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  • Artikel  (73)
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  • 1
    Digitale Medien
    Digitale Medien
    Springer
    Journal of inorganic and organometallic polymers and materials 5 (1995), S. 217-236 
    ISSN: 1572-8870
    Schlagwort(e): Polysilane ; NMR ; pyrolysis ; randomization
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Bimodal molecular weight distributions of alternating copolymers of the type (Me2Si−R2Si−SiMe2) n , where R=hexyl and butyl, were obtained by polymerization of BrSiMe2−R2Si−Me2SiBr, using the Wurtz coupling method. Analysis of the samples by pyrolysis GC MS and solution29Si NMR indicated that some randomization occurred, due to cleavage of the original Si−Si bonds in the monomer. The extent of randomization was significantly greater in the high molecular weight fractions. Based on the nature of the rings from the py MGC/MS traces and the number on nonads found in the29Si spectra, two types of randomization processes have been proposed, involving backbiting followed by (1) ring expulsion or (2) redistribution.
    Materialart: Digitale Medien
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  • 2
    ISSN: 1572-8927
    Schlagwort(e): Hydrogen-1 ; carbon-13 ; nitrogen-15 ; NMR ; magnesiumisothiocyanate complexes
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract A hydrogen-1, carbon-13, and nitrogen-15 NMR study of magnesium(II)-isothiocyanate complexation in aqueous mixtures has been completed. At temperatures low enough to slow proton and ligand exchange, separate1H,13C, and15N NMR signals are observed for coordinated and bulk water molecules and anions. The1H NMR spectra reveal signals for the hexahydrate and the mono-through triisothiocyanato complexes, as well as two small signals attributed to [Mg(H2O)5(OH)]1+ and [Mg(H2O)4(OH)(NCS)]. Accurate hydration numbers were obtained from signal area integrations at each NCS− concentration. In the15N NMR spectra, signals also were observed for the mono-through triisothiocyanato complexes, and a small signal believed to be due to [Mg(H2O)4(OH)(NCS)]. Coordination number contributions for NCS− were measured from these spectra and when combined with the hydration numbers they totalled essentially six at each anion concentration. Signals for [Mg(H2O)5(NCS)]1+ through [Mg(H2O)3(NCS)3]1− also were observed in the13C NMR spectra and the area evaluations were comparable to the15N NMR results. An analysis of the magnitude and sign of the coordinated NCS− chemical shifts identified the nitrogen atom as the anion binding site. All spectra indicated [Mg(H2O)5(NCS)]1+ and [Mg(H2O)4(NCS)2] were the dominat isothiocyanato complexes over the entire range of anion concentrations. The inability to detect evidence for complexes higher than the triisothiocyanato reflects the competitive binding ability of water molecules and perhaps the decreased electrostatic interaction between NCS− and negatively charged higher complexes.
    Materialart: Digitale Medien
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  • 3
    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.
    Materialart: Digitale Medien
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  • 4
    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
    Materialart: Digitale Medien
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  • 5
    ISSN: 1572-8773
    Schlagwort(e): chlorophyll a ; energy transfer ; fluorescence ; mercury ions ; photosystem ; phycobilisomes ; Synechococcus 6301
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract Synechococcus PCC 6301 cells grown in the presence of low sublethal levels of (about 2 μ m) mercury induced alterations in chlorophyll (Chl) a absorption without significant alterations in phycocyanin. Chl a fluorescence emission in Hg2+ -raised cells showed a large (about 18 nm) blue shift in the peak emission. No major spectral changes in phycobilisome (PBsome) emission characteristic were noticed, indicating major structural alterations in Chl-protein complexes by incubation with Hg2+ ions. Low temperature (77 K) emission spectra of cells grown in the presence of Hg2+ showed a loss of the characteristic Chl a emission band at 695 nm (F695), which is known to be linked to photosystem II photochemistry and to originate from the Chl a of core antenna polypeptide CP 47 of photosystem II. The SDS-PAGE polypeptide profile of thylakoids indicates a loss of a polypeptide(s) with a molecular mass between 40 and 60 k Da by Hg2+ incubation of cells. Our results suggest that prolonged incubation of Synechococcus 6301 cells with low concentrations of Hg2+ affects the Chl a spectral properties and the structure of Chl-protein complexes.
    Materialart: Digitale Medien
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  • 6
    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.
    Materialart: Digitale Medien
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  • 7
    Digitale Medien
    Digitale Medien
    Springer
    Biology and fertility of soils 20 (1995), S. 17-23 
    ISSN: 1432-0789
    Schlagwort(e): Soil organic matter ; Hot water extract ; Field experiment ; Soil biomass ; Temporal variations ; Soil fertility ; NMR ; Analytical pyrolysis
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Geologie und Paläontologie , Land- und Forstwirtschaft, Gartenbau, Fischereiwirtschaft, Hauswirtschaft
    Notizen: Abstract Hot water-soluble organic matter was extracted from soil samples collected weekly between April and October in untreated and NPK+farmyard manure-fertilized plots in the 88-year-old Static Experiment (Loess Chernozem) at Bad Lauchstädt, Germany. As shown by solid-state 13C-nuclear magnetic resonance spectroscopy (13C-NMR) combined with pyrolysis-field ionization mass spectrometry this organic matter fraction was largely composed of carbohydrates and N-containing compounds, in particular amino-N species and amides. This composition and the low pyrolysis temperatures (mainly between 300 and 500°C) indicated its origin from soil biomass and root exudates and lysates, and its presence in the soil solution or weakly adsorbed by soil minerals and humic macromolecules. Long-term fertilization with NPK+farmyard manure resulted in larger mean concentrations of hot water-extracted C and N (0.933 and 0.094 g kg-1) than soil management without fertilization (0.511 and 0.056 g kg-1). The C and N extracted by hot water were in the range of 3–5% of total soil C and N. In the two treatments distinct temporal changes were observed, which appeared to be related to population dynamics of soil organisms, root growth and decomposition, and climatic influences on soil.
    Materialart: Digitale Medien
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  • 8
    ISSN: 1432-1017
    Schlagwort(e): Myelin basic protein ; Palmitoyllysophosphatidylcholine ; NMR ; EPR ; C D ; Ultracentrifugation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Physik
    Notizen: Abstract The stoichiometry of palmitoyllysophosphatidylcholine/myelin basic protein (PLPC/MBP) complexes, the location of the protein in the lysolipid micelles, and the conformational changes occurring in the basic protein and peptides derived from it upon interaction with lysolecithin micelles were investigated by circular dichroic spectropolarimetry, ultracentrifugation, electron paramagnetic resonance (EPR) and 31P, 13C, and 1H nuclear magnetic resonance spectroscopy (NMR), and electron microscopy. Ultracentrifugation measurements indicated that well-defined complexes were formed by the association of one protein molecule with approximately 141 lysolipid molecules. Small-angle X-ray scattering data indicated that the PLPC/MBP complexes form particles with a radius of gyration of 3.8 nm. EPR spectral parameters of the spin labels 5−, and 16-doxylstearate incorporated into lysolecithin/basic protein aggregates, and 13C- and 1H-NMR relaxation times of PLPC indicated that the addition of the protein did not affect the environment and location of the labels and the organization of the lysolipid micelles. The data suggested that MBP lies primarily near the surface of the micelles, with segments penetrating beyond the interfacial region into the hydrophobic interior, but without any part of the protein being protected against rapid exchange of its amide groups with the aqueous environment. The basic protein acquired about 20% α-helix when bound to lysolipid micelles. Circular dichroic spectra of sequential peptides derived by cleavage of the protein revealed the formation of α-helical regions in the association with lysolecithin. Specific residues in myelin basic protein that participated in binding to the micelles were identified from magnetic resonance data on changes in the chemical shifts and intensities of assigned resonances, and line broadening of peaks by fatty acid spin-labels incorporated into the micelles.
    Materialart: Digitale Medien
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  • 9
    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.
    Materialart: Digitale Medien
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  • 10
    ISSN: 1572-8951
    Schlagwort(e): Bichromophoric molecules ; intramolecular energy transfer ; synthesis ; fluorescence ; X-Ray structure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The design, structures and spectral properties of a number of bichromophoric molecules are presented. These bichromophoric molecules are composed of an aromatic ring connected by two methylene chains to an α-diketone moiety. Both absorption and emission spectra can be attributed to a superposition of the individual spectra of the separate chromophores. The critical transfer radius for electronic energy transfer from the aromatic (donor) chromophore to the α-diketone (acceptor) chromophore was calculated from the spectral overlap between the fluorescence spectrum of the aromatic moiety and the absorption spectrum of the α-diketone moiety. The results show that this series of molecules is well suited for a mechanistic study of short-range intramolecular electronic energy transfer.
