-13, and nitrogen-15 NMR study of magnesium(II)-isothiocyanate complexation in aqueous mixtures has been completed. At temperatures low enough to slow proton and ligand exchange, separate1H,13C, and15N NMR signals are observed for coordinated and bulk water molecules and anions. The1H NMR spectra reveal signals for the hexahydrate and the mono-through triisothiocyanato complexes, as well as two small signals attributed to [Mg(H2O)5(OH)]1+ and [Mg(H2O)4(OH)(NCS)]. Accurate hydration numbers were obtained from signal area integrations at each NCS− concentration. In the15N NMR spectra, signals also were observed for the mono-through triisothiocyanato complexes, and a small signal believed to be due to [Mg(H2O)4(OH)(NCS)]. Coordination number contributions for NCS− were measured from these spectra and when combined with the hydration numbers they totalled essentially six at each anion concentration. Signals for [Mg(H2O)5(NCS)]1+ through [Mg(H2O)3(NCS)3]1− also were observed in the13C NMR spectra and the area evaluations were comparable to the15N NMR results. An analysis of the magnitude and sign of the coordinated NCS− chemical shifts identified the nitrogen atom as the anion binding site. All spectra indicated [Mg(H2O)5(NCS)]1+ and [Mg(H2O)4(NCS)2] were the dominat isothiocyanato complexes over the entire range of anion concentrations. The inability to detect evidence for complexes higher than the triisothiocyanato reflects the competitive binding ability of water molecules and perhaps the decreased electrostatic interaction between NCS− and negatively charged higher complexes.
    Materialart: Digitale Medien
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  • 4
    Digitale Medien
    Digitale Medien
    Springer
    Journal of solution chemistry 25 (1996), S. 1029-1039 
    ISSN: 1572-8927
    Schlagwort(e): 18-Crown-6 ; barium ; methanol ; exchange kinetics ; bimolecular mechanism ; NMR
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Exchange kinetics of Ba2+-18-crown-6 complex in deuterated methanol solution was studied by proton NMR line-shape analysis of a series of solutions containing equal population of free and complexed 18-crown-6, but varying concentration of the macrocycle, at various temperatures. From −33 to 37°C, the predominant mechanism for the exchange of the ligand between the two sites is a bimolecular pathway which is characterized by the following activation parameters:E a=47±2 kJ-mol−1; ΔH ≠=45±2 kJ-mol−1; ΔS ≠=−8±4 J-mol−1-K−1. However, the contribution of a dissociative mechanism with activation parametersE a=36±5 kJ-mol−1, ΔH ≠=33±5 kJ-mol−1 and ΔS ≠=104±18 J-mol−1-K−1 becomes more important at higher temperatures.
    Materialart: Digitale Medien
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  • 5
    ISSN: 1572-8927
    Schlagwort(e): Hydrogen-1 ; carbon-13 ; nitrogen-15 ; NMR ; lutetium(III) ; isothiocyanate ; complexation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract A direct, low-temperature hydrogen-1, carbon-13, and nitrogen-15 nuclear magnetic resonance study of lutetium(III)-isothiocyanate complex formation in aqueous solvent mixtures has been completed. At −100°C to −120°C in water-acetone-Freon mixtures, ligand exchange is slowed sufficiently to permit the observation of separate1H,13C, and15N NMR signals for coordinated and free water and isothiocyanate ions. In the13C and15N spectra of NCS−, resonance signals for five complexes are observed over the range of concentrations studied. The13C chemical shifts of complexed NCS− varied from −0.5 ppm to −3 ppm from that of free anion. For the same complexes, the15N chemical shifts from free anion were about −11 ppm to −15 ppm. The magnitude and sign of the15N chemical shifts identified the nitrogen atom as the binding site in NCS−. The concentration dependence of the13C and15N signal areas, and estimates of the fraction of anion bound at each NCS−:Lu3+ mole ratio, were consistent with the formation of [(H2O)5Lu(NCS)]2+ through [(H2O)Lu(NCS)5]2−. Although proton and/or ligand exchange and the resulting bulk-coordinated signal overlap prevented accurate hydration number measurements, a good qualitative correlation of the water1H NMR spectral results with those of13C and15N was possible.
    Materialart: Digitale Medien
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  • 6
    Digitale Medien
    Digitale Medien
    Springer
    BioMetals 9 (1996), S. 66-72 
    ISSN: 1572-8773
    Schlagwort(e): calcium ; ceruloplasmin ; prothrombin
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract Binding of calcium to human and sheep ceruloplasniin was investigated by metal substitution with manganese and competitive displacement of bound manganese by calcium monitored by electron paramagnetic resonance spectroscopy. The K d for calcium was found to be 1.4mm. Magnesium also bound to ceruloplasmin, with K d = 0.3 and 0.7 mm for the human and sheep protein, respectively. The thermal stability of ceruloplasmin, as studied by differential scanning calorimetry, was affected by calcium but not by magnesium. A considerable increase of the T m value, from 73.8 to 83.1°C, was observed for sheep ceruloplasmin in the presence of calcium. The T m value of the human protein was only slightly altered by calcium (from 85.1 to 87°C). The interaction of ceruloplasmin with the chromatographic material used for its isolation, Sepharose 4B derivatized with chloroethylamine, was weakened by calcium. This allowed us to set up a novel purification scheme that made it possible to efficiently isolate ceruloplasmin and prothrombin from plasma with the same single-step chromatography.
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  • 7
    Digitale Medien
    Digitale Medien
    Springer
    BioMetals 9 (1996), S. 29-37 
    ISSN: 1572-8773
    Schlagwort(e): calcium ; fibroblasts ; potassium ; transport ; zinc
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract The influence of K+ and Ca2+ on Zn2+ transport into cultured human fibroblasts was investigated. Zn2+ uptake was markedly reduced in the presence of both valinomycin and nigericin (electrogenic and electroneutral K + ionophores, respectively), and by reduction in the transmembrane K+ gradient produced by replacement of extracellular K+ with Na+, suggesting that Zn2+ may be driven by a Zn2+/K+ counter-transport system. To test the counter-transport hypothesis, we used 86Rb as an analog of K + for efflux studies. The rate of Rb+ efflux was 3760 times that of Zn2+ uptake, thus the component of K+ involved in the Zn2+ counter-transport system was only a small proportion of the total K+ efflux. In investigating the effect of Ca2+ on Zn2+ uptake, we identified two components: (1) a basal Zn2+ uptake pathway, independent of hormonal or growth factors which does not require extracellular Ca2+ and (2) a Ca2+-dependent mechanism. The absence of Ca2+ decreased Zn2+ uptake, while increasing extracellular C+a2+ stimulated Zn2+ uptake. The effect was mediated by Ca2+ influx as the ionophores A23187 and ionomycin also stimulated Zn2+ uptake. We could not ascribe the Ca2+ effect to known Ca2+ influx pathways. We conclude that Zn2+ uptake occurs by a K+-dependent process, possibly by Zn2+/K+ counter-transport and that a component of this is also Ca2+-dependent.
    Materialart: Digitale Medien
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  • 8
    Digitale Medien
    Digitale Medien
    Springer
    BioMetals 9 (1996), S. 21-28 
    ISSN: 1572-8773
    Schlagwort(e): biosorption ; decontamination ; cadmium ; calcium ; magnesium
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract Alkali extracted mycelial biomass from Aspergillus niger, referred to as Biosorb, was found to sequester metal ions (Cd2+, Cu2+, Zn2+, Ni2+ and Co2+) efficiently both from dilute and concentrated solutions upto 10% of its weight (w/w). Sequestration of metal ions from a mixture was also efficient but with attendant antagonisms. The kinetics of metal binding by Biosorb indicated that it is a rapid process and about 70–80% of the metal is removed from solution in 5 min followed by a slower rate. The mechanism of metal binding is shown to be due to exchange of calcium and magnesium ions of the Biosorb during which equimolar concentrations of both the ions were released into the medium. Following this an efficient procedure for the regeneration and reuse of Biosorb was standardized by washing the biosorbent with calcium and magnesium solution (0.1 m). Biosorbents prepared from Neurospora, Fusarium and Penicillium also exhibited similar mechanisms for metal ion binding, though they had a lower metal binding capacity when compared with Biosorb. Chemical modification of carboxylic acid functional groups of the Biosorb resulted in loss of 90% of metal binding capacity which could not be restored even on regeneration. The significance of this finding on the metal sequestration mechanisms of microbial biosorbents is discussed.
    Materialart: Digitale Medien
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  • 9
    ISSN: 1572-8773
    Schlagwort(e): iron ; siderophore ; Yersinia enterocolitica ; structure ; NMR
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract Clinical isolates of Yersinia enterocolitca, which belong to mouse-lethal serotypes, produce the siderophore yersiniophore. Siderophore production was shown to be iron regulated and to reach maximum production in late log phase. Yersiniophore is a fluorescent siderophore with maximum excitation at 270 nm and a major emission peak at 428 nm. Absorption maxima were seen at 210 and 250 nm with a low broad peak from 280 to 320 nm. Purification of unchelated yersiniophore for structural analysis was made difficult by low yields (1–2 mg mg-1), and susceptibility to acid hydrolysis, oxidation and possibly polymerization. Yersinophore was therefore purified as an Al3+ chelate, which was found to be stable in solution for several weeks. To purify Al3+-yersiniophore, unchelated yersiniophore was first extracted from culture supernatants with dichloromethane, concentrated by rotary evaporation and adsorbed to a DEAE-sephacel column. Al3+-yersiniophore was eluted with 0.01 m AlCl3 and further purified by HPLC. The structure was established by a combination of elemental analysis, high resolution mass spectrometry and two-dimensional NMR experiments. Yersiniophore is a phenolate-thiazole siderophore with the formula C21H24N3O4S3Al and a molecular weight of 505.07404 when chelated to Al3+. The structure of yersiniophore was determined to be closely related to the structures of pyochelin, produced by Pseudomonas aeruginosa, and anguibactin, produced by Vibrio anguillarum.
    Materialart: Digitale Medien
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  • 10
    Digitale Medien
    Digitale Medien
    Springer
    BioMetals 9 (1996), S. 241-244 
    ISSN: 1572-8773
    Schlagwort(e): cadmium ; calcium ; cell wall ; Ulva lactuca
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract Electron microscopy, in conjunction with X-ray microanalysis, was used to investigate the effects of exposure to cadmium on the elemental composition of the macroalgaUlva lactuca. The cell wall was the only region of the cell to show any marked change in chemical composition as a result of exposure to cadmium, with less calcium evident in cadmium-treated thallus compared with untreated thalli. The cell wall ofU. lactuca is a complex structure made up of polysaccharides consisting of many-branched chains composed mostly of rhamnose and galactose subunits. Some of the hydroxyl groups on the subunits are substituted by sulphate groups. Borate is associated with the rhamnose subunits, which contain no sulphate groups, and calcium binds to borate, cross-linking the rhamnose groups. The borate-calcium complex adds rigidity to the cell wall; the replacement of calcium by cadmium will, therefore, influence the rigidity of the thallus. The ecological significance of this work is discussed with respect to the ability of the alga to withstand grazing or emersion.
    Materialart: Digitale Medien
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  • 11
    ISSN: 1572-8927
    Schlagwort(e): Carbon-13 ; nitrogen-15 ; NMR ; europium-nitrate complexes ; europium-isothiocyanate complexes
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract A direct, low-temperature nuclear magnetic resonance spectroscopic study of europium(III)-nitrate contact ion-pairing has been completed, and preliminary results for europium(III)-isothiocyanate have been obtained. In water-acetone-Freon mixtures, at −110°C to −120°C, four15N NMR signals are observed for coordinated nitrate ion. Area evaluations of the signals and their concentration dependence indicate the formation of Eu(NO3)2+, Eu(NO3) 2 1+ , and two higher complexes, possibly the tetra-, with either the penta-or hexanitrato. This correlates well with similar15N NMR results obtained for Ce(III), Pr(III), Nd(III), and Sm(III). As a result of a higher dielectric constant, complex formation is significantly less in water-methanol mixtures, wheein only three complexes form with Eu(NO3) 2 1+ dominating at the highest anion concentrations. Competitive complexing experiments in water-methanol also were made by35Cl NMR chemical shift and linewidth measurements, as well as15N NMR. Initial experiments with the Eu3+-NCS− system show four coordinated anion signals, displaced from the bulk anion peak by about −250 ppm and −2,500 ppm in the13C and15N NMR spectra, respectively. Area evaluations are consistent with the presence of Eu(NCS)2+ through Eu(NCS) 4 1- in these solutions. A consideration of the chemical shifts identified the nitrogen atom as the site of binding in the NCS−. A discussion of these preliminary results, as well as those for several other metal-ions, will be presented.
    Materialart: Digitale Medien
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  • 12
    Digitale Medien
    Digitale Medien
    Springer
    Monatshefte für Chemie 127 (1996), S. 219-225 
    ISSN: 1434-4475
    Schlagwort(e): 4-Phosphoranylidene-5(4H)-oxazolones ; Phosphorus ylides ; 5(4H)-Oxazolone enolate ion equivalent ; 5-(4H)-Oxazolones ; NMR
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Zusammenfassung 4-Phosphoranyliden-5(4H)-oxazolone, eine sehr wenig bekannte Gruppe der Phosphor-ylide, wurden auf einfache Weise nach einem neuen Eintopfverfahren mit guten Ausbeuten hergestellt. Als Ausgangsverbindungen wurden 4-unsubtituierte-5-(4H)-Oxazolone (1) eingesetzt, die unter der Einwirkung von Addukten wie Ph3P-Br2, Bu3P-Br2, Ph3P-CCl4 oder Ph3P-CBr4 in Anwesenheit von Triethylamin in CH2Cl2 bei Zimmertemperatur die Titelverbindungen liefern. Die spektroskopischen Eigenschaften der Ylide werden berichtet und diskutiert.
    Notizen: Summary 4-Phosphoranylidene-5(4H)-oxazolones (2), a hardly known class of phosphorus ylides, were readily prepared from 4-unsubstituted-5-(4H)-oxazolones (1) by treatment with Ph3P-Br2, Bu3P-Br2, Ph3P-CCl4, or Ph3P-CBr4 adducts in the presence of triethylamine in CH2Cl2 at room temperature in a novel, efficient one-pot procedure. The spectroscopic properties of the ylides are reported and discussed.
