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On the Prebiotic Synthesis of D-Sugars Catalyzed by L-Peptides: Assessments from First-Principles Calculations

Authors

  • Dr. David Cantillo,

    Corresponding author
    1. Department of Organic and Inorganic Chemistry, University of Extremadura, Avda. de Elvas s/n, 06006 Badajoz (Spain)
    2. Current address: Christian Doppler Laboratory for Microwave Chemistry, Institute of Chemistry, Karl-Franzens University Graz, 8010 Graz (Austria)
    • Department of Organic and Inorganic Chemistry, University of Extremadura, Avda. de Elvas s/n, 06006 Badajoz (Spain)
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  • Prof. Martín Ávalos,

    1. Department of Organic and Inorganic Chemistry, University of Extremadura, Avda. de Elvas s/n, 06006 Badajoz (Spain)
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  • Prof. Reyes Babiano,

    1. Department of Organic and Inorganic Chemistry, University of Extremadura, Avda. de Elvas s/n, 06006 Badajoz (Spain)
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  • Prof. Pedro Cintas,

    1. Department of Organic and Inorganic Chemistry, University of Extremadura, Avda. de Elvas s/n, 06006 Badajoz (Spain)
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  • Prof. José L. Jiménez,

    1. Department of Organic and Inorganic Chemistry, University of Extremadura, Avda. de Elvas s/n, 06006 Badajoz (Spain)
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  • Prof. Juan C. Palacios

    1. Department of Organic and Inorganic Chemistry, University of Extremadura, Avda. de Elvas s/n, 06006 Badajoz (Spain)
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Abstract

What accounts for a particular chiral selection in the case of a few sugars of prebiotic relevance, thereby mirroring the asymmetry observed in nature? By using first-principles calculations, the generation of pentoses from glycolaldehyde (the initial product of the autocatalytic formose reaction), which has been detected in outer space), has been modeled by using L-Val-L-Val as a primeval catalyst. Our theoretical study provides insight into the mechanism of this reaction and satisfactorily explains a few key molecular events. Our rationale agrees with the reported experimental data and shows that the D-configuration is only favored for ribose. L-pentoses are usually favored in the presence of L-configured dipeptides, as observed experimentally, although no chiral selection could be observed in the case of xylose. These results confirm that a prebiotic sugar soup could be fine-tuned in the presence of shorter peptides as catalysts and that D-ribose would have also resulted in an advantageous imbalance for further amplification and chemical evolution.

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