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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.
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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.
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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.
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  • 6
    ISSN: 1572-8773
    Schlagwort(e): BET ; biosorption ; cadmium ; cobalt ; copper ; Freundlich ; NMR ; Scatchard ; Ulva lactuca ; zinc
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract The metabolism-independent metal binding characteristics of Ulva lactuca were investigated using both freeze-dried thalli and cell walls stripped of intracellular material by incubation in Triton-X followed by methanol. Biosorption of Cd, Zn, Cu and Co by freeze-dried thallus was concentration-dependent and followed Freundlich and Langmuir isotherms. The Freundlich plot suggested that freeze-dried U. lactuca had the greatest binding affinity for Cu compared with Cd, Zn and Co. The BET (Brunauer–Emmett–Teller) plot, which indicates a more complex form of adsorption, and the Scatchard plot were not adequate models for Cu adsorption. The Scatchard plot of Cd suggested that two Cd binding sites were available on the freeze-dried thallus, with the second, lower affinity site only becoming available at Cd loading capacities greater than 4.9mmol g dry wt. Cd nuclear magnetic resonance (NMR) studies confirmed that two binding sites were available for Cd on the freeze-dried algal powder, though only one was available on the cell wall, and that the affinity of the binding sites was greater for Cu than for Cd. The results of the NMR experiments suggested that Cd binds to oxygen-containing functional groups in the algal powder and on the cell wall. It is proposed that sulphate or hydroxyl groups attached to polysaccharide subunits are possible sites.
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  • 7
    ISSN: 1572-8773
    Schlagwort(e): copper(II) 3,5-diisopropylsalicylate ; EPR ; human serum albumin ; NMR
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract The copper(II) complex of 3,5-diisopropylsalicylate is a lipophilic water-insoluble binuclear complex, Cu(II) (3,5-DIPS) , that has attracted interest because of a wide range of pharmacological activities. This study was undertaken to examine bonding interactions between the complex and human serum albumin (HSA) to help elucidate the mode of transport of the complex in vivo. Electron paramagnetic resonance, numerical magnetic resonance and UV-visible absorption spectroscopic studies were performed using 200 μM aqueous solutions (pH 7.5) of HSA to which had been added up to three molar equivalents of CuCl , CuSO , or Cu(II) (3,5-DIPS). Both EPR and UV-visible spectra demonstrated the presence of more than one copper bonding site on HSA, and proton NMR spectra showed that the 3,5-DIPS ligand is also bonded to HSA. These results indicate that there is no observable direct coordination of the ligand to copper in the presence of HSA, and that the majority of the copper and 3,5-DIPS bond to HSA at separate sites. Addition of solid Cu(II) (3,5-DIPS) to HSA at pH 7.5 similarly resulted in spectra that suggest that there are no ternary Cu(II)(3,5-DIPS), Cu(II)(3,5-DIPS) , or Cu(II) (3,5-DIPS) complexes formed with HSA. It is concluded that any ternary complexes formed in the presence of HSA are below the spectroscopic detection limits and represent less than 5% of the total copper. © Rapid Science 1998.
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  • 8
    ISSN: 1572-8773
    Schlagwort(e): aluminum ion ; glycerol kinase ; NMR ; spermine ; yeast
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract Aluminum ion inhibited yeast glycerol kinase competitively with respect to the substrate MgATP. The K value of the enzyme for aluminum ion was about 3 μM. Spermine at physiological concentrations prevented glycerol kinase from the inhibition by aluminum ion. Nuclear magnetic resonance spectroscopy showed the specific elimination by spermine of aluminum from the metal-ATP complex, but no dissociation of MgATP complex by spermine. Inhibition by aluminum ion of glycerol kinase as well as hexokinase can reduce the utilization of energy fuel in yeast. Change in polyamine concentration may control energy production in vivo, and is responsible for the development of age-related aluminum toxicity. © Rapid Science 1998.
    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
    ISSN: 1572-8927
    Schlagwort(e): Hydrogen-1 ; carbon-13 ; nitrogen-15 ; cadmium-113 ; NMR ; infrared ; zinc(II) ; cadmium(II) ; isothiocyanate ; complexation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract A study of zinc(II) and cadmium(II) complexes with isothiocyanate ion has been completed, using a low-temperature, multinuclear magnetic resonance technique that permits the observation of separate resonance signals for bound and free ligand, and Cd(II) metal ion. The Zn2+–NCS− complexes were studied by 1H, 13C, and 15N NMR spectroscopy. In the 1H spectra, the intensity of the coordinated water signal, corresponding to a Zn(II) hydration number of six in the absence of NCS−, decreases dramatically as this anion is added, indicating the complexing process involves more than a simple 1:1 ligand replacement. The 13C and 15N NMR spectra reveal signals for four species, most reasonably assigned to a series of tetrahedrally coordinated Zn2+–NCS− complexes. In the Cd2+–NCS− solution spectra, the 13C and 15N signals for four complexes also are observed and they are three line patterns, corresponding to a doublet from 113Cd J-coupling, and a dominant central peak, resulting from bonding to magnetically inactive Cd isotopes. The 113Cd spectra, showing signals for four complexes, correlate well in all respects with the 13C and 15N results, including coupling in specific cases. The spectral results for both metal ions reflect binding at the nitrogen atom of NCS−, with the complexes changing from an octahedral to a tetrahedral configuration when doing so. Confirming evidence for these conclusions also was provided by several infrared measurements of these metal–ion systems.
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  • 11
    ISSN: 1572-8927
    Schlagwort(e): Carbon-13 ; nitrogen-15 ; chlorine-35 ; NMR ; samarium(III) ; isothiocyanate ; Sm3+ − NCS− complexes ; water–acetone–Freon ; water–methanol
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Multinuclear magnetic resonance studies of trivalent lanthanide inner-shell ion-pairing with nitrate and isothiocyanate are continuing. For NCS− solutions in water–acetone–Freon mixtures at low temperature, generally −100 to −125°C, ligand exchange is slow enough to permit the observation of 13C and 15N NMR signals for coordinated and free anions. For samariuni(III) solutions, four coordinated NCS−signals, displaced about +35 ppm and +250 ppm from free anion, are observed in the 13C and 15N NMR spectra, respectively. The 13C and 15N NMR data are complementary, showing a signal area concentration dependence and measured coordination numbers consistent with the formation of Sm(NCS)2+ through Sm(NCS) 4 1 . The coordination numbers reach a maximum of about three moles of NCS− per mole of Sm(III) with both nuclides, a result confirmed by spectral appearance showing the dominance of Sm(NCS)3 at the highest concentration studied. An analysis of the chemical shifts indicates that binding occurs at the nitrogen atom of NCS−. In water–methanol, due to the higher dielectric constant of such mixtures, coordination was less extensive. A competitive binding study with Ci− by 35Ci NMR demonstrated conclusively the superior coordinating ability of NCS−.
    Materialart: Digitale Medien
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  • 12
    ISSN: 1572-8927
    Schlagwort(e): carbon-13 ; nitrogen-15 ; chlorine-35 ; NMR ; cerium(III)–isothiocyanate complexes ; water–acetone–Freon ; water–methanol
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract A study of lanthanide complexation with isothiocyanate is underway using a multinuclear magnetic resonance technique. For isothiocyanate solutions in water–acetone–Freon mixtures at low temperature, −85–−125°C, ligand exchange is slow enough to permit the observation of 13C and 15N NMR signals for coordinated and free anions. For the Ce3+–NCS− system, four coordinated anion signals, displaced from the free anion signal by about +450 to +550 ppm for 15N and +50 to +80 ppm for 13C, are observed. The 13C and 15N spectral data are complementary, showing a signal area concentration dependence and measured coordination numbers consistent with the formation of Ce(NCS)2+ through Ce(NCS)1- 4. In water–methanol, the extent of complexing is decreased, presumably because of the higher dielectric constant of this medium. In addition, the results of a competitive study of NCS− and Cl− ion binding, carried out using 35Cl NMR, is presented.
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  • 13
    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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  • 14
    Digitale Medien
    Digitale Medien
    Springer
    Topics in catalysis 5 (1998), S. 133-147 
    ISSN: 1572-9028
    Schlagwort(e): NMR ; catalysis ; high pressure ; dynamic equilibria ; magnetization transfer ; sapphire tube ; gas phase ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract High resolution NMR techniques are applicable to a variety of aspects of catalysis. Methods for studying homogeneously-catalyzed systems under high gas pressure are described along with approaches for obtaining mechanistic and dynamic information. Many of the same techniques may be applied to heterogeneous catalysis by following the reaction chemistry by gas phase NMR.
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  • 15
    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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  • 16
    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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  • 17
    ISSN: 1434-4475
    Schlagwort(e): Diphenylphosphanyl substituted 5-fluoro-uracils ; X-ray structure determination ; Tautomerism ; NMR ; Vibrational and mass spectra
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary 5-Fluoro-uracil (1) reacts with chloro-diphenylphosphane to 5-fluoro-N(1), N(3)-bis(diphenylphosphanyl)uracil (3) which was characterized by X-ray crystallography, IR, and mass spectra.19F,31P{1H},13C{1H}, and1H NMR spectra indicate that3 rearranges inTHF solution to some extent to the tautomeric 5-fluoro-O(2), O(4)-bis(diphenylphosphanyl)uracil (4). If the solvent contains traces of water, Ph2P(O)-PPh2 (6) and uracil derivatives are formed by hydrolysis.