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  • 13
    ISSN: 1434-4475
    Schlagwort(e): Cyclopentadienylruthenium(II) complexes ; Diphosphazane ligands ; Crystal structures ; IR ; Raman ; NMR ; UV/VIS ; Mass spectra ; Hydrogen bridging bonds
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary This synthetic and structural work describes a series of half-sandwich cyclopentadienylruthenium(II) complexes containing the diphosphazane ligands [(C6H5)2P]2NR (R=H:Hdppa,1a;R=CH3:dppma,1b;R=C2H5:dppea,1c;R=Li:Lidppa,1d). Treatment of1a, d with CpRuCl(PPh3)2 (Cp=η5-C5H5, Ph=C6H5,2) in a molar ratio of 1:1 in boiling aromatic hydrocarbons affords the neutral complexes CpRuCl(Hdppa) (3) and CpRu(dppa)PPh3 (6). The ionic complexes [CpRu(Ph2P-NR-(PPh2)PPh3)Cl (R=CH3:4a;R=C2H5:4b) are formed by the reaction of1b,c with2. One pot reactions of1a–c with2 in the presence of NH4PF6 in boiling CH3OH give only the ionic compounds [CpRu(Ph2P-NR-PPh2)(PPh3)]PF6 (R=H, CH3, C2H5;5a–c). The sulfur dioxide and hydride complexes [CpRu(Hdppa)η1-SO2]Cl (7) and CpRu(H)Hdppa (8) are obtained by the interaction of3 with SO2 or NaOCH3. All compounds are characterized as far as possible by IR, Raman,31P{1H} NMR,1H NMR,13C{1H} NMR, FD mass spectra, and their conductivity in CH2Cl2 solution. The X-ray crystal structures of3 and5a reveal that the P(1)-N(1)-P(2) angle of the coordinated ligand1a in both complexes is reduced to about 100° in comparison to free uncoordinated1a (119°). This small angle leads to a short P(1)–P(2) bond distance of 259.4 pm in3 and 254.3 pm in5a. The molecules of3 are connected by intermolecular (NH...Cl) hydrogen bridging bonds forming chains along thez axis of the unit cell. The crystals of5a contain two independent pairs of ions in the unit cell (Z=8). In5a no hydrogen bonds exist between the NH-groups and the PF 6 − anions.
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  • 14
    Digitale Medien
    Digitale Medien
    Springer
    Monatshefte für Chemie 126 (1995), S. 233-239 
    ISSN: 1434-4475
    Schlagwort(e): Enaminoketones ; Lupin alkaloid ; Multiflorine ; NMR ; Nucleophilic methylation ; Stereospecificity
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Zusammenfassung Multiflorin (1), ein Lupin-Nebenalkaloid, ergibt bei Umsetzung mit Methyllithium oder Methylmagnesiumiodid 4S-4-Hydroxy-4-methyl-2,3-didehydrospartein (2) und 2S-2-Methyl-4-oxospartein (3) als Hauptprodukte. Ihre NMR-spektroskopisch (1H und13C) aufgeklärte räumliche Struktur weist auf eine Stereoselektivität der erwähnten Reaktionen hin. Die beobachteten nucleophilen 1,2- und 1,4-Additionen zeigen, daß sich die Regiospezifität der Einwirkung von MeLi oder MeMgl auf Multiflorin von jener bis jetzt bekannter Alkylierungen von Enaminoketonen unterscheidet.
    Notizen: Summary Multiflorine (1) — a minor lupine alkaloid — treated by methyl lithium or methyl magnesium iodide affords 4S-4-hydroxy-4-methyl-2,3-didehydrosparteine (2) and 2S-2-methyl-4-oxosparteine (3), respectively, as the dominating products. Their steric structure, determined by1H and13C NMR techniques, points to stereospecific preferences of these reactions. The observed nucleophilic 1,2- and 1,4-additions indicate that regiospecificity of the action of MeLi or MeMgI on multiflorine is different from that of the so far known similar alkylation of other enamino ketones.
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  • 15
    Digitale Medien
    Digitale Medien
    Springer
    Monatshefte für Chemie 126 (1995), S. 1011-1019 
    ISSN: 1434-4475
    Schlagwort(e): Precursors of strigol analogues ; Michael reaction ; NMR ; Molecular modelling
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Zusammenfassung BasenkatalysierteMichael-Addition von 5-Nitropentan-2-on-ethylenketal (1) und Cyclohex-2-enon (2), anschließende Entfernung der Schutzgruppe und darauffolgende Aldolkondensation liefert isomer 8-Methyl-5-nitro-1-octalone (5a,b). Struktur, relative Konfiguration und Konformation von5a und5b wurden mittels1H- und13C-NMR-Spektroskopie aufgeklärt.
    Notizen: Summary Base catalyzedMichael addition of 5-nitropentan-2-one ethylene ketal (1) and cyclohex-2-enone (2), subsequent deprotection, and intramolecular aldol condensation yields the 8-methyl-5-nitro-1-octalone isomers (5a,b). The structure, relative configuration, and conformation of5a and5b were elucidated utilizing the results of1H and13C NMR investigations
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  • 16
    ISSN: 1434-4475
    Schlagwort(e): NMR ; Thia crown ethers ; Conformation ; Molecular mechanics calculation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Zusammenfassung Aus Tetrachlorbrenzcatechin-bisallylether (1) und Schwefeldichlorid wurden neben der 1,10-Dithia-dibenzo-18-krone-64 die 9- und 10-Ring-Derivate2 und3 erhalten. In der 10-Ring-Verbindung wurde erstmaligMarkovnikov- undanti-Markovnikov-Konstitution der β-Chlor-thio-Gruppierung in einem Thiamakrocyclus nebeneinander vorgefunden. Das isolierte Diastereomere von3 zeigt bei Temperaturen unter −50 °C zwei Konformere. Die Signalzuordnung war mit homo-und heteronuklearen COSY- sowie mit phasensensitiven NOESY-Spektren möglich. Mit Hilfe molekülmechanischer Rechnungen konnten aus den13C-NMR-Verschiebungen und den vicinalen H,H-Kopplungskonstanten die Vorzugskonformeren und die relative Konfiguration bestimmt werden.
    Notizen: Summary Addition of sulfur dichloride to tetrachlorocatechol-bisallylether (1) yields the 9- and 10-ring thia crown ether derivatives2 and3, respectively, together with the dithia-18-crown-6-ether4. The 10-membered ring compound3 represents the first thia macrocycle containing bothMarkovnikov andanti-Markovnikov constitution of the β-chloro-thio structural segments in the same molecule. By1H and13C NMR spectroscopy, equal amounts of two preferred conformers of the only isolated diastereomer of3 were observed at temperatures below −50°C. The signals were assigned to these conformers using COSY, HETCOR, and phase sensitive NOESY spectra at low temperatures. The preferred conformations and the relative configuration were determined using the different effects of γ gauche -and γ anti -positions in13C NMR chemical shifts and analyzing vicinal3 J H,H coupling constants. These results were confirmed by molecular mechanics calculations.
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  • 17
    ISSN: 0948-5023
    Schlagwort(e): Sialidase ; NMR ; Protein modelling ; Molecular dynamics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The success of knowledge-based homology modelling is critically dependent on the predictive potency of the program structure-based calculations, which attempt to translate homologous sequences into three-dimensional structures, and on the actual relevance of the crystal structure for the protein topology. As quality control, experimental data for selected parameters of the protein′s conformation are required. Using the crystal structure of the sialidase of Salmonella typhimurium as framework for model building of the homologous enzyme from Clostridium perfringens, a set of energy-minimised conformers is derived. These proteins present e.g. Tyr, Trp and His residues with an assessable area on the surface, since the side chains of these amino acid residues are responsive to chemically induced dynamic nuclear polarization (CIDNP), monitored by NMR. Hence, as first lesson, a comparative analysis for model-derived and experimentally determined values can be performed. The second lesson of this study concerns the notable impact of single amino acid substitutions (Tyr/Phe, Cys/Ser) on the surface accessibility of the CIDNP-reactive amino acid side chains in mutant forms of the sialidase. Corroborating the predictions from the theoretical calculations, the spectra of the engineered mutants reveal marked and non-uniform alterations. Thus, the effect of apparently rather conservative amino acid substitutions on a distinct conformational aspect of this protein, even at distant sites, should not be underestimated.
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  • 18
    Digitale Medien
    Digitale Medien
    Springer
    Catalysis letters 38 (1996), S. 115-121 
    ISSN: 1572-879X
    Schlagwort(e): NMR ; acid catalysis ; pentene
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract 13C NMR study of “conjunct polymerisation” of 1-pentene in 95% sulfuric acid demonstrated that this is a carbenium ion reaction, where the esters are the precursors of carbenium ions. In the first step of the reaction a complicated mixture of primary and secondary mono- and dipentyl esters is formed. In an excess of the acid the esters are decomposed yielding aliphatic carbenium ions, which are then involved in secondary reactions resulting in the final products. Similar to heterogeneous catalysis on zeolites, the steady state concentration of the aliphatic carbenium ions during the reaction is, however, too low for their direct detection by NMR.
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  • 19
    Digitale Medien
    Digitale Medien
    Springer
    Catalysis letters 31 (1995), S. 267-272 
    ISSN: 1572-879X
    Schlagwort(e): MCM-41 synthesis ; NMR ; FTIR
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The synthesis of MCM-41 mesoporous compounds with Si/Al ratios as low as 2 without observing the presence of octahedral Al in27AlMAS NMR is reported. FTIR spectra of chemisorbed pyridine indicated that MCM-41 materials in their protonated form exhibit both Brønsted and Lewis acid sites.
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  • 20
    ISSN: 1572-879X
    Schlagwort(e): MCM-41 synthesis ; alkali-free gel ; n-heptane cracking ; NMR
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract MCM-41 mesoporous molecular sieve materials are synthesised using aqueous ammonia solution to adjust the pH of the reactant gel. Highly ordered MCM-41 with Si/Al ratio as low as 14 was obtained and characterised by27A1 MAS NMR, XRD, N2-adsorption, benzene sorption, and NH3-TPD measurements. The acidity of MCM-41 materials obtained in this system was conveniently generated through straightforward calcination of the as-synthesised sample. More mild acidic sites generated could be due to the avoidance of the multiple calcination procedure and/or the trace sodium species which are the poisons to Brønsted acid. The catalytic activities forn-heptane cracking and isomerization ofm-xylene were investigated, and these were in accordance with the known properties of MCM-41.
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  • 21
    Digitale Medien
    Digitale Medien
    Springer
    Catalysis letters 41 (1996), S. 47-53 
    ISSN: 1572-879X
    Schlagwort(e): CuZSM-5 ; lanthanum ; DeNOx ; XRD ; NMR ; XPS ; ISS
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The effects of high temperature steam treatment on the activity and selectiv ity of CuZSM-5 catalysts for the selective catalytic reduction of NO with propene have been examined. Loss of activity and selectivity on steam treatment is due to framework dealumination of the zeolite, which causes migration of Cu out of the zeolite pores to the external surface. Pre-exchange of the zeolite with La3+ cations inhibits the dealumination, preventing migration of Cu to the surface and allowing the catalyst to retain high activity and N2 selectivity after steam treatment. The deactivation of the catalysts was monitored using X-ray powder diffraction, magic angle spinning27Al and29Si nuclear magnetic resonance, X-ray photoelectron spectroscopy and ion scattering spectroscopy.
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  • 22
    ISSN: 1432-1327
    Schlagwort(e): Key words Solution structure ; Paramagnetic biomolecules ; NMR ; Cytochrome c
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract  The availability of NOE constraints and of the relative solution structure of a paramagnetic protein permits the use of pseudocontact shifts as further structural constraints. We have developed a strategy based on: (1) determination of the χ tensor anisotropy parameters from the starting structure; (2) recalculation of a new structure by using NOE and pseudocontact shift constraints simultaneously; (3) redetermination of the χ tensor anisotropy parameters from the new structure, and so on until self-consistency. The system investigated is the cyanide derivative of a variant of the oxidized Saccharomyces cerevisiae iso-1-cytochrome c containing the Met80Ala mutation. The structure has been substantially refined. It is shown that the analysis of the deviation of the experimental pseudocontact shifts from those calculated using the starting structure may be unsound, as may the simple structure refinement based on the pseudocontact shift constraints only.
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  • 23
    ISSN: 1432-1327
    Schlagwort(e): Key words Ferredoxin ; Iron-sulfur clusters ; NMR ; Hyperfine shifts ; Magnetic interactions
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract  The oxidized Fe7S8 ferredoxin from Bacillus schlegelii, containing both [Fe3S4]+ and [Fe4S4]2+ clusters, has been investigated by 1H NMR spectroscopy. An extensive sequence-specific assignment of the hyperfine-shifted resonances has been obtained by making use of a computer-generated structural model. The pattern and the temperature dependence of the hyperfine shifts of the β-CH2 protons of the cysteines coordinating the [Fe3S4]+ cluster are rationalized in terms of magnetic interactions between the iron ions. The same approach holds for the hyperfine coupling with 57Fe. It is shown that the magnetic interactions are more asymmetric in Fe7S8 ferredoxins than in Fe3S4 ferredoxins. The NMR non-observability of the β-CH2 protons of coordinated cysteines in the one-electron-reduced form has been discussed.
