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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
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 24 (1985), S. 1863-1879 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Molecular mechanical calculations were done on complexes of ethidium cation with various base-paired deoxydinucleoside monophosphates [(ApT)2, (TpA)2, (A2 · T2), (GpC)2, (CpG)2, and (G2 · C2)] and deoxyhexanucleoside pentaphosphates [(ATATAT)2, (TATATA)2, (A6 · T6), (GCGCGC)2, (CGCGCG)2, and G6 · C6]. Relative binding energies, sequence preferences, and conformational aspects of the intercalation complexes were studied. The most detailed models used (an all-atom force field) gave results in good agreement with previous calculations and experimental work. Less-sophisticated models did not perform as well.
    Additional Material: 5 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 39 (1996), S. 591-614 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Molecular dynamics simulations of the water-solvated, β-hairpin-forming linear peptide Y-Q-N-P-D-G-S-Q-A (one-letter amino acid code) [F. J. Blanco et al. (1993) J. Am. Chem. Soc. 115, 5887-5888] were performed at simulation temperatures of 278 K and 270 K. At 278 K, the overall β-hairpin state remained stable for approximately 2.06 ns, after which it underwent an unfolding transition to a more disordered, random coil-like state that was maintained for the remainder of the 3.50-ns simulation. A comparison of experimental Hα-Cα order parameters determined at 278 K with order parameters derived from the simulation revealed that the β-hairpin state is consistent with the experimental results, whereas the random coil-like state yields order parameters that are all much lower than the experimental values. This indicates that the random coil-like state is not highly populated in the experimental system. An examination of the dynamic behavior of the simulated peptide/solvent system indicated that a lower temperature may yield a more stable trajectory. At 270 K, the β-hairpin conformation remained stable for approximately 2.32 ns, after which the peptide again unfolded and maintained a less-ordered state for the remainder of the 3.50-ns simulation. The less-ordered state observed at 270 K is more compact than the disordered state observed at 278 K; the former may represent a folding intermediate. The folded state is stabilized primarily by a number of transient hydrogen bonding interactions, including hydrogen bonds between Tyr-1 O and Ala-9 HN, between Asn-3 HN and Ser-7 O, and between the side chain of Asn-3 and backbone groups of Asp-5, Gly-6, and Ser-7. The 270 K simulation was restarted at 2.10 ns, with a single loose nuclear Over-hauser effect (NOE) upper-bound distance restraint of 5.5 Å added between Gln-2 Hα and Gln-8 Hα. This single restraint maintained folded conformations for the remaining 10.50 ns of the trajectory. The restraint was frequently violated (i.e., the restraint potential frequently took on nonzero values) during the period between about 0.24 and 6.51 ns of the restrained trajectory. Between about 6.51 and 8.04 ns of the restrained trajectory, the restraint remained well-satisfied, demonstrating a transiently stable, alternate-folded conformational state during this period. These results indicate that even long (by today's standards), ∼ 1 ns timescale trajectories may not always be sufficient to prove the long-term stability of the native state in simulations of biomolecules, and that apparently converged states may only be metastable. © 1996 John Wiley & Sons, Inc.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 33 (1993), S. 1631-1641 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have obtained the UV excited resonance Raman spectra of five mononucleotides bound to cisplatin and to carboplatin using excitation in resonance with the first electronic absorption bands of the nucleotide bases. Substantial changes in the spectra are observed following interaction with both platinum drugs, indicating modifications to nucleotide structure. Pt (II) binds to base portions of the nucleotide molecules, altering their normal modes of vibration significantly. We present comparative data of cisplatin and carboplatin, and discuss the implications of these results. The kinetics of the drug/nucleotide reactions differ, but final products are found to be similar. © 1993 John Wiley & Sons, Inc.
    Additional Material: 10 Ill.
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  • 6
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title compound 4 was prepared in 54% overall yield from eucarvone (5). On triplet sensitization 4 gives two products resulting from a 1,2-acyl shift (8 and 9), whereas singlet excitation of 4 causes decarbonylation and ketene elimination (4 → 10 and 11).
    Additional Material: 1 Ill.
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  • 7
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and photolysis of the spirocyclobutanones 4-7 incorporating a cyclohexa-, cyclohepta- and cyclooctadiene moiety, respectively, is described. On triplet excitation, these compounds undergo isomerization via a 1,2-acyl shift involving one or both double bonds of the diene system. The presence of a gem-dimethyl group as in 1, 4 and 7 dramatically changes the photoproduct distribution, since only these substrates leads to the products 3, 29 and 34 resulting from vinylogous ring closure (Scheme 5). Those substrates without methyl substitution (5 and 6) give only products of a rearrangement involving one double bond.
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  • 8
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: On 1n,π*-excitation, the title compound 2 undergoes a photoinduced intramolecular [4 + 2]-cycloaddition affording the tetracyclic enol ether 3 as the only product in 79% yield. The assigned structure of 3 was confirmed by its conversion to the p-nitrobenzoate 6 whose structure was determined by X-ray analysis.
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  • 9
    ISSN: 0887-6134
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Like most dyes, Basic Yellow 2 (BY-2) fades upon prolonged exposure to light. Light-induced fading is a complex process that is also affected by heat and humidity. In order to better understand the photodegradation process and to identify the various photodegradation products of BY-2, fabric samples and solutions containing BY-2 were exposed to a variety of fading conditions. The analysis of faded BY-2 dyed fabric extracts by high-performance liquid chromatography/mass spectrometry (HPLC/MS) indicated the reduction and hydrolysis of the C=NH2+ group to form primarily benzophenone derivatives, as well as various demethylated products. Due to the absence of fragmentation in the thermospray spectra (only [M + H]+ ions were observed) the dye extracts were analyzed by gas chromatography/mass spectrometry (GC/MS) to confirm the identity of the degradation products. Many of the degradation products were sufficiently volatile for analysis by GC/MS. Mass spectra of the photodegradation products of BY-2 exhibited molecular ions and structurally important fragment ions to complement the thermospray data. The mass spectral data indicated that the most prevalent degradation product formed was ((CH3)2NC6H4)2C=0 (Michler's ketone). Hydrolysis of the C=NH2+ group to C=0 is the main color-destroying reaction in the fading of BY-2. Demethylation products which can alter the shades of color were also detected in the faded BY-2 samples.
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  • 10
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 759-767 
    ISSN: 0887-624X
    Keywords: oligoetherimide ; cyclic oligomer ; macrocyclic imide ; bisphenol silylether ; fluorophthalimide ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Macrocyclic oligoetherimides were synthesized by means of Kricheldorf's nucleophilic aromatic substitution polycondensation. A solution containing equimolar quantities of bis(trimethylsilyl ether) of bisphenol and arylenebis(fluorophthalimide) was continuously added into a high boiling solvent containing CsF catalyst under a pseudo-high dilution condition. The resulting reaction mixture contained a high yield of cyclic oligomers which could be isolated by solvent extraction. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 759-767, 1997
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