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  • 18
    ISSN: 1434-4475
    Schlagwort(e): Aminyl radicals ; ESR ; NMR ; Pyrazoles ; Triarylaminium cation radicals
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Beschreibung / Inhaltsverzeichnis: Zusammenfassung Die substituierten 3-Anilino-1,5-diphenylpyrazole1a–i wurden mit Pb(OAc)4 in Benzol oder CH2Cl2 oxidiert. Die intermediären Aminylradikale3f–i wurden ESR-spektroskopisch bei der Oxidation der im Anilinrest methylsubstituierten Pyrazole1f–i nachgewiesen. Die ESR-spektroskopisch nach Oxidation der Pyrazole1a–e beobachteten Radikalintermediate interpretieren wir als Kationradikale6a–e. Diese werden durch Weiteroxidation der Dimeren4a–e gebildet, deren Struktur durch NMR-Untersuchungen und15N-Markierung bewiesen wurde.
    Notizen: Summary Substituted 3-anilino-1,5-diphenylpyrazoles1a–i were oxidized with Pb(OAc)4 in benzene or CH2Cl2 solution. The ESR measurements confirmed the formation of aminyl radicals3f–i frompara-CH3 substituted pyrazoles1f–i. The radical intermediates from unsubstituted pyrazoles1a–e were assigned to triarylaminium cation radicals These were generated by consecutive oxidation of the dimeric products4a–e whose structure was proven by NMR spectroscopy and15N labeling.
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  • 19
    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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  • 20
    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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  • 21
    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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  • 22
    ISSN: 0948-5023
    Schlagwort(e): Keywords Thiacrown ether ; NMR ; Pt(II) complexes ; Molecular dynamic simulations ; Ring interconversion
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract   Maleonitrile-dithiacrown ethers mn-12S2O2 - mn-21S2O5 (mn = maleonitrile) are preorganized S2On+1-coronands (n = 1–4) which force B, AB and A class metal ions into mixed S/O coordination spheres. Moreover, they form chelate complexes with MX2 salts (M = Pd, Pt; X = Cl, Br), which were studied in this paper. The structures of mn-S2On+1 and [PtCl2(mn-S2On+1)] (n = 2, 3) were investigated theoretically by empirical and semiempirical methods using SYBYL (TRIPOS force field) and MSI/DISCOVER97 (ESFF force field). mn-12S2O2 was investigated experimentally by X-ray analysis and 1D and 2D NMR spectroscopy in solution and the complex formation was studied by 1H, 13C and 195Pt NMR titration experiments, respectively. S-inversion was also investigated in order to determine the ring corresponding interconversional barriers. Different orientations of the macrocyclic ring system mn-18S2O4 and of its transition states are shown.
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  • 23
    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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  • 24
    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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  • 25
    ISSN: 1572-879X
    Schlagwort(e): zeolites ; chemicals ; NMR ; alkane activation ; reaction mechanism ; in situ investigation ; alkylation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Solid-state MAS NMR is a powerful technique to study heterogeneous catalysts and the way by which they operate. In situ MAS NMR has been demonstrated to be a powerful method to understand reaction mechanisms, to study the nature, dynamics and reactivity of surface intermediates and active sites, and to characterize structural modifications in the catalyst itself, in particular when using 13C strategically labelled substrates. In this paper, three examples selected from our own work are used to illustrate the potential of in situ MAS NMR. They are the formation of cumene and its isomerization to n-propylbenzene on zeolite H-ZSM-11, the activation of propane at low temperature and the alkylation of benzene with propane on zeolite H-ZSM-5, and the characterization of the aluminophosphate molecular sieve VPI-5 structure with temperature. Studies of the alkylation of benzene with propene confirmed that cumene was the primary reaction product. The undesired n-propylbenzene by-product results from the intermolecular reaction between cumene and benzene, enhanced by molecular shape-selective effects in medium pore size zeolites (e.g., H-ZSM-11). It explains why large pore zeolites, e.g., zeolite Beta, are used commercially today for this process. Propane can be activated at low temperature (ca. 573 K) on bifunctional medium pore size zeolites possessing intimately related acidic Brønsted sites and a dehydrogenation function provided by Ga or Zn species. In Ga/H-ZSM-5 catalysts, at 573 K, the activation of propane was shown to occur via a protonated pseudocyclopropane (PPCP) intermediate (or transition state). The latter evolves in a manner that can be formally described by the formation of CH 3 + , C2H 2 + , and C3H 7 + carbenium ion intermediates. These species can react with olefins, alkanes, or other electron-rich molecules such as benzene. The primary reaction products of the reaction of propane with benzene are n-propylbenzene (in small amount), ethylbenzene and toluene. Their subsequent reactions lead eventually to toluene and xylenes as the final products. In the structural characterization of VPI-5, 27Al, 31P, and 27Al nutation MAS NMR spectra show that, at 294 K, fully hydrated VPI-5 contains three equally populated Al and P crystallographic sites and that one-third of Al is 6-coordinate. The VPI-5 structure then belongs to the P63 space group. Above 353 K, VPI-5, fully or partially hydrated, undergoes a structural transformation to a higher framework symmetry, i.e., the P63cm space group. The transformation occurs at nearly the same temperature in both cases, indicating that the breakdown of the hydrogen-bonded helical water structure inside the VPI-5 pores is not a factor in the process.
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  • 26
    Digitale Medien
    Digitale Medien
    Springer
    BioMetals 11 (1998), S. 213-222 
    ISSN: 1572-8773
    Schlagwort(e): calmodulin ; fluorescence spectroscopy ; metal ions ; NMR
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract Calmodulin is an important second messenger protein which is involved in a large variety of cellular path-ways.Calmodulin is sensitive to fluctuations in the intracellular Ca levels and is activated by the bindingof four Ca ions. In spite of the important role it plays in signal transduction pathways, it shows a surpris-inglybroad specificity for binding metal ions. Using 15N-Gly biosynthetically-labelled calmodulin, we havestudied the binding of different metal ions to calmodulin, including K+, Na+, Ca, Mg, Zn, Cd, Pb, Hg, Sr, La and Lu, by 1H, 15N HMQC NMR experiments. The effects of these ions on the substrate-bindingability of calmodulin have also been studied by fluorescence spectroscopy of the single tryptophan residue in a 22-residue synthetic peptide encompassing the skeletal muscle myosin light chain kinase calmod-ulin-binding domain. Most of these metal ions can activate a calmodulin target enzyme to some extent,though they bind to calmodulin in a different manner. Mg, which is of direct physiological interest, has adistinct site-preference for calmodulin, as it shows the highest affinity for site I in the N-terminal domain,while the C-terminal sites III and IV are the high affinity binding sites for Ca (as well as for Cd ). At ahigh concentration of Mg and a low concentration of Ca, calmodulin can bind Mg in its N-terminallobe while the C-terminal domain is occupied by Ca; this species could exist in resting cells in which the Mg level significantly exceeds that of Ca. Moreover, our data suggest that the toxicity of Pb-which,like Sr, binds with an equal and high affinity to all four sites-may be related to its capacity to tightlybind and improperly activate calmodulin.
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  • 27
    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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  • 28
    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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  • 29
    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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  • 30
    ISSN: 1572-879X
    Schlagwort(e): RT synthesis ; thermal analysis ; NMR
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The room-temperature (RT) synthesis of MCM-41 mesoporous compounds with high substitution levels of aluminium (Si / Al = 1.5) is achieved in a minimum time of synthesis. The compound shows similar characteristics to hydrothermally synthesized materials. 27Al NMR study confirms the presence of tetrahedral aluminium in as-synthesized material as well as in the calcined material without observing the presence of octahedral aluminium after calcination.
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  • 31
    Digitale Medien
    Digitale Medien
    Springer
    Catalysis letters 62 (1999), S. 1-13 
    ISSN: 1572-879X
    Schlagwort(e): acid catalysis ; zeolites ; temperature‐programmed desorption ; microcalorimetry ; NMR
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract With a proper understanding of the nature of solid acidity, zeolites and other solid acids have great potential for replacing homogeneous acids in a wide range of catalytic applications. This paper describes results from our laboratory on the characterization and description of the acid sites in high‐silica zeolites, especially H‐MFI. A crucial observation from this work is the identification of stoichiometric adsorption complexes, one molecule per framework Al, for a wide range of adsorbates, including amines, alcohols, nitriles, ketones, and thiols. Examples are given in which temperature‐programmed desorption is used to identify these complexes and characterize their initial chemistries. Calorimetric measurements on the 1:1 complexes have been used to compare the enthalpies of protonation in the zeolite to enthalpies of protonation in the gas phase and in aqueous phase and to demonstrate that a gas‐phase basis provides better predictive capabilities. The issue of carbenium‐ion stabilities is discussed, as well as the unusual catalytic properties of acid sites formed by framework substitution of Fe. The effect of sorption and cavity size on reactions is described. Finally, the problems associated with trying to define or characterize solid acids by using ammonia TPD or 13C NMR isotropic shifts of ketones without proper consideration of the complicated nature of these techniques are discussed.
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  • 32
    ISSN: 0948-5023
    Schlagwort(e): Keywords: Thiocrown ether ; NMR ; Ag(I) complexes ; Molecular Dynamic simulations
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The preferred conformations and the complexional behaviour of mn-12S2O2 were studied by means of both NMR spectroscopy and molecular modelling. Furthermore, the AgI complexes of this ligand mn-12S2O2 were also studied by molecular mechanical calculations.