    Materialart: Digitale Medien
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  • 11
    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.
    Materialart: Digitale Medien
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  • 12
    Digitale Medien
    Digitale Medien
    Springer
    Molecular and cellular biochemistry 148 (1995), S. 39-44 
    ISSN: 1573-4919
    Schlagwort(e): diabetes mellitus ; cardiomyopathy ; hydralazine ; cardiomyocytes ; fatty acids ; fluorescence ; trans-parinaric acid ; cis-parinaric acid ; plasma membrane fatty acid binding protein
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie , Medizin
    Notizen: Abstract Chronic treatment with the antihypertensive drug hydralazine did not affect the hyperglycemic state of streptozotocin (STZ)-diabetic rats but did prevent the serum hyperlipidemia that is synonymous with these diabetic animals. After 6 weeks, untreated STZ-diabetic rats exhibited a 659% increase in serum triglycerides and 292% increase in serum cholesterol versus age-matched non-diabetic rats. Hydralazine-treated STZ-diabetic rats had serum triglyceride and cholesterol levels that did not differ from controls. Myocytes from control rats showed a preference for binding of the unsaturated fatty acid analog cis-parinaric acid vs the saturated fatty acid analog trans-parinaric acid. This preference was not altered in STZ-diabetic rat myocytes; hydralazine-treatment of STZ-diabetic rats also showed no change in fatty acid preference. STZ-diabetes caused a decrease in the affinity (Kd) for the trans, but not the cis-parinaric acid. However, total binding of both analogs was increased in STZ-diabetes. Hydralazine treatment of STZ-diabetic rats resulted in even greater total binding of both analogs. Affinity for the trans analog was further decreased in these hydralazine-treated rats, but the affinity for the cis analog was increased beyond control animals. These results suggest that the diabetic state influences the binding characteristics of the myocardial PM-FABP and that hydralazine, while reducing serum lipids in diabetes, has complex effects on the fatty acid binding by this protein.
    Materialart: Digitale Medien
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  • 13
    Digitale Medien
    Digitale Medien
    Springer
    Molecular and cellular biochemistry 151 (1995), S. 91-98 
    ISSN: 1573-4919
    Schlagwort(e): intracellular calcium ; barium ; Indo-1 ; fluorescence ; calcium channels
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie , Medizin
    Notizen: Abstract The fluorescent chelator Indo-1 can make simultaneous determinations of two intracellular ion concentrations, such as [Ca2+] and [Cd2+], or [Ca2+] and [Ba2+], in a normal cell suspension. The second ion can be detected even if its spectrum when bound to Indo-1 is same as for the calcium-bound or the ion-free Indo-1, as long as there is a change in height. This is because the mathematical analysis uses not only the spectral shape, but also takes into account increases in total signal intensity. For maximum accuracy, whole spectra were analyzed. When 3 mM [Ba2+] was added to a B cell line that had been stimulated with anti-immunoglobulin to open receptor operated calcium channels, there was a sudden drop in 400 nm Indo-1 fluorescence. Spectral analysis showed that this was due to a drop in intracellular [Ca2+], which was consistent with blockage of the receptor-operated calcium current by extracellular Ba2+. The conductance for Ba2+ was also observable as a slow rise in total fluorescence. There was also a slow increase in intracellular [Ca2+] as barium accumulated in the cell, which was tentatively attributed to blockage of the plasma membrane calcium pump by intracellular Ba2+.
    Materialart: Digitale Medien
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  • 14
    ISSN: 1573-4935
    Schlagwort(e): ATPase ; calcium ; conformational change ; EDANS ; fluorescence ; sarcoplasmic reticulum
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract Changes in the fluoresence ofN-acetyl-N′-(5-sulfo-1-naphthyl)ethylenediamine (EDANS), being attached to Cys-674 of sarcoplasmic reticulum Ca2+-ATPase without affecting the catalytic activity, as well as changes in the intrinsic tryptophan fluorescence were followed throughout the catalytic cycle by the steady-state measurements and the stopped-flow spectrofluorometry. EDANS-fluorescence changes reflect conformational changes near the ATP binding site in the cytoplasmic domain, while tryptophan-fluorescence changes most probably reflect conformational changes in or near the transmembrane domain in which the Ca2+ binding sites are located. Formation of the phosphoenzyme intermediates (EP) was also followed by the continuous flow-rapid quenching method. The kinetic analysis of EDANS-fluorescence changes andEP formation revealed that, when ATP is added to the calcium-activated enzyme, conformational changes in the ATP binding site occur in three successive reaction steps; conformational change in the calcium enzyme substrate complex, formation of ADP-sensitiveEP, and transition of ADP-sensitiveEP to ADP-insensitiveEP. In contrast, the ATP-induced tryptophan-fluorescence changes occur only in the latter two steps. Thus, we conclude that conformational changes in the ATP binding site in the cytoplasmic domain are transmitted to the Ca2+-binding sites in the transmembrane domain in these latter two steps.
    Materialart: Digitale Medien
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  • 15
    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.
    Materialart: Digitale Medien
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  • 16
    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.
    Materialart: Digitale Medien
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  • 17
    ISSN: 1573-4943
    Schlagwort(e): Botulinum ; circular dichroism ; Clostridium ; ELISA ; fluorescence ; interaction ; neurotoxin binding protein ; secondary structure ; tyrosine exposure
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Type E botulinum neurotoxin is produced byClostridium botulinum along with a neurotoxin binding protein which helps protect the neurotoxin from adversepH, temperature, and proteolytic conditions. The neurotoxin binding protein has been purified as a 118-kDa protein. Secondary structure content of the neurotoxin binding protein as revealed by far-UV circular dichroism spectroscopy was 19% α-helix, 50%β-sheets, 28% random coils, and 3%β-turns. This compared to 22% α-helix, 44%β-sheets, 34% random coils, and noβ-turns of the type E botulinum neurotoxin. The complex of the two proteins revealed 25%α-helix, 45%β-sheets, 27% random coils, and 3%β-turns, suggesting a significant alteration at least in theα-helical folding of the two proteins upon their interaction. Tyrosine topography is altered considerably (28%) when the neurotoxin and its binding protein are separated, indicating strong interaction between the two proteins. Gel filtration results suggested that type E neurotoxin binding protein clearly complexes with type E neurotoxin. The interaction is favored at lowpH as indicated by an initial binding rate of 8.4 min−1 atpH 5.7 compared to 4.0 min−1 atpH 7.5 as determined using a fiber optic-based biosensor. The neurotoxin and its binding protein apparently are of equivalent antigenicity, as both reacted equally on enzyme-linked immunosorbent assay to polyclonal antibodies raised against the toxoid of their complex.
    Materialart: Digitale Medien
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  • 18
    ISSN: 1573-4943
    Schlagwort(e): 5-Hydroxytryptophan ; tryptophan ; insulin analogs ; fluorescence
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Use of insulin's intrinsic tyrosine absorption and fluorescence to monitor its interaction with the insulin receptor is limited because the spectral properties of the receptor tryptophan residues mask the spectral properties of the hormone tyrosine residues. We describe the synthesis of an insulin analog where A14 tyrosine is replaced by a tryptophan analog, 5-hydroxytryptophan. This insulin is spectrally enhanced since 5-hydroxytryptophan has an absorption band above 300 nm which is at lower energies than the absorption of tryptophan. Steady-state and time-resolved fluorescence parameters indicate that 5-hydroxytryptophan reports the same information about the environment of the A14 side chain as does the corresponding tryptophan-containing insulin. The synthetic hormone is a full agonist compared to porcine insulin, but has slightly reduced specific activity. Consequently, this spectrally enhanced insulin analog will be useful for hormone-receptor interaction studies since it can be observed by both absorption and fluorescence even in the presence of the tryptophan-containing receptor.
    Materialart: Digitale Medien
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  • 19
    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.