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  • 24
    ISSN: 1432-1327
    Schlagwort(e): Key words Cytochrome c3 ; Mutagenesis ; Redox-Bohr ; NMR ; EPR ; Cooperativity
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract  Reduction of the haems in tetrahaem cytochromes c 3 is a cooperative process, i.e., reduction of each of the haems depends on the redox states of the other haems. Furthermore, electron transfer is coupled to proton transfer (redox-Bohr effect). Two of its haems and a strictly conserved nearby phenylalanine residue, F20, in Desulfovibrio vulgaris (Hildenborough) cytochrome c 3 form a structural motif that is present in all cytochromes c 3 and also in cytochrome c oxidase. A putative role for this phenylalanine residue in the cooperativity of haem reduction was investigated. Therefore, this phenylalanine was replaced, with genetic techniques, by isoleucine and tyrosine in D. vulgaris (Hildenborough) cytochrome c 3. Cyclic voltammetry studies revealed a small increase (30 mV) in one of the macroscopic redox potentials in the mutated cytochromes. EPR showed that the main alterations occurred in the vicinity of haem I, the haem closest to residue 20 and one of the haems responsible for positive cooperativities in electron transfer of D. vulgaris cytochrome c 3. NMR studies of F20I cytochrome c 3 demonstrated that the haem core architecture is maintained and that the more affected haem proton groups are those near the mutation site. NMR redox titrations of this mutated protein gave evidence for only small changes in the relative redox potentials of the haems. However, electron/electron and proton/electron cooperativity are maintained, indicating that this aromatic residue has no essential role in these processes. Furthermore, chemical modification of the N-terminal amino group of cytochrome c 3 backbone, which is also very close to haem I, had no effect on the network of cooperativities.
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  • 25
    ISSN: 1432-1327
    Schlagwort(e): Key words Multihaem cytochromes ; Cytochrome c551.5 ; Cytochrome c3 ; Sulfate-reducing bacteria ; NMR
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract  The trihaem cytochrome c 551.5, formerly known as cytochrome c 7, from the organism Desulfuromonas acetoxidans, has been studied in the reduced state by 2D proton NMR. The haem proton resonances were assigned, and several nuclear Overhauser enhancements (NOEs) between resonances arising from different haems were detected and assigned. The relative orientations of the three haems were calculated by fitting both the intensities of the interhaem NOEs and the magnitudes of the ring current shifts of the haem resonances, following the strategy previously used by the authors to reassess the X-ray structure of the haem core in tetrahaem cytochrome c 3 from Desulfumicrobium baculatum. It is concluded that, although the comparison of the protein sequence with those of the tetrahaem cytochromes c 3 shows that in cytochrome c 551.5 about 40% of the sequence is deleted, including the region involved in the attachment of the second of the four haems, this does not induce any significant rearrangement of the remaining three haems other than a slight decrease in the iron-iron distance between two of the haems, namely those corresponding to haems I and IV of cytochrome c 3.
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  • 26
    Digitale Medien
    Digitale Medien
    Springer
    Theoretical chemistry accounts 92 (1995), S. 61-65 
    ISSN: 1432-2234
    Schlagwort(e): NMR ; Nuclear spin coupling constant ; Maximum bond order hybrid orbital ; Phosphorus-carbon coupling ; Net atomic charge
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary The novel generalized correlation of the nuclear spin-spin coupling constants with the atomic hybrids and net charges is employed to give a new relationship for calculating the directly bonded phosphorus-carbon coupling constants by use of the maximum bond order hybrid orbital procedure together with the extended Hückel molecular orbital calculation. The calculated coupling constants of phosphorus-carbon are all in good agreement with the experimental data, which shows that the new relationship obtained in the present paper is quite satisfactory for calculation of the phosphorus-carbon coupling constants.
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  • 27
    ISSN: 1572-9001
    Schlagwort(e): NMR ; distance geometry ; cluster analysis ; absolute configuration ; fusaproliferin
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The absolute configuration of fusaproliferin, a toxic metabolite produced byFusarium proliferation, was determined by the combined use of1H NMR and distance geometry. The configuration of double bonds has been determined in agreement with NOESY buildup data. An R configuration for C10 was determined using Mosher's method. Processing the constraints obtained from NOESY experiments with a distance geometry program, a limited number (80) of possible structures was derived. An agglomerative nonhierarchical method of clustering was used in order to place these structures into classes suggested by the data, and not previously defined in any way. This statistical method showed that indeed the structures could be grouped in four classes. One of these classes is represented by a single structure, with the highest sum of violations and was discarded. All other structures have the same chirality; respectively S for C14 and R for C15. In solution the overall conformation is quite well defined in the region of the five-member ring and the planes of double bonds C2–C3 and C11–C12, while near to C8 and C9 internal flexibility appears evident.
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  • 28
    ISSN: 1573-4919
    Schlagwort(e): regucalcin ; calcium-binding protein ; insulin ; calcium ; gene expression ; rat liver
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie , Medizin
    Notizen: Abstract The effect of refeeding on the expression of Ca2+-binding protein regucalcin mRNA in the liver of fasted rats was investigated. When rats were fasted overnight, the hepatic regucalcin mRNA level was reduced about 70% of that in feeding rats. Refeeding produced a remarkable elevation of hepatic regucalcin mRNA level (about 150–170% of fasted rats). Liver regucalcin concentration was appreciably increased by refeeding, although it was not altered by fasting. The oral administration of glucose (2 g/kg body weight) to fasted rats caused a significant increase in hepatic regucalcin mRNA level. Moreover, hepatic regucalcin mRNA level was clearly elevated by a single subcutaneous administration of insulin (10 and 100 U/kg) to fasted rats. The hormonal effect was not further enhanced by the simultaneous administration of calcium chloride (250 mg Ca/kg) to fasted rats, although calcium administration stimulated regucalcin mRNA expression in the liver. The present study suggests that the expression of hepatic regucalcin mRNA stimulated by refeeding is significantly involved in the action of insulin and/or calcium as stimulating factors.
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  • 29
    ISSN: 1573-4919
    Schlagwort(e): calcium ; calcium channels ; smooth muscle ; sarcolemma ; coronary artery
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie , Medizin
    Notizen: Abstract Tension generation and Ca2+ flux in smooth muscle varies depending upon the diameter of a vessel and its location. The purpose of the present investigation was to determine if the biochemical characteristics of the Na+−Ca2+ exchanger and the Ca2+ channel differ in sarcolemmal membrane preparations isolated from a large conduit vessel (thoracic aorta) or from large and small coronary arteries. We also investigated the possibility of differences between sarcolemmal membranes isolated from coronary arteries dissected from the right and left ventricles. The purification of the sarcolemmal membranes was of a similar magnitude amongst the different groups. Contamination of the sarcolemmal membranes with other membranous organelles was negligible and similar amongst the groups. The Km and Vmax of Na+-dependent Ca2+ uptake in sarcolemmal vesicles was similar amongst the groups. Calcium channel characteristics were examined by measuring [3H]PN200-110 binding to sarcolemmal vesicles. The right coronary artery membranes from both large and small caliber vessels exhibited a higher Kd and the small right coronary artery sarcolemmal preparation had a lower maximal binding density for [3H] PN200-110. The results suggest that the right coronary artery, and in particular the small diameter right coronary artery, possesses altered Ca2+ channel characteristics in isolated sarcolemmal membranes.
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  • 30
    Digitale Medien
    Digitale Medien
    Springer
    Molecular and cellular biochemistry 154 (1996), S. 123-132 
    ISSN: 1573-4919
    Schlagwort(e): rat pancreas ; cholecystokinin-octapeptide ; magnesium ; calcium ; secretion ; cyclic AMP
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie , Medizin
    Notizen: Abstract This study investigates the effect of magnesium (Mg2+) on the secretory responses and the mobilization of calcium (Ca2+) and Mg2+ evoked by cholecystokinin-octapeptide (CCK-8) in the exocrine rat pancreas. In the isolated intact perfused pancreas CCK-8 (10−10 M) produced marked increases in juice flow and total protein output in zero and normal (1.1 mM) extracellular Mg2+ [Mg2+]o compared to a much reduced secretory response in elevated (5 mM and 10 mM) [Mg2+]o Similar effects of perturbation of [Mg2+]o on amylase secretion and 45Ca2+ uptake (influx) were obtained in isolated pancreatic segments. In pancreatic acinar cells loaded with the fluorescent bioprobe fura-2 acetomethylester (AM), CCK-8 evoked marked increases in cytosolic free Ca2+ concentration [Ca2+]i in zero and normal [Mg2+]o compared to a much reduced response in elevated [Mg2+]o Pretreatment of acinar cells with either dibutyryl cyclic AMP (DB2 cAMP) or forskolin had no effect on the CCK-8 induced changes in [Ca2+]i. In magfura-2-loaded acinar cells CCK-8 (10−8 M) stimulated an initial transient rise in intracellular free Mg2+ concentration [Mg2+]i followed by a more prolonged and sustained decrease. This response was abolished when sodium Na+ was replaced with N-methyl-D-glucamine (NMDG). Incubation of acinar cells with 10 mM Mg2+ resulted in an elevation in [Mg2+]i. Upon stimulation with CCK-8, [Mg2+]i. decreased only slightly compared with the response obtained in normal [Mg2+]o. CCK-8 caused a net efflux of Mg2+ in pancreatic segments; this effect was abolished when extracellular sodium [Na+]o was replaced with either NMDG or choline. The results indicate that Mg2+ can regulate CCK-8-evoked secretory responses in the exocrine pancreas possibly via Ca2+ mobilization. Moreover, the movement of Mg2+ in pancreatic acinar cells is dependent upon extracellular Na+.
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  • 31
    Digitale Medien
    Digitale Medien
    Springer
    Molecular and cellular biochemistry 146 (1995), S. 179-186 
    ISSN: 1573-4919
    Schlagwort(e): Ca2+-ATPase ; calcium ; nuclear DNA ; DNA fragmentation ; regucalcin ; regenerating rat liver
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie , Medizin
    Notizen: Abstract The alteration of calcium content, Ca2+-ATPase activity, DNA content and DNA fragmentation in the nuclei of regenerating rat liver was investigated. Liver was surgically removed about 70% of that of sham-operated rats. the reduced liver weight by partial hepatectomy was completely restored at 3 days after the surgery. Regenerating liver significantly increased Ca2+-ATPase activity and DNA content in the nuclei between 1 and 5 days after hepatectomy. The nuclear calcium content was clearly increased from 2 days after hepatectomy. The increase of Ca2+-ATPase activity in regenerating liver was clearly inhibited by the presence of trifluoperazine (10 μM), staurosporine (2.5 μM) and dibucaine (10 μM), which are inhibitors of calmodulin and protein kinase, in the enzyme reaction mixture. However, the nuclear enzyme activity in normal rat liver was not significantly altered by these inhibitors. Meanwhile, the increase of nuclear DNA content in regenerating liver was completely blocked by the administration of trifluoperazine (2.5 mg/100 g body weight), suggesting an involvement of calmodulin. Now, the nuclear DNA fragmentation was significantly decreased in regenerating liver, suggesting that this decrease is partly contributed to the increase in nuclear DNA content. The present study clearly demonstrates that regenerating liver enhances nuclear Ca2+-ATPase activity and induces a corresponding elevation of nuclear calcium content. This Ca2+-signaling system may be involved in the regulation of nuclear DNA functions in regenerating rat liver.
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  • 32
    Digitale Medien
    Digitale Medien
    Springer
    Molecular and cellular biochemistry 148 (1995), S. 67-72 
    ISSN: 1573-4919
    Schlagwort(e): regucalcin ; calcium ; protease ; calpain ; rat liver cytosol
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie , Medizin
    Notizen: Abstract The increasing effect of regucalcin, isolated from rat liver cytosol, on neutral proteolytic activity in the hepatic cytosol was characterized. The proteolytic activity was markedly elevated by the addition of regucalcin (0.1–0.5 μM) in the absence of Ca2+. This increase was not significantly altered by the presence of diisopropylfluorophsophate (DPF;2.5 mM)—although DFP caused a significant decrease in the proteolytic activity. Regucalcin (0.25 μM) additively enhanced the dithiothreitol (DTT; 1.0 mM)—increased proteolytic activity, while the regucalcin or DTT effect was completely abolished by NEM (5 mM), indicating that regucalcin may act on the SH group in proteases. Also, regucalcin (0.25 μM) enhanced the effect of Ca2+ (10 μM) increasing liver proteolytic activity, suggesting that regucalcin does not influence on the active sites for Ca2+ in proteases. Moreover, the proteolytic activity of regucalcin (0.25 μM) was significantly decreased by the presence of calpastatin (24 μg/ml), an inhibitor of Ca2+-activated neutral protease (calpain). Now, regucalcin (0.25 μM) increased about 7-fold the activity ofm-calpain isolated from rabbit skeletal muscle. These observations demonstrate that regucalcin directly activates cysteinyl-proteases. Regucalcin may have a role as a potent proteolytic activator in the cytoplasm of liver cells.
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  • 33
    Digitale Medien
    Digitale Medien
    Springer
    Molecular and cellular biochemistry 149-150 (1995), S. 203-212 
    ISSN: 1573-4919
    Schlagwort(e): calcium ; mitochondria ; FAD-glycerol 3-phosphate dehydrogenase ; pyruvate dehydrogenase ; oxoglutarate dehydrogenase ; isocitrate dehydrogenase
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie , Medizin
    Notizen: Abstract In mammalian cells, increases in calcium concentration cause increases in oxidative phosphorylation. This effect is mediated by the activation of four mitochondrial dehydrogenases by calcium ions; FAD-glycerol 3-phosphate dehydrogenase, pyruvate dehydrogenase, NAD-isocitrate dehydrogenase and oxoglutarate dehydrogenase. FAD-glycerol 3-phosphate dehydrogenase, being located on the outer surface of the inner mitochondrial membrane, is exposed to fluctuations in cytoplasmic calcium concentration. The other three enzymes are located within the mitochondrial matrix. While the kinetic properties of all of these enzymes are well characterised, the molecular basis for their regulation by calcium is not. This review uses information derived from calcium binding studies, analysis of conserved calcium binding motifs and comparison of amino acid sequences from calcium sensitive and non-sensitive enzymes to discuss how the recent cloning of several subunits from the four dehydrogenases enhances our understanding of the ways in which these enzymes bind calcium. FAD-glycerol 3-phosphate dehydrogenase binds calcium ions through a domain which is part of the polypeptide chain of the enzyme. In contrast, it is possible that the calcium sensitivity of the other dehydrogenases may involve separate calcium binding subunits.
