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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Journal of molecular evolution 15 (1980), S. 21-28 
    ISSN: 1432-1432
    Keywords: β-radiolysis ; Asymmetric radiolysis ; Vester-Ulbricht Hypothesis ; Origin of optical activity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary We have extended earlier experiments on the radiolysis of DL-tryptophan using32Pβ-radiation to longer reaction times, observing complete destruction of the tryptophan by secondary, non-radiolytic processes. We have also undertaken the irradiation of DL-leucine with32Pβ's at -196°, achieving radiolyses to the extents of ca. 20–30%, but observing no concomittant asymmetric bias. The implications of these observations are discussed with regard to the Vester-Ulbricht mechanism for the origin of optical activity.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Journal of the American Chemical Society 101 (1979), S. 1049-1050 
    ISSN: 1520-5126
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Origins of life and evolution of the biospheres 10 (1980), S. 255-263 
    ISSN: 1573-0875
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences
    Notes: Abstract By way of investigating possible mechanisms for the abiotic amplification of small enantiomeric excesses (e.e.'s) in almost racemic mixtures of amino acid enantiomers, we have undertaken a quantitative study of the base-initiated partial polymerization of leucine and valineN-carboxy-anhydride (NCA) enantiomer mixtures containing known excesses of both theR- andS-forms. Polymerization to the extent ofca. 50% of leucine NCA having an 8–70% e.e. of either theR- orS-enantiomer led to an e.e. enhancement in the polymer, which contained a 12–84% e.e. of that enantiomer which predominated in the original monomer NCA. A corresponding decrease in the e.e. of the initially predominant enantiomer was noted in the unpolymerized residue from each reaction. Polymerization to the extent of 25–50% of mixtures of valine NCA enantiomers containing a 12–13% e.e. of eitherR- orS-isomer led to polymers showing a 7–8%decrease in the e.e. of the initially predominant enantiomer, and to an increase of its e.e. in the unpolymerized residue. These divergent results, the latter of which is quite novel, are compared with earlier qualitative results in the literature and are discussed briefly from the viewpoint of both mechanism and the amplification of optical activity.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Geo-marine letters 16 (1996), S. 3-10 
    ISSN: 1432-1157
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences
    Notes: Abstract Early diagenetic properties of Amazon shelf muds are dominated by nonsulfidic Fe and Mn cycling, resulting in relatively little S deposition compared to previously studied marine margin environments. Despite abundant potential reactants typical of sulfidic deposits, authigenic sulfides represent only ~ 10% of diagenetically reduced Fe, and DOP (degree of pyritization) is only ~0.02. The average C/S (wt wt−1) ratio of buried sediment below the zone of SO4 2- reduction is ~ 7.4, ~ 2.6 times more than the commonly assumed modern shelf average of ~ 2.8. The deltaic burial rate forΣS is ~ 0.65 × 106 tons yr−1. Relatively lowΣS deposition is promoted by terrestrial weathering that delivers reactive oxide debris, but apparently depends most strongly on reoxidation and rapid burial by intense physical reworking and fluid-mud formation. Diagenetic models of S distributions demonstrate rapid sediment reworking (~ 10–100 cm yr−1 as apparent advection), substantialΣS reoxidation (84–98%), and in one case, massive sediment deposition of up to ~ 5 m of sediment in ~ 1 year. Extremely low DOP coupled with dominance by nonsulfidic reduced-Fe minerals and lack of biogenic sedimentary structures may be an indicator in marine organic-rich muds of intense physical reworking under oxygenated waters.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Origins of life and evolution of the biospheres 11 (1981), S. 331-335 
    ISSN: 1573-0875
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences
    Notes: Abstract A mixture of D- and L-leucine N-Carboxyanhydride (NCA) having an enantiomeric composition of 65.6% L- and 34.4% D-isomer (i.e. 31.2% enantiomeric excess (e.e.)) was polymerized to the extent of 52% with sodium methoxide initiator to yield a polyleucine product the enantiomeric composition of which was 72.7% L- and 27.3% D-leucine (45.4% e.e.). This polymer was in turn partially hydrolyzed by acid, whereupon the unhydrolyzed polyleucine residue was found to have an enantiomeric composition of 77.5% L- and 22.5% D-leucine (55.0% e.e.). Thus the e.e. increase in the partial polymerization step (14.2%) and the partial hydrolysis step (9.6%) combined to total 23.8% for the overall polymerization-hydrolysis sequence. On the basis of these model experiments it is proposed that repetitive partial polymerization hydrolysis reactions, driven by environmental dry-wet cycles, might have been operative on the primitive Earth to engender the abiotic evolution of optically enriched polypeptides.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Origins of life and evolution of the biospheres 9 (1979), S. 279-290 
    ISSN: 1573-0875
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences
    Notes: Abstract A number of optically active amino acids, both in the solid state and as sodium or hydrochloride salts in aqueous solution, have been exposed to ionizing radiation from a 3000 Ci60Co γ-ray source to see if radioracemization might accompany their well-known radiolysis. γ-Ray doses causing 55–68% radiolysis of solid amino acids typically engendered 2–5% racemization, while aqueous solutions of the sodium salts of amino acids which underwent 53–66% radiolysis showed 5–11% racemization. Amino acid hydrochloride salts in aqueous solution, on the other hand, showed little or no radioracemization accompanying their radiolysis. Both radiolysis, and radioracemization were roughly proportional to γ-ray dose in the range studied (1–36×106 rads). Mechanisms for the radioracemization of amino acids in the solid state and as aqueous sodium salts are discussed, and the absence of radioracemization for aqueous hydrochloride salts is rationalized. Isovaline, a non-protein amino acid which has been isolated from the Murchison meteorite, contains no α-hydrogen atom and is therefore incapable of racemizationvia the chemical mechanisms by which ordinary amino acids racemize. Nevertheless, isovaline suffers radioracemization in the solid state to an extent comparable to that shown by ordinary amino acids, as do its sodium and hydrochloride salts in the solid state. The sodium salt of isovaline in aqueous solution, however, fails to racemize during its radiolysis. Several implicaitons of the newly described phenomenon of radiomization are pointed out for the fields of geochemistry and cosmochemistry.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Origins of life and evolution of the biospheres 11 (1981), S. 119-134 
    ISSN: 1573-0875
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences
    Notes: Abstract Our earlier experiments are briefly reviewed, involving the abiotic generation of optical activity by exposure of DL-amino acids to various “chiral” physical forces. The enantiomeric enrichments so obtained were low, however, and additional experiments were undertaken with the objective of abiotically enhancing such small enantiomeric excesses. D≠L Mixtures of leucine N-carboxy anhydride gave enantiomerically enriched polymers on partial polymerization, while valine NCA mixtures behaved oppositely. Leucine polymers were also found to hydrolyze stereoselectively, providing for additional enantiomenic enhancement. A repetitive sequence of partial polymerization-hydrolysis steps is suggested as a possible mechanism for the abiotic genesis of optically enriched polypeptides on the primitive Earth.
    Type of Medium: Electronic Resource
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  • 8
    Publication Date: 1979-02-01
    Print ISSN: 0002-7863
    Electronic ISSN: 1520-5126
    Topics: Chemistry and Pharmacology
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  • 9
    Publication Date: 2005-01-01
    Print ISSN: 0021-8561
    Electronic ISSN: 1520-5118
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Process Engineering, Biotechnology, Nutrition Technology
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  • 10
    Publication Date: 2004-12-01
    Print ISSN: 0304-4203
    Electronic ISSN: 1872-7581
    Topics: Geosciences
    Published by Elsevier
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