    Materialart: Digitale Medien
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  • 20
    Digitale Medien
    Digitale Medien
    Springer
    The protein journal 14 (1995), S. 373-379 
    ISSN: 1573-4943
    Schlagwort(e): Pantetheinase ; second-derivative spectroscopy ; fluorescence ; enzymatic activity
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The denaturation of pantetheinase (pantetheine hydrolase, EC 3.5.1.-) was followed in guanidinium chloride using tyrosyl and tryptophanyl residues as probes in connection with change in enzymatic activity. Movements of tryptophanyl and tyrosyl residues during denaturation were studied by second-derivative and fluorescence spectroscopy and the number of these amino acids present in the protein was calculated from spectroscopic data. Pantetheinase shows a very high resistance to denaturation, being completely unfolded at guanidinium chloride concentration higher than 6.5 M. Monitoring enzymatic activity shows that inactivation of the enzyme occurred before noticeable conformational changes were detected and it is suggested that the conformation of the active site is flexible and easily perturbable compared to the protein as a whole. This inactivation is reversible, as shown by renaturation experiments. Second-derivative and fluorescence spectra showed also that tyrosyl and tryptophanyl residues are largely exposed in the native protein, confirming its hydrophobic behavior.
    Materialart: Digitale Medien
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  • 21
    ISSN: 1573-4943
    Schlagwort(e): α-Lactalbumin ; selective disulfide bond cleavage ; sodium dodecyl sulfate ; secondary structure ; fluorescence
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Four disulfide bridges of bovineα-lactalbumin (α-lact) were selectively reduced to obtain its derivatives with three, two, and zero disulfide bridges (designated as 3SS, 2SS, and OSSα-lact, respectively). The original helicity was almost maintained in 3SSα-lact missing only the Cys6-Cysl20 bridge. Upon the reduction of both Cys28-Cys111 and Cys6-Cys120 bridges, various changes occurred in the protein. In particular, the maximum fluorescence of 1-anilinonaphthalene-8-sulfonic acid was observed in this stage. Upon the reduction of all disulfide bridges, the hydrophobic box of the protein, formed by Trp60, Ile95, Tyr103, and Trp104, was disrupted and an internal helical structure was destroyed. The conformation of each derivative was examined mainly in a solution of sodium dodecyl sulfate. In the surfactant solution, the helicity increased from 33% to 37% in 3SSα-lact, from 26% to 31% in 2SSα-lact, and from 18% to 37% in OSSα-lact, as against from 34% to 44% in intactα-lact. On the other hand, the tryptophan fluorescence of each derivative was affected in very low surfactant concentrations, suggesting that the tertiary structure considerably changed prior to the secondary structural change in the surfactant solution.
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  • 22
    ISSN: 1432-0878
    Schlagwort(e): Adrenals ; Morphology ; Steroids ; Gas chromatography ; Mass spectrometry ; Clarias gariepinus (Teleostei)
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Abstract Interrenal-like tissue in male African catfish is localized in paired organs, situated retroperitoneally anterior of the kidney. Histological and enzyme-histochemical (3β-hydroxysteroid dehydrogenase) reactions were carried out on sections of these organs in order to localize steroid-producing cells. In vitro incubations were carried out to determine the steroidogenic capacity of the interrenal-like tissue. Twenty-one steroids could be identified and quantified in the incubation medium, by means of gas chromatography followed by mass spectrometry. Cortisol, 5α-and 5β-androstanedione and androstenedione together comprised about 80% of the total steroid content. In a previous study, twenty testicular steroids were detected in plasma after castration. In the present investigation we have shown that most of these steroids can be produced by the interrenal-like tissue, which thus can be considered as an extra-testicular source of gonadal steroids.
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  • 23
    ISSN: 1432-0878
    Schlagwort(e): Key words: Adrenals ; Morphology ; Steroids ; Gas chromatography ; Mass spectrometry ; Clarias gariepinus (Teleostei)
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Medizin
    Notizen: Abstract. Interrenal-like tissue in male African catfish is localized in paired organs, situated retroperitoneally anterior of the kidney. Histological and enzyme-histochemical (3β-hydroxysteroid dehydrogenase) reactions were carried out on sections of these organs in order to localize steroid-producing cells. In vitro incubations were carried out to determine the steroidogenic capacity of the interrenal-like tissue. Twenty-one steroids could be identified and quantified in the incubation medium, by means of gas chromatography followed by mass spectrometry. Cortisol, 5α- and 5β-androstanedione and androstenedione together comprised about 80% of the total steroid content. In a previous study, twenty testicular steroids were detected in plasma after castration. In the present investigation we have shown that most of these steroids can be produced by the interrenal-like tissue, which thus can be considered as an extra-testicular source of gonadal steroids.
    Materialart: Digitale Medien
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  • 24
    ISSN: 1612-1112
    Schlagwort(e): Gas chromatography ; Retention-structure correlation ; Molecular descriptors ; Polycyclic aromatics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary Statistical and factor analysis have been used to test the ability of several molecular descriptors to predict the retention indexes (I) of polycyclic aromatic hydrocarbons determined on SPB-5 and SPB-20 stationary phases. Regression analysis with both columns showed that linear regression with connectivity index and bending energy of the molecules as independent variables gave the best correlation coefficients. ΔI 20–5, considered to be a measure of the polar forces in retention, gave a good correlation with the van der Waals radii of the molecules, or strain, and bending energy.
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  • 25
    Digitale Medien
    Digitale Medien
    Springer
    Chromatographia 41 (1995), S. 15-22 
    ISSN: 1612-1112
    Schlagwort(e): Gas chromatography ; Average velocity of carrier gas ; Compressibility of carrier gas ; Pneumatic parameters of carrier gas
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary This report was conceived as a source for the relations between five pneumatic parameters of carrier gas-inlet and outlet pressure, inlet and outlet velocity, and average velocity. Any pair of these parameters can be independent while the remaining three can be expressed as functions of the independent pair. As the total number of the independent pairs is ten, thirty different functions describing relations between arbitrary independent pairs and dependent parameters can be identified. All thirty were derived below together with the complete set of bounds for variations of independent parameters. To derive some relations, a third order rational equation had to be solved. Some properties of that solution are discussed. A simple case of vacuum operations with zero outlet pressure has also been considered.
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  • 26
    Digitale Medien
    Digitale Medien
    Springer
    Chromatographia 41 (1995), S. 37-42 
    ISSN: 1612-1112
    Schlagwort(e): Gas chromatography ; Temperature programming ; Isothermal measurements ; Column efficiency ; Dead time
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary If the dependence of HETP on temperature is specified under isothermal conditions, it is possible to predict the HETP for programmed temperature elution and subsequently peak width at half-height. This requires knowledge of isothermal retention time at retention temperature, which is computed by means of a model including the variation with temperature of dead time estimated from 3 homologs with carbon number: n, (n+j), (n+jk), where n, j and k are any integers. Predicted and measured peak widths corresponded within 4–9%.
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  • 27
    Digitale Medien
    Digitale Medien
    Springer
    Chromatographia 41 (1995), S. 678-684 
    ISSN: 1612-1112
    Schlagwort(e): Gas chromatography ; Solid phase micro extraction ; Graphitized carbon black ; Volatile organic compounds
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary This paper presents the results obtained using fused-silica fibers coated with graphitized carbon black (Carbograph-Alltech) for solid-phase microextraction (SPME). The extraction and calibration curves relative to organic micro-pollutants present in gaseous and aqueous samples are reported. Examples of applications of this extraction procedure to GC and GC-MS analysis of organic micro-pollutants in actual samples are also reported.
    Materialart: Digitale Medien
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  • 28
    Digitale Medien
    Digitale Medien
    Springer
    Chromatographia 41 (1995), S. 697-701 
    ISSN: 1612-1112
    Schlagwort(e): Gas chromatography ; New stationary phase ; Packed columns ; Specific retention volumes ; Activity coefficients
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary The synthesis of 3-bromo-4-(4-methylbenzyloxy)azobenzene (BMBOA) and its use as a stationary phase in packed columns are described. Chromatographic characteristics such as column efficiency, polarity (McReynolds constants) and operating temperature range were studied. Retention factors, specific retention volumes and activity coefficients for alcohols, esters, ketones, aromatic hydrocarbons andn-alkanes were determined. Phenols and 2,3, and 4-chlorobenzyl chlorides were separated on the new phase. Based on experimental data some assumptions were made on the possible types of intermolecular forces between solute and solvent.