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  • 33
    ISSN: 1432-1327
    Schlagwort(e): Key words Vanadium ; Erythrocyte ; NMR ; Oxidative stress ; Diabetes
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract  The action of vanadate on intact human erythrocytes was studied by 1H spin echo and 51V NMR spectroscopy as a model for the behaviour of vanadium(V) complexes in experimental diabetes. Vanadate is reduced by the intact erythrocyte at the expense of intracellular glutathione which rapidly depletes from the intracellular volume. Using the blocking agent 4,4′-diisothio-cyanatostilbene-2,2′-disulfonic acid (DIDS), which specifically blocks the anion transporter, vanadate reduction could be inhibited and glutathione depletion arrested. Thus, for the reaction with the intact cell to occur, vanadium(V) must cross the cell wall, possibly via the anion transporter. Nitrofurantoin was used to inhibit glutathione reductase in the erythrocyte suspensions. Under these conditions, treatment of the cells with vanadate induced glutathione oxidation prior to depletion. A study of the reaction of vanadate with haemolysate indicates that, without the influence of the membrane, rapid oxidation of glutathione to glutathione disulfide by the vanadyl cation occurs with no glutathione depletion, and that under these conditions vanadate reduction is incomplete. This study generates a model for the behaviour of vanadium complexes in vivo, providing a basis for the rational design and synthesis of new vanadium-based agents as insulin mimics. In essence, vanadium is transported across the membrane as vanadate(V), is reduced in situ by glutathione, and becomes complexed to a wide range of intracellular binding sites. Exchange reactions between glutathione and sulfhydryl groups present on haemoglobin and membrane lead to the depletion of glutathione from the cytosol.
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  • 34
    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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  • 35
    ISSN: 1432-1327
    Schlagwort(e): Key words Bacillus pasteurii ; cytochrome c553 ; electrochemistry ; NMR
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract  Direct cyclic voltammetry and 1H NMR spectroscopy have been combined to investigate the electrochemical and spectroscopic properties of cytochrome c 553 isolated from the alkaliphilic soil bacterium Bacillus pasteurii. A quasi-reversible diffusion-controlled redox process is exhibited by cytochrome c 553 at a pyrolitic graphite edge microelectrode. The temperature dependence of the reduction potential, measured using a non-isothermal electrochemical cell, revealed a discontinuity at 308 K. The thermodynamic parameters determined in the low-temperature range (275–308 K;ΔS°′=–162.7±1.2 J mol–1 K–1, ΔH°′=–53.0±0.5 kJ mol–1, ΔG°′=–4.5±0.1 kJ mol–1, E°′=+47.0±0.6 mV) indicate the presence of large enthalpic and entropic effects, leading, respectively, to stabilization and destabilization of the reduced form of cytochrome c 553. Both effects are more accentuated in the high-temperature range (308–323 K;ΔS°′=–294.1±8.4 J mol–1 K–1, ΔH°′=–93.4±3.1 kJ mol–1, ΔG°′=–5.8±0.6 kJ mol–1, E°′=+60.3±5.8 mV), with the net result being a slight increase of the standard reduction potential. These thermodynamic parameters are interpreted using the compensation theory of hydration of biopolymers as indicating the extrusion, upon reduction, of water molecules from the hydration sphere of the cytochrome. The low-T and high-T conformers differ by the number of water molecules in the solvation sphere: in the high-T conformer, the number of water molecules extruded upon reduction increases, as compared to the low-T conformer. The ionic strength dependence of the reduction potential at 298 K, treated within the frame of extended Debye-Hückel theory, yields values of E °′ (I=0) =–25.4±1.4 mV, z red=–11.3, and z ox=–10.3. The pH dependence of the reduction potential at 298 K shows a plateau in the pH range 7–10 and an increase at more acidic pH, allowing the calculation of pK O=5.5 and pK R=5.7, together with the estimate of the reduction potentials of completely protonated (+71 mV) and deprotonated (+58 mV) forms of cytochrome c 553. 1H NMR spectra of the oxidized paramagnetic cytochrome c 553 indicate the presence of a His-Met axial coordination of the low-spin (S=1/2) heme iron, which is maintained in the temperature interval 288–340 K at pH 7 and in the pH range 4.8–10.0 at 298 K. The temperature dependence of the hyperfine-shifted signals shows both Curie-type and anti-Curie-type behavior, with marked deviations from linearity, interpreted as indicating the presence of a fast equilibrium between the low-T and high-T conformers, having slightly different heme electronic structures resulting from the T-induced conformational change. Increasing the NaCl concentration in the range 0–0.2 M causes a slight change of the 1H NMR chemical shifts of the hyperfine-shifted signals, with no influence on their linewidth. The calculated lower limit value of the apparent affinity constant for specific ion binding is estimated as 5.2±1.1 M–1. The pH dependence of the isotropically shifted 1H NMR signals of the oxidized cytochrome displays at least one ionization step with pK O=5.7. The thermodynamic and spectroscopic data indicate a large solvent-derived entropic effect as the main cause for the observed low reduction potential of B. pasteurii cytochrome c 553.
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  • 36
    ISSN: 1432-1327
    Schlagwort(e): Key words Heme protein ; NMR ; paramagetic ; contact ; pseudocontact ; axial ligand
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract  The effect of axial ligand nodal plane orientation on the contact and pseudocontact shifts of a symmetrical low-spin octamethylferriheme center has been calculated as a function of the angle of the axial ligand. Simple Hückel techniques have been used to estimate the contact contribution, and values obtained from model hemes, together with counter-rotation of the g-tensor, have been used to estimate the pseudocontact contribution, for the eight β-pyrrole methyl and four meso-H positions. It is found that the maximum and minimum contact shifts occur when the axial ligand is aligned at an angle of ±15° to the meso-H axes of the heme, rather than when the axial ligand plane lies along the porphyrin nitrogens, as assumed previously by some investigators. For systems having one planar axial ligand or two ligands in parallel planes, the contact and pseudocontact contributions at the meso-H positions are comparable in size (at least on the basis of simple Hückel estimates), while the contact contribution clearly dominates the isotropic shifts of the heme methyls. Allowing for the substituent effect of the 2,4-vinyls of protohemin, or the 2,4-thioethers of hemin c, as well as the average diamagnetic shifts of the heme methyls and meso-H, plots of the predicted shifts as a function of axial ligand nodal plane orientation have been constructed for hemin b- and c-containing proteins. Excellent agreement in the order of shifts, and reasonable agreement in the sizes of the observed shifts, is observed in the majority of the ferriheme proteins for which the methyl and meso-H resonances have been assigned and proton shifts reported. Plots have also been constructed for hemin c-containing proteins having the two axial ligand nodal planes oriented at relative angles of 40°, 70°, and 80°. Excellent agreement in the order of shifts, and reasonable agreement in the magnitudes of the observed shifts, is observed in all cases of bacterial cytochromes which do not fit the plots that assume the ligands are in parallel planes, except one – the cytochrome c-552 of Nitrosomonas europae. Except for this case, where the order of the predicted methyl shifts at any angle of the axial ligands disagrees with the observed, the reasons can usually be attributed to a large dihedral angle between two axial ligand nodal planes, to strong H-bonding interactions involving His and/or CN– ligands, or to off-axis binding of one (or both) axial ligand(s). Ruffling of the porphyrin ring may also contribute to the contact shift in as yet undefined ways. Hence, despite the simplicity of the calculations, the agreement with observed data is highly satisfying and the concept of the importance of axial ligand plane orientation on the observed proton shifts of heme proteins is fully confirmed.
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  • 37
    ISSN: 1432-1327
    Schlagwort(e): Key words Reduced cytochrome c ; Solution structure ; NMR ; Heme proteins ; Electron transfer proteins
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract  In the frame of a broad study on the structural differences between the two redox forms of cytochromes to be related to the electron transfer process, the NMR solution structure of horse heart cytochrome c in the reduced form has been determined. The structural data obtained in the present work are compared to those already available in the literature on the same protein and the presence of conformational differences is discussed in the light of the experimental method employed for the structure determination. Redox-state dependent changes are analyzed and in particular they are related to the role of propionate-7 of the heme. Also some hydrogen bonds are changed upon reduction of the heme iron. A substantial similarity is observed for the backbone fold, independently of the oxidation state. At variance, some meaningful differences are observed in the orientation of a few side chains. These changes are related to those found in the case of the highly homologous cytochrome c from Saccharomyces cerevisiae. The exchangeability of the NH protons has been investigated and found to be smaller than in the case of the oxidized protein. We think that this is a characteristic of reduced cytochromes and that mobility is a medium for molecular recognition in vivo.
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  • 38
    ISSN: 1432-1327
    Schlagwort(e): Key words Ruthenium ; Nucleotides ; Dimethyl sulfoxide ; Anticancer ; NMR
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract  Both cis- and trans-RuCl2(DMSO)4 (cis-Ru and trans-Ru) react with ApG, GpA, d(ApG) and d(GpA) to yield products with bifunctional metal coordination of the bases. For each dinucleotide one major product and several minor species are formed. This is in contrast to previous results on analogous reactions between trans-Ru and d(GpG) where a substantial amount of an intermediate species was found. The rates of reaction between dinucleotides and cis-Ru are approximately 20-fold slower than for trans-Ru. The compounds formed with the two isomers exhibit identical proton NMR spectra, suggesting the same coordination mode for ruthenium in the final product. The two purine bases are coordinated to ruthenium through N7 in a head-to-head conformation with the glycosidic angles being in the anti range. Coupling constants indicate a relatively pure 3′-endo conformation for the 5′-sugar and mainly 2′-endo for the 3′-sugar. The similar bifunctional binding mode of cis- and trans-Ru(II) with dinucleotides as evident from the NMR spectra are in contrast to the different mode of interaction suggested earlier for cis- and trans-Ru complexes with DNA. trans-Ru interacts with the deoxyoctanucleotide d(CCTGGTCC), giving two main products during the first 2 h of incubation time. Four H8 guanine resonances are shifted downfield, characteristic of N7 metal coordination. The products are not analyzed in detail, but it is suggested that the structures may be described as two chiral G(N7/N7) chelates.
