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  • 1
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    NOAA/National Ocean Service/National Centers for Coastal Ocean Science | Silver Spring, MD
    In:  http://aquaticcommons.org/id/eprint/2199 | 403 | 2011-09-29 19:28:38 | 2199 | United States National Ocean Service
    Publication Date: 2021-07-12
    Description: The toxicity of sediments in Biscayne Bay and many adjoining tributaries was determined as part of a bioeffects assessments program managed by NOAA’s National Status and Trends Program. The objectives of the survey were to determine: (1) the incidence and degree of toxicity of sediments throughout the study area; (2) the spatial patterns (or gradients) in chemical contamination and toxicity, if any, throughout the study area; (3) thespatial extent of chemical contamination and toxicity; and (4) the statistical relationships between measures of toxicity and concentrations of chemicals in the sediments.The survey was designed to characterize sediment quality throughout the greater Biscayne Bay area. Surficial sediment samples were collected during 1995 and 1996 from 226 randomly-chosen locations throughout nine major regions. Laboratory toxicity tests were performed as indicators of potential ecotoxicological effects in sediments. A battery of tests was performed to generate information from different phases (components) of the sediments. Tests were selected to represent a range in toxicological endpoints from acute to chronic sublethal responses. Toxicological tests were conducted to measure: reduced survival of adult amphipods exposed to solid-phase sediments; impaired fertilization success and abnormal morphological development in gametes and embryos, respectively, of sea urchins exposed to pore waters; reduced metabolic activity of a marine bioluminescentbacteria exposed to organic solvent extracts; induction of a cytochrome P-450 reporter gene system in exposures to solvent extracts; and reduced reproductive success in marine copepods exposed to solid-phase sediments.Contamination and toxicity were most severe in several peripheral canals and tributaries, including the lower Miami River, adjoining the main axis of the bay. In the open basins of the bay, chemical concentrations and toxicity generally were higher in areas north of theRickenbacker Causeway than south of it. Sediments from the main basins of the bay generally were less toxic than those from the adjoining tributaries and canals. The differenttoxicity tests, however, indicated differences in severity, incidence, spatial patterns, and spatial extent in toxicity. The most sensitive test among those performed on all samples, a bioassay of normal morphological development of sea urchin embryos, indicated toxicity was pervasive throughout the entire study area. The least sensitive test, an acute bioassay performed with a benthic amphipod, indicated toxicity was restricted to a very small percentageof the area.Both the degree and spatial extent of chemical contamination and toxicity in this study area were similar to or less severe than those observed in many other areas in the U.S. The spatial extent of toxicity in all four tests performed throughout the bay were comparable tothe “national averages” calculated by NOAA from previous surveys conducted in a similar manner.Several trace metals occurred in concentrations in excess of those expected in reference sediments. Mixtures of substances, including pesticides, petroleum constituents, trace metals, and ammonia, were associated statistically with the measures of toxicity. Substances most elevated in concentration relative to numerical guidelines and associated with toxicity included polychlorinated biphenyls, DDT pesticides, polynuclear aromatic hydrocarbons, hexachloro cyclohexanes, lead, and mercury. These (and other) substances occurred in concentrations greater than effects-based guidelines in the samples that were most toxic in one or more of the tests. (PDF contains 180 pages)
    Description: Center for Coastal Monitoring and Assessment
    Keywords: Ecology ; Pollution ; Chemistry
    Repository Name: AquaDocs
    Type: monograph
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  • 2
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    NOAA/National Ocean Service/National Centers for Coastal Ocean Science | Silver Spring, MD
    In:  http://aquaticcommons.org/id/eprint/2200 | 403 | 2011-09-29 19:28:23 | 2200 | United States National Ocean Service
    Publication Date: 2021-07-12
