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Transketolase reaction under credible prebiotic conditions
Ronald Breslow1, Chandrakumar Appayee
1Department of Chemistry, Columbia University, New York, NY 10027, USA. rb33@columbia.edu
Prebiotic chemistry reveals cyanide ion, not thiamine pyrophosphate (TPP), catalyzed early transketolase reactions. This suggests simpler, cyanide-driven sugar synthesis before the evolution of TPP-dependent enzymes.
Area of Science:
- Biochemistry
- Prebiotic Chemistry
- Astrobiology
Background:
- Modern transketolase reactions utilize thiamine pyrophosphate (TPP) as a crucial cofactor.
- Understanding early biochemical pathways is key to understanding the origin of life.
Purpose of the Study:
- To investigate alternative catalysts for transketolase reactions under prebiotic conditions.
- To explore the role of cyanide ion in early sugar metabolism.
Main Methods:
- Simulated prebiotic conditions were used to test cyanide ion as a catalyst for transketolase.
- Fructose and glyceraldehyde were reacted in the presence of cyanide ion.
Main Results:
- Cyanide ion effectively catalyzed the conversion of fructose and glyceraldehyde to erythrose and xylulose.
- The products were identical to those formed in modern TPP-catalyzed reactions, but lacked phosphate groups.
- Cyanide demonstrated higher catalytic efficiency than TPP in simple solution.
Conclusions:
- Cyanide ion likely served as an early catalyst for transketolase reactions before the advent of TPP.
- The evolution of TPP-dependent enzymes may have been driven by cyanide's toxicity to metalloproteins in an oxygenated atmosphere.
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