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  • 1
    ISSN: 1432-1017
    Keywords: Tryptophan ; Tyrosine ; Phenylalanine Dielectric constant ; Solvent
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Physics
    Notes: Abstract A tunable fourth derivative UV absorbance method based on a variable spectral shift has been developed and compared to the Savitzky-Golay method and the analytical derivative. The parameters of the method were optimised for the analysis of the UV absorbance spectra of the aromatic amino acids to quantify the effect of decreasing solvent polarity on their fourth derivative spectra. The wavelength of the highest maximum (λmax) (for tyrosine and phenylalanine) or the amplitude of the highest maximum (Amax) (for tryptophan), were shown to depend linearly on the dielectric constant of the solvent, ranging from water to cyclohexane. The only effect of pressure in the 1 to 500 MPa range is a small decrease in the fourth derivative amplitude. This method appears therefore as a suitable tool to evaluate changes of the dielectric constant in the vicinity of the aromatic amino acids in proteins which undergo pressure induced structural changes.
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  • 2
    ISSN: 1432-1017
    Keywords: Adrenodoxin ; Methanol dehydrogenase ; Ribonuclease ; Molten globule ; Protein dissociation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Physics
    Notes: Abstract The structural basis and the thermodynamics of pressure induced reversible spectral transitions in the fourth derivative ultraviolet absorbance spectra of proteins were analysed as described in the preceding paper. Three proteins were studied: adrenodoxin (a small iron-sulphur protein that serves as an electron donor for cytochrome P450scc), ribonuclease A, and methanol dehydrogenase (a tetrameric protein). Fourth derivative spectroscopy is used to probe important mechanistic aspects of these proteins. For adrenodoxin, the results suggest that one or two phenylalanines interact with the iron-sulphur redox centre. High pressure denaturation of ribonuclease leads to a molten globule like structure that also occurs as an intermediate in the high temperature induced denaturation process. This state is characterised by the local dielectric constant in the vicinity of tyrosines. Methanol dehydrogenase was found to be very stable towards pressure. High pressure appears to strengthen the interaction between the two α-subunits possibly through the increased interaction of four tryptophans with other aromatic amino acids.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Contributions to mineralogy and petrology 125 (1996), S. 167-185 
    ISSN: 1432-0967
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences
    Notes: Abstract  The Aurora volcanic field, located along the northeastern margin of Mono Lake in the Western Great Basin, has erupted a diverse suite of high-K and shoshonitic lava types, with 48 to 76 wt% SiO2, over the last 3.6 million years. There is no correlation between the age and composition of the lavas. Three-quarters of the volcanic field consists of evolved (〈4 wt% MgO) basaltic andesite and andesite lava cones and flows, the majority of which contain sparse, euhedral phenocrysts that are normally zoned; there is no evidence of mixed, hybrid magmas. The average eruption rate over this time period was ∼200 m3/km2/year, which is typical of continental arcs and an order of magnitude lower than that for the slow-spreading mid-Atlantic ridge. All of the Aurora lavas display a trace-element signature common to subduction-related magmas, as exemplified by Ba/Nb ratios between 52 and 151. Pre-eruptive water contents ranged from 1.5 wt% in plagioclase-rich two-pyroxene andesites to ∼6 wt% in a single hornblende lamprophyre and several biotite-hornblende andesites. Calculated oxygen fugacities fall within –0.4 and +2.4 log units of the Ni-NiO buffer. The Aurora potassic suite follows a classic, calc-alkaline trend in a plot of FeOT/MgO vs SiO2 and displays linear decreasing trends in FeOT and TiO2 with SiO2 content, suggesting a prominent role for Fe-Ti oxides during differentiation. However, development of the calc-alkaline trend through fractional crystallization of titanomagnetite would have caused the residual liquid to become so depleted in ferric iron that its oxygen fugacity would have fallen several log units below that of the Ni-NiO buffer. Nor can fractionation of hornblende be invoked, since it has the same effect as titanomagnetite in depleting the residual liquid in ferric iron, together with a thermal stability limit that is lower than the eruption temperatures of several andesites (∼1040–1080°C; derived from two-pyroxene