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  • 39
    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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  • 40
    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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  • 41
    ISSN: 1432-1327
    Schlagwort(e): NMR ; Superoxide dismutase ; Solution structure ; Monomeric mutants ; Structure-function relationship
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: 2 , has RMSD values with respect to the average structure of 0.94 ± 0.14 Å2 and 1.50 ± 0.14 Å2 for the backbone and the heavy atoms, respectively. The overall folding, which includes the classical eight-stranded Greek-key β-barrel and a short α-helix, is very close to that of the previously characterized monomeric mutant E133QM2SOD and to that of wild-type SOD. The region involved in the subunit-subunit interactions in the dimeric protein is confirmed to be disordered in the monomeric species. It is also observed that a sizable rearrangement of the charged groups of the electrostatic loop and of Arg143 takes place in the monomeric species. The width of the active site channel, both at its entrance and at the bottleneck of the active site, is discussed in the light of the influence on the enzymatic activity and the latter with respect to the overall charge. It is also confirmed that the NH proton of His63 shields the Cu(I) from the bulk solvent, thus supporting the suggestion that superoxide may interact with the reduced metal ion in an outer-sphere fashion.
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  • 42
    ISSN: 1432-1327
    Schlagwort(e): Key words Cooperativity ; Cytochrome c3 ; NMR ; Paramagnetic ; Redox-Bohr
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract  The thermodynamic model of five interacting charge centres (four haems and an ionisable centre), which was used in the characterisation of the thermodynamic properties of Desulfovibrio vulgaris (Hildenborough) cytochrome c 3 (c 3DvH), is now used to reevaluate the thermodynamic properties in Desulfovibrio vulgaris (Miyazaki F) cytochrome c 3 (c 3DvM) on the basis of published data (Park, J.-S., Ohmura, T., Kano, K., Sagara, T., Niki, K., Kyogoku, Y. and Akutsu, H. (1996) Biochim. Biophys. Acta 1293, 45–54). Contrary to the assertion of Park et al. (1996), the pH dependence of the proton chemical shifts of haem methyls in c 3DvM in several stages of oxidation is well described by the model, which involves both homotropic (e–/e–) and heterotropic (e–/H+) cooperativity. This shows that the pH dependence observed for c 3DvM is not significantly more complicated than that observed for c 3DvH. Since the parameters which we now obtain for c 3DvM are generated with the same model as those from c 3DvH, albeit using less precise data, it is possible to make a preliminary comparison of the thermodynamic properties of these two proteins and of their role in energy transduction. The extrinsic dipolar shifts generated for each methyl group by each of the four haems in c 3DvM are also determined. A novel method for approximating the magnetic susceptibility tensors is used: the orientations of the principal axes of the tensors have been shown to be closely related to the geometry of the axial ligands, which is available from the X-ray structure of c 3DvM, and the components of the tensors are extrapolated from EPR g values. The inclusion of the calculated haem extrinsic contributions clearly describes the pH dependence of the haem methyls in the core of the protein, close to other haems. This description is most remarkable in the case of the haem methyl 21CH3 II I, for which the "unusual pH dependence" commented on by Park et al. (1996) is easily explained using the thermodynamic parameters determined by our model together with the calculated extrinsic dipolar shifts, thus providing a test of the analysis.
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  • 43
    Digitale Medien
    Digitale Medien
    Springer
    JBIC 2 (1997), S. 744-749 
    ISSN: 1432-1327
    Schlagwort(e): Key words Aminopeptidase ; Streptomyces ; Dinuclear ; NMR ; Co2+ ; Cu2+
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract  Streptomyces griseus aminopeptidase has been characterized to have a dinuclear active site and to follow a dinuclear hydrolytic mechanism by means of activity assay, optical, and NMR spectroscopy. A sequential binding of Co2+ to the dinuclear sites in 20 mM Mes buffer at pH 6.1 has also been established. The results from these studies suggest that the two metal sites have a five-coordination sphere, with at least one coordinated His each. A di-Cu2+-substituted derivative of the enzyme has been prepared which exhibits a 1H NMR spectrum with sharp hyperfine-shifted signals, again indicating the presence of a dinuclear active site. This 1H NMR spectrum with sharp hyperfine-shifted features represents a first of its kind for a di-Cu2+ center in metalloproteins.
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  • 44
    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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  • 45
    ISSN: 1432-1327
    Schlagwort(e): Key words Cytochrome c6 ; Anabaena PCC 7119 ; EPR ; NMR ; Redox-Bohr
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract  A soluble monoheme c–type cytochrome c 6 has been isolated from the cyanobacterium Anabaena PCC 7119. It is a basic protein, with a molecular mass of 9.7 kDa, which accepts electrons from Anabaena ferredoxin in the ferredoxin-NADP+reductase-dependent NADPH cytochrome c reductase activity assay. The turnover of the reaction has an optimum pH at 7.5. Flavodoxin can also replace ferredoxin in this assay, but with only 20% efficiency. Plastocyanin from Anabaena PCC 7119, as well as the c 6 cytochromes from the green algae Chlorella fusca and Monoraphidium braunii are also shown to accept electrons from Anabaena ferredoxin. The reduction potential of cytochrome c 6 at pH 6.7 was determined to be 338 mV and is pH dependent, with pK a ox=8.4±0.1 and pK a red≈9.5. The ferric and ferrous cytochrome forms and their pH equilibria have been studied using visible, EPR and 1H-NMR spectroscopies. The amino acid sequence and the visible and NMR spectroscopic data indicate that the heme iron has a methionine-histidine axial coordination in the pH range 5–11. However, the EPR data for the ferricytochrome are complex and show that in this pH range five distinct forms are present. Between pH 5 and 9 the spectrum is dominated by two rhombic species, with g–values at 2.94, 2.29, 1.43 and at 2.84, 2.34, 1.56, which interconvert with a pK a of 8.4. The NMR data also show a main interconversion between two cytochrome forms at this pH, which coincides with that determined from the pH dependence of the reduction potential. Both these forms were associated with a methionine-histidine heme-iron coordination by correlation with the visible and NMR spectral data, although having crystal field parameters atypical for this type of coordination. Anabaena cytochrome c 6 is one more example of a heme protein for which the widely used crystal field analysis of the EPR data (truth diagram) fails to unequivocally determine the type of heme-iron ligation.
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  • 46
    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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  • 47
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 50 (1997), S. 625-632 
    ISSN: 1572-8943
    Schlagwort(e): DSC ; NMR ; 8-quinolinol compounds ; TG-DTG ; stability ; thermal decomposition
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Solid M-Ox compounds, whereM represents Mg(II), Zn(II), Pb(II) and NbO(III), and Ox is 8-quinolinol, have been prepared. Thermogravimetry, derivative thermogravimetry (TG, DTG), differential scanning calorimetry (DSC), nuclear magnetic resonance (NMR) and infrared absorption spectra (IR) have been used to characterize and to study the thermal stability and thermal decomposition of these compounds.
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  • 48
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 56 (1999), S. 1059-1063 
    ISSN: 1572-8943
    Schlagwort(e): dehydration ; miscibility ; NMR ; polymer blend ; poly(2-hydroxyethyl methacrylate) (PHEMA) ; poly(methacrylic acid) (PMAA) ; TG ; TMDSC
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Miscibility and dehydration of poly(2-hydroxyethyl methacrylate) and poly(methacrylic acid) (PHEMA/PMAA) blends were investigated by temperature modulated DSC (TMDSC), TG and solid-state 13C NMR methods. TMDSC spectra and 1H spin-relaxation times showed that the blends are homogeneous on a scale of 5-10 nm for all compositions. From TG and 13C NMR, we elucidated that the mass loss of the blends at 300°C is ascribed to the dehydration between the hydroxyl group of PHEMA and the carboxyl group of PMAA.
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  • 49
    ISSN: 1572-9001
    Schlagwort(e): Magnetic anisotropy ; NMR ; shielding cone ; shielding value ; GIAO ; ethene ; alkenes
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Nuclei of hydrogen atoms located over a carbon-carbon double bond in the presence of a strong magnetic field experience a perturbed magnetic field caused primarily by the magnetic anisotropy of the π bond. However, the commonly used theoretical model for predicting the shielding effect of an alkene double bond on hydrogen nuclei is sometimes inconsistent with the observed proton NMR chemical shifts in structures that have covalently bonded hydrogens located over a carbon-carbon double bond. We have used the ab initio gauge including atomic orbital (GIAO) method to calculate isotropic shielding values and to determine the proton NMR shielding increments for a simple model system: methane held at various positions over ethene. These shielding increments calculated for one proton of methane have been mapped as a function of their position in Cartesian coordinates relative to the center of ethene. A mathematical function has been fit to this three-dimensional shielding increment surface at each of four distances from the face of the ethene molecule. Additionally, a single mathematical equation has been developed for predicting the shielding caused by the carbon-carbon double bond in ethene. In contrast to the traditionally employed shielding model, our results predict deshielding for protons within 3 Å above the center of a carbon-carbon double bond, consistent with experimental observations in several molecular systems. The NMR shielding increments predicted by this equation are compared to observed shielding increments in some test alkenes.
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  • 50
    Digitale Medien
    Digitale Medien
    Springer
    Structural chemistry 9 (1998), S. 419-427 
    ISSN: 1572-9001
    Schlagwort(e): NMR ; coupling constants ; cis and trans 1,2-diphenylcyclobutane ; angular dependence ; structure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract A new reaction scheme for obtaining cis and trans 1,2-diphenylcyclobutane is described. Using 1H-NMR at 600 MHz, full spectral assignment was made for both isomers, obtaining all J coupling constants and chemical shifts. NMR results on cis and trans 1,2-diphenylcyclobutane are compared with the vicinal coupling constants obtained by the Barfield–Smith equations from the literature internal and dihedral angles of cyclobutane. In the trans isomer, in agreement with previous results on halo-cyclobutanes, the conformation with the phenyls in the pseudo-di-equatorial position is strongly preferred. On the contrary, the cis isomer fluctuates between the two equivalent conformations: phenyl pseudo-axial and pseudo-equatorial.