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  • 29
    Digitale Medien
    Digitale Medien
    Springer
    Chromatographia 40 (1995), S. 28-32 
    ISSN: 1612-1112
    Schlagwort(e): Gas chromatography ; Linear temperature programming ; Tekler-equation extension ; Retention index precalculation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary An extension of Rohrschneider's concept to the field of the linear temperature programmed gas liquid chromatography, is proposed, which is based on Antoine's equation for the temperature dependence of the reduction index of Takács et al. and Tekler. The new method presented in this paper, applied to retention data of two stationary phases of low polarity, PS-255 and OV-105, gives a new possibility of precalculating retention data.
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  • 30
    Digitale Medien
    Digitale Medien
    Springer
    Chromatographia 40 (1995), S. 550-556 
    ISSN: 1612-1112
    Schlagwort(e): Gas chromatography ; Open tubular columns ; Short chain fatty acids ; Intestinal fluids
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary A capillary gas-liquid chromatography method for the analysis of free short chain fatty acids in intestinal samples was developed. Analytical results obtained with intestinal samples are influenced not only by high molecular mass matrix constituents but also by matrix components with a molecular weight smaller than 5000 daltons. To achieve a faithful transfer of SCFA into the chromatographic system it was important to avoid accumulation of involatile deposits on the surface of the inlet liner. Cleaning of the inlet linear lead to a significant weakening of matrix effects. The method described, using an Innowax column, is more effective, particularly with respect to precision and sensitivity, and is clearly superior to packed columns. The capillary is the column of choice for the separation of short fatty acids in samples from the small intestine and stomach.
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  • 31
    Digitale Medien
    Digitale Medien
    Springer
    Chromatographia 41 (1995), S. 726-727 
    ISSN: 1612-1112
    Schlagwort(e): Gas chromatography ; Retention indices ; Correlation equations ; n-Alkenes ; n-Alkynes
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary The correlation equations between Kovats retention indices ofn-alkenes andn-alkynes, column temperature and number of carbon atoms in molecules of these compounds on OV-101, OV-225 and PEG 20M capillary columns have been calculated. The two variable equationI=A+B·n+C/T give a good fit and are the simplest for prctical use.
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  • 32
    ISSN: 1573-5176
    Schlagwort(e): Rhodophyta ; red alga ; Hypnea musciformis ; carrageenans ; extraction ; kappa-carrageenase ; oligosaccharides ; fractionation ; NMR
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Abstract Dried powder of Hypnea musciformis was extracted with water at pH 7 after an initial short pre-treatment with cold, diluted HCl. Carrageenans were isolated by alcohol precipitation after an amylase treatment and a filtration of the extracts. The yields at 25 and 90 °C were 25 and 75% (w/w) of the dry alga, with molecular weights (Mw) corresponding to 194 000 and 245 000, respectively. The chemical structure was dominated by G4S-DA-(kappa-carrageenan or carrageenose 4′-sulphate). A simple fractionation procedure for kappa-carrageenase hydrolysates, based on stirring in different enthanol/water mixtures, is introduced. NMR analysis showed that oligosaccharides with a repeating DA-G4S structure were the main constituents in the enzymic hydrolysates of the carrageenans from Hypnea musciformis. These oligosaccharides were solubilized in an ethanol concentration from 96 to 48% (v/v). In some enzyme resistant fractions D6S-G4S and DA2S-G4S sequences and D2S,6S unites were detected by 13C-NMR.
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  • 33
    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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  • 34
    Digitale Medien
    Digitale Medien
    Springer
    Pharmaceutical research 12 (1995), S. 380-386 
    ISSN: 1573-904X
    Schlagwort(e): microviscosity ; viscosity ; malononitrile ; diffusion ; fluorescence ; p-(N-dimethylaminocinnamylidene) malononitrile
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Three molecules were investigated for their ability to distinguish variations in the microviscosity of the surrounding medium. Julolidinemalononitrile (JMN), p-(N-dimethylaminobenzylidene) malononitrile (BMN), and p-(N-dimethylaminocinnamylidene) malononitrile (CMN) were dissolved in media of various micro- and bulk viscosities. The fluorescence intensity of each dissolved probe and the bulk viscosity of each medium were measured. In solutions of low molecular weight substances, where the micro- and bulk viscosities are expected to correspond, the fluorescence behavior of each probe was a function of bulk viscosity and was independent of solution composition. In contrast, in aqueous solutions of methyl-cellulose, the fluorescence behavior of the probes corresponds to microviscosities significantly lower than the measured bulk viscosities. Thus, the probes are useful in resolving the microviscosity from bulk viscosity of neat liquid and solution systems. The sensitivity of the probes to viscosity is in the order JMN 〉 BMN 〉 CMN. Due to its limited water solubility, JMN is not particularly useful for pharmaceutical systems. CMN is the preferred probe for these applications due to its high fluorescence intensity over a large viscosity range.
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  • 35
    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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  • 36
    Digitale Medien
    Digitale Medien
    Springer
    Plant systematics and evolution 194 (1995), S. 55-67 
    ISSN: 1615-6110
    Schlagwort(e): Onagraceae ; Clarkia ; Gas chromatography ; mass spectrometry ; monoterpenes ; benzyl esters ; floral fragrances ; intraspecific variation ; moth pollination
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Abstract Clarkia breweri (Onagraceae) is the only species known in its genus to produce strong floral fragrance and to be pollinated by moths. We used gas chromatography-mass spectrometry (GC-MS) to identify 12 abundant compounds in the floral headspace from two inbred lines ofC. breweri. These volatiles are derived from two biochemical pathways, one producing acyclic monoterpenes and their oxides, the other leading from phenylalanine to benzoate and its derivatives. Linalool and linalool oxide (pyran form) were the most abundant monoterpenoids, while linalool oxide (furan form) was present at lower concentrations. Of the aromatic compounds detected, benzyl acetate was most abundant, whereas benzyl benzoate, eugenol, methyl salicylate, and vanillin were present as minor constituents in all floral samples. The two inbredC. breweri lines differed for the presence of the additional benzenoid compounds isoeugenol, methyleugenol, methylisoeugenol, and veratraldehyde. We also analyzed floral headspace fromC. concinna, the likely progenitor ofC. breweri, whose flowers are odorless to the human nose. Ten volatiles (mostly terpenoids) were detected at low concentrations, but only when headspace was collected from 20 or more flowers at a time. Trans-β-ocimene was the most abundant floral compound identified from this species. Our data are consistent with the hypothesized recent evolution of floral scent production and moth pollination inC. breweri.
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  • 37
    Digitale Medien
    Digitale Medien
    Springer
    Colloid & polymer science 273 (1995), S. 1174-1178 
    ISSN: 1435-1536
    Schlagwort(e): Cotton fibers ; dye ; adsorption ; calorimetry ; zeta potential ; fluorescence ; degree of whiteness
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: Abstract Fluorescent whitening agents (FWA) are used to improve the whiteness of cellulose fabrics. It is well known but not completely understood that the fluorescence decreases (chemical and physical mechanisms of distinguishing) above a certain FWA concentrationc crit. This reduction of fluorescence correlates very well with the alteration of the adsorption process studied by calorimetry and zeta potential measurements. The results obtained by these methods indicate that the adsorption mechanism is different at concentrations below and abovec crit. The reduction of the intensity of fluorescence, the degree of whiteness and the zeta potential are caused by the adsorption of a second layer of fluorescent whitening agents. This second layer reduces the zeta potential due to a shielding effect and reduces the whiteness and fluorescence by a bathochromic shift of the reflection curves. The final effect is a reduction of the total reflection.
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  • 38
    ISSN: 1435-1536
    Schlagwort(e): Blockcopolymer ; poly(ethylene oxide) poly(propylene oxide) ; light scattering ; fluorescence ; aggregation ; micelle ; phase behavior
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: Abstract The phase behavior and aggregation properties of block copolymers of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (Pluronics, poloxamers) in aqueous solution have recently attracted much attention. Both experimental and theoretical studies are reviewed, not comprehensively, but with the focus on studies, partly cooperative, partly independent, performed by groups in Uppsala (light scattering and fluorescence), Roskilde (rheology and calorimetry), Risø (SANS), Graz (x-ray and speed of sound), and Lund (theoretical model calculations). The phase behavior of these copolymers is similar in many respects to that of conventional nonionic surfactants, with the appearance of hexagonal, cubic, and lamellar liquid crystalline phases at high concentrations. In the isotropic solution phase the critical concentration for micelle formation is strongly temperature dependent, and at a given concentration the monomer to micelle transition occurs gradually over a broad temperature range, partly due to the broad size polydispersity of both the PO- and EO-blocks. For some Pluronic copolymers a transition from globular to long rod-like micelles occurs above a transition temperature, resulting in a strong and sudden increase of viscosity and viscoelasticity of the solution. Size and aggregation numbers have been determined for the globular micelles in some cases, and also the rod-like micelles have been characterized. NMR and fluorescence measurements have provided further information on the properties of the micellar core and mantle. In combination, results from different measurements on the same Pluronics material indicate that the aggregation number of the micelles increases with the temperature, whereas the hydrodynmic radius varies much less. The PEO-mantle of the micelles seems to contract with increasing temperature. The core appears to contain appreciable amounts of PEO in addition to PPO (and also some water). The segregation between core and mantle is not as distinct as in normal micelles, a conclusion which is in line with the predictions from the model calculations.