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  • 34
    Digitale Medien
    Digitale Medien
    Springer
    Molecular and cellular biochemistry 149-150 (1995), S. 263-265 
    ISSN: 1573-4919
    Schlagwort(e): NO synthase ; toxic metals ; signal transduction ; calcium
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie , Medizin
    Notizen: Abstract This study was designed to evaluate thein vitro effects of transition heavy metal cations on activity of constitutive isoform of nitric oxide synthase (cNOS) in rat brain. NOS activity was determined in the cytosolic fractions of rat cerebral hemispheres by conversion of3H-L-arginine to3H-L-citrulline. Different concentrations of mercury (Hg2+), nickel (Ni2+), manganese (Mn2+), zinc (Zn2+), cadmium (Cd2+), lead (Pb2+) and calcium (Ca2+) were tested on NOS activity. While all the cations caused inhibition, there were differences in the apparent inhibition constants (Ki) among the cations. With the exception of calcium ion no other cation required preincubation with the enzyme preparation. These results indicate that while calcium ion modulate cNOS activity at regulatory site(s), inhibitory influence of toxic heavy metal cations may be exerted on the catalytic site(s) either by direct binding to it or by interfering with the electron transfer during catalysis.
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  • 35
    ISSN: 1573-4919
    Schlagwort(e): nitric oxide ; endotoxin ; cardiomyocytes ; guanosine 3′, 5′-cyclic monophosphate ; calcium ; ADP-ribosylation ; phosphorylation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie , Medizin
    Notizen: Abstract To evaluate the effects of the in vivo endotoxin treatment of the rat on (1) the contractile responses in the subsequently isolated papillary muscle to adrenergic and cholinergic agonists and (2) the biochemical parameters (cyclic GMP, nitric oxide synthesis, protein phosphorylation and ADP-ribosyslation) in the subsequently isolated cardiomyocytes. Following the in vivo endotoxin treatment (4 mg/kg i.p., 18 h), contractile responses to increasing amounts of isoprenaline or to increasing amounts of oxotremorine in the presence of a fixed amount of isoprenaline were determined in isolated papillary strips. Activities of nitric oxide synthase, guanylyl cyclase, as well as phosphorylation of phospholamban and troponin-inhibitory subunit, and pertussis toxin-catalyzed and endogenous ADP-ribosylations were determined in the intact cardiomyocytes and subcellular fractions. The increase in the force of contraction by isoprenaline was reduced, while its inhibition by oxotremorine was greater in the endotoxin-treated papillary strips. The activities of both nitric oxide synthase, primarily of the inducible form of the enzyme, and cytosolic guanylyl cyclase were higher while the phosphorylations of both phospholamban and troponin-inhibitory subunit were of lesser magnitude in the cardiomyocytes following the in vivo endotoxin treatment. Pertussis toxin-catalyzed ADP-ribosylation of the 41 kDa polypeptide, which is the alpha subunit of Gi, was also decreased. The results of the present study support the postulate that alterations in both the cyclic AMP and cyclic GMP signalling cascade contribute to the myocardial dysfunction caused by endotoxin and cytokines.
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  • 36
    ISSN: 1573-4919
    Schlagwort(e): endothelin-1 ; ventricular cardiomyocytes ; contraction ; calcium ; heart failure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie , Medizin
    Notizen: Abstract Endothelin (ET-1) is found at elevated concentrations in the plasma of patients with heart failure and in animal models of cardiomyopathy. The peptide is a potent positive inotropic agent, the effects of which are mediated by increases in cytosolic Ca2+ in cardiomyocytes. The object of this study was to investigate at the cellular level, the actions of ET-1 on contractile function and on Ca2+ currents in heart-failed ventricular myocardium. Male New Zealand White rabbits (8 wks) were treated with twice weekly injections of epirubicin (4 mg/kg/wk, n=7) or with saline (n=7) for 6 wks, followed by a washout period of 2 wks. Ventricular cardiomyocytes were isolated from rabbit hearts using Langendorff perfusion with collagenase; contractile function was examined using a video microscopy method, and L-type Ca2+ currents were recorded using a whole-cell patch-clamp technique. ET-1 produced a concentration-dependent increase in contractile response (% increase from basal value) to a maximum at 1 nM ET-1 of 69 ± 11% (mean ± S.D.) in control cardiomyocytes and 33 ± 6% in heart-failed cells. However, there was no significant change in the EC50 obtained with ET-1 for healthy (0.31 ± 0.1 nM) and for failed cardiomyocytes (0.24 ± 0.1 nM). The effects of ET-1 on L-type Ca2+ channels were similar with a peak amplitude at 1 nM ET-1 of −3.26 ± 0.8 ⋬ in control cardiomyocytes and −3.32 ± 0.9 nA in heart-failed cells. The attenuation of the contractile response to ET-1 in heart-failed cells may reflect a desensitization of ET receptors as a consequence of elevated circulating levels of ET and was not reflected by alteration of transmembrane Ca2+ conductance. It is probable, therefore, that multiple signalling pathways are involved in the actions of ET on ventricular myocardium.
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  • 37
    Digitale Medien
    Digitale Medien
    Springer
    Molecular and cellular biochemistry 163-164 (1996), S. 125-130 
    ISSN: 1573-4919
    Schlagwort(e): cardiac myocytes ; early after depolarisations ; delayed after depolarisations ; calcium ; sarcoplasmic reticulum ; noradrenaline
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie , Medizin
    Notizen: Abstract We investigated the effect of 10−8 M noradrenaline (NA) on [Ca2+], and electrical activity of single myocytes of guinea-pig ventricular myocardium loaded with Indo 1-AM. Membrane potential was recorded by means of the patch electrode and patch amplifier set to the current clamp mode. Cells were stimulated at a rate of 30/min by 3 ms pulses of the current injected through the recording electrode. Superfusion of NA resulted in slight shortening of action potentials (APs), increase in rate of rise and amplitude of the respective Ca2+ transients, and appearance of secondary Ca2+ transients of two kinds: 1. appearing before repolarisation of AP and decay of the preceding Ca2+ transient were completed and 2. appearing between the APs. We named them early after-transients (EAT) and delayed after-transients (DAT), respectively. Without any additional intervention EATS caused some prolongation of APs duration and DATs resulted in subthreshold delayed after-depolarisations (DADS). When sarcolemmal K+ conductance was decreased by tetraethylammonium (TEA) in the patch electrode or 20 μM BaCl2 in the Tyrode solution, EATs initiated early after depolarizations (EADs) and DATs initiated suprathreshold DADs triggering full-sized APs. Superfusion of 30.0 mM Na+ (replaced with LiCl) resulted in reduction of AP duration by -70% and appearance of DATs. Also, the frequent multiple oscillations of Ca 2+ concentration were often observed. Neither DATs nor the oscillations had any affect on electrical activity of the cells. Their electrogenicity could not be increased by TEA or 20.0 μM Ba2+. EATs and DATs and their respective EADs and DADs could not be initiated by NA or low Na+ superfusion in the cells pretreated with 2 × 10−7 M thapsigargin, a selective blocker of Ca2+-ATPase of sarcoplasmic reticulum (SR). We conclude that in contrast to the current hypothesis, EADs can be initiated by Ca2+ released early in the cardiac cycle from the overloaded SR, and that electrogenicity of both types of Ca2+ oscillations critically depends on the sarcolemmal K+ conductance.
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  • 38
    Digitale Medien
    Digitale Medien
    Springer
    Molecular and cellular biochemistry 151 (1995), S. 39-47 
    ISSN: 1573-4919
    Schlagwort(e): 7B2 ; calcium ; protein aggregation ; secretogranins ; protein sorting
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie , Medizin
    Notizen: Abstract To study the behavior of the neuroendocrine polypeptide 7B2 in the presence of calcium, various fragments of this molecule were produced inEscherichia coli as fusion proteins to glutathione S-transferase (GST). Addition of millimolar concentrations of Ca2+ to purified preparations of hybrid molecules carrying the N-terminal segment of 7B2 induced precipitation in a manner dependent on protein and cation concentrations. This precipitation occurred at pH 7.5 but not at pH 5.2. It was augmented by 4 and 8 mM ATP, and reduced by 12 and 24 mM ATP. ADP had a similar but weaker effect. Calcium failed to cause precipitation of GST alone or of GST fused to the C-terminal peptide 7B2156–186. However, when the latter protein was mixed with a GST protein carrying a short fragment of the N-terminal region of 7B2, both proteins were precipitated by calcium. Except for the pH dependence, the behavior of 7B2 fusion proteins in the presence of calcium and adenosine nucleotides are reminiscent of those exhibited by chromogranins and secretogranins, which, like 7B2, are acidic proteins found in the secretory granules of a variety of neuroendocrine cells. As suggested for other granins, this property may underlie the segregation of 7B2 fragments into secretory granules.
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  • 39
    Digitale Medien
    Digitale Medien
    Springer
    Molecular and cellular biochemistry 151 (1995), S. 55-60 
    ISSN: 1573-4919
    Schlagwort(e): regucalcin ; calcium ; gene expression ; kidney damage ; rat kidney cortex
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie , Medizin
    Notizen: Abstract The alteration of Ca2+-binding protein regucalcin mRNA expression in the kidney cortex of rats administered cisplatin and cephaloridine, which can induce kidney damage, was investigated. Cisplatin (0.25, 0.5 and 1.0 mg/100 g body weight) or cephaloridine (25, 50 and 100 mg/100 g) was intraperitoneally administered in rats, and 1, 2 and 3 days later they were sacrificed. The alteration in serum findings after the administration of cisplatin (1.0 mg/100 g) or cephaloridine (50 and 100 mg/100 g) demonstrated chemically induced kidney damage; blood urea nitrogen (BUN) concentration increased markedly and serum inorganic phosphorus or calcium concentration decreased significantly. Moreover, the administration of cisplatin (1.0 mg/100 g) or cephaloridine (100 mg/100 g) caused a remarkable increase of calcium content in the kidney cortex of rats, indicating kidney damage. The expression of regucalcin mRNA in the kidney cortex was markedly reduced by the administration of cisplatin or cephaloridine in rats, when the mRNA levels were analyzed by Northern blotting using rat liver regucalcin cDNA (0.9 kb). The mRNA decreases were seen with the used lowest dose of cisplatin or cephaloridine. The present study clearly demonstrates that the mRNA expression of Ca2+-binding protein regucalcin in the kidney cortex of rats is decreased by chemically induced kidney damage.
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  • 40
    ISSN: 1573-4919
    Schlagwort(e): hyperthyroid heart ; high energy phosphates ; oxidative metabolism ; cardiac work ; calcium ; 31P-NMR spectroscopy
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie , Medizin
    Notizen: Abstract The effect of calcium activation on energy production was investigated in isolated perfused hearts from rats treated with triiodothyronine (T3) during 15 days (0.2 mg/kg/day) and in hearts of rats allowed to recover after T3-treatment during 15 days. Changes in phosphorylated compound concentrations were followed in the isolated hearts perfused with a glucose-pyruvate medium by 31P-NMR spectroscopy, when the external calcium concentration was increased from 0.5–1, 1.5 and 2 mM. As expected, T3-treatment resulted in the hypertrophy of the heart (50% increase in HW/BW) that was nearly reversible 15 days after discontinuation of the treatment. When compared to controls, creatine, phosphocreatine (PCr) and glycogen contents were lower (58, 24 and 17% decrease respectively) in the hypertrophied hearts and higher (10, 14 and 18% respectively) after regression of hypertrophy. Intracellular pH, ATP, inorganic phosphate concentrations and the phosphorylation potential were not altered under T3-treatment and after regression of hypertrophy, while calculated free ADP concentration was lower in hypertrophied hearts (control: 40±2 μM, T3-treatment: 21±1 μM, regression: 37±1 μM). Increasing the calcium concentration induced a similar increase in left ventricular developed pressure in the three groups of hearts, with inorganic phosphate concentration increasing with cardiac work. The PCr concentration slightly decreased while the ATP concentration did not change. In spite of different initial PCr concentrations, the evolutions of PCr and Pi concentrations for each stepwise increase in external calcium were similar in the three groups. It is concluded that, in spite of the well-known decrease in efficiency induced by the drug, the mechanisms of PCr (ATP) production ramain able to respond to an acute moderate increase in energy demand provoked by a physiological stimulus. This adaptation also persists after the treatment when the energy metabolism balance is apparently improved.
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  • 41
    Digitale Medien
    Digitale Medien
    Springer
    Molecular and cellular biochemistry 151 (1995), S. 149-155 
    ISSN: 1573-4919
    Schlagwort(e): SERCA2 ; ATPase ; calcium ; transport ; vascular
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie , Medizin
    Notizen: Abstract Pig coronary artery cultured smooth muscle cells were skinned using saponin. In the presence of an ATP-regenerating system and oxalate, the skinned cells showed an ATP-dependent azide insensitive Ca2+-uptake which increased linearly with time for 〉1 h. The Ca2+-uptake occurred with Km values of 0.20±0.03 μM for Ca2+ and 400±34 μM for MgATP2−. Thapsigargin and cyclopiazonic acid inhibited this uptake with IC50 values of 0.13±0.02 and 0.56±0.04 μM, respectively. These properties of SR Ca2+-pump are similar to those reported for membrane fractions isolated from fresh smooth muscle of coronary artery and other arteries. However, optimum pH of the uptake in the skinned cells (6.2) was lower than that reported previously using isolated membranes (6.4–6.8).
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  • 42
    Digitale Medien
    Digitale Medien
    Springer
    Molecular and cellular biochemistry 154 (1996), S. 113-121 
    ISSN: 1573-4919
    Schlagwort(e): heart cells ; nucleus ; calcium ; R-type channel ; excitation-contraction coupling ; pacemaker activity ; Fura-2 ; Fluo-3 ; confocal microscopy
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie , Medizin
    Notizen: Abstract In the present study, Fluo-3 Ca2+ measurement and confocal microscopy techniques were used in order to localize cytosolic [ ]c and nuclear [ ]n free Ca2+ distribution in resting and spontaneously contracting single heart cells from 10-day-old chick embryos. In resting single cells, the concentration of Ca2+ in the cytoplasm was lower than that in the nucleus. Increasing cytosolic free Ca2+ from 100–1600 nM gradually increased [Ca2+]n with a maximum capacity near 1200 nM. Results from Fura-2 microfluorometry and Fluo-3 confocal microscopy suggest a potential cross talk between the increase of cytosolic free Ca2+ and the uptake and release of Ca2+ by the nucleus during spontaneous contraction of single myocytes. Calcium waves in spontaneously contracting cells were found to spread from one cell to the next with the nucleus acting as a fluorescent beacon in which Ca2+ levels remained elevated for several milliseconds even after cytosolic Ca2+ had returned to near basal values. These results strongly suggest that the nucleus plays a negative and positive feedback role in controlling cytosolic free Ca2+ concentration during excitation-contraction coupling in heart cells.