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  • 51
    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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  • 52
    ISSN: 1572-9001
    Schlagwort(e): Magnetic anisotropy ; NMR ; shielding cone ; isotropic shielding ; GIAO ; (de)shielding surface ; alkenes
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract In a strong magnetic field, nuclei located over a carbon-carbon double bond experience NMR shielding effects that are the net result of the magnetic anisotropy of the nearby double bond and various other intramolecular shielding effects. We have used GIAO, a subroutine in Gaussian 4, to calculate isotropic shielding values and to predict the proton NMR shielding increment for a simple model system: methane held in various orientations and positions over ethene. The average proton NMR shielding increments of several orientations of methane have been plotted versus the Cartesian coordinates of the methane protons relative to the center of ethene. A single empirical equation for predicting the NMR shielding experienced by protons over a carbon-carbon double bond has been developed from these data. The predictive capability of this equation has been validated by comparing the shielding increments for several alkenes calculated using our equation to the experimentally observed shielding increments. This equation predicts the NMR shielding effects more accurately than a previous model that was based on only one orientation of methane over ethene. Deshielding is predicted by this equation for protons over the center and within about 3 Å of a carbon-carbon double bond. This result is in contrast to predictions made by the long-held “shielding cone” model based on the McConnell equation found in nearly every textbook on NMR, but is consistent with experimental observations.
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  • 53
    Digitale Medien
    Digitale Medien
    Springer
    Journal of sol gel science and technology 13 (1998), S. 61-64 
    ISSN: 1573-4846
    Schlagwort(e): cadmium sulfide nanocrystals ; sol-gel transition ; aggregation ; NMR ; small angle X-ray scattering (SAXS) ; thin films
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The preparation of concentrated sols and transparent stiff gels of II-VI semiconductors nanocrystals is reported. A two-step process for the production of cadmium sulfide is reported. Sol stabilization and gelation control are achieved through successive passivation and depassivation of the surface of the nanocrystals which are complexed with thiols. The mechanisms driving the aggregation and the gelation are explained on the basis of NMR and SAXS experiments. Thin films as well as monoliths can be produced. The general principles of the method presented are not restricted to chalcogenide systems and thus enlarge the domain of application of the inorganic sol-gel process.
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  • 54
    ISSN: 1573-4919
    Schlagwort(e): vanadate effects ; glycolysis ; intracellular sodium ; NMR ; perfused rat hearts ; ischemia-reperfusion
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie , Medizin
    Notizen: Abstract Vanadium compounds have been shown to cause a variety of biological and metabolic effects including inhibition of certain enzymes, alteration of contractile function, and as an insulin like regulator of glucose metabolism. However, the influence of vanadium on metabolic and ionic changes in hearts remains to be understood. In this study we have examined the influence of vanadate on glucose metabolism and sodium transport in isolated perfused rat hearts. Hearts were perfused with 10 mM glucose and varying vanadate concentrations (0.7‐100 μM) while changes in high energy phosphates (ATP and phosphocreatine (PCr)), intracellular pH, and intracellular sodium were monitored using 31P and 23Na NMR spectroscopy. Tissue lactate, glycogen, and (Na+, K+)-ATPase activity were also measured using biochemical assays. Under baseline conditions, vanadate increased tissue glycogen levels two fold and reduced (Na+, K+)-ATPase activity. Significant decreases in ATP and PCr were observed in the presence of vanadate, with little change in intracellular pH. These changes under baseline conditions were less severe when the hearts were perfused with glucose, palmitate and b-hydroxybutyrate. During ischemia vanadate did not limit the rise in intracellular sodium, but slowed sodium recovery on reperfusion. The presence of vanadate during ischemia resulted in attenuation of acidosis, and reduced lactate accumulation. Reperfusion in the presence of vanadate resulted in a slower ATP recovery, while intracellular pH and PCr recovery was not affected. These results indicate that vanadate alters glucose utilization and (Na+, K+)-ATPase activity and thereby influences the response of the myocardium to an ischemic insult.
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  • 55
    Digitale Medien
    Digitale Medien
    Springer
    Topics in catalysis 8 (1999), S. 81-86 
    ISSN: 1572-9028
    Schlagwort(e): NMR ; zeolite ; mechanism
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract In situ NMR has been extensively applied in the past decade to obtain basic mechanistic information about reactions in heterogeneous catalysis. Most studies in the literature have employed either sealed glass ampoules of catalyst and adsorbate that are heated outside of the NMR probe or variable temperature studies of samples sealed in magic‐angle spinning (MAS) rotors. In situ NMR studies of sealed samples fail to duplicate the conditions of temperature, reagent introduction and product removal found in bench‐top microreactor studies of catalysis. Previous attempts to more closely duplicate the conditions in flow reactors have motivated NMR studies using temperature jumps and the development of MAS probes with reagent flow. These methods have not yet achieved the time scales of several seconds or tenths of seconds that are typical of catalytic reactions. The pulse‐quench catalytic reactor has been developed to permit NMR studies of catalyst samples that have been prepared under actual reaction conditions. Pulse‐quench studies have provided evidence in support of a carbon‐pool mechanism for methanol‐to‐gasoline chemistry on HZSM‐5 and led to the identification of a pentamethylbenzenium cation formed in a zeolite by the alkylation of benzene with excess methanol.
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  • 56
    Digitale Medien
    Digitale Medien
    Springer
    Topics in catalysis 9 (1999), S. 35-42 
    ISSN: 1572-9028
    Schlagwort(e): CIT-6 ; zincosilicate ; zinc beta ; NMR
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract A new, large pore zincosilicate denoted CIT-6 with the framework topology of zeolite beta has been synthesized from reaction mixtures containing Li+, Zn2+ and tetraethylammonium hydroxide (TEAOH) as a structure-directing agent (SDA). The effects of the concentrations of Li+, Zn2+ and TEAOH on the preparation of CIT-6 are investigated and it is shown that there are critical ranges in concentration for all three components for the crystallization of pure CIT-6. The incorporation of Zn2+ into the CIT-6 framework is confirmed by 29Si MAS-NMR and ion exchange results. CIT-6 is the first molecular sieve to contain framework zinc sites accessible to organic molecules.
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  • 57
    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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  • 58
    Digitale Medien
    Digitale Medien
    Springer
    Journal of sol gel science and technology 14 (1999), S. 39-48 
    ISSN: 1573-4846
    Schlagwort(e): polysiloxanes ; oxycarbide glasses ; NMR ; mass spectrometry ; pyrolysis
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The polymer-to-glass transformation in the Si-C-O system usually involves cross-linking reactions at the C sites, which transform for example ≡Si– $$\underline {\text{C}} $$ H3 sites into $$\underline {\text{C}} $$ (Si)4 sites, leading to the formation of a silicon oxycarbide network. Identification of the various C sites that form during pyrolysis under inert atmosphere is rather difficult from 13C MAS-NMR spectra, due to strong overlap of resonance lines, which prevents an accurate determination of the chemical shift values. This paper reports on the use of a spectral editing technique called Inversion Recovery Cross Polarization (IRCP), which, when combined with Cross Polarization (CP) technique, allows us to identify and quantify the formation of Si- $$\underline {\text{C}} $$ H2-Si bridges during the early stages of the pyrolytic transformation of a polysiloxane containing Si–CH3 and Si–H groups. Several Si-C-O systems characterized by the same initial number of Si–CH3 bonds but with increasing number of Si–H bonds, have been investigated by MAS-NMR as well as thermogravimetric analysis coupled with mass spectrometry (TG/MS). The Si—H bonds play clearly an active role in the insertion of C atoms within the silica network.
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  • 59
    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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  • 60
    Digitale Medien
    Digitale Medien
    Springer
    Journal of sol gel science and technology 14 (1999), S. 7-25 
    ISSN: 1573-4846
    Schlagwort(e): black glass ; silicon oxycarbide ; Nicalon ; NMR ; Raman ; TEM ; high temperature stability ; surface chemistry ; network carbon ; elemental carbon ; structure ; free carbon ; FTIR ; nanocomposite ; silicon carbide
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The first attempts to introduce carbon into glass date back to 1951. But up until recently, the use of carbon or carbide raw materials, and the oxidation, volatilization and decomposition that accompany high temperature melting, have limited the synthesis of true silicon oxycarbide glasses. Here, the term silicon-oxycarbide refers specifically to a carbon-containing silicate glass wherein oxygen and carbon atoms share bonds with silicon in the amorphous, network structure. Thus, there is a distinction between black glass, which contains only a second-phase dispersion of elemental carbon, and oxycarbide glasses which usually contain both network carbon and elemental carbon. In addition to exploring the unique properties and applications of these glasses, per se, they are also of interest for developing models of the residual amorphous phases in polymer-derived silicon-carbide and silicon-nitride ceramics. The application of sol/gel techniques to glass synthesis has significantly advanced the development and characterization of silicon oxycarbide glasses. In this approach, alkyl-substituted silicon alkoxides, which are molecular precursors containing oxygen and carbon functionalities on the silicon, can be hydrolyzed and condensed without decomposition or loss of the carbon functional group. A low-temperature (〈1000°C) heat-treatment of the gel creates a glassy silicate material whose molecular structure consists of an oxygen/carbon anionic network. In addition, there is always a blackening of the material due to elemental carbon, which forms during pyrolysis and densification of the gel. The nature of the network carbon, and especially the distribution and form of the elemental carbon, are fundamental to the structure and properties of these novel materials. Their chemical and physical characteristics as revealed by NMR, Raman and TEM are discussed in the overview. In addition, the high temperature stability of these glasses (up to 1750°C), and the effect of hot-pressing, are described. It will be shown that the silicon oxycarbide network is stable up to 1000–1200°C. The network carbon is terminated with hydrogen (i.e., CH, =CH2 and –CH3), and with polyaromatic carbon (i.e., nC6Hx) wherein most of the elemental carbon resides. These glasses can be described as molecular composites of polyaromatic graphene-rings dispersed in a silicon oxycarbide network. After heating to temperatures in excess of 1000–1200°C, the oxycarbide network decomposes through the loss of hydrogen, and a two- or three-phase glass-ceramic consisting of nanocrystalline graphite, silicon carbide, and amorphous silica or cristobalite, is created. Some of the properties and applications of these glasses/glass-ceramics for coatings, composites and porous solids are summarized.