thermometry). Unless some progressive oxidation process occurs, fractionation of titanomagnetite or hornblende cannot explain a calc-alkaline trend in which all erupted lavas have oxygen fugacites ≥ the Ni-NiO buffer. In contrast to fractional crystallization, closed-system equilibrium crystallization will produce residual liquids with an oxygen fugacity that is similar to that of the initial melt. However, the eruption of nearly aphryic lavas argues against tapping from a magma chamber during equilibrium crystallization, a process that requires crystals to remain in contact with the liquid. A preferred model involves the accumulation of basaltic magmas at the mantle-crust interface, which solidify and are later remelted during repeated intrusion of basalt. As an end-member case, closed-system equilibrium crystallization of a basalt, followed by equilibrium partial melting of the gabbro will produce a calc-alkaline evolved liquid (namely, high SiO2 and low FeOT/MgO) with a relative f O 2 (corrected for the effect of changing temperature) that is similar to that of the initial basalt. Differentiation of the Aurora magmas by repeated partial melting of previous underplates in the lower crust rather than by crystal fractionation in large, stable magma chambers is consistent with the low eruption rate at the Aurora volcanic field.
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  • 4
    ISSN: 1432-0967
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences
    Notes: Abstract  Pleistocene-Holocene volcanism in the Jalisco block of western Mexico is confined to two conspicuous grabens, where potassic eruptives range from absarokites (48–52% SiO2) and minettes (49–54% SiO2) through basaltic andesites (53–57% SiO2), the most voluminous type, to andesites and their lamprophyric equivalent spessartite (58–62% SiO2); there are no contemporary rhyolitic rocks. This suite has high concentrations of Mg, Cr (〈550 ppm) and Ni (〈450 ppm) accompanied by large concentrations of K, P, Ba (〈4000 ppm) and Sr (〈5000 ppm) and elements such as LREE and Zr (〈600 ppm). No combination of crystal fractionation and/or crustal contamination can reproduce the compositional range of these magmas, which nevertheless are believed to be genetically related because of their proximity in time and space. Hydrous minerals in the lamprophyres and the typical absence of plagioclase phenocrysts in both basaltic andesites and andesites reflect the relatively high concentrations of water in the magmas, which suppressed the crystallisation of feldspar. Experimental verification of the minimal amounts of water required to reproduce the phenocryst assemblages in selected rocks range from 3.5 to 6%. During ascent in a volcanic conduit, andesitic magma may lose water and consequently precipitate plagioclase, or it may ascend more rapidly, retaining more of its initial water, which stabilises phenocrysts of hornblende at the expense of plagioclase. Our estimates of water concentrations, which are consistent with the various low pressure phenocryst assemblages, will be minimal for the magmas in their source regions, and the process of magmatic dewatering on ascent may be typical in well established volcanic conduits. In accord with the compositions of phenocrystic olivine in the basaltic andesites and the minettes, the values of FeO and Fe2O3 of the bulk lavas and scoriae are demonstrably pristine. As a consequence, there are two characteristic features of the Mascota suite: the high range of relative oxygen fugacities (ΔNNO=1–5) and the high Mg# (MgO/MgO+FeO) that ranges from 0.70 to 0.91 (with only one andesite as low as 0.66). From the evidence of phlogopite phenocrysts, a partial melt involving phlogopite would have a higher Mg# than one from olivine (Fo90) and pyroxene alone. As the Mascota series shows a correlation between K2O and Mg#, we conclude that it was generated by partial fusion of the mantle wedge, with a variable contribution of phlogopite and apatite from veins throughout the lherzolitic assemblage. In conformity with an origin by varying increments of partial fusion of a phlogopite-bearing mantle, all incompatible elements vary linearly with Ti (or K) as if phlogopite (+apatite) in the source dominated their contribution to the partial melts. Fluids from dehydration of the subducting slab presumably deposit hydrous and other minerals in veins in the mantle wedge and also increase its redox state. As the Mascota volcanism occurs in grabens closer to the trench than the main andesite arc, it is concluded that the eruption of these small volumes of hydrous magmas require the tectonically favored ascent paths offered by the extensional grabens to reach the surface from their mantle sources.