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  • 43
    ISSN: 1573-4919
    Schlagwort(e): hydroxyl radical ; oxidant ; hydrogen peroxide ; smooth muscle tissue ; mitochondria ; calcium
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie , Medizin
    Notizen: Abstract We sought to investigate the mechanism(s) by which the oxidant H2O2 stimulates Ca2+ release from mitochondria of bovine pulmonary vascular smooth muscle tissue and to test the hypothesis that hydroxyl radical is involved in this phenomenon. Treatment of the smooth muscle tissue with 1 mM H2O2 dramatically stimulated hydroxyl radical generation as measured by methane (CH4) production by GLC using dimethylsulfoxide (DMSO) as the substrate. Pretreatment of the mitochondria with the hydroxyl radical scavanger dimethylthiourea (DMTU) prevented the increase in CH4 production caused by H2O2. In the absence of EGTA, H2O2 caused stimulation of Ca2+ release from mitochondria occurred with a lag time of about 4 min. Addition of EGTA to Ca2+ loaded mitochondria resulted an immediate loss of Ca2+ and that has been found to be augmented by H2O2. The release of Ca2+ by H2O2 did not appear to occur with concommitant increase in sucrose entry into, K+ release from, and swelling of mitochondria when the Ca2+ cycling was prevented by EGTA. These observations suggested that H2O2-mediated Ca2+ release from bovine pulmonary vascular smooth muscle tissue mitochondria occurred (i) through the involvement of hydroxyl radical; (ii) via specific pathway(s); and (iii) did not appear to happen primarily via nonspecific ‘pore’ formation.
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  • 44
    Digitale Medien
    Digitale Medien
    Springer
    Molecular and cellular biochemistry 149-150 (1995), S. 175-182 
    ISSN: 1573-4919
    Schlagwort(e): rat pancreas ; cholecystokinin ; magnesium ; calcium ; acetylcholine ; amylase secretion
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie , Medizin
    Notizen: Abstract Application of either acetylcholine (ACh, 10−5 M) or cholecystokininoctapeptide (CCK-8, 10−8 M) to the isolated rat pancreas elicited large increases in amylase secretion, radiolabelled45Ca2+ influx and cytosolic free calcium [Ca2+]i levels in zero and normal (1.1 mM) extracellular magnesium [Mg2+]o. Elevated [Mg2+]o significantly (p〈0.001) reduced the secretagogueevoked secretory responses and Ca2+ mobilisation. Stimulation of pancreatic segments with either ACh (10−5 and 10−6 M) or CCK-8 (10−8 and 10−10 M) resulted in marked elevation in Mg2+ concentration in effluent samples (net efflux). On removal of either ACh or CCK-8, Mg2+ concentration returned to resting level. In pancreatic acinar cells loaded the flourescent dye magfura, ACh and CCK-8 evoked marked reduction in cytosolic free Mg2+ concentration [Mg2+]i compared to the resting value of 0.82±0.03 mM (n=50) in normal medium in the absence of secretagogues. In elevated [Mg2+]o (10 mM) medium, [Mg2+]i rises to 0.98±0.04 mM (n=6). Addition of CCK-8 led to only a small reduction in [Mg2+ i in elevated [Mg2+]o. In Mg2+ loaded pancreatic acinar cells, Mg2+ is released in a time dependent manner and this efflux of Mg2+ was sensitive to sodium, extracellular amiloride (1 mM), dinitrophenol (10 mM) and lidocaine (1 mM). The results indicate that Mg2+ is acting as an intracellular messenger to regulate the mobilisation of Ca2+ which in turn mediates enzyme secretion.
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  • 45
    Digitale Medien
    Digitale Medien
    Springer
    Journal of computer aided molecular design 10 (1996), S. 89-99 
    ISSN: 1573-4951
    Schlagwort(e): Conformation ; Molecular dynamics ; NMR
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary Proctolin (Arg-Tyr-Leu-Pro-Thr) was the first insect neuropeptide to be chemically characterised. It plays an essential role in insect neurophysiology and is involved in muscular contraction and neuromodulation. Elements of secondary structure in solution have been studied by comparing data obtained from NMR and molecular dynamics simulations. Different secondary structural requirements are associated with agonist and antagonist activities. A favoured conformation of proctolin has an inverse γ-turn, comprising an intramolecular hydrogen bond near the C-terminal end between Thr NH and Leu CO. Antagonists have a more compact structure resembling a ‘paperclip’ loop, containing an intramolecular hydrogen bond between Tyr NH and Pro CO, possibly stabilised by a salt bridge between the N- and C-terminal groups. A cyclic analogue retains antagonist activity and resembles a β-bulge loop, also comprising intramolecular hydrogen bonds between Tyr NH and Pro CO and Thr CO. These models may offer feasible starting points for designing novel compounds with proctolinergic activity.
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  • 46
    Digitale Medien
    Digitale Medien
    Springer
    Bioscience reports 15 (1995), S. 263-281 
    ISSN: 1573-4935
    Schlagwort(e): ATPase ; calcium ; structure ; X-ray crystallography
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract Electron crystallographic studies on membrane crystals of Ca2+-ATPase reveal different patterns of ATPase-ATPase interactions depending on enzyme conformation. Physiologically relevant changes in Ca2+ concentration and membrane potential affect these interactions. Ca2+ induced difference FTIR spectra of Ca2+-ATPase triggered by photolysis of caged Ca2+ are consistent with changes in secondary structure and carboxylate groups upon Ca2+ binding; the changes are reversed during ATP hydrolysis suggesting that a phosphorylated enzyme form of low Ca2+ affinity is the dominant intermediate during Ca2+ transport. A two-channel model of Ca2+ translocation is proposed involving the membrane-spanning helices M2–M5 and M4, M5, M6 and M8 respectively, with separate but interacting Ca2+ binding sites.
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  • 47
    ISSN: 1573-4935
    Schlagwort(e): ATPase ; calcium ; transport
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract The coupling of the chemical reaction of ATP hydrolysis to the transport of calcium from the cytoplasm into the lumen of sarcoplasmic reticulum vesicles can be defined by a set of rules that define alternating changes in the specificities of the enzyme for catalysis of chemical and physical reactions.
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  • 48
    ISSN: 1573-4935
    Schlagwort(e): ATPase ; calcium ; conformational change ; EDANS ; fluorescence ; sarcoplasmic reticulum
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract Changes in the fluoresence ofN-acetyl-N′-(5-sulfo-1-naphthyl)ethylenediamine (EDANS), being attached to Cys-674 of sarcoplasmic reticulum Ca2+-ATPase without affecting the catalytic activity, as well as changes in the intrinsic tryptophan fluorescence were followed throughout the catalytic cycle by the steady-state measurements and the stopped-flow spectrofluorometry. EDANS-fluorescence changes reflect conformational changes near the ATP binding site in the cytoplasmic domain, while tryptophan-fluorescence changes most probably reflect conformational changes in or near the transmembrane domain in which the Ca2+ binding sites are located. Formation of the phosphoenzyme intermediates (EP) was also followed by the continuous flow-rapid quenching method. The kinetic analysis of EDANS-fluorescence changes andEP formation revealed that, when ATP is added to the calcium-activated enzyme, conformational changes in the ATP binding site occur in three successive reaction steps; conformational change in the calcium enzyme substrate complex, formation of ADP-sensitiveEP, and transition of ADP-sensitiveEP to ADP-insensitiveEP. In contrast, the ATP-induced tryptophan-fluorescence changes occur only in the latter two steps. Thus, we conclude that conformational changes in the ATP binding site in the cytoplasmic domain are transmitted to the Ca2+-binding sites in the transmembrane domain in these latter two steps.
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  • 49
    ISSN: 1573-4935
    Schlagwort(e): ATPase ; calcium ; sarcoplasmic reticulum ; translocation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract Three experimental systems are described including sarcoplasmic reticulum (SR) vesicles, reconstituted proteoliposomes, and recombinant protein obtained by gene transfer and expression in foreign cells. It is shown that the Ca2+ ATPase of sarcoplasmic reticulum (SR) includes an extramembranous globular head which is connected through a stalk to a membrane bound region. Cooperative binding of two calcium ions occurs sequentially, within a channel formed by four clustered helices within the membrane bound region. Destabilization of the helical cluster is produced following enzyme phosphorylation by ATP at the catalytic site in the extramembranous region. The affinity and orientation of the Ca2+ binding site are thereby changed, permitting vectorial dissociation of bound Ca2+ against a concentration gradient. A long range linkage between phosphorylation and Ca2+ binding sites is provided by an intervening peptide segment that retains high homology in cation transport ATPases, and whose function is highly sensitive to mutational perturbations.
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  • 50
    Digitale Medien
    Digitale Medien
    Springer
    Bioscience reports 15 (1995), S. 341-349 
    ISSN: 1573-4935
    Schlagwort(e): ATPase ; calcium ; sarcoplasmic reticulum ; thapsigargin
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract Several reports have documented that thapsigargin is a potent inhibitor of the SR Ca2+ ATPase isolated from cardiac or skeletal muscle. We have characterized the specificity of this agent in intact rat cardiac myocytes using cells maintained in the whole cell voltage clamp configuration. We have shown that thapsigargin decreases the magnitude of the Ca2+ transient and the twitch by about 80% while it slows the decay rate for these responses. These changes were not accompanied by any alterations in sarcolemmal currents or in the trigger Ca2+ generated by the inward calcium current. Taken together these results reveal that the action of thapsigargin is restricted to the SR Ca2+ ATPase in intact cardiac myocytes. Furthermore, it is demonstrated unambiguously that SR intracellular Ca2+ stores are an absolute requirement for the development of contractile tension in rat heart myocytes. It is shown that thapsigargin is a valuable probe to examine the importance of SR pools of Ca2+ and the role of the Ca2+ ATPase in intact myocytes as well as in genetically altered heart cells.
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  • 51
    Digitale Medien
    Digitale Medien
    Springer
    Bioscience reports 15 (1995), S. 377-385 
    ISSN: 1573-4935
    Schlagwort(e): ATPase ; calcium ; sarcoplasmic reticulum
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract We propose an overview of the mechanism of Ca2+ transport through the sarcoplasmic reticulum membrane via the Ca2+-ATPase. We describe cytoplasmic calcium binding, calcium occlusion in the membrane and lumenal calcium dissociation. A channel-like structure is discussed and related to structural data on the membranous domain of the Ca2+-ATPase.
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  • 52
    Digitale Medien
    Digitale Medien
    Springer
    Bioscience reports 15 (1995), S. 55-63 
    ISSN: 1573-4935
    Schlagwort(e): water transport mechanisms ; NMR ; rat erythrocytes ; tritium effects
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract The inhibition of water diffusion across the rat erythrocyte membrane was studied by NMR using two basically different types of inhibitory agents: PCMB andin vivo irradiation. The contribution of lipid and protein to water permeability revealed the inhibitory effect of each pathway. Internal contamination with tritium (25–115 mGy) reduces water permeability due to protein modifications; for doses higher than 100 mGy the lipid mediated mechanism seems also to be impaired. The same procedure enables one to assess the extent to which the higher water permeability of rat, compared to human, erythrocyte is due to one of the two pathways.
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  • 53
    Digitale Medien
    Digitale Medien
    Springer
    Bioscience reports 16 (1996), S. 107-113 
    ISSN: 1573-4935
    Schlagwort(e): ATPase ; calcium ; expression systems ; sarcoplasmic reticulum
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract In recent years, expression of rabbit sarcoplasmic reticulum (SR) Ca2+-ATPase in heterologous systems has been a widely used strategy to study altered enzymes generated by site-directed mutagenesis. Various eukaryotic expression systems have been tested, all of them yielding comparable amounts of recombinant protein. However, the relatively low yield of recombinant protein obtained so far suggests that novel purification techniques will be required to allow further characterization of this enzyme based on direct ligand-binding measurements.
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  • 54
    ISSN: 1573-4935
    Schlagwort(e): ATPase ; calcium ; magnesium ; plasma membrane ; polyols ; organic solutes ; sarcoplasmic raticulum ; urea
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract Organic solutes such as urea, methylamines, polyols and amino acid can accumulate in the cytoplasm of cells to compensate for hyperosmotic conditions in the external medium. Whereas urea is considered to be typical of solutes that destabilize structure and function of proteins, methylamines, polyols and some amino acids appear to have the opposite effect, and can also compensate for the perturbing effects of urea. These effects have been extensively analyzed for a variety of proteins in terms of global changes in enzyme structure and acceleration or inhibition of overall reaction rates. Here the influence of these solutes on sarcoplasmic reticulum and plasma membrane (Ca2+ + Mg2+)ATPases is reviewed. The focus is on the changes induced by “perturbing” and “stabilizing” solutes at specific steps of the catalytic cycles of these enzymes, which can run forward (leading to ATP hydrolysis) and backward (leading to ATP synthesis). Structural changes promoted by osmolytes are correlated with functional changes, especially those that are related to energy coupling.