    Description: The toxicity of sediments in Sabine Lake, Texas, and adjoining Intracoastal Waterway canals was determined as part of bioeffects assessment studies managed by NOAA’s National Status and Trends Program. The objectives of the survey were to determine: (1) the incidence and degree of toxicity of sediments throughout the study area; (2) the spatial patterns (or gradients) in chemical contamination and toxicity, if any, throughout the study area; (3) the spatial extent of chemical contamination and toxicity; and (4) the statistical relationships between measures of toxicity and concentrations of chemicals in the sediments.Surficial sediment samples were collected during August, 1995 from 66 randomly-chosen locations. Laboratory toxicity tests were performed as indicators of potential ecotoxicological effects in sediments. A battery of tests was performed to generate information from different phases (components) of the sediments. Tests were selected to represent a range in toxicological endpoints from acute to chronic sublethal responses. Toxicological tests were conducted to measure: reduced survival of adult amphipods exposed to solid-phase sediments; impaired fertilization success and abnormal morphological development in gametes and embryos, respectively, of sea urchins exposed to pore waters; reduced metabolic activity of a marine bioluminescent bacteria exposed to organic solvent extracts; and induction of a cytochrome P-450 reporter gene system in exposures to solvent extracts of the sediments.Chemical analyses were performed on portions of each sample to quantify the concentrations of trace metals, polynuclear aromatic hydrocarbons, and chlorinated organic compounds. Correlation analyses were conducted to determine the relationships between measures of toxicity and concentrations of potentially toxic substances in the samples.Based upon the compilation of results from chemical analyses and toxicity tests, the quality of sediments in Sabine Lake and vicinity did not appear to be severely degraded. Chemical concentrations rarely exceeded effects-based numerical guidelines, suggesting that toxicant-induced effects would not be expected in most areas. None of the samples was highly toxic in acute amphipod survival tests and a minority (23%) of samples were highly toxic in sublethal urchin fertilization tests. Although toxic responses occurred frequently (94% of samples) in urchin embryo development tests performed with 100% pore waters, toxicity diminished markedly in tests done with diluted pore waters. Microbial bioluminescent activity was not reduced to a great degree (no EC50 〈0.06 mg/ml) and cytochrome P-450 activity was not highly induced (6 samples exceeded 37.1 ug/g benzo[a]pyrene equivalents) in tests done with organic solvent extracts. Urchin embryological development was highly correlated with concentrations of ammonia and many trace metals. Cytochrome P450 induction was highly correlated with concentrations of a number of classes of organic compounds (including the polynuclear aromatic hydrocarbons and chlorinated compounds). (PDF contains 51 pages)
    Description: Center for Coastal Monitoring and Assessment
    Keywords: Ecology ; Pollution ; Chemistry
    Repository Name: AquaDocs
    Type: monograph
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  • 3
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Di-p-hydrido-bis[1,3-propanbis(dicyclohexylphosphin)]dinickel(Ni—Ni) - Der Bindungszustand in einem Dreizentren-Wasserstoff-überbrückten Ni—Ni-SystemDie Kristallstruktur der Titelverbindung [(C6H11)2PCH2CH2CH2P(C6H11)2NiH]2 (1) wurde aus 4051 Reflexen abgeleitet und zu einem R-Wert von 0.044 verfeinert. Lageparameter aller Wasserstoffatome konnten einer Differenz-Fourier-Synthese entnommen werden. Die Struktur der diamagnetischen Verbindung setzt sich aus zwei P2Ni-Untereinheiten zusammen, welche zweifach mit Wasserstoffatomen (Ni—H 1.6 Å) überbrückt sind. Hierdurch ergibt sich ein bindender Ni—Ni-Abstand von 2.441(1) Å. Im Kristallgitter bilden die Ebenen durch die P2Ni-Untereinheiten einen Interplanarwinkel von 63.3°. Theoretische Betrachtungen sagen für das freie Molekül eine quadratisch planare Anordnung voraus, doch ergibt sich für die Drehbewegung zur beobachteten Geometrie nur eine flache Potentialenergiefläche. Die gefundene Verdrillung resultiert aus starken intramolekularen Abstoßungskräften zwischen den Cyclohexylgruppen der zwei P2Ni-Einheiten.
    Notes: The crystal structure of the title compound, [(C6H11)2PCH2CH2CH2P(C6H11)2NiH]2 (1), has been determined from 4051 reflections and refined to a final R-value of 0.044. The positions of the hydrogen atoms (bridging and non-bridging) have been determined from a difference Fourier synthesis. The molecular structure of the diamagnetic compound consists of subunits doubly-bridged by hydrogen atoms. The Ni—Ni and average Ni—H distances are 2.441 and 1.6 Å, respectively. In the solid state the two planes of the P2Ni units form a dihedral angle of 63.3°. Theoretical considerations predict a square-planar structure for the idealized molecule with a soft potential energy surface for a twisting motion towards the observed geometry. The observed twist is the result of severe intramolecular repulsions between the cyclohexyl groups of the two P2Ni units.
    Additional Material: 2 Ill.
