Formation of pyrophosphate, tripolyphosphate, and phosphorylimidazole with the thioester, N, S-diacetylcysteamine, as the condensing agent

@article{Weber1981FormationOP,
  title={Formation of pyrophosphate, tripolyphosphate, and phosphorylimidazole with the thioester, N, S-diacetylcysteamine, as the condensing agent},
  author={Arthur L. Weber},
  journal={Journal of Molecular Evolution},
  year={1981},
  volume={18},
  pages={24-29}
}
  • A. Weber
  • Published 1 December 1981
  • Biology
  • Journal of Molecular Evolution
SummaryReaction of 0.20M orthophosphate with 0.20M N,S-diacetylcysteamine in 0.40M imidazole at pH 7.0 or 8.0 under drying conditions at 50°C for 6 days yields pyrophosphate and tripolyphosphate in the presence and absence of 0.10M divalent metal ion. The efficiency of utilization of N,S-diacetylcysteamine in the formation of pyrophosphate linkages ranges from 3 – 8% under the above conditions. The thioester, N,S-diacetylcysteamine, and imidazole are required for phosphoanhydride formation… 

Formation of the thioester, N-acetyl, S-lactoylcysteine, by reaction of N-acetylcysteine with pyruvaldehyde in aqueous solution

  • A. Weber
  • Biology, Chemistry
    Journal of Molecular Evolution
  • 2005
The decrease in the percent yield at higher pyruvaldehyde concentrations suggests that during its formation the thioester is not only consumed by hydrolysis, but also by reaction with some substance in the pyruValdehyde preparation.

Model for prebiotic pyrophosphate formation: Condensation of precipitated orthophosphate at low temperature in the absence of condensing or phosphorylating agents

The large and negative activation entropies found in aqueous media with calcium ions and in a medium containing 11.3 M dimethyl sulfoxide with magnesium ions suggest that the reaction was favored by a hydrophobic phenomenon at the surface of solid Pi, which could serve as a model for prebiotic formation of PPi.

Prebiotic formation of ‘energy-rich’ thioesters from glyceraldehyde and N-acetylcysteine

  • A. Weber
  • Biology, Chemistry
    Origins of life and evolution of the biosphere
  • 2005
The ‘energy-rich’ thioester is formed from low concentrations of glyceraldehyde and N-acetylcysteine under anaerobic conditions at ambient temperature in aqueous solutions of sodium phosphate, and the significance of these reactions to the origin of life is discussed.

Nonenzymatic formation of “energy-rich” lactoyl and glyceroyl thioesters from glyceraldehyde and a thiol

  • A. Weber
  • Biology
    Journal of Molecular Evolution
  • 2005
A second energyrich thioester, N-acetyl-S-glyceroylcysteine, is also produced from glyceraldehyde when these reactions are carried out in the presence of oxygen and to a limited extent in the absence of oxygen.

Alanine synthesis from glyceraldehyde and ammonium ion in aqueous solution

  • A. Weber
  • Biology
    Journal of Molecular Evolution
  • 2005
Alanine synthesis in the presence of thiol probably proceeds via alanyl thioester, which is produced by rearrangement of the imine of the hemithioacetal of pyruvaldehyde, a product of glyceraldehyde dehydration.

Prebiotic Amino Acid Thioester Synthesis: Thiol-Dependent Amino Acid Synthesis from Formose Substrates (Formaldehyde and Glycolaldehyde) and Ammonia

  • A. Weber
  • Chemistry, Biology
    Origins of life and evolution of the biosphere
  • 2004
Alanine synthesis was also seen in similar reactions containing only 10 mM each of aldehyde substrates, ammonia, and thiol, and the prebiotic significance of these reactions that use the formose reaction to generate sugar intermediates that are converted to reactive amino acid thioesters is discussed.

Prebiotic polymerization: Oxidative polymerization of 2,3-dimercapto-l-propanol on the surface of iron(III) hydroxide oxide

  • A. Weber
  • Biology
    Origins of Life and Evolution of the Biosphere
  • 2005
The oxidation of 2,3-dimercapto-l-propanol by ferric ions on the surface of iron(III) hydroxide oxide (Fe(OH)O) yielded polydisulfide oligomers, which resulted in polymerization occurred readily at low dithiol concentration under mild aqueous conditions and the relationship to prebiotic polymer synthesis is discussed.

A physicochemical orthophosphate cycle via a kinetically stable thermodynamically activated intermediate enables mild prebiotic phosphorylations

The incorporation of orthophosphate from scarce geochemical sources into the organic compounds essential for life under mild conditions is a fundamental challenge for prebiotic chemistry and this system demonstrates a general strategy for how to maximise the usage of scarce resources based upon cycles which accumulate and then release activated intermediates.

Oligoglyceric acid synthesis by autocondensation of glyceroyl thioester

  • A. Weber
  • Biology
    Journal of Molecular Evolution
  • 2005
The autocondensation of the glyceroyl thioesterS-glycersoyl-ethanethiol yielded oligoglyceric acid, and the size and yield of the oligoglycersic acid products increased when the concentration of the thioesters was increased.
...

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  • A. Weber
  • Biology
    Journal of Molecular Evolution
  • 2005
The thioester, N,S-diacetylcysteine, is formed during the illumination of phosphate buffered (pH 7.0) aqueous solutions of acetaldehyde and N,N′-Diacetolcystine with ultraviolet light and its yield progressively increases as ultraviolet light below 239 nm, 253 nm and 281 nm is cut off with optical filters.

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