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  • 5
    ISSN: 1432-0967
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences
    Notes: Abstract  Alkali basalts and nephelinites from the volcanic province of northern Tanzania contain pyroxene and nepheline that show evidence for chemical and/or isotopic disequilibria with their host magmas. Olivine, pyroxene, nepheline and plagioclase all appear to be partially xenocrystic in origin. Five whole rock/mineral separate pairs have been analyzed for Sr, Nd, and Pb isotopic compositions. The 206Pb/204Pb ratios are distinct by as much as 20.94 (whole rock) vs. 19.10 (clinopyroxene separate). The Sr and Nd isotopic disequilibria vary from insignificant in the case of nepheline, to Δ 87Sr/86Sr of 0.0002 and ΔɛNd of 0.7 in the case of clinopyroxene. The mineral chemistry of 25 samples indicates the ubiquitous presence of minerals that did not crystallize from a liquid represented by the host rock. The northern Tanzanian magmas are peralkaline and exhibit none of the xenocrystic phases expected from crustal assimilation. The disequilibria cannot be the result of mantle source variations. Rather the xenocrystic phases present appear to have been derived from earlier alkali basaltic rocks or magmas that were contaminated by the crust. Material from this earlier magma was then mixed with batches of magma that subsequently erupted on the surface. Disequilibrium in volcanic rocks has potentially serious consequences for the use of whole rock data to identify source reservoirs. However, mass balance calculations reveal that the 206Pb/204Pb isotopic compositions of the erupted lavas were changed by less than 0.25% as a result of this indirect crustal contamination.
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Physics and chemistry of minerals 26 (1998), S. 83-99 
    ISSN: 1432-2021
    Keywords: Key words heat capacity ; silicate glasses ; glass transition ; silicate liquids ; configurational heat capacity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract  The heat capacities of 29 glasses and supercooled liquids in the Na2O-SiO2, Na2O-Al2O3-SiO2, Na2O-(FeO)-Fe2O3-SiO2, and Na2O-TiO2-SiO2 systems were measured in air from 328 to 998 K with a differential scanning calorimeter. The reproducibility of the data determined from multiple heat capacity runs on a single crystal MgO standard is within ± 1% of the accepted values at temperatures ≤ 800 K and within ± 1.5% between 800 and 1000 K. Within the resolution of the data, the heat capacities of sodium silicate and sodium aluminosilicate liquids are temperature independent. Heat capacity data in the supercooled liquid region for the sodium silicates and sodium aluminosilicates were combined and modelled assuming a linear compositional dependence. The derived values for the partial molar heat capacities of Na2O, Al2O3, and SiO2 are 112.35 ± 0.42, 153.16 ± 0.82, and 76.38 ± 0.20 J/gfw · K respectively. The partial molar heat capacities of Fe2O3 and TiO2 could not be determined in the same manner because the heat capacities of the Fe2O3- and TiO2-bearing sodium silicate melts showed varying degrees of negative temperature dependence. The negative temperature dependence to the configurational C P may be related to the occurrence of sub-microscopic domains (relatively polymerized and depolymerized) that break down to a more homogeneous melt structure with increasing temperature. Such an interpretation is consistent with data from in situ Raman, Mössbauer, and X-ray absorption fine structure (XAFS) spectroscopic studies on similar melts.
