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  • 1995-1999  (8)
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Origins of life and evolution of the biospheres 25 (1995), S. 539-547 
    ISSN: 1573-0875
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences
    Notes: Abstract We report here on configurational and conformational studies undertaken on the bromofluoro-1,4-benzodiazepinooxazole derivative I, which has previously been found capable of undergoing total spontaneous resolution under racemizing conditions. Due to its bridgehead N-atom I may exist in any of four diastereomeric forms,C r N r (orC s N s ) andC r N s (orC s N r ). Molecular mechanics calculations revealed that in their lowest energy conformations theC r N r (orC s N s ) diastereomers were favored over theC r N s (orC s N r ) diastereomers by some 3.42 kcal/mol, while semi-empirical quantum mechanical calculations indicated heats of formation also favoring theC r N (orC s N s ) diastereomers by 3.83 kcal/mol. The1H NMR spectra of the three crystalline modifications (α, β andγ) of I were examined in acetone, and found to be identical. These data, combined with the results of the above calculations, suggest that I exists in methanol or methanol-acetone solutions as theC r N (orC s N s ) enantiomer prior to its racemization.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Origins of life and evolution of the biospheres 26 (1996), S. 27-45 
    ISSN: 1573-0875
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences
    Notes: Abstract Historically, parity violation at the contemporary biomolecular level (i.e., only L-amino acids in proteins and D-sugars in DNA and RNA) has been postulated to be the inevitable result of parity violations at the elementary particle level, involving eitherβ-decay electrons or parity violating energy differences (PVEDs)between enantiomers. These two chiral biases have in turn allegedly impressed a small but persistent chirality onto prebiotic chemistry which, after appropriate amplification, has culminated in our contemporary homochiral biopolymers. Experiments and controversies pertaining to the efficacy of these two chiral biases are reviewed briefly, with the conclusions that: a) there is no experimental evidence supporting the capability ofβ-decay electrons or other spinpolarized chiral particles to generate chiral molecules, and b) only theoretical calculations, but no experimental evidence, support the allegation of a causal relation between PVEDs and biomolecular homochirality. We here attempt to examine the latter allegation experimentally. Spontaneous resolution under racemization conditions (SRURC) during the crystallization of the bromofluoro-1,4-benzodiazepinooxazole derivativeI is capable of affording products of high enantiomeric purity. This process, which involves very efficient stereoselective autocatalysis, has now been examined statistically. If PVED effects are operative, the SRURC of racemicI should provide, either exclusively or with a strong and consistent bias, only one enantiomer of crystallineI. However, crystallization experiments of racemicI showed no bias in its SRURC, leading to the conclusion that PVED effects are ineffective in dictating a preferred chirality in this system. Several earlier experiments in the literature leading to a similar conclusion as to the inefficacy of PVED effects in promoting a preferred chirality are noted.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Origins of life and evolution of the biospheres 25 (1995), S. 175-190 
    ISSN: 1573-0875
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences
    Notes: Abstract The crucial role of homochirality and chiral homogeneity in the self-replication of contemporary biopolymers is emphasized, and the experimentally demonstrated advantages of these chirality attributes in simpler polymeric systems are summarized. The implausibility of life without chirality and hence of a biogenic scenario for the origin of chiral molecules is stressed, and chance and determinate abiotic mechanisms for the origin of chirality are reviewed briefly in the context of their potential viability on the primitive Earth. It is concluded that all such mechanisms would be non-viable, and that the turbulent prebiotic environment would require an ongoing extraterrestrial source for the accumulation of chiral molecules on the primitive Earth. A scenario is described wherein the circularly polarized ultraviolet synchrotron radiation from the neutron star remnants of supernovae engenders asymmetric photolysis of the racemic constituents in the organic mantles on interstellar dust grains, whereupon these chiral constituents are transported repetitively to the primative Earth by direct accretion of the interstellar dust or through impacts of comets and asteroids.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Origins of life and evolution of the biospheres 25 (1995), S. 401-414 
    ISSN: 1573-0875
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences