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  • 4
    ISSN: 1022-1344
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The semiclassical spectral method (SSM), which employs molecular dynamics and spectral estimators to determine transition frequencies between quantum energy levels in molecular and atomic systems, is extended to include calculations for linear polymer chains. Average differences between harmonic and transition frequencies for the symmetric and asymmetric stretch modes of polyethylene are reported to be around 50 cm-1 with smaller average frequency shifts for the other group vibration dispersion curves for a certain potential surface describing the macromolecule.
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  • 5
    ISSN: 1022-1344
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: When three atoms in a bend sequence move into a linear configuration, any torsional angle involving those three atoms becomes undefined and its Cartesian derivatives singular. In molecular dynamics simulations, this is most likely to occur during and after a bond-breaking process, leading to spuriously large torsional forces and energies which invalidate the simulation. By including appropriate bend angle switching functions in torsional interaction terms, one may approach the linear bend limit in a well-defined manner and make torsional forces vanish around this limit, as expected on physical grounds. Although this expense can be greatly reduced by observing that any internal force must not move the center of mass of the particles involved. Several approximations explored in this paper can reduce this effort even further.
    Additional Material: 2 Ill.
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  • 6
    ISSN: 1022-1344
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In a recent study we found the classical dynamics of a polyethylene (PE) chain to exhibit low dimensional chaos at temperatures as low as a few Kelvin. These results strongly suggest that classical molecular dynamic simulations in polymer systems can grossly overestimate vibrational motion, which consequently results in disordered structures. In contrast, quantum mechanical calculations using Internal Coordinate Quantum Monte Carlo (an improved method with an initial conjecture for the correct wave function) indicate that the quantum ground state for a three-dimensional model PE chain is far more rigid than determined from molecular dynamics (MD) simulations, even at energies as low as a small fraction of the ground state energy. This result casts uncertainty on the reliability of MD estimates of dynamical or structural quantities relevant to the study of some macromolecular systems.
    Additional Material: 3 Ill.
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  • 7
    ISSN: 1075-4261
    Keywords: X-ray photoelectron spectroscopy ; surface analysis ; MUC1 mucin ; structure ; glycosylation ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Physics
    Notes: X-ray photoelectron spectroscopy (XPS) is a surface sensitive analytical technique that measures the binding energy of electrons in atoms and molecules on the surface of a material. XPS was used to determine the distribution of the oligosaccharide side chains in the glycoprotein, MUC1 mucin. Low-resolution XPS spectra provided elemental composition of MUC1 mucin (fully glycosylated), mucin polypeptide (nonglycosylated), and carbohydrates found in mucin. The nitrogen content of MUC1 mucin was determined to be intermediate between the mucin polypeptide and the carbohydrates. Assuming a uniform distribution of carbohydrate on MUC1 mucin, the average thickness of the carbohydrate layer was calculated to be 4.9 nm using the low-resolution N 1s signals. High-resolution XPS spectra give detailed information about the chemical bonding of the surface molecules. Calculations based on the high-resolution O 1s spectra showed a carbohydrate thickness of 6.6 nm. These experimentally determined values agree reasonably well with an estimated 5 nm of carbohydrate thickness from a simple model which assume that the core protein is a rodlike molecule approximately 5 nm in diameter. Although the carbohydrate coating on the MUC1 mucin appears to be thick enough to cover the core protein entirely, fully glycosylated breast milk MUC1 mucin is susceptible to proteolytic digestion without removal of any oligosaccharide side chain, suggesting areas of exposed core protein. A possible explanation is that the oligosaccharide side chains may form patches of carbohydrate along the core protein with regions of exposed core protein. © 1998 John Wiley & Sons, Inc. Biospectroscopy 4: 257-266, 1998
    Additional Material: 7 Ill.
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  • 8
    ISSN: 0306-042X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Key steps in a proposed automated system for polypeptide sequencing utilizing a liquid chromatograph mass spectrometer computer system have been tested with mixtures containing up to six model oligopeptides. At the low nanomole level it was possible to obtain complete sequence information for all components in many, but not all, of the mixtures tried. Interpretation of the results is complicated by the presence of numerous side-products formed in the derivatization process. Minimization of such impurities will be necessary to reduce the ambiguity of the sequence information resulting from more complex mixtures, such as those expected from the degradation of larger polypeptides, and to reduce sample requirements to the subnanomole level. However, the present system appears to have unique advantages over other proposed automated methods.
    Additional Material: 5 Ill.
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  • 9
    ISSN: 0173-2803
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Basel : Wiley-Blackwell
    Die Makromolekulare Chemie, Rapid Communications 10 (1989), S. 377-381 
    ISSN: 0173-2803
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
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