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  • 55
    Digitale Medien
    Digitale Medien
    Springer
    Journal of sol gel science and technology 4 (1995), S. 151-162 
    ISSN: 1573-4846
    Schlagwort(e): sol-gel transition ; rheology ; siloxane ; NMR
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Ormosils are well-known organic-inorganic sol-gel derived materials also called heteropolysiloxanes. This paper presents two basic heteropolysiloxane structures where the organic part is either a short organic chain bridging two silicon atoms for the first material or an organic polymer backbone for the second. Their synthesis is detailed and a variety of experimental techniques (IR, 13C and 29Si NMR and CP-MAS NMR, GPC) have been employed to investigate the chemical structure of these new materials. Their mechanical properties, more precisely their viscoelastic behaviour, have been evaluated using dynamic rheological techniques. The storage and loss moduli have been followed during the sol-gel transition at fixed and variable oscillation frequencies. The results have been correlated to the 29Si CP-MAS NMR informations concerning the network polycondensation and compared to a pure inorganic sol-gel material prepared from tetraethoxysilane.
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  • 56
    Digitale Medien
    Digitale Medien
    Springer
    Journal of sol gel science and technology 6 (1996), S. 139-149 
    ISSN: 1573-4846
    Schlagwort(e): titanosiloxanes ; siloxanes ; hydrolysis ; condensation ; structural units ; NMR
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The structural units in diphenylsilanediol/titanium-isopropoxide solutions with molar ratio Si:Ti between 1:0.1 and 1:5 were examined by means of 29Si and 17O NMR. The main component in solutions with molar ratio Si/Ti=1:0.1 is the chain-like octaphenyltetrasiloxanediol. With increasing Ti-isopropoxide content (1:0.25–1:05) Si−O−Ti units of the spirocyclic titanosiloxane Ti[O5Si4(C6H5)8]2 prevail in the solutions accompanied by the chain-like tetrasiloxanediol. The 29Si NMR spectra of 1:1 solutions indicate a lot of different Si containing building units with chemical shifts mainly between-40 and-46 ppm. The signals with a chemical shift between-40 and-46 ppm are probably caused by Si atoms which are connected via oxygen bridges directly (Si−O−Ti) or indirectly (Si−O−Si−O−Ti) with titanium. Contrary to the 1:1 solutions only one or two different species with Si−O−Ti units are present in high Ti-alkoxide containing solutions (1:5). 29Si and 17O NMR results reveal a quick hydrolysis of the Ti−O−Si bonds to titanium-oxo-hydroxo-polymers and phenylsiloxanediols or their isopropyl esters after the addition of water to the solutions. This separation into species only containing either Ti−O−Ti or Si−O−Si bonds can entail a decreased homogeneity of the reaction products on a molecular level.
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  • 57
    Digitale Medien
    Digitale Medien
    Springer
    Journal of sol gel science and technology 6 (1996), S. 279-285 
    ISSN: 1573-4846
    Schlagwort(e): sol-gel process ; siloxane cross-linking ; gelation ; NMR ; SANS
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract We have studied by 29Si NMR and small angle neutron scattering the cross-linking by formation of siloxane bridges of two amino-epoxy-silane molecules at different concentration in acidic water. We relate our observations to the fact that one of the studied systems never gels, while the second one displays a concentration threshold for gelation that is accounted for by percolation theory.
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  • 58
    Digitale Medien
    Digitale Medien
    Springer
    The protein journal 14 (1995), S. 115-126 
    ISSN: 1573-4943
    Schlagwort(e): NMR ; high-potential iron protein ; 15N assignment ; heteronuclear correlation ; paramagnetic
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The15N resonances in reduced and oxidizedChromatium vinosum high-potential iron protein have been assigned by use of1H-1H COSY spectra and1H-15N HMQC, HMQC-COSY, and HMQC-NOESY spectra. Unambiguous assignment of 70 of 85 backbone15N resonances in the reduced protein and 62 of 85 resonances in the oxidized protein are made, as are 12 of 21 side-chain15N resonances.
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  • 59
    ISSN: 1573-4943
    Schlagwort(e): Interleukin-5 ; carboxy-terminal truncations ; NMR ; protein stability
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The C-terminal region of interleukin-5 has previously been suggested to be important for biological activity [Mackenzieet al., (1991),Mol. Immunol. 28, 155–158; Kodamaet al. (1991),Biochem. Biophys. Res. Commun. 178, 514–519]. We have investigated this region by making a series of truncation mutants. The proteins were expressed inEscherichia coli, purified from inclusion bodies, and were able to refold with the disulfide homodimeric topology typical of interleukin-5. Analysis of the truncated carboxy-terminal proteins in an interleukin-5-dependent proliferation assay on TF-1 cells showed a rapid loss of activity as the C-terminal was shortened by more than two amino acids. This loss of biological activity correlated with a drop in binding affinity to both theα chain of the receptor and the high-affinity complex consisting of theα andβ subunits. Analysis of the proteins by1H-NMR showed that the truncated mutants have higher exchange rates with solvent, indicating a less rigid structure. The carboxy-terminal region is therefore necessary to maintain the stability of the four-helix bundle and to orient correctly the important residues of the fourth helix. Inspection of the structure determined by X-ray crystallography shows that Trp-110 acts as the major residue in anchoring the fourth helix.
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  • 60
    ISSN: 1573-9171
    Schlagwort(e): sodium alkyls ; lithium alkyls ; NMR ; synthesis
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract 1H,23Na, and7Li NMR spectra of 2-ethyl hexylsodiurn, 2-ethylhexyllithium, and isobutyllithium obtained in the reaction of the corresponding alkyl chlorides and metals have been recorded. The1H N MR signal for the protons of the CH2Na group is shifted upheld compared with that for the protons of the CH2Li group (doublets at δ -0.88 and δ -0.83, respectively). The composition of the products of reaction of 2-ethylhexyl chloride with sodium depends on the form of the metal reagent employed. The use of sodium balls with diameter up to 2 mm results in the formation of products containing ionic chlorine (30–50 % with respect to Na); the reaction with the dispersion proceeds faster and the reaction product is chlorine-free. The23Na NMR spectra of these substances are also different, which is explained by the formation of 2-ethylhexylsodium complexes with NaCl in the former case.
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  • 61
    Digitale Medien
    Digitale Medien
    Springer
    Russian chemical bulletin 44 (1995), S. 2179-2182 
    ISSN: 1573-9171
    Schlagwort(e): ɛ-caprolactam ; caprolactamates of magnesium ; calcium ; strontium, and barium ; anionic polymerization of lactams
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Caproiactamates of alkaline-earth metals and magnesium of the general formula $${\text{M[}}{\text{O}}]_2 $$ , where M = Mg, Ca, Sr, and Ba, were synthesized from alkoxides, hydrides, and organometallic compounds of these metals and ɛ-caprolactam. The catalytic activities of caprolactamates obtained under conditions of anionic polymerization of ɛ-caprolactam were compared. It was demonstrated that the purest caprolactamates and, hence, the most effective catalysts of anionic polymerization of lactams can be obtained from organometallic and hydride compounds of these metals. The reactivities of alkoxides of the alkaline-earth metals and magnesium increase in metallation reactions of ɛ-caprolactam in the order Mg 〈 Ca 〈 Sr 〈 Ba.
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  • 62
    ISSN: 1573-4986
    Schlagwort(e): O-acetyl GM3 ; equine erythrocytes ; NMR
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Novel mono-O-acetylated GM3s, one containing 9-O-acetylN-glycolyl neuraminic acid and another containing 6′-O-acetyl galactose, were isolated as a mixture from equine erythrocytes, and the structures were characterized by one- and two-dimensional proton nuclear magnetic resonance (NMR) and fast atom bombardment-mass spectrometry (FAB-MS). The position of theO-acetyl residue was identified by the downfield shift of the methylene protons at C-9 ofN-glycolyl neuraminic acid (9-O-Ac GM3) and C-6 of galactose (6′-O-Ac GM3) in the NMR spectrum, in comparison to the respective non-acetylated counterparts. To confirm the presence of 6′-O-Ac GM3, theO-acetylated GM3 mixture was desialylated withArthrobacter neuraminidase, giving 6-O-acetyl galactosyl glucosylceramide, the structure of which was estimated by NMR and FAB-MS, together with non-acetylated lactosylceramide with a ratio of 1:1.
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  • 63
    ISSN: 1573-4986
    Schlagwort(e): gangliosides ; N-glycolyl-neuraminic acid ; NMR ; conformation ; nOe
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The conformational properties of the oligosaccharide chain of GM1 ganglioside containingN-glycolyl-neuraminic acid, β-Gal-(1-3)-β-GalNAc-(1-4)-[α-Neu5Gc-(2-3)]-β-Gal-(1-4)-β-Glc-(1-1)-Cer, were studied through NMR nuclear Overhauser effect investigations on the monomeric ganglioside in dimethylsulfoxide, and on mixed micelles of ganglioside and dodecylphosphocholine in water. Several interresidual contacts for the trisaccharide core-β-GalNAc-(1-4)-[α-Neu5Gc-(2-3)]-β-Gal-were found to fix the relative orientitation of the three saccharides, while the glycosidic linkage of the terminal β-Gal-was found to be quite mobile as the β-Gal-(1-3)-β-GalNAc-disaccharide exists in different conformations. These results are similar to those found for two GM1 gangliosides containingN-acetyl-neuraminic acid and neuraminic acid [1].
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  • 64
    ISSN: 1573-4986
    Schlagwort(e): glycopeptide ; NMR ; proteoglycan ; serglycin ; secondary structure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract We present complete1H NMR assignments for two synthetic glycopeptides representative of the carbohydrateprotein linkage region of serglycin proteoglycans. The peptides are: Ser(Galp-Xylp)-Gly-Ser-Gly-Ser(Galp-Xylp)-Gly and, Ser(Galp-Xylp)-Gly-Ser(Galp-Xylp)-Gly-Ser(Galp-Xylp)-Gly. A number of 2D NMR spectra together with a 3D NOESY-TOCSY spectrum were acquired at 600 MHz to complete the assignments of the glycopeptides dissolved in water with 40% trifluoroethanol. Preliminary analysis of the NMR data suggests folded structures for the glycopeptides.
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  • 65
    Digitale Medien
    Digitale Medien
    Springer
    Glycoconjugate journal 13 (1996), S. 487-494 
    ISSN: 1573-4986
    Schlagwort(e): Blood group A glycosphingolipids ; monoclonal antibody ; NMR ; mass spectrometry
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract In this study, the antibody 3G9-A was assayed for activity against human erythrocyte glycosphingolipids. The antibody was found to recognize glycosphingolipid components from blood group A erythrocytes but not glycosphingolipids from blood group B or O erythrocytes. Subsequent investigation revealed that the glycosphingolipid components recognized by the antibody were also recognized by a blood group A specific monoclonal antibody. The structures of two of the isolated active glycosphingolipid components were structurally characterized using proteon nuclear magnetic resonance (1H NMR) and gas chromatography-mass spectrometry (GC-MS) techniques and were found to consist of two blood group A glycosphingolipids; the type 2 chain Ab and type 3 chain Aa glycosphingolipids. Subsequent analysis of the remaining active components by GC-MS and immunostaining techniques revealed that all of the active components were blood group A glycosphingolipids. Furthermore, structural studies of the active components suggested that the epitope of the antibody consisted of the group A trisaccharide, GalNAcα1,3(Fucα1,2)Gal.
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  • 66
    Digitale Medien
    Digitale Medien
    Springer
    Chemistry of heterocyclic compounds 31 (1995), S. 1071-1078 
    ISSN: 1573-8353
    Schlagwort(e): NMR ; 1H NMR ; 13C NMR ; 17O NMR ; 15N NMR ; aziridine-carboxylates ; configurational analysis ; conformational analysis
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract A confrgurational and conformational study of NH, N-acetyl- and N-sulfonylaziridine carboxylates is performed by1H ,13C,17O, and15N NMR spectroscopy. The presence of acetyl and su fonyl groups on the ring nitrogen atom seems to reduce greatly the configurational stability at nitrogen.
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  • 67
    Digitale Medien
    Digitale Medien
    Springer
    Pharmaceutical research 13 (1996), S. 44-51 
    ISSN: 1573-904X
    Schlagwort(e): LDL ; LDL models ; synchrotron radiation ; X-ray solution scattering ; NMR ; solvent evaporation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Purpose. Drug free and drug loaded protein-free low density lipoprotein (LDL) models consisting mainly of phospholipids, cholesterol, cholesterol esters, and triglycerides in ratios found for physiological LDL have been prepared. Their physicochemical characteristics were compared with those of physiological LDL. Methods. Different characterization methods were used: photon correlation spectroscopy, transmission electron microscopy, X-ray solution scattering, and 1H nuclear magnetic resonance spectroscopy (NMR). Results. Particle sizes are highly dependent on the preparation method and in particular on the homogenization conditions. Electron microscopy indicates that the size distributions of model systems are much broader than those of physiological LDL. The X-ray solution scattering patterns of the model systems display a temperature dependent maximum near 3.8 nm similar to that found in the patterns of physiological LDL. NMR indicates a comparable mobility of the lipid molecules in model particles and in physiological LDL. The influence of drug loading is similar to that found earlier for physiological LDL. In particular, the incorporation of the anti-cancer drug WB 4291 seems to have a fluidizing effect on the lipids in the core region of the particles. Conclusions. The preparation method of LDL model systems is of crucial importance as only the solvent evaporation method yielded systems in the size range of physiological LDL with acceptable high lipid concentrations. The fluidizing influence of temperature and drug incorporation (WB 4291) may be a disadvantage in drug targeting.
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  • 68
    Digitale Medien
    Digitale Medien
    Springer
    Bioscience reports 15 (1995), S. 445-462 
    ISSN: 1573-4935
    Schlagwort(e): Myosin II ; cyclic GMP ; calcium ; motility ; myosin heavy chain kinase ; myosin light chain kinase ; signal transduction
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract This review is concerned with the roles of cyclic GMP and Ca2+ ions in signal transduction for chemotaxis ofDictyostelium. These molecules are involved in signalling between the cell surface cyclic AMP receptors and cytoskeletal myosin II involved in chemotactic cell movement. Evidence is presented for uptake and/or eflux of Ca2+ being regulated by cyclic GMP. The link between Ca2+, cyclic GMP and chemotactic cell movement has been explored using “streamer F” mutants whose primary defect is in the structural gene for the cyclic GMP-specific phosphodiesterase. This mutation causes the mutants to produce an abnormally prolonged peak of cyclic GMP accumulation in response to stimulation with the chemoattractant cyclic AMP. The production and relay of cyclic AMP signals is normal in these mutants, but certain events associated with movement are (like the cyclic GMP response) abnormally prolonged in the mutants. These events include Ca2+ uptake, myosin II association with the cytoskeleton and regulation of both myosin heavy and light chain phosphorylation. These changes can be correlated with changes in the shape of the amoebae after chemotactic stimulation. Other mutants in which the accumulation of cyclic GMP in response to cyclic AMP stimulation was absent produced no myosin II responses. A model is described in which cyclic GMP (directly or indirectly via Ca2+) regulates accumulation of myosin II on the cytoskeleton by regulating phosphorylation of the myosin heavy and light chain kinases.