    Notes: Abstract Since the bromofluoro-1,4-benzodiazepinooxazole derivativeI may undergo spontaneous resolution on crystallization from methanol solution, it provides an ideal substrate on which to study the phenomenon of enantioselective autocatalysis involving spontaneous resolution under racemizing conditions (srurc). in order to augment the understanding of factors which might be important in such a process we have now undertaken to study the racemization ofI in more detail by observing its rate under a wide variety of experimental conditions.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Origins of life and evolution of the biospheres 29 (1999), S. 215-219 
    ISSN: 1573-0875
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences
    Notes: Abstract Having concluded that abiotic terrestrial mechanisms would have been ineffectual for the origin of terrestrial homochirality, we have proposed an alternative extraterrestrial scenario involving stereoselective ultraviolet photolysis of the racemic constituents of interstellar grain mantles by circularly polarized synchrotron radiation from neutron stars, followed by terrestrial accretion of the resulting chiral molecules via cometary impact. Recently L. Keszthelyi (1995) has reviewed a number of our arguments and advanced several erroneous calculations and conclusions purporting to negate them. We offer here points of rebuttal to Keszthelyi's criticisms, and support our inferences with recent data regarding indigenous enantiomeric excesses of L-amino acids in the Murchison meteorite.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Origins of life and evolution of the biospheres 29 (1999), S. 329-332 
    ISSN: 1573-0875
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences
    Notes: Abstract Recent investigations of stable isotope ratios of amino acids from the Murchison meteorite have shown them to be of unambiguous extraterrestrial origin, and examinations of their enantiomeric compositions, where terrestrial contamination can be excluded, have found a consistent excess of L-enantiomers. One explanation for this observation has been the asymmetric photolysis of racemic extraterrestrial amino acids by circularly polarized light (CPL) in the synchrotron radiation from orbiting electrons around the pulsar remnants of supernovae. Mason (1997) has attempted to discredit this mechanism on the grounds that circular dichroism (CD) bands for optically active molecules alternate in sign and sum to zero over the entire spectrum, and hence enantioselective photochemical reactions cannot be induced by broad band CPL. We submit arguments disputing this conclusion and present reasons for expecting that broad band CPL synchrotron radiation would be quite capable of inducing asymmetric photolysis, particularly in aliphatic amino acids.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Origins of life and evolution of the biospheres 29 (1999), S. 317-328 
    ISSN: 1573-0875
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences
    Notes: Abstract We have attempted to appraise experimentally the allegation that minute chemical and physical differences due to the parity violating energy difference (PVED) between enantiomers are, after suitable autocatalytic amplification, ultimately responsible for the homochirality of contemporary biomolecules. The autocatalytic amplification technique employed involved the spontaneous resolution under racemizing conditions (SRURC) of a conglomerate during crystallization, and the system studied was the known crystallization of P(+)- or M(–)-tri-o-thymotide (TOT) as its optically active inclusion compound (clathrate) with benzene. Our premise was that if a PVED effect were operative, there should be a strong and consistent bias favoring the crystallization of one enantiomer of the TOT-benzene clathrate. Repetitive preparations of the clathrate, however, yielded crystalline products showing random optical activity. These results thus afford no evidence whatsoever for stereoselective bias due to a PVED, and are in accord with earlier statistical studies demonstrating random SRURC in other conglomerate crystallizations, again indicating the inefficacy of PVEDs to promote a preferred chirality in such systems.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Origins of life and evolution of the biospheres 29 (1999), S. 615-624 
    ISSN: 1573-0875
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences
    Notes: Abstract The chirality amplification mechanism proposed by Yamagata in 1966, relying on an Accumulation Principle which involved the parity violating energy difference (1 + ε) presumed to be operative at each step in the formation of a homochiral biopolymer, is briefly surveyed historically. The Accumulation Principle is then examined analytically and found to be incapable of producing a unique homochiral polymer in any realistic polymerization process. The extension of the Accumulation Principle to crystallizations which afford enantiomorphic crystals is also scrutinized and found to be misapplied and invalid.
    Type of Medium: Electronic Resource
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