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  • 39
    ISSN: 1435-1536
    Schlagwort(e): Micelles ; micelle size ; fluorescence ; polar additives
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: Abstract The steady-state fluorescence quenching technique was used to investigate the effect of the presence of a series of alcohol homologues of mid-sized straight chain on the size of mixed micelles of sodium dodecyl sulfate (SDS). We used pyrene at concentration of ca. 10−6M, where only its monomer exhibits any fluorescence, as fluorescent probe, and cetylpiridinium chloride at concentrations in the range (1–9)×10−5 M as quencher. This technique allows one to determine the micellar aggregation number. The number of alcohol molecules per micelle was calculated from reported values for the micelle-water partition coefficient. On the assumption of spherical micelles, their hydrophobic radii was then calculated. The hypothesis that micelle size is determined by the available surface area per charged headgroup is discussed in the light of the results obtained.
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  • 40
    ISSN: 1573-5079
    Schlagwort(e): fluorescence ; LHC I-680 ; LHC I-730 ; light-harvesting complex I (LHC I) ; PS I
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Abstract With the new method of anion exchange perfusion chromatography we have devised an extremely rapid technique to subfractionate spinach Photosystem I into its chlorophyll a containing core complex and various components of the Photosystem I light-harvesting antenna (LHC I). The isolation time for the LHC I subcomplexes following solubilisation of native Photosystem I was reduced from 50 h using traditional density centrifugation procedures down to only 10–25 min by perfusion chromatography. Within this very short period of isolation, LHC I has been obtained as subfractions highly enriched in Lhca2+3 (LHC I-680) and Lhca1+4 (LHC I-730). Moreover, other highly enriched subfractions of LHC I such as Lhca2, Lhca3 and Lhca1+2+4 were obtained where the later two populations have not previously been obtained in a soluble form and without the use of SDS. These various subfractions of the LHC I antenna have been characterised by absorption spectroscopy, 77 K fluorescence-spectroscopy and SDS-PAGE demonstrating their identities, functional intactness and purity. Furthermore, the analyses located a chlorophyll b pool to preferentially transfer its excitation energy to the low energy F735 chromophore, and located specifically the origin of the 730 nm fluorescence to the Lhca4 component. It was also revealed that Lhca2 and Lhca3 have identical light-harvesting properties. The isolated Photosystem I core complex showed high electron transport capacity (1535 μmoles O2 mg Chl−1 h−1) and low fluorescence yield (0.4%) demonstrating its high functional integrity. The very rapid isolation procedure based upon perfusion chromatography should in a significant way facilitate the subfractionation of Photosystem I proteins and thereby allow more accurate functional and structural studies of individual components.
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  • 41
    ISSN: 1573-5079
    Schlagwort(e): circular dichroism (CD) ; cyanobacteria ; energy transfer ; fluorescence ; light-harvesting antennae ; photosynthesis ; core particle ; allophycocyanin
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Abstract We have constructed a mutant Synechococcus sp. PCC 7942, termed R2HECAT, in which the entire phycobilisome rod operon has been deleted. In the whole cell absorption spectra of R2HECAT, the peak corresponding to phycocyanin (PC), λmax≈620 nm, could not be detected. However, a single pigment-protein fraction with λmax=654 nm could be isolated on sucrose gradients from R2HECAT. Analysis of this pigment-protein fraction by non-denaturing PAGE indicates an apparent molecular mass of about 1200–1300 kDa. On exposure to low temperature, the isolated pigment-protein complex dissociated to a protein complex with a molecular mass of about 560 kDa. When analysed by SDS-PAGE, the pigment-protein fraction was found to consist of the core polypeptides but lacked PC, 27, 33, 30, and the 9 kDa polypeptides which are a part of the rods. All the chromophore bearing polypeptides of the core were found to be chromophorylated. CD as well as absorption spectra showed the expected maxima around 652 and 675 nm from allophycocyanin (APC) and allophycocyanin B (APC-B) chromophores. Low temperature fluorescence and excitation spectra also showed that the core particles were fully functional with respect to the energy transfer between the APC chromophores. We conclude that PC and therefore the rods are dispensable for the survival of Synechococcus sp. PCC 7942. The results indicate that stable and functional core can assemble in absence of the rods. These rod-less phycobilisome core is able to transfer energy to Photosystem II.
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  • 42
    ISSN: 1476-5535
    Schlagwort(e): antifouling ; biofilms ; bioluminescence ; Sea nine 211 ; fluorescence ; polydimethylsiloxane ; Vibrio harveyi ; on-line monitoring
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: Abstract A laminar flow biofilm-monitoring system was used to determine the efficacies of three antifouling (AF) coatings and five fouling-release (FR) coatings againstVibrio harveyi attachment. On-line measurements of tryptophan fluorescence and bioluminescence from each coating, normalized to an upstream stainless steel coupon, were used to determine the effects of AF and FR surfaces on biofilm formation. The AF coatings consisted of 5, 10, and 35 wt% Sea Nine 211 (C9211) incorporated into a vinyl copolymer. Both the 10 and 35 wt% coatings significantly inhibited biofilm biomass development measured by tryptophan fluorescence compared to the stainless steel control.V. harveyi bioluminescence was significantly greater than tryptophan fluorescence in cells attached to these coatings, suggesting that bioluminescence expression may be a marker for cellular stress or toxicity in biofilms. Five different polydimethylsiloxane (PDMS) FR coatings did not inhibit biofilm formation under low flow conditions. However, four PDMS coatings demonstrated decreased biomass levels compared to stainless steel after exposure to a shear stress of 330 dynes cm−2. There was no toxic additive in these coatings; bioluminescence and tryptophan fluorescence were proportional.
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  • 43
    Digitale Medien
    Digitale Medien
    Springer
    Colloid & polymer science 273 (1995), S. 1163-1173 
    ISSN: 1435-1536
    Schlagwort(e): Thermothickening ; associative polymers ; lower critical solution temperature ; shear-thinning behavior ; fluorescence
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: Abstract A new kind of water-soluble polymer was obtained by grafting side chains, characterized by a phase separation on heating (Lower Critical Solution Temperature LCST), on a hydrosoluble backbone. For semidilute solutions, the side chains associate as the temperature exceeds a critical temperature (T ass), which is close to their LCST. Microdomains are formed which act like physical crosslinking units between the main chains, and an increase in the aqueous solution viscosity is observed. Systems based on 2-Acrylamido-2-methyl propane sulfonic acid (AMPS) backbone and polyethylene oxide (PEO) side chains were developed. Their rheological behavior in both dilute and semi-dilute states was studied by varying differents parameters such as polymer and salt concentrations, grafting ratio, etc. Fluorescence measurements indicate the formation of hydrophobic microdomains on heating, in agreement with the thickening properties of the solutions.
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  • 44
    ISSN: 1573-5079
    Schlagwort(e): antenna connectivity ; flash preillumination ; fluorescence ; Photosystem 2 efficiency ; proton gradient ; Qa reduction
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Abstract Photosystem 2 photochemical efficiency, measured as the rate of Qa reduction, was observed to be inhibited by preillumination with single turnover flashes, whilst Fo and Fm were not affected. Such inhibition was reversed by the uncoupler nigericin or by incubating the thylakoids in the dark for ca. 2 min after the preillumination. The presence of ATP in micromolar concentrations increased the time of dark recovery from the inhibition. The inhibition of fluorescence rise was not changed when 70% of the excitation energy available in the antenna was quenched by dinitrobenzene. Quantitative analysis of the observed fluorescence induction indicates that this phenomenon is due to the inhibition of the photochemical reaction itself. Uncouplers such NH4Cl were unable to reverse the inhibition and only a few flashes of saturating intensity (10 or less) were required for the onset of it. This suggests that protons localised in domains rather than a pH gradient between the thylakoid lumen bulk solution and the external one are involved in this regulation of PS 2 efficiency.