    Materialart: Digitale Medien
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  • 69
    ISSN: 1573-4935
    Schlagwort(e): Yeast ; Ca++-ATPases ; phylogenetic tree ; calcium
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract Calcium is an essential second messenger in yeast metabolism and physiology. So far, only four genes coding for calcium translocating ATPases had been discovered in yeast. The recent completion of the yeastSaccharomyces cerevisiae genome allowed us to identify six new putative Ca++-ATPases encoding genes. Protein sequence homology analysis and phylogenetic classification of all putative Ca++-ATPase gene products from the yeastsSaccharomyces cerevisiae andSchizosacchraomyces pombe reveal three clusters of homologous proteins. Two of them comprises seven proteins which might belong to a new class of P-type ATPases of unknown subcellular location and of unknown physiological function.
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  • 70
    Digitale Medien
    Digitale Medien
    Springer
    Bioscience reports 16 (1996), S. 343-350 
    ISSN: 1573-4935
    Schlagwort(e): dHGF ; hepatocyte ; protein kinase A ; calcium
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract Parathyroid hormone (PTH) mobilises calcium in the hepatocyte, an effect which is abolished by verapamil and staurosporine. In our study parathyroid hormone was shown to act additively to dHGF in inducing hepatocyte DNA synthesis. It is also shown that PTH induced the production of inositol 1,4,5 trisphosphate (IP3) andc-fos expression at early times in culture. Co-incubation of PTH and dHGF with ac-fos antisense oligodeoxynucleotide inhibited hepatocyte DNA synthesis, indicating that the additive effect of PTH is correlated with the induction ofc-fos. H-89, a PKA specific inhibitor, inhibited the PTH effect on IP3 production as well as the PTH effect on hepatocyte DNA synthesis. Verapamil and staurosporine also inhibited the PTH effect in dHGF-induced DNA synthesis. Therefore it is suggested that PKA mediated at a great extent the co-stimulatory effects of PTH on hepatocyte proliferation via IP3 production.
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  • 71
    Digitale Medien
    Digitale Medien
    Springer
    Pharmaceutical research 13 (1996), S. 535-541 
    ISSN: 1573-904X
    Schlagwort(e): bile salt ; phospholipid ; diffusion ; mucin ; NMR
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Purpose. The objective of this study is to evaluate the effect of the mucous layer on the transport of the drug-solubilizing bile salt/phosphatidylcholine (BS/PC) aggregates. Methods. The self-diffusion coefficient of BS/PC aggregates in bovine submaxillary mucin (BSM) was measured by Fourier-transform pulsed-field gradient spin-echo (FT-PGSE) 1H NMR spectroscopy. Results. In spite of the complexity of the mixture, the FT-PGSE technique allowed the unambiguous determination of the diffusivity of PC and 1H2HO (HDO, natural abundance in D2O). With a series of BS/ PC total lipid concentrations ranging from 1 to 7 g/dl, a progressive decrease in the effective diffusivity of HDO was observed with an increase in the both the BSM and total lipid concentration. The effective diffusivity of PC decreased with increasing lipid concentrations in the presence of mucin, while in the controls it increased. After correcting the effective diffusivity of PC for the obstruction effect of mucin, the size of the BS/PC mixed micelle was assessed. It appears that PC associates with BSM resulting in a decrease in the available PC for micellization. This reduces the average size of the mixed micelle within the mucous layer. Conclusions. The aggregation state of BS/PC micelle is altered by the presence of mucin which would have a direct impact on the transport of dietary lipid and solubilized drug through the aqueous boundary layer of the intestinal tract.
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  • 72
    Digitale Medien
    Digitale Medien
    Springer
    Pharmaceutical research 13 (1996), S. 1815-1820 
    ISSN: 1573-904X
    Schlagwort(e): elastase inhibitor ; monocyclic β-lactam ; NMR ; stability
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Purpose. The objective was to evaluate the degradation profile of the elastase inhibitor DMP 777 and lay the foundation for formulation development. Methods. The pKa was determined by potentiometric titration in mixed-aqueous solvents. The degradation kinetics were studied as a function of pH, buffer concentration, ionic strength, methanol concentration and temperature using a stability-indicating HPLC assay. The degradation products were identified by LC-MS, NMR, and by comparison with authentic samples. Results. The pKa for the protonated piperazine nitrogen was estimated to be 7.04. The pH-rate profile is described by specific acid-, water-, and specific base-catalyzed pathways. The pH of maximum stability is in the range of 4 to 4.5 where water is the principal catalyst in the reaction. Buffer catalysis, primary salt effects and medium effects were observed. The proposed mechanism for acid catalyzed degradation is the rarely observed AAL1 which involves alkyl-nitrogen heterolysis. The driving force for the reaction appears to lie in the stability of the benzylic carbocation. The proposed mechanism for base catalyzed degradation is BAC2 which involves β-lactam ring opening. The β-lactam ring of DMP 777, a monolactam, appears to be as reactive as that in benzylpenicillin in the k OH controlled region where a similar mechanism of hydrolysis should be operative. A contributing factor to this increased reactivity may lie in the reduced basicity of the β-lactam nitrogen making it a good leaving group. Conclusions. The degradation profile indicates that development of a solution dosage form of DMP 777 with adequate shelf-life stability at room temperature is feasible.
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  • 73
    ISSN: 1573-904X
    Schlagwort(e): cholesterol ; differential scanning calorimetry ; drug delivery ; electron microscopy ; fluorescence quenching ; long circulating liposomes ; NMR
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Purpose. The purpose of this study was to investigate polyethyleneglycol (PEG)-phosphatidylethanolamine (PE) conjugate interaction with cholesterol-phospholipid mixtures in an attempt to explain the effect of cholesterol on liposome circulation time. Methods. Differential scanning calorimetry, NMR, electron microscopy, dynamic light scattering and fluorescence spectroscopy were the major methods used. Results. Studies performed in the absence of cholesterol indicated the formation of three distinct physical states depending on the chain length of PEG in PEG-PE. Mixed micelle formation was observed at concentrations of PEG( 1,000)-DPPE above 7 mol% of lipid. Phase separated lamellae were observed at all concentrations of PEG( 12,000)-DPPE (Bedu-Addo et al. Pharm. Res. 13:710–717 (1996)). Upon incorporation of high concentrations of cholesterol 〉30 mol% into the lipid bilayer, the formation of phase separated lamellae was completely inhibited and the formation of mixed micelles significantly reduced. At high concentrations of PEG( 1,000)-PE, solubilization of the bilayer occurred with preferential solubilization of cholesterol over phosphati-dylcholine. Maximum steric stabilization (surface protection) was observed with low concentrations of short chain PEG-PE and high concentrations of cholesterol. Conclusions. The study provides a physical mechanism for the following observations: the blood circulation time is significantly increased or decreased with liposomes highly enriched with cholesterol or PEG-PE respectively.
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  • 74
    ISSN: 1573-904X
    Schlagwort(e): 2′,3′,5′-triacetyl-6-azauridine ; prodrug ; hydrolysis ; pH-profile ; arrhenius plots ; CI-MS ; NMR ; liquid chromatography
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Purpose. The purposes were to study the kinetics of hydrolysis of 2′,3′,5′-triacetyl-6-azauridine ( 1 ) in aqueous solution (µ = 0.5) and to identify the main intermediates and products of the reaction. Methods. A stability indicating isocratic LC assay was used to study the rate of degradation of 1 A gradient LC assay was used to study the time courses of the degradants. The products of hydrolysis were isolated by preparative liquid chromatography and identified by 1H-NMR and CI-MS. The pKa value was obtained by potentiometric titration. Results. At 36.8°C, the pH-rate profile of 1 in water was adequately described by a four-term rate equation. The intermediates were identified as the primary and secondary di-acetates, and the primary and secondary mono-acetates. The final product was 6-azauridine. Conclusions. A simplified kinetic scheme could be used to describe the concentration-time profiles of 1, the intermediates and the final product.
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  • 75
    Digitale Medien
    Digitale Medien
    Springer
    Colloid & polymer science 274 (1996), S. 1-7 
    ISSN: 1435-1536
    Schlagwort(e): NMR ; nonionic surfactant ; lamellar phase ; shear-induced structure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: Abstract The lamellar phases of two aqueous ethylene oxide surfactants, tetra(ethylene oxide) dodecyl ether and hexa(ethylene oxide) dodecyl ether, have been investigated by deuterium nuclear magnetic resonance spectroscopy during shear. The evolution of the shear-induced NMR line shapes and their dependence on surfactant concentration, shear geometry and shear history is analyzed. Two of three previously described shear-induced states (Diat O, Roux D, Nallet F (1993) J Phys II France 3: 1427–1452), namely the state of aligned lamellae with the layer normal parallel to the velocity gradient, which occurs at low shear rates, and the vesicular state at intermediate shear rates are found and identified by their characteristics NMR line shapes.
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  • 76
    Digitale Medien
    Digitale Medien
    Springer
    Colloid & polymer science 274 (1996), S. 191-196 
    ISSN: 1435-1536
    Schlagwort(e): Vulcanization ; NMR ; NMR imaging ; vulcametry ; simulations
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: Abstract For the first time, in situ NMR measurements were performed during sulfur vulcanization of unfilled SBR. A vulcanization device was constructed for use in combination with a standard microimaging probe in a vertical bore NMR magnet.1H-linewidth measurements are correlated with cure simulations in a vulcameter to explain the increase of the linewidth during the vulcanization. Inhomogeneous heating conditions in the sample result in an inhomogeneous course of the vulcanization as a function of time. The spatial dependence of this process was monitored by NMR imaging.
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  • 77
    Digitale Medien
    Digitale Medien
    Springer
    Biogeochemistry 32 (1996), S. 195-220 
    ISSN: 1573-515X
    Schlagwort(e): acidification ; acid neutralizing capacity ; aluminum ; calcite ; calcium ; liming ; nitrogen cycling ; soil chemistry ; soil solutions ; spodosols
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Geologie und Paläontologie
    Notizen: Abstract Soil solution chemistry was investigated at a forested watershed draining into Woods Lake. N.Y. as part of the Experimental Watershed Liming Study (EWLS). The objective of this study was to assess the response of soil water to watershed treatment of calcite (CaCO3). This material was applied in an effort to mitigate the effects of acidic atmospheric deposition. Soil solutions draining Oa and Bs horizons in reference subcatchments were characterized by low pH and acid neutralizing capacity (ANC) due to elevated concentrations of SO 4 2− , NO 3 − and organic anions relative to the sum of base cation (CB Ca2+, Mg2+, Na+, K+) concentrations. Seasonal and spatial variation of pH andANC in soil solutions appeared to belargely controlled by variations in the concentrations of dissolved organic acids which, in turn, were regulated by reactions of Al with soil organic matter. Nitrate was positively correlated and SO2+ was negatively correlated with Ca2+ and Al concentrations in reference soil solutions, indicating that changes in NO 3 − influences spatial and seasonal variations in Ca2+ and Al concentrations. On this basis, NO 3 − appears to be important in soil acidification and the dynamics of drainage water acidity. Comparison of our results with historical data for the site showed declines in concentrations of SO 4 2− , which are consistent with decreases in emissions of SO4, in the eastern U.S. and atmospheric deposition of SO 4 2− , to the Adirondack region. Mineral soil solutions have shown large increases in concentrations of NO 3 − . Declines in concentrations of CB and increases in concentrations of Al have occurred over the last ten years, suggesting depletion of soil pools of exchangeable basic cations and increased sensitivity to acidic deposition. Calcite (CaCO3) treatment of 6.89 Mg/ha resulted in a significant increase of Ca2+, ANC and pH in both Oa and Bs horizon soil solutions. Soil water response to CaCO3 addition was most evident during the first year after treatment, apparently due to macropore transport of particulate and dissolved CaCO3 However, increases in ANC and pH in the mineral soil waters were not sustained and appeared insufficient to result in substantial improvement in surface water quality over the 43 month study period.
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  • 78
    ISSN: 1573-515X
    Schlagwort(e): biogeochemical processes ; calcium ; chaparral ; magnesium ; Mediterranean ecosystem ; weathering rate
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Geologie und Paläontologie
    Notizen: Abstract Large earthen-walled lysimeters at the San Dimas Experimental Forest in southern California present a unique opportunity to assess vegetation effects on biogeochemical processes and cation release by weathering in controlled soil-vegetation systems where archived samples of soil parent material are available for comparison. The lysimeters were filled in 1937 with homogenized fine sandy loam derived on site from the weathering of diorite, and planted in 1946 with scrub oak (Quercus dumosa) and Coulter pine (Pinus coulteri). Changes in base cation contents were measured in above-ground biomass, and total and exchangeable soil pools to a depth of 1 meter. All cations in the non-exchangeable soil pool decreased relative to the initial fill material, indicating release by weathering. Sodium and K were depleted from both exchangeable and non-exchangeable pools of the soils. Plant uptake of Na was minimal, whereas K storage in vegetation exceeded the loss from the exchangeable soil pool. In both soil-vegetation systems, but especially for oak, there was an increase in exchangeable Ca and Mg. For all base cations, storage in above-ground biomass was greater for oak, whereas losses by weathering from the non-exchangeable soil pool were greater under pine. Strong evidence supports biocycling as a controlling mechanism resulting in greater Ca and Mg release by weathering under pine. In addition, decreases in non-exchangeable Ca and Mg were strongly correlated to decrease in Si under oak, whereas no correlation was observed under pine. We conclude that weathering reactions or stoichiometry differed between vegetation types.