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Pharmacy world & science 18 (1996), S. 142-147 
    ISSN: 1573-739X
    Keywords: CP20 ; deteriprone ; 1,2-dimethyl-3-hydroxypyrid-4-one ; DMHP ; Iron overload ; L1 ; Oral iron chelator ; Pharmaceutical analysis ; Quality control ; Standardization ; Synthesis ; Transfusional hemosiderosis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The oral iron chelator deferiprone (1,2-dimethyl-3-hydroxypyrid-4-one, DMHP, L1 or CP20) can be a useful drug in patients with transfusional hemosiderosis. From 1987 about 1000 patients in 16 countries have taken this drug on the base of clinical trials or compassionate use. Since this compound is only available as a raw substance, it is important to ascertain its purity before bringing the drug into a pharmaceutical formulation. Because deferiprone is administered chronically and in high doses, intake of potential toxic impurities can be substantial. In this article a proposal for the quality control of deferiprone is presented in the form of a pharmaceutical monograph. This includes the analytical methods required for identification, purity checking and assay. Furthermore the way we synthesized the drug to get hold of it in a pure form is described. This synthesis is also used in manufacturing the drug commercially. The monograph can be used as a guideline for standardization of the quality of deferiprone to be used for further study and treatment.
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Journal of porous materials 1 (1995), S. 139-153 
    ISSN: 1573-4854
    Keywords: microporous ; sol-gel ; silica ; pore size ; adsorption
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Gas physisorption is a generally used technique for the characterization of porous solids. Microporous solids, however, need a different approach compared to mesoporous solids due to enhanced adsorption in pores of molecular dimensions. Therefore, conventional theories and models can not be used. The application of physisorption for microporous solids, and the interpretation of the isotherms is elucidated. Some models presented in literature for pore size assessment in the micropore range are discussed. Based on a number of criteria, the Horváth-Kawazoe model, modified for cylindrical pore geometry, is selected. N2 adsorption measurments on zeolites were performed to calibrate the method and to show the applicability and physical justification. Typical data obtained from experiments on non-supported microporous silica membrane top-layers show that the pore size distribution of these materials is bimodal, with a strong maximum at an effective diameter of 0.5 nm, and a weaker maximum at 0.75 nm.
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Journal of porous materials 2 (1995), S. 141-149 
    ISSN: 1573-4854
    Keywords: sorption ; microporous ; ceramic membranes ; gas separation ; gas transport
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Sorption experiments with H2, CO2, CH4 and iso-C4H10 were performed on microporous SiO2 and SiO2/TiO2 (30 mol% TiO2) non-supported membrane top-layers using volumetric and gravimetric techniques. For silica, the sorption capacity decreases in the order CO2〉iso-C4H10〉CH4〉H2 at temperatures 〈373 K. The isosteric heat of adsorption q st is 23, 24, 10 and 6 kJ·mol−1 for respectively CO2, iso-C4H10, CH4 and H2. The sub-atmospheric adsorption isotherms are of Henry-type for temperatures equal and higher than 348 K for CO2, temperatures higher than 373 K for iso-C4H10, temperatures equal and higher than 194 K for H2 and for temperatures equal and higher than 273 K for CH4. The sorption capacity for the SiO 2/TiO 2 sample was only slightly lower than for silica, as may be expected due to the lower porosity.
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  • 10
    ISSN: 1434-6079
    Keywords: PACS. 42.65.Tg Optical solitons; nonlinear guided waves 42.65.-k Nonlinear optics 52.35.Mw Nonlinear waves and nonlinear wave propagation (including parametric effects, mode coupling, ponderomotive effects, etc.)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract: A two-dimensional axisymmetric model of the propagation of intense femtosecond laser pulses through dispersion-free transparent media is described. The effects of diffraction, nonlinear Kerr effect (instantaneous and retarded) and multiphoton ionisation are included. Numerical results concerning air and other gases are discussed. In particular, time self-compression of femtosecond pulses is predicted. Stable self-guided pulses are simulated, in agreement with recent experimental observations.
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