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  • 61
    Digitale Medien
    Digitale Medien
    Springer
    Journal of sol gel science and technology 13 (1998), S. 457-460 
    ISSN: 1573-4846
    Schlagwort(e): hybrid organic-inorganic materials ; gel drying ; molecular dynamics ; NMR ; sol-gel transition ; confinement
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract A new experimental approach to study the porosity of hybrid organic-inorganic glasses is reported. It relies upon nuclear magnetic resonance observation of molecular guest dynamics. It is shown that in MTEOS xerogels, there exists an interconnected organic-rich network in which organic guests are trapped and can eventually diffuse. The interpore translational diffusion is strongly activated and its spatial extension gives information on the pore connectivity, whose decay is characterized by the interpore jump probability given by the theoretical model.
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  • 62
    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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  • 63
    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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  • 64
    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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  • 65
    ISSN: 1573-4943
    Schlagwort(e): Thrombin receptor peptide ; NMR ; conformation ; bioactivity
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The conformational properties of the pentapeptide Ser-Phe-Leu-Leu-Arg (P5), a human thrombin receptor-derived sequence forming part of a tethered ligand which activates the thrombin receptor, and its more active amide derivative Ser-Phe-Leu-Leu-Arg-NH2 (P5-NH2), have been studied by proton NMR spectroscopy in dimethylsulfoxide. Measurements of nuclear Overhauser effects, performed using two-dimensional rotating frame nuclear Overhauser (ROESY) and one-dimensional nuclear Overhauser enhancement (NOE) spectroscopy, revealed that P5 exists mainly in an extended conformation. However, proton–proton 1D-NOEs between Phe CαH and Ser CαH, Leu3 CαH and Leu3 NH, and Leu4 CαH and Leu4 NH, as well as between the Ser and Arg sidechains, also implicated a minor conformer for P5 having a curved backbone and a near-cyclic structure. In contrast to P5, measurements of NOEs and ROEs for P5-NH2 revealed a more stabilized cyclic structure which may account for its higher biological potency. Thus strong interresidue sequential NH (i)–NH (i + 1) interactions, as well as C-terminal carboxamide to N-terminal side-chain interactions, i.e., Arg CONH2 to Phe ring and Arg CONH2 to Ser $$C_\alpha /C_{\beta \beta '} $$ , observed at lower levels of the ROESY spectrum, supported a curved backbone structure for SFLLR-NH2. Since the higher potaency P5-NH2 analogue adopts predominantly a cyclic structure, a cyclic bioactive conformation for thrombin receptor agonist peptides is suggested.
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  • 66
    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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  • 67
    ISSN: 1573-501X
    Schlagwort(e): combinatorial library ; hydrophobic collapse ; NMR ; n-substituted glycines ; structure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Synthesis and screening of combinatorial librariesfor pharmaceutical lead discovery is a rapidlyexpanding field. Oligo-N-substituted glycines (NSGs)were one of the earliest sources of moleculardiversity in combinatorial libraries. In one of thefirst demonstrations of the power of combinatorialchemistry, two NSG trimers, CHIR-2279 and CHIR-4531,were identified as nM ligands for two 7-transmembraneG-protein-coupled receptors. The NMR characterizationof these two lead compounds was undertaken to verifycovalent connectivity and to determine solutionconformations, if any. The sequential chemical shiftassignments were performed using a new strategy forassigning 1H and 13C resonances of NSGs. The conformational preferences were then determined inboth an aqueous co-solvent system and an organicsolvent to probe the effects of hydrophobic collapse. NSGs are expected to be more flexible than peptidesdue to the tertiary amide, with both cis andtrans amide bond conformations being accessible. Solution NMR studies indicate that although CHIR-2279and CHIR-4531 have identical backbones and termini,and very similar side chains, they do not display thesame solution conformational characteristics.
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  • 68
    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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  • 69
    ISSN: 1573-4943
    Schlagwort(e): Cytochrome c ; assignments ; ferrocytochrome c ; NMR ; 1H NMR ; 13C NMR
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Yeast iso-1 cytochrome c is a naturally occurring protein that possesses an unusually reactive Cysl02 that imbues iso-1 with a complicated solution chemistry which includes spontaneous dimerization and poorly characterized redox reactions. For this reason previous studies of this typical member of the c-type cytochromes have been relegated to variant proteins in which the 102 position has been mutated, with most common changes involving serine and threonine. However, we have determined sequential 1H resonance assignments for the wild-type native protein because it is the actual participant in yeast mitochondrial electron transfer processes and because the wild-type native protein should be the fundamental assignment basis. In addition to 1H resonance assignments for 97 of 106 amino acids, we have also provided an extensive database of long-range NOEs. Comparison of these NOEs and a chemical shift index based upon α-H resonances has lead to identification of solution secondary structural elements that are consistent with the solid-state crystal structure. Although there is currently no efficient expression system that would facilitate isotope labeling of iso-1 cytochrome c, we tried to assess the usefulness of future heteronuclear experiments by using natural-abundance 1H/13C HMQC experiments to unambiguously assign 35 α-C resonances.
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  • 70
    Digitale Medien
    Digitale Medien
    Springer
    Physics and chemistry of minerals 26 (1998), S. 14-30 
    ISSN: 1432-2021
    Schlagwort(e): Key words ab initio ; NMR ; silicates ; structure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Geologie und Paläontologie , Physik
    Notizen: Abstract  In order to gain insight into the correlations between 29Si, 17O and 1H NMR properties (chemical shift and quadrupolar coupling parameters) and local structures in silicates, ab initio self-consistent field Hartree-Fock molecular orbital calculations have been carried out on silicate clusters of various polymerizations and intertetrahedral (Si-O-Si) angles. These include Si(OH)4 monomers (isolated as well as interacting), Si2O(OH)6 dimers (C2 symmetry) with the Si-O-Si angle fixed at 5° intervals from 120° to 180°, Si3O2(OH)8 linear trimers (C2 symmetry) with varying Si-O-Si angles, Si3O3(OH)6 three-membered rings (D3 and C1 symmetries), Si4O4(OH)8 four-membered ring (C4 symmetry) and Si8O12(OH)8 octamer (D4 symmetry). The calculated 29Si, 17O and 1H isotropic chemical shifts (δi Si, δi O and δi H) for these clusters are all close to experimental NMR data for similar local structures in crystalline silicates. The calculated 17O quadrupolar coupling constants (QCC) of the bridging oxygens (Si-O-Si) are also in good agreement with experimental data. The calculated 17O QCC of silanols (Si-O-H) are much larger than those of the bridging oxygens, but unfortunately there are no experimental data for similar groups in well-characterized crystalline phases for comparison. There is a good correlation between δi Si and the mean Si-O-Si angle for both Q 1 and Q 2, where Q n denotes Si with n other tetrahedral Si next-nearest neighbors. Both the δ i O and the 17O electric field gradient asymmetry parameter, η of the bridging oxygens have been found to depend strongly on the O site symmetry, in addition to the Si-O-Si angle. On the other hand, the 17O QCC seems to be influenced little by structural parameters other than the Si-O-Si angle, and is thus expected to be the most reliable 17O NMR parameter that can be used to decipher Si-O-Si angle distribution information. Both the 17O QCC and the 2H QCC of silanols decrease with decreasing length of hydrogen bond to a second O atom (Si-O-H···O), and the δ i H increase with the same parameter.
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  • 71
    Digitale Medien
    Digitale Medien
    Springer
    Theoretical chemistry accounts 102 (1999), S. 72-77 
    ISSN: 1432-2234
    Schlagwort(e): Key words: Fullerenes ; Tetrahedral symmetry ; IR active ; Raman active ; NMR
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract. On analyzing the topological structures of the three types of tetrahedral fullerenes (which consist only of triangles and hexagons), (1) C n (T d ,n=12h 2; h=1,2,…), (2) C n (T d ,n=4h 2;h=1,2,…), and (3) C n (T,n=4(h 2+hk+k 2);h〉k,h,k=1,2,…), we have obtained theoretically the Infrared and Raman active modes by means of the derived formulas for the decomposition of their nuclear motions into irreducible representations, and the 13C NMR spectra with natural abundance for 13C by using the distribution functions for all of the tetrahedral (T d and T) fullerenes, respectively.
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  • 72
    Digitale Medien
    Digitale Medien
    Springer
    Magnetic resonance materials in physics, biology and medicine 3 (1995), S. 95-98 
    ISSN: 1352-8661
    Schlagwort(e): pacing ; triggering ; NMR ; perfused heart
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Medizin , Physik
    Notizen: Abstract This work reports a low-cost and versatile electronic device designed to trigger NMR acquisitions from the cardiac cycle of an isolated perfused heart, or to perform electrical stimulation of the heart. The triggering is synchronised with the pressure curve of the perfused heart. The cardiac pacing is achieved from pulses of the NMR system, or by an internal pulse generator, in order to be operated separately from the NMR instrument.
