Springer Nature is making SARS-CoV-2 and COVID-19 research free. View research | View latest news | Sign up for updates

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

  • 117 Accesses

  • 22 Citations

Summary

The “energy-rich” thioester, N-acetyl-S-lactoylcysteine, is formed under anaerobic conditions from glyceraldehyde and N-acetylcysteine at ammbient temperature in aqueous solutions of sodium phosphate (pH 7.0). The conversion of glyceraldehyde to lactoyl thioester occurs at a rate of about 0.4%/day in reactions with 10 mM glyceraldehyde, 10 mM thiol, and 500 mM sodium phosphate (pH 7.0). Thioester formation proceeds at an estimated efficiency of 76%, since a similar reaction with 12.5 mM thiol yields 50.7% lactate at 6 months from only 66.5% of the glyceraldehyde (or its isomer, dihydroxyacetone). The formation of lactoyl thioester most likely occurs by the phosphate-catalyzed dehydration of glyceraldehyde to give pyruvaldehyde, which combines with thiol to form a hemithioacetal that rearranges to the thioester. 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. In the presence of oxygen the formation of glyceroyl thioester continues until the thiol disappears completely by oxidation. The significance of these reactions to the energetics of the origin of life is discussed.

This is a preview of subscription content, log in to check access.

Abbreviations

Ac-Cys:

N-acetylcysteine

Ac-Cys(Glc):

N-acetyl-S-glyceroylcysteine

Ac-Cys(Lac):

N-acetyl-S-lactoylcysteine

TBDMS:

tert-butyldimethylsilyl group

References

  1. Bar-Nun A, Hartman H (1978) Synthesis of organic compounds from carbon monoxide and water by UV photolysis. Orig Life 9:93–101

  2. Beck A, Orgel LE (1965) The formation of condensed phosphate in aqueous solution. Proc Natl Acad Sci USA 54:664–667

  3. Beck WS (1957) Carbohydrates: assay of triose phosphates. In: Colowick SP, Kaplan NO (eds) Methods in enzymology, vol III. Academic Press, New York, p 201

  4. Buvet R (1977) Compared energetics of primordial and biological metabolisms. Orig Life 8:361–370

  5. Canuto VM, Levine JS, Augustsson TR, Imhoff CL (1982) UV radiation from the young Sun and oxygen and ozone levels in the prebiological palaeoatmosphere. Nature 296:816–820

  6. Corey EJ, Venkateswarlu A (1972) Protection of hydroxyl groups as tert-butyldimethylsilyl derivatives. J Am Chem Soc 94:6190–6191

  7. Davis KA, Williams GR (1969) Glyoxalase I, a lyase or an oxidoreductive isomerase? Can J Biochem 47:553–556

  8. Decker K, Jungermann K, Thauer RK (1970) Energy production in anaerobic organisms. Angew Chem Int Edit 9:138–158

  9. Degani Ch, Halmann M (1968) Alkaline reactions of glucose 6-phosphate. J Am Chem Soc 90:1313–1317

  10. De Wilt HGJ, Kuster BFM (1971) The oxidation ofd-glucose andd-fructose with oxygen in aqueous, alkaline solutions. Carbohydr Res 19:5–15

  11. Fedoronko M, Konigstein J (1969) Kinetics of mutual isomerization of trioses and their dehydration to methylglyoxal. Coll Czech Chem Commun 34:3881–3894

  12. Ferris JP (1968) Cyanovinyl phosphate: A prebiological phosphorylating agent? Science 161:53–54

  13. Gabel NW, Ponnamperuma C, (1967) Model for origin of monosaccharides. Nature 216:453–455

  14. Garrison WM, Morrison DC, Hamilton JG, Benson AA, Calvin M (1951) Reduction of carbon dioxide in aqueous solutions by ionizing radiation. Science 114:416–418

  15. Gasparic J, Churacek J (1978) Laboratory handbook of paper and thin-layer chromatography. John Wiley & Sons, New York, p 331

  16. Getoff N, Scholes G, Weiss J (1960) Reduction of carbon dioxide in aqueous solutions under the influence of radiation. Tetrahedron Lett 17–23

  17. Grassetti DR, Murray JF (1969) The use of 2,2′-dithiobis-(5-nitropyridine) as a selective reagent for the detection of thiols. J Chromatogr 41:121–123

  18. Green JW (1980) Oxidative reactions and degradations. In: Pigman W, Horton D (eds) The carbohydrates, vol 1B. Academic Press, New York, p 1101

  19. Gutsche CD, Redmore D, Buriks RS, Nowotny K, Grassner H, Armbruster CW (1967) Base-catalyzed triose condensations. J Am Chem Soc 89:1235–1245

  20. Hall SS, Doweyko AM, Jordan F (1978) Glyoxalase I enzyme studies. 4. General base catalyzed enediol proton transfer rearrangement of methyl- and phenylglyoxalglutathionylhemithiol acetal to S-lactoyl- and S-mandeloylglutathione followed by hydrolysis. A model for