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  • 45
    ISSN: 1612-1112
    Schlagwort(e): Gas chromatography ; Phosphine ; Flame photometric detection ; Anaerobic bacteria
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary A gas chromatographic method is presented which distinguishes phosphine from hydrogen sulfide and other possible headspace gases of anaerobic microbial cultures. In anaerobic cultures spiked with phosphine, this gas is recovered in the liquid and gaseous phase down to 10 pg per ml of gas or liquid. No biogenically produced phosphine was found. Phosphine in amounts as small as 30 ng per 1 can be stored for several days in glass bottles covered with rubber septa, filled with nitrogen, in the presence or absence of water or of an anaerobic bacterial culture. Due to the selectivity of the detector and the retention characteristics of the porous layer open tubular polymer column alkanes, alkenes and organosulfur compounds routinely found in anaerobic bacterial headspaces do not interfere with the analytical quantification of phosphine.
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  • 46
    ISSN: 1612-1112
    Schlagwort(e): Gas chromatography ; Liquid crystals ; Internal and external NO2 compounds ; Transition temperature ; Analytical properties
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary Thermal and analytical properties of two liquid crystals containing internal [2-nitro, 3-methyl 4-(4-heptylbenzoyloxy) 4′-methylazobenzene] and external NO2 [2,3-dimethyl 4-(4-heptylbenzoyloxy) 4′-nitroazobenzene] have been investigated by gas chromatography. Transitions temperatures are determined by inverse gas chromatography using standard columns. Good agreement with values determined by differential scanning calorimetry are found. Analytical capabilities of the two liquid crystals are shown in glass capillary columns. Compared to examples in the literature, the crystals used separated different kinds of solutes. In addition, high molecular mass solutes were eluted at relatively low temperatures. Typical separations are observed for hydrocarbon positional isomers, aromatic hydrocarbons, geometric isomers, and volatile aroma compounds. Comparison between the performance of internal and external, NO2-liquid crystals is made.
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  • 47
    Digitale Medien
    Digitale Medien
    Springer
    Chromatographia 41 (1995), S. 722-725 
    ISSN: 1612-1112
    Schlagwort(e): Gas chromatography ; Mixed stationary phases ; Distilled beverages ; Direct analysis
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary The analysis of spirits with a single stationary phase is still an unsolved problem; the two amyl alcohols, ethyl acetate and acetal are not separated on a polar column, methanol and acetaldehyde coelute from an apolar column. Trials with coupled columns of different polarities showed that optimum results were obtained with a 40 m capillary column, comprising 6 m of Carbowax 20 M, 12 m of 1∶1 Carbowax 20M:OV1 mixture and 30 m of PS 264. Best results were achieved when a 1 m retention gap was used, injecting a small amount of sample and using a 7 cm syringe needle.
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  • 48
    ISSN: 1612-1112
    Schlagwort(e): Gas chromatography ; Column liquid chromatography ; Polychlorinated biphenyls ; Cod liver oil
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary By application of a chromatographic column filled with Supelclean ENVI-Carb/Celite and elution with three solvents of different polarity three PCB fractions were obtained. Fraction A contained poly-ortho PCBs, Fraction B mono-ortho PCBs, and Fraction C non-ortho PCBs. The Supelclean ENVI-Carb/Celite column was used in combination with a sample preparation procedure for pre-cleaning of acid-stable chlorinated hydrocarbons such as DDT and its metabolites, HCH isomers, and regulation-relevant PCB congeners. The method was optimized using standard solutions of 55 PCB congeners, 8 chlorinated pesticides and contaminated cod liver oil samples. The influence of traces of remaining matrix on the elution profile of the organochlorine compounds on Supelclean ENVI-Carb/Celite was observed. Quantitation was carried out by GC-ECD with fused silica capillary columns of different polarity.
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  • 49
    ISSN: 1612-1112
    Schlagwort(e): Gas chromatography ; Pentacyclic triterpenes ; Maytenus aquifolium Martius ; Maytenus ilicifolia Martius ; Phytopharmaceuticals
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary We report a method for the analysis of triterpenes in aqueous alcoholic extracts ofM. ilicifolia orM. aquifolium leaves, using high temperature capillary gas chromatography in polar columns (OV-17-OH). These species are popularly known in Brazil as “espinheira santa” and have proven antiulcer properties. The method consists of the pre-concentration of the triterpenes from the aqueous alcoholic extract, followed by GC analysis, which permits the determination of the presence of friedelan-3-ol and friedelin. Direct comparison with several triterpenol standards that are usually found in falsified “espinheira santa” samples but are absent in the authentic drug, showed that GC analysis clearly allows detection of the presence of friedelan-3-ol and friedelin and, therefore, permits distinguishing between authentic and false “espinheira santa” aqueous alcoholic extracts.
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  • 50
    Digitale Medien
    Digitale Medien
    Springer
    Chromatographia 40 (1995), S. 417-420 
    ISSN: 1612-1112
    Schlagwort(e): Gas chromatography ; Organophosphate pesticides ; Vegetables ; Pesticide residue analysis
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary A rapid and efficient multiresidue extraction procedure using ethyl acetate and sodium sulfate has been applied to the analysis of diazinon, methamidophos, chlorpyrifos, malathion, parathion, parathion-methyl, dimethoate and monocrotophos residues in many different kinds of vegetables. No cleanup step was required Concentrated extracts were analysed by gas chromatography with flame photometric detection in phosphorus mode. Recovery studies were performed in six kinds of matrices at two fortification levels. Recoveries were in the range 80–115%. The limit of quantification of the analytical method has been estimated as 0.01 ppm for diazinon, methamidophos and malathion, 0.03 ppm for chlorpyrifos, parathion, parathion-methyl and dimethoate and 0.1 ppm for monocrotophos. Experiments showed that potentially it should be possible to develop a rapid and universally applicable method for organophosphate pesticide residues in different matrices.
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  • 51
    ISSN: 1612-1112
    Schlagwort(e): Gas chromatography ; Continuous preconcentration method ; Vitamins D2 and D3 ; Pharmaceutical preparations
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary A continuous-flow method that combines on-line preconcentration and isolation with gas chromatography for the direct determination of vitamins D2 and D3 in oily solutions is reported. A silica gel column permits preconcentration and isolation of analytes from the vitamin D matrix, although some triglyceride (ca. 25%) is also retained. To overcome problems associated with the low volatility of triglycerides, their retained fraction is further transesterified with potassium methylate to fatty acid methyl esters after elution. The proposed method was applied to the determination of vitamin D in pharmaceutical preparations.
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  • 52
    ISSN: 1612-1112
    Schlagwort(e): Gas chromatography ; Cholesterol ; Direct injection ; Saponification
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary A rapid and direct gas chromatographic (GC) method for determining free cholesterol in milk fat using a capillary column and programmed-temperature vaporizerinjector was assayed. It was compared with other procedures involving saponification of fat, solvent extraction of unsaponifiable matter—with and without fractionation by thin-layer chromatography—and transformation of sterols into silyl derivatives prior to GC analysis. This paper proposes an alternative to other published procedures. Repeatability of the method was assessed and the coefficient of variation determined as 2.1%. The alternative saponification method exhibited comparable accuracy (coefficient of variation=1.8%). Recovery ranged from 99.1% to 105.6%.
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  • 53
    Digitale Medien
    Digitale Medien
    Springer
    Chromatographia 41 (1995), S. 107-111 
    ISSN: 1612-1112
    Schlagwort(e): Gas chromatography ; Metal complex stationary phases ; Specific interactions ; N-benzoylthiourea groups
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary Silica was modified with γ-aminopropyltriethoxylsilane, and then the amino group was converted into an N-benzoylthiourea compound. Treatment with anhydrous CuCl2 solution, gave a copper(II) complex on the surface. In order to estimate the ability of the complex to interact specifically with electron donors, a number of retention parameters were determined for three groups of compounds showing electron-donor properties: ketones, ethers and nitroalkanes. On the basis of the results, the effect of adsorbate structure on the strength of specific interactions was established. The packings studied may be useful for the analysis of the mixtures of ketones, ethers, and nitroalkanes.