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  • 73
    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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  • 74
    ISSN: 1573-4986
    Schlagwort(e): acetolysis ; IL-6 ; MALDI-TOF-MS ; mannan ; NMR ; poly(glycerophosphate) structure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Previously, we showed that quantitatively minor several glycolipids only less than 5% of the lipoteichoic acid (LTA) fraction from Enterococcus hirae ATCC 9790 possessed cytokine-inducing activity, whereas the major component (over 90%) did not [Suda et al. (1995) FEMS Immun Med Microbiol 12:97–112]. The major inactive component was shown to have the chemical structure as was proposed for the LTA by Fischer [Hashimoto et al. (1997) J Biochem 121:779–86], suggesting that so-called LTA is not a cytokine-inducing component in the Gram-positive bacteria. In the present paper, the structure of the hydrophilic part of one of the cytokine-inducing glycolipid tentatively named GL4 is elucidated. GL4 was first subjected to hydrolysis with aqueous HF to give a polysaccharide and a mixture of low molecular weight products. The polysaccharide was composed mainly of highly branching mannan as concluded from NMR and MS analyses of its acetolysis products. The low molecular weight products consisted of phosphate and glycerol, suggesting the presence of a poly(glycerophosphate) structure in the original GL4. From these observations, the hydrophilic part of GL4 was shown to consist of mannose-rich polysaccharide and poly(glycerophosphate), the latter being bound to the former by a phosphodiester linkage.
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  • 75
    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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  • 76
    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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  • 77
    ISSN: 1573-4986
    Schlagwort(e): Chemically induced dynamic nuclear polarization (CIDNP) ; carbohydrate-protein interaction ; NMR
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The side chains of tyrosine, tryptophan and histidine are able to produce CIDNP (Chemically Induced Dynamic Nuclear Polarization) signals after laser irradiation in the presence of a suitable radical pair-generating dye. Elicitation of such a response in proteins implies surface accessibility of the respective groups to the light-absorbing dye. In principle, this technique allows the monitoring of the effect of ligand binding to a receptor and of site-directed mutagenesis on conformational aspects of any protein if CIDNP-reactive amino acids are involved. The application of this method in glycosciences can provide insights into the protein-carbohydrate interaction process, as illustrated in this initial model study for several N-acetyl-glucosamine-binding lectins of increasing structural complexity as well as for a wild type bacterial sialidase and its mutants. Experimentally, the shape and intensity of CIDNP signals are determined in the absence and in the presence of specific glycoligands. When the carbohydrate is bound, CIDNP signals of side chain protons of tyrosine, tryptophan or histidine residues can be broadened and of reduced intensity. This is the case for hevein, pseudo-hevein, the four hevein domains-containing lectin wheat germ agglutinin (WGA) and the cloned B-domain of WGA 1 (domB) representing one hevein domain. This response indicates either a spatial protection by the ligand or a ligand-induced positioning of formerly surface-exposed side chains into the protein’s interior part, thereby precluding interaction with the photo-activated dye. Some signals of protons from the reactive side chains can even disappear when the lectin-ligand complexes are monitored. The ligand binding, however, can apparently also induce a conformational change in a related lectin that causes the appearance of a new signal, as seen for Urtica dioica agglutinin (UDA) which consists of two hevein domains. Additionally, the three CIDNP-reactive amino acids are used as sensors for the detection of conformational changes caused by pH variations or by deliberate amino acid exchanges, as determined for the isolectins hevein and pseudo-hevein as well as for the cloned small sialidase of Clostridium perfringens and two of its mutants. Therefore, CIDNP has proven to be an excellent tool for protein-carbohydrate binding studies and can be established in glycosciences as a third biophysical method beside X-ray-crystallography and high-resolution multidimensional NMR studies which provides reliable information of certain structural aspects of carbohydrate-binding proteins in solution.
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  • 78
    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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  • 79
    ISSN: 1573-4986
    Schlagwort(e): Monte Carlo ; NMR ; ROESY ; AMBER
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The title compound is a cyclic oligosaccharide having six glucopyranose residues linked alternatively by α-(1→4) and β-(1→6) glycosidic linkages. Like cyclodextrin analogues it is expected to exhibit an internal cavity and to form inclusion complexes with other species. In order to investigate its conformational preferences, an extensive conformational search was carried out using a combination of Metropolis Monte-Carlo (MMC) procedure in the glycosidic torsion angle space and molecular mechanics procedures. To this end a specific program (METROCYCLIX) was developed. To reduce the MMC search, conformational maps of parent disaccharides were considered as starting entries. Fully minimized conformations were gathered into families using a clustering technique based on RMS fitting over the glycosidic torsion angle values. A wide range of local energy minima were identified in spite of ring closure conditions that constrained the structure of the oligosaccharide. Low energy conformers were stabilized by intramolecular interactions between distant residues. From the Bolzmann population of the best structures derived from the clustering results, various average properties were calculated and compared with experimental data obtained by high resolution NMR. Interpretation of these experimental values (heteronuclear coupling constants, rotating frame nuclear Overhauser effects, relaxation times) relies on the use of Karplus like equations (coupling constants) and analysis of the full relaxation rate matrix treatment (ROE). The quality of the molecular modelling strategy used is assessed by the agreement obtained between calculated and measured observables.
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  • 80
    Digitale Medien
    Digitale Medien
    Springer
    Journal of porous materials 4 (1997), S. 245-251 
    ISSN: 1573-4854
    Schlagwort(e): fly ash ; zeolite Y ; ageing ; seeding ; NMR
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: Abstract Zeolite Y was selectively synthesised by treating Tarong fly ash in a hydrothermal system. The effects of ageing and seeding on the formation of the resultant phases, crystallisation kinetics, and gel chemistry of Si and Al were investigated. Most of the Si and Al components in the Tarong fly ash could be effectively transformed into zeolite Y in the presence of seeds but not the mineral phase, like mullite. The maximum crystallinity of zeolite Y obtained was 72%. The cation-exchange capacity (CEC) of the fly ash was 0.08 mmol/g but increased to 3.2 mmol/g after a proper treatment. Crystallisation of zeolite materials from fly ash is quite different from that of normal zeolite synthesis because the sources of Si and Al are relatively less reactive and other cation ions (e.g., K+, Mg2+) are present in fly ash. Zeolite P is a competitive phase present in the resulting products that could be eliminated by employing the seeding method. NMR study demonstrated that ageing plays an important role in enhancing the hydrothermal condition during which both Si and Al in fly ash dissolved into a basic solution and reacted to form ring-like structures, and further to zeolite materials. Seeding can selectively induce the formation of zeolite Y and eliminate the processes of induction and nucleation.
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  • 81
    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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  • 82
    Digitale Medien
    Digitale Medien
    Springer
    Glycoconjugate journal 15 (1998), S. 209-216 
    ISSN: 1573-4986
    Schlagwort(e): conformational analysis ; molecular dynamics ; NMR ; free energy ; perturbation ; oligosaccharide ; polysaccharide ; GLYCAM
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Computational methods have had a long history of application to carbohydrate systems and their development in this regard is discussed. The conformational analysis of carbohydrates differs in several ways from that of other biomolecules. Many glycans appear to exhibit numerous conformations coexisting in solution at room temperature and a conformational analysis of a carbohydrate must address both spatial and temporal properties. When solution nuclear magnetic resonance data are used for comparison, the simulation must give rise to ensemble-averaged properties. In contrast, when comparing to experimental data obtained from crystal structures a simulation of a crystal lattice, rather than of an isolated molecule, is appropriate. Molecular dynamics simulations are well suited for such condensed phase modeling. Interactions between carbohydrates and other biological macromolecules are also amenable to computational approaches. Having obtained a three-dimensional structure of the receptor protein, it is possible to model with accuracy the conformation of the carbohydrate in the complex. An example of the application of free energy perturbation simulations to the prediction of carbohydrate-protein binding energies is presented.
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  • 83
    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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  • 84
    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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  • 85
    Digitale Medien
    Digitale Medien
    Springer
    Perspectives in drug discovery and design 15-16 (1999), S. 41-60 
    ISSN: 1573-9023
    Schlagwort(e): dipole moment ; neurotoxin ; NMR ; potassium channel ; scorpion ; structure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Scorpion venom contains various toxins which block ion-channels, responsible for either sodium, potassium, calcium or chloride membrane permeation. This review focuses on the three-dimensional structure of scorpion toxins specific for potassium channels, and on their structure–activity relationships. The overall fold of all these toxins is similar, despite their various specificities towards different types of potassium channels. Fine studies of the influence of punctual mutations of both toxins and channels have converged on a precise description of the scorpion toxins functional maps. From this knowledge, it now becomes possible to predict the specificity of a newly described scorpion toxin. The way is thus now open that leads to the design of new potent synthetic potassium channel blockers which in turn could be used as therapeutic drugs.