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  • 79
    Digitale Medien
    Digitale Medien
    Springer
    Journal of bioenergetics and biomembranes 28 (1996), S. 219-230 
    ISSN: 1573-6881
    Schlagwort(e): Ion transport ; action potential ; ion channels ; calcium ; sodium ; voltage-dependent gating
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie , Physik
    Notizen: Abstract Voltage-gated sodium and calcium channels are responsible for inward movement of sodium and calcium during electrical signals in cell membranes. Their principal subunits are members of a gene family and can function as voltage-gated ion channels by themselves. They are expressed in association with one or more auxiliary subunits which increase functional expression and modify the functional properties of the principal subunits. Structural elements which are required for voltage-dependent activation, selective ion conductance, and inactivation have been identified, and their mechanisms of action are being explored through mutagenesis, expression in heterologous cells, and functional analysis. These experiments reveal that these two channels are built on a common structural theme with variations appropriate for functional specialization of each channel type.
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  • 80
    Digitale Medien
    Digitale Medien
    Springer
    Journal of chemical ecology 22 (1996), S. 2209-2219 
    ISSN: 1573-1561
    Schlagwort(e): Allelopathy ; aquatic plant ; bioassay ; Nuphar lutea ; alkaloids ; NMR ; nupharolutine ; 6,6′-dihydroxythiobinupharidine ; Nymphaeaceae
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract Two of the majorNuphar alkaloids, nupharolutine and 6,6′-dihydroxythiobinupharidine, were isolated from the aquatic perennial herbNuphar lutea (L.) Sibth. & Sm., yellow water lily. In a lettuce seedling bioassay of the two pure compounds, the former was inactive and the latter was highly inhibitory of radicle elongation at concentrations greater than 2 ppm. Structures and stereochemistry of the two compounds were confirmed by DEPT,1H-1H COSY,1H-13C COSY, and1H-1H NOESY experiments.
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  • 81
    Digitale Medien
    Digitale Medien
    Springer
    Journal of chemical ecology 21 (1995), S. 663-691 
    ISSN: 1573-1561
    Schlagwort(e): Diet ; calcium ; carnivore ; herbivore ; omnivore ; oral homeostasis ; proline-rich proteins ; saliva ; secretion ; tannin
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract We review information on the structure of proline-rich proteins (PRPs), their various functions related to oral homeostasis and dietary tannin, and the structural basis of these functions. Consideration of the multifunctional nature of these salivary proteins helps explain both the subtle and large variations found in structure and secretion rates both within individuals and between species. We propose that the ancestral function of PRPs is in maintaining oral homeostasis and that counteracting dietary tannins by binding with them is a derived function. PRPs are effective in oral homeostasis at low secretion levels, whereas counteracting tannin depends on high secretion levels. In the dietary habits ranging from carnivores through omnivores to exclusively planteaters, the dietary nitrogen level is progressively reduced, and plant allelochemical intake, including tannins, increases. We suggest that during this evolution from meat-eater to plant-eater, there was some point in omnivory at which selective pressure from nitrogen limitations, arising from a low nitrogen/high tannin diet, became sufficiently great for the evolution of increased secretion level and diversification of PRPs for dealing with tannin. If this hypothesis is correct, carnivorous mammals should secrete low levels of PRPs for oral homeostasis, but should never secrete high levels, unless they are secondarily carnivorous. Omnivores consuming a diet of very little animal tissue but higher levels of tannin-containing foliage or fruit should generally have the capacity to produce high levels of salivary PRPs. Browsers and frugivores should also produce high levels of PRPs, but grazers may have reduced secretion rates depending on the antiquity of the dietary habit. This hypothesis is consistent with the limited information available on the abundance, type, and distribution of PRPs in mammals. Studies are suggested which would test the functional and evolutionary arguments presented.
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  • 82
    Digitale Medien
    Digitale Medien
    Springer
    Journal of chemical ecology 21 (1995), S. 1191-1215 
    ISSN: 1573-1561
    Schlagwort(e): Ourebia ourebi ; Bovidae ; mammalian semiochemicals ; mammalian pheromones ; exocrine secretion ; preorbital secretion ; dimethyl disulfide derivatization ; skipped dienes ; chemical-ionization mass spectrometry ; NMR
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract Using gas chromatography-mass spectrometry in conjunction with ancillary techniques such as chemical ionization with different reactant gases, determination of the position of double bonds by means of dimethyl disulfide derivatization, and finally gas chromatographic and mass spectrometric comparison with authentic synthetic material, 75 constituents were identified in the preorbital secretion of the male oribi,Ourebia ourebi. The secretion contains compounds with long-chain, unbranched structures similar to those found in many other preorbital secretions but with a finite volatility range, in contrast to the seemingly endlessly increasing chain lengths typical of other preorbital secretions.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 83
    Digitale Medien
    Digitale Medien
    Springer
    Journal of inclusion phenomena and macrocyclic chemistry 25 (1996), S. 313-325 
    ISSN: 1573-1111
    Schlagwort(e): Inclusion complex ; tolbutamide ; permethyl-β-cyclodextrin ; hypoglycemic effect ; glucose level ; NMR ; FT-IR
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The formation of a stable inclusion complex between tolbutamide and permethyl-β cyclodextrin was systematically studied. It shows that permethyl-β-CD forms a 1 : 1 complex with tolbutamide. Its molecular structure was elucidated by physicochemical methods including IR and high field NMR analysis. The influence of pennethyl-β-cyclodextrin on the hypoglycemic effect of tolbutamide was evaluated by measuring the blood glucose level. The reduction in plasma glucose was significantly greater when the rabbits were treated with the complex than with tolbutamide alone. The enhancement of the bioavailability of tolbutamide by permethyl-β-cyclodextrin is likely attributed to the molecular inclusion effect.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 84
    Digitale Medien
    Digitale Medien
    Springer
    Journal of inclusion phenomena and macrocyclic chemistry 26 (1996), S. 233-241 
    ISSN: 1573-1111
    Schlagwort(e): Biliar acid ; 2-hydroxypropyl-β-cyclodextrin ; interaction studies ; IR ; NMR ; DSC ; XRD
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The interaction of two biliar acids (chenodeoxycholic acid and cholic acid) with 2-hydroxypropyl-β-cyclodextrin (HPβCD) in solution and in the solid state was studied using different techniques. The formation of an inclusion complex with a 1:1 stoichiometry was suggested by the phase solubility studies. Both differential scanning calorimetry and X-ray diffractometry exhibited the amorphous state of the complex. The inclusion of both biliar acids into the HPβCD cavity was confirmed by the13C-NMR studies. Cholic acid showed a weaker affinity with respect to chenodeoxycholic acid probably owing to the presence of a hydroxyl group onC(12) (12α) close to the complexation site.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 85
    Digitale Medien
    Digitale Medien
    Springer
    Journal of inclusion phenomena and macrocyclic chemistry 26 (1996), S. 243-251 
    ISSN: 1573-1111
    Schlagwort(e): Crown ethers ; Li+ ion ; mixed-solvent ; complex stability ; NMR
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Proton NMR spectroscopy was used to study the complexation reaction between lithium ion and 12-crown-4, 15-crown-5 and 18-crown-6 in a number of binary acetonitrile-nitrobenzene mixtures. In all cases the exchange between free and complexed crowns was fast on the NMR time scale and only a single population average1H signal was observed. Formation constants of the resulting 1:1 complexes in different solvent mixtures were determined by computer fitting of the chemical shift-mole ratio data. There is an inverse relationship between the complex stability and the amount of acetonitrile in the mixed solvent. It was found that, in all solvent mixtures used, 15-crown-5 forms the most stable complex with Li+ ion in the series.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 86
    Digitale Medien
    Digitale Medien
    Springer
    Journal of inclusion phenomena and macrocyclic chemistry 24 (1996), S. 1-17 
    ISSN: 1573-1111
    Schlagwort(e): Calixarene ; inclusion ; structure ; NMR ; dynamics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Despite the proliferation of structural studies on calixarene host-guest compounds, some important structural details remain obscure. In particular, the ubiquitous disorder of the calixt-butyl group often hinders a detailed determination of the non-bonding interactions between host and guest. We propose and develop a synoptic approach in which several complementary characterization techniques (X-ray diffraction and NMR) provide a powerful means of assessing the interplay of structure and dynamics in calixarene-guest compounds. The simplet-butylcalix[4]arene-guest compounds (guest = toluene, nitrobenzene, cyclohexane,n-pentane, l-chlorobutane) are examined with this approach, and new structural and dynamic features are uncovered.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 87
    Digitale Medien
    Digitale Medien
    Springer
    Journal of inclusion phenomena and macrocyclic chemistry 26 (1996), S. 209-218 
    ISSN: 1573-1111
    Schlagwort(e): Cyclodextrins ; bicyclo[3.3.1]nonanes ; complexation ; NMR
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The formation and structure of inclusion complexes of 2,6- and 2,9-substituted bicyclo[3.3.1]nonanes withα- andβ-cyclodextrin (CD) has been investigated by high-resolution1H NMR spectroscopy.α- andβ-CD were found to form 1:1 inclusion complexes and the binding constants were estimated from titration studies. 2D ROESY experiments provided insight into the structure of the complexes.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 88
    Digitale Medien
    Digitale Medien
    Springer
    International journal of peptide research and therapeutics 2 (1995), S. 121-124 
    ISSN: 1573-3904
    Schlagwort(e): Backbone cyclization ; Substance P ; NMR ; Molecular dynamics ; Conformational analysis
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary Structure-activity relationships of cyclic substance P (SP) analogs were extensively studied in our laboratories utilizing the new concept of backbone cyclization. Employing the C-terminal hexapeptide SP6–11, we examined the influence of chemical changes in peptides containing backbone-to-amino-end cyclization. These changes in the ring have significant influence on activity, and should be carefully designed in order to optimize pharmacological feature.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 89
    Digitale Medien
    Digitale Medien
    Springer
    International journal of peptide research and therapeutics 3 (1996), S. 53-60 
    ISSN: 1573-3904
    Schlagwort(e): Gramicidin S ; Cyclic peptide ; Synthesis ; Cyclization ; NMR
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary A simple method is described for the facile synthesis of gramicidin S and six other analogs, using standard solidphase synthetic technology and a single solution-phase cyclization step. The peptides were purified to homogeneity and characterized by plasma desorption time-of-flight mass spectrometry and NMR spectroscopy. Complete 1H NMR assignments for all seven peptides (in aqueous solution) are presented. Unlike previous approaches, the presented method is simple, automatable, rapid (less than three days), high-yielding, requires no side-chain protection during cyclization, and appears to be generally applicable to the preparation of a variety of related head-to-tail cyclic peptides.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 90
    ISSN: 1573-3904
    Schlagwort(e): Biosurfactant ; Lipopeptide ; NMR ; Hydrophobic substitution
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary Bacillus subtilis coproduces several surfactin variants that are powerful biosurfactants and have potential applications in biology and industry. A single amino acid substitution in the heptapeptide moiety of surfactins strongly modifies their properties. To better establish structure-activity relationships and to search new variants with enhanced properties, Bacillus subtilis was grown into two modified culture media. Two new variants were isolated by chromatographic methods and studied by NMR spectroscopy. As planned, modifications consisted in the substitution of the l-valine residue at the fourth position by a more hydrophobic residue, i.e., leucine or isoleucine. These [Leu4]- and [Ile4]surfactins have a higher affinity for hydrophobic solvents and a twice improved surfactant power. Structure-property correlations were confirmed by analysis of the hydrophobic residue distribution in the three-dimensional model of the structure of surfactin in solution.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 91
    Digitale Medien
    Digitale Medien
    Springer
    International journal of peptide research and therapeutics 2 (1995), S. 59-70 
    ISSN: 1573-3904
    Schlagwort(e): Opioid peptide ; NMR ; Enkephalins ; Micelles ; Dodecylphosphocholine
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary Opioid peptides are thought to interact with the cell membrane in their biological journey to the membrane-bound receptor. Both organic solvents and model membranes have been used previously to determine the stable solution conformations of peptide hormones. Leucine enkephalin has been studied in a number of different environments, but with limited resolution. Here it is shown that leucine enkephalin forms a stable type IV β-turn structure in dodecylphosphocholine micelles. We have observed a highly solvent-shielded amide proton with no evidence for a complementary hydrogen bond acceptor. The structural details of the peptide as determined by NMR spectroscopy in solution are described.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 92
    Digitale Medien
    Digitale Medien
    Springer
    International journal of peptide research and therapeutics 2 (1995), S. 161-164 
    ISSN: 1573-3904
    Schlagwort(e): Cyclised peptide ; Dioxopiperazine ; Thiazolidine ; NMR ; Computer modelling
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary Conformationally constrained peptidomimetics of the Lys-Pro sequence have been obtained using a new polycyclic structure. Bicyclic compounds containing a dioxopiperazine-thiazolidine fused ring have been synthesised starting from N-lysyl-4-ethoxycarbonylthiazolidine-2-carboxylic acid. The carboxyl group in either position 2 or 4 of the thiazolidine ring was reacted with the N-terminal amino group, giving different regioisomers. NMR and computer modelling were used to study the configuration of isomers and the lysine side-chain orientation with respect to the pseudoproline ring.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 93
    Digitale Medien
    Digitale Medien
    Springer
    International journal of peptide research and therapeutics 2 (1995), S. 239-242 
    ISSN: 1573-3904
    Schlagwort(e): Pseudopeptide ; Triphosgene ; Beta-turn ; NMR ; FT-IR ; X-ray diffraction
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary For the sake of improving synthetic methods and evaluating the conformational perturbation induced by the substitution of AzAsx for the Asx residue in the cognate dipeptide R-CO-Asx-Pro-NHR′, we prepared the AzAsx-dipeptide sequence by making use of the crystalline triphosgene. This reagent allows, in situ and under very mild experimental conditions, both the carbonylation and the activation of the properly substituted and N-protected hydrazine before coupling with the proline partner. With regard to conformational behaviour, the azadipeptide sequence displays a β-fold, unlike the cognate dipeptide which adopts an Asx-turn.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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