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  • 54
    ISSN: 1612-1112
    Schlagwort(e): Gas chromatography ; Matrix solid phase dispersion (MSPD) ; Fruit and vegetables ; Pesticide residues ; Selective detectors
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary A comparison between different element selective detectors for the determination of organophosphorus and organochlorine pesticide residues, from fruit and vegetables, was performed by capillary GC with electron capture detector (ECD), nitrogen phosphorus detector (NPD), flame photometric detector (FPD) in the sulphur and phosphorus modes, and mass spectrometry detector (MSD) in selected ion monitoring (SIM) mode. Pesticides were extracted from the different foodstuffs by Matrix Solid Phase Dispersion (MSPD). Recoveries of 41–108 % with relative standard deviation of 2–14 % in the concentration range 0.5–10 μg L−1 were obtained in oranges, lemons, grapefruit, pears, plums, lettuces and tomatoes. The results demonstrated that the extracts of all the samples can be analyzed by the detectors used since no interfering co-extracted compounds were detected.
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  • 55
    Digitale Medien
    Digitale Medien
    Springer
    Chromatographia 41 (1995), S. 553-560 
    ISSN: 1612-1112
    Schlagwort(e): Column liquid chromatography ; Gas chromatography ; Experimental design ; Modelling
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary Experimental Design methodology allows the modelling and optimization of the chromatographic separation of similar pesticides (triazine family) by GC and HPLC. The GC separation of simazin and atrazin is well modelled by a first degree equation, involving injected volume, carrier gas pressure and rising oven temperature. The LC is modelled by a second degree equation, depending on injected volume, eluent flow and composition. These calculated models allow easy optimization of the separations, using isoresponse curves.
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  • 56
    ISSN: 1612-1112
    Schlagwort(e): Gas chromatography ; Organic volatile pollutants ; Adsorbents ; Breakthrough volumes ; Thermal desorption
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary A comparison of some adsorbents, commonly used for trapping trace volatile organic pollutants followed by thermal desorption, is presented. The evaluation has been performed on 12 compounds representative of the main classes of organic substances. Breakthrough volumes and desorption recoveries have been measured. Every adsorbent gave good results for a range of compounds, but none were able to cover all the compounds examined. Thus, a multilayer trap utilising the best features of each adsorbent was introduced with very good results.
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  • 57
    ISSN: 1612-1112
    Schlagwort(e): Gas chromatography ; Enantiomer separation ; Chiral polysiloxane ; Amino acids ; Physicochemical properties
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary The polysiloxane backbone of the gas chromatography phase Chirasil-Val has been modified by replacing one methyl group per dialkylsiloxy unit by pentyl and hexyl groups, respectively. The new phases offer the advantage of reduced polarities and softening points, while the separation factors (α) of enantiomeric pairs of N,O-trifluoroacetyl amino acid propyl esters show small but intriguing deviations from those determined on Chirasil-Val.
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  • 58
    ISSN: 1612-1112
    Schlagwort(e): Gas chromatography ; Atomic emission detection ; Aqueous samples ; Solid-phase extraction ; Organophosphorus pesticides
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary An on-line, solid-phase extraction gas chromatography atomic-emission detection (SPE-GC-AED) system has been set up using an on-column interface to transfer 100 μl of desorbing solvent to the GC part of the system. Analytical characteristics such as recovery, precision and linearity of calibration plots were comparable with those of the off-line combination of SPE-GC-AED using organophosphorus pesticides as test compounds. The fully on-line set-up causes a marked improvement in detection because of the quantitative transfer of the analytes from the SPE module to the GC: detection limits are as low as 5–20 ng l−1 for the analysis of 10 ml raw and spiked surface water samples using the phosphorus channel. Detection levels can be further enhanced by processing up to 100 ml samples. The integrated analytical system is robust. The potential of the on-line set up has been demonstrated for the analysis of surface water and waste water.
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  • 59
    ISSN: 1612-1112
    Schlagwort(e): Gas chromatography ; Column liquid chromatography ; On-line coupling ; Ion-exchange membrane ; Ion-pair reagent
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary In order to enable the coupling of reversed-phase liquid chromatography (RPLC) with capillary gas chromatography (GC), the performance of an anion-exchange micromembrane device has been studied to remove the ion-pair reagent methanesulphonic acid from an acetonitrile/water LC eluent. The regenerant in the membrane was tetrabutylammonium hydroxide dissolved in acetonitrile/water, which effects an anion-exchange of methanesulphonate ions for regenerant hydroxide ions. The efficiency of the exchange process was found to be 99.9%. This enabled the direct introduction of the LC eluent, free of ions and with the proper acetonitrile/water ratio, into the GC. The applicability of the on-line LC-micromembrane-GC system has been illustrated for the potential drug eltoprazine, which is quantitatively recovered with a coefficient of variation for standard solutions of 3% at the 150 μg/ml analyte level.
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  • 60
    ISSN: 1612-1112
    Schlagwort(e): Gas chromatography ; ASPEC ; Trazodone in plasma ; Method automation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary An automated sample preparation module, (the automated sample preparation with extraction columns, ASPEC), was interfaced with a capillary gas chromatograph (GC) by means of an on-column interface. The system was optimised for the determination of the antidepressant trazodone in plasma. The clean-up of untreated plasma was carried out with disposable C18 cartridges, using several washing steps. The analyte was desorbed with methanol, the extract was diluted on-line with buffer and preconcentrated on a PLRP-S trapping column. The trapping column was dried by purging with nitrogen gas. Desorption (phase switching) of the trapping column was carried out with ethyl acetate which was introduced into a retention gap using partially concurrent solvent evaporation conditions. Trazodone was determined by GC with flame ionisation detection (FID). With a 1 ml sample, this resulted in a detection limit for trazodone in plasma of 3 ng/ml. The system showed good linearity and repeatability in the range 0.01–1 μg/ml, thus covering the range of pharmacokinetic/dynamic-to-therapeutic concentrations of trazodone in plasma. Preliminary results for benzodiazepines are promising. They indicate that the use of a selective detector such as the nitrogen/phosphorus detector, is to be recommended.
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  • 61
    ISSN: 1612-1112
    Schlagwort(e): Gas chromatography ; Packed column separations ; C1−C4 alcohols ; Ethers ; Gasoline
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary A number of oxygenated compounds such as C1−C4 alcohols, methyl tert-butyl ether (MTBE), and tertamyl methyl ether (TAME) are increasingly being used in gasoline as octane boosters and to reduce vehicular emissions. Monitoring of individual oxygenates in gasoline is important for quality control and regulatory purpose. Although, several analytical methods based on gas chromatography have been reported, a need was still felt to develop a simple and cost effective method of analysis. In this paper, a packed column gas chromatographic method is described for the analysis of C1−C4 alcohols, MTBE and TAME over a wide concentration range (2–20% V/V) in gasoline. The method involves determination of alcohols and ethers separately on two different columns. The alcohols are determined on a 20 ft column packed with poly(ethylene glycol) 400 as a stationary phase while the ethers are analysed on a 20 ft OPN-Poracil C column. The analysis of alcohols on poly(ethylene glycol) 400 column also provides data on aromatic components of gasoline.
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  • 62
    Digitale Medien
    Digitale Medien
    Springer
    Chromatographia 41 (1995), S. 183-186 
    ISSN: 1612-1112
    Schlagwort(e): Gas chromatography ; Correlation equation ; Alkylbenezenes
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary A detailed statistical analysis, comparing the validity of the best literature recommended equations for prediction of retention indices of alkylbenzenes on squalane and methylsilicone stationary phases with the unified retention index concept, is presented. A comparison with literature sources shows that the unified retention index provides the smallest residual error. Hence, it can be applied for prediction purposes.
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  • 63
    ISSN: 1612-1112
    Schlagwort(e): Gas chromatography ; Reversed-flow technique ; Catalysis ; Ring opening
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary Kinetic parameters for the ring opening of cyclohexane over modified ZSM-5 zeolites can be measured simultaneously under non-steady state conditions using reversed-flow gas chromatography. At relatively low temperatures, the main product detected and measured was propene. The mathematical relations used for the calculation of adsorption-desorption rate constants, surface reaction rate constants and adsorption equilibrium constants for the reactant cyclohexane are different from previously studied catalytic reactions, owing to the different experimental arrangement for feeding the catalytic bed. The diffusion bands obtained experimentally for reactant or product are described by the sum of two or three exponential functions of time, respectively. From the exponential coefficients of time and the pre-exponential factors, all determined by simple PC programs, the above kinetic parameters are calculated.