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  • 86
    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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  • 87
    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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  • 88
    ISSN: 1573-904X
    Schlagwort(e): ionization ; solubilization ; bile salts ; micelles ; NMR ; partition coefficient
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Purpose. The aqueous solubility and the extent of solubilization and ionization constant in sodium taurodeoxycholate (NaTDC) solutions of a series of benzoic acid and aniline derivatives were measured as a basis to characterize and thereby help predict the nature of the interaction of drugs with bile aggregates. Methods. The aqueous solubility and the solubilization of two series of compounds, 4-alkyl benzoic acids and 4-alkyl anilines, was measured as a function of NaTDC in 0 and 150 mM NaCl. The ionization constants were determined in water and in 50 mM NaTDC at sodium chloride concentrations of 0, 75 and 150 mM by spectrophotometric titration. The diffusion coefficients of NaTDC and the solutes were measured by pulsed-field gradient spin echo NMR spectroscopy. Results. The aqueous solubilities decreased with increasing alkyl chain length in both series, and the aniline derivatives had larger solubilities than the benzoic acid derivatives. The number of moles of solute solubilized per mole of bile salt ranged from 0.17 to 0.31 for the benzoic acid derivatives and from 1.3 to 3.0 for the aniline derivatives. The pKa values of the benzoic acid derivatives in the presence of NaTDC were higher relative to the controls, and the difference in the pKa (ΔpKa,obs) increased with increasing chain length. With the aniline derivatives, the pKa values were also shifted to higher values in NaTDC relative to the control but only in the absence of salt. The presence of the solute caused a decrease in the diffusion coefficient of NaTDC, and the diffusion coefficients of the solutes decreased with increasing alkyl chain length. With the hexyl derivatives, the diffusion coefficient of the solute was smaller than the diffusion coefficient of the bile salt. The chemical shift of the protons attached to carbon 18 and 19 of the bile salt were decreased to a greater extent in the presence of the solutes than the protons attached to carbon 26. Conclusions. Both the solubilization and ionization behavior of solutes were affected by the presence of bile salt aggregates. The surface potential and effective polarity of NaTDC aggregates were found to be dependent on the alkyl chain length for these two homologous series of solutes. The solubilization ratio was largely independent of alkyl chain length, but the unitary partition coefficient was dependent on both the alkyl chain length as well as ionization state. The derivatives reduced the diffusivity of the micelles suggesting the formation of larger sized aggregates and the solutes (hexyl derivatives) appear to favor association with the larger sized aggregates. The phenyl ring of the solutes appears to be oriented parallel to the plane of the steroid frame with preferential positioning near the hydrophobic rings.
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  • 89
    ISSN: 1573-904X
    Schlagwort(e): 13C-edited ; NMR ; retinol ; retinoic acid ; β-lactoglobulin
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Purpose. Vitamin A (retinol) and its metabolites comprise the natural retinoids. While the biological action of these molecules are thought to be primarily mediated by ca. 55 kDa nuclear retinoic acid receptors, a number of structurally similar 15-20 kDa proteins are involved in the transport, and possibly metabolism, of these compounds. The milk protein β-lactoglobulin B (β-LG) is an 18 kDa protein which binds retinol and may be involved in oral delivery of retinol to neonates. β-LG also binds drugs and other natural products and is of potential interest as a protective delivery vehicle. Methods. To examine the conformation of the model retinoid β-ionone both in solution and when bound to β-LG, NMR and computational methods have been employed. Results. Taken together, NMR studies of β-ionone in solution measuring scalar and dipolar coupling, as well as CHARMm calculations, suggest β-ionone prefers a slightly twisted 6-s-cis conformation. Isotope-edited NMR studies of l3C-labeled β-ionones bound to β-LG, primarily employing the HMQC-NOE experiment, suggest β-ionone also binds to β-LG in its 6-s-cis conformation. Conclusions. The methods employed here allow estimates of protein-bound ligand conformation. However, additional sites of ligand labeling will be necessary to aid in binding site localization.
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  • 90
    ISSN: 1573-904X
    Schlagwort(e): peptide delivery ; conformation ; Caco-2 cells ; membrane permeability ; NMR ; CD
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Purpose. To determine how restricted conformational flexibility of hexapeptides influences their cellular permeation characteristics. Methods. Linear (Ac-Trp-Ala-Gly-Gly-X-Ala-NH2; X = Asp, Asn, Lys) and cyclic (cyclo[Trp-Ala-Gly-Gly-X-Ala]; X = Asp, Asn, Lys) hexapeptides were synthesized, and their transport characteristics were assessed using the Caco-2 cell culture model. The lipophilicities of the hexapeptides were determined using an immobilized artificial membrane. Diffusion coefficients used to calculate molecular radii were determined by NMR. Two-dimensional NMR spectroscopy, circular dichroism, and molecular dynamic simulations were used to elucidate the most favorable solution structure of the cyclic Asp-containing peptide. Results. The cyclic hexapeptides used in this study were 2−3 times more able to permeate (e.g., Papp = 9.3 ± 0.3 × 10−8 cm/sec, X = Asp) the Caco-2 cell monolayer than were their linear analogs (e.g., Papp = 3.2 ± 0.3 × 10−8 cm/sec, X = Asp). In contrast to the linear hexapeptides, the flux of the cyclic hexapeptides was independent of charge. The cyclic hexapeptides were shown to be more lipophilic than the linear hexapeptides as determined by their retention times on an immobilized phospholipid column. Determination of molecular radii by two different techniques suggests little or no difference in size between the linear and cyclic hexapeptides. Spectroscopic data indicate that the Asp-containing linear hexapeptide exists in a dynamic equilibrium between random coil and β-turn structures while the cyclic Asp-containing hexapeptide exists in a well-defined compact amphophilic structure containing two β-turns. Conclusions. Cyclization of the linear hexapeptides increased their lipophilicities. The increased permeation characteristics of the cyclic hexapeptides as compared to their linear analogs appears to be due to an increase in their flux via the transcellular route because of these increased lipophilicities. Structural analyses of the cyclic Asp-containing hexapeptide suggest that its well-defined solution structure and, specifically the existence of two β-turns, explain its greater lipophilicity.
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  • 91
    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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  • 92
    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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  • 93
    Digitale Medien
    Digitale Medien
    Springer
    Pharmaceutical research 14 (1997), S. 676-680 
    ISSN: 1573-904X
    Schlagwort(e): ibuprofen ; metabolites ; NMR ; HPLC
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 94
    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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  • 95
    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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  • 96
    Digitale Medien
    Digitale Medien
    Springer
    Colloid & polymer science 275 (1997), S. 67-72 
    ISSN: 1435-1536
    Schlagwort(e): Key words Gelatin ; gel formation ; NMR ; viscoelasticity ; circular dichroism
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: Abstract  Network formation of gelatin gel is known to consist of three-dimensionally cross-linked triple helices among polypeptide chains. The effects of added low molecular weight mono-ols, diols and polyols on the higher-order structure formation of gelatin chains were investigated using the following measurements: melting temperature, viscoelasticity and spin-lattice relaxation time (T 1) of H17 2O of gels, and circular dichroism spectra of diluted gelatin solutions. Furthermore, hydration behaviors of these hydroxy compounds were evaluated from the dynamic hydration numbers (n DHN) derived from T 1 of H17 2O in the solutions. It was found that network structures of gelatin gels containing hydoxy compounds were influenced by the number and position of hydroxyl groups as well as the number of carbon atoms of these coexisting compounds. The effect of hydroxyl groups of hydroxy compounds was considered to stabilize the helices among gelatin chains. Especially, the addition of polyols with large number of hydroxyl groups increased the number of cross-linking junctions in the gel networks, which consist of the aggregation among the helices. On the contrary, the effect of carbon atoms of hydroxy compounds is to disturb the formation of the helices and the aggregation among the helices.
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  • 97
    Digitale Medien
    Digitale Medien
    Springer
    Journal of inclusion phenomena and macrocyclic chemistry 33 (1999), S. 307-319 
    ISSN: 1573-1111
    Schlagwort(e): cyclodextrins β and γ ; thyroxine ; thyroid hormones ; inclusion complex ; NMR
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Thyroxine T4 and its derivatives (T3, T2) are very sparingly soluble in aqueous solutions even in the form of salts. In the presence of β or γ-cyclodextrins and in buffered basic solution, their solubilities are increased by inclusion in the cavity. The inclusion of these hormones in cyclodextrins was investigated by 1H-NMR in order to derive the influence of the number and position of the iodine atoms, and of the ionization state of the phenol group on the inclusion geometries.
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  • 98
    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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  • 99
    ISSN: 1435-1536
    Schlagwort(e): Key words Interaction ; anionic surfactant ; polyvinylpyrrolidone ; ESR ; NMR
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: Abstract  The interaction between anionic surfactants and polyvinylpyrrolidone (PVP) are investigated using 13C NMR, ESR spectroscopy and surface tension measurements at the air/water interface. The behavior of single-chained surfactant, sodium dodecyl sulphonate (AS), is compared with that of the double-chained surfactant, sodium bis(2-ethylhexyl) phosphate (NaDEHP). The results showed that a surfactant–polymer complex of “necklace and head structure” is formed in AS aqueous solutions in the presence of PVP due to the hydrophobic interaction between PVP and AS. The AS micelles nucleate on the polymer hydrophobic sites, and the mobility of the AS head groups is not affected. But, for NaDEHP surfactant, it was found that PVP is little effective in influencing the monomer–micelle equilibrium and no surfactant– polymer complex formed in the NaDEHP aqueous solution.
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  • 100
    Digitale Medien
    Digitale Medien
    Springer
    Rheologica acta 36 (1997), S. 618-627 
    ISSN: 1435-1528
    Schlagwort(e): NMR ; viscometry ; shear flow ; liquid-crystalline polymer ; nematic solvent
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Abstract The flow behavior of a highly concentrated solution of a nematic side-chain liquid crystal polymer in a low molecular mass nematic solvent is investigated by deuterium nuclear magnetic resonance with simultaneous measurement of the shear viscosity in a cone-and-plate NMR viscometer. The director orientation under shear in the magnetic field is determined from the quadrupole splitting of the NMR spectra. The orientation as a function of shear rate is analyzed in terms of the Ericksen-Leslie-Parodi theory, yielding the Leslie coefficients μ 2 and μ 3 and thus the flow alignment parameter λ. From the combined analysis of orientation and viscosity as a function of shear rate a total of four independent viscosity parameters is obtained for the nematic solution. The value determined for the flow-alignment parameter, λ≈0.2, and the analysis of the data based on Brochard's theory show that the polymer is of the non-flow-aligning type and has a slightly prolate shape.
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