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  • 64
    ISSN: 1612-1112
    Schlagwort(e): Gas chromatography ; Binary stationary phase ; Self-associating phase components ; Retention model
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary The dependence of specific retention by a binary stationary phase in GC can be expressed as the sum of the products of the specific retention of the pure components times their respective volume fractions. In this study, however, one component has a site, which is not only mainly responsible for the selectivity, but also participates in strong self-association. This requires introduction of a concentration-dependent factor (μx) in the corresponding term of the equation correlating Vg mix x with x. In the GC resolution of N-trifluoroacetyl-amino acid isopropyl esters on a binary phase, N-lauroyl-L-amino t-butyl amide-squalane, data for the values of μx were obtained. Adapting a previously developed LC retention model to the above GC data, an equation was derived for the dependence of μx on the weight fraction (x) of the selector, namely μx=√1/x. This relationship permits calculation of retention volumes on the binary phase for a given x, as well as corresponding resolution coefficients of enantiomeric amino acid derivatives with generally excellent agreement with experiment. The chirality of the system is not relevant to application of the equation.
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  • 65
    Digitale Medien
    Digitale Medien
    Springer
    Chromatographia 41 (1995), S. 419-423 
    ISSN: 1612-1112
    Schlagwort(e): Gas chromatography ; Headspace analysis ; Microcapillary columns ; Short columns ; Volatile compounds
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary A new method of analysis using headspace gas chromatography with microcapillary columns is proposed. Small diameter (50 μm I.D.) fused-silica capillary columns with non-extractable SE-54 and PS-255 polysiloxane stationary phases were used for the analysis of low boiling organic compounds. The small diameter columns possess the usual very high efficiency so that the method can be employed for the headspace analysis of complex mixtures. The use of short microcolumns reduces the analysis times in comparison to conventional capillary columns. Good performances were obtained in the analysis of volatile compounds in some lemon essential oil, perfumes, and water samples.
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  • 66
    Digitale Medien
    Digitale Medien
    Springer
    Chromatographia 41 (1995), S. 594-598 
    ISSN: 1612-1112
    Schlagwort(e): Gas chromatography ; Capillary column ; Bicyclic spiro ketones ; Tricyclic spiro ketones ; Retention index at different temperatures ; Retention vs stationary phase polarity
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary The separation of some aromatic bicyclic and tricyclic spiro ketones on fused silica capillary columns coated with polydimethylsiloxane, cyanopropylmethylsiloxane and poly(ethylene glycol) stationary phases was investigated. Retention indices were determined at two temperatures in order to enable understanding of the compounds' chromatographic behaviour. The respective standard deviation values were 0.8, 0.5 and 0.3 index units. The influence of the polarity of the stationary phases on the chromatographic retention of these cyclic spiro ketones is discussed.
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  • 67
    Digitale Medien
    Digitale Medien
    Springer
    Journal of chemical ecology 21 (1995), S. 1191-1215 
    ISSN: 1573-1561
    Schlagwort(e): Ourebia ourebi ; Bovidae ; mammalian semiochemicals ; mammalian pheromones ; exocrine secretion ; preorbital secretion ; dimethyl disulfide derivatization ; skipped dienes ; chemical-ionization mass spectrometry ; NMR
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract Using gas chromatography-mass spectrometry in conjunction with ancillary techniques such as chemical ionization with different reactant gases, determination of the position of double bonds by means of dimethyl disulfide derivatization, and finally gas chromatographic and mass spectrometric comparison with authentic synthetic material, 75 constituents were identified in the preorbital secretion of the male oribi,Ourebia ourebi. The secretion contains compounds with long-chain, unbranched structures similar to those found in many other preorbital secretions but with a finite volatility range, in contrast to the seemingly endlessly increasing chain lengths typical of other preorbital secretions.
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  • 68
    Digitale Medien
    Digitale Medien
    Springer
    Journal of inclusion phenomena and macrocyclic chemistry 23 (1995), S. 259-267 
    ISSN: 1573-1111
    Schlagwort(e): Cyclodextrin ; complex ; fluorescence ; ultraviolet ; warfarin ; chromatography
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Inclusion of anticoagulant drugs within the cavity of methyl-β-cyclodextrin in aqueous solution was studied by ultraviolet absorption, fluorimetry and reversed-phase liquid chromatography. Formation constants were obtained for complex formation of methyl-β-cyclodextrin with warfarin and 8-chlorowarfarin.
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  • 69
    Digitale Medien
    Digitale Medien
    Springer
    International journal of peptide research and therapeutics 2 (1995), S. 121-124 
    ISSN: 1573-3904
    Schlagwort(e): Backbone cyclization ; Substance P ; NMR ; Molecular dynamics ; Conformational analysis
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary Structure-activity relationships of cyclic substance P (SP) analogs were extensively studied in our laboratories utilizing the new concept of backbone cyclization. Employing the C-terminal hexapeptide SP6–11, we examined the influence of chemical changes in peptides containing backbone-to-amino-end cyclization. These changes in the ring have significant influence on activity, and should be carefully designed in order to optimize pharmacological feature.
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  • 70
    ISSN: 1573-3904
    Schlagwort(e): Biosurfactant ; Lipopeptide ; NMR ; Hydrophobic substitution
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary Bacillus subtilis coproduces several surfactin variants that are powerful biosurfactants and have potential applications in biology and industry. A single amino acid substitution in the heptapeptide moiety of surfactins strongly modifies their properties. To better establish structure-activity relationships and to search new variants with enhanced properties, Bacillus subtilis was grown into two modified culture media. Two new variants were isolated by chromatographic methods and studied by NMR spectroscopy. As planned, modifications consisted in the substitution of the l-valine residue at the fourth position by a more hydrophobic residue, i.e., leucine or isoleucine. These [Leu4]- and [Ile4]surfactins have a higher affinity for hydrophobic solvents and a twice improved surfactant power. Structure-property correlations were confirmed by analysis of the hydrophobic residue distribution in the three-dimensional model of the structure of surfactin in solution.
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  • 71
    Digitale Medien
    Digitale Medien
    Springer
    International journal of peptide research and therapeutics 2 (1995), S. 59-70 
    ISSN: 1573-3904
    Schlagwort(e): Opioid peptide ; NMR ; Enkephalins ; Micelles ; Dodecylphosphocholine
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary Opioid peptides are thought to interact with the cell membrane in their biological journey to the membrane-bound receptor. Both organic solvents and model membranes have been used previously to determine the stable solution conformations of peptide hormones. Leucine enkephalin has been studied in a number of different environments, but with limited resolution. Here it is shown that leucine enkephalin forms a stable type IV β-turn structure in dodecylphosphocholine micelles. We have observed a highly solvent-shielded amide proton with no evidence for a complementary hydrogen bond acceptor. The structural details of the peptide as determined by NMR spectroscopy in solution are described.
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  • 72
    Digitale Medien
    Digitale Medien
    Springer
    International journal of peptide research and therapeutics 2 (1995), S. 161-164 
    ISSN: 1573-3904
    Schlagwort(e): Cyclised peptide ; Dioxopiperazine ; Thiazolidine ; NMR ; Computer modelling
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary Conformationally constrained peptidomimetics of the Lys-Pro sequence have been obtained using a new polycyclic structure. Bicyclic compounds containing a dioxopiperazine-thiazolidine fused ring have been synthesised starting from N-lysyl-4-ethoxycarbonylthiazolidine-2-carboxylic acid. The carboxyl group in either position 2 or 4 of the thiazolidine ring was reacted with the N-terminal amino group, giving different regioisomers. NMR and computer modelling were used to study the configuration of isomers and the lysine side-chain orientation with respect to the pseudoproline ring.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 73
    Digitale Medien
    Digitale Medien
    Springer
    International journal of peptide research and therapeutics 2 (1995), S. 239-242 
    ISSN: 1573-3904
    Schlagwort(e): Pseudopeptide ; Triphosgene ; Beta-turn ; NMR ; FT-IR ; X-ray diffraction
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Summary For the sake of improving synthetic methods and evaluating the conformational perturbation induced by the substitution of AzAsx for the Asx residue in the cognate dipeptide R-CO-Asx-Pro-NHR′, we prepared the AzAsx-dipeptide sequence by making use of the crystalline triphosgene. This reagent allows, in situ and under very mild experimental conditions, both the carbonylation and the activation of the properly substituted and N-protected hydrazine before coupling with the proline partner. With regard to conformational behaviour, the azadipeptide sequence displays a β-fold, unlike the cognate dipeptide which adopts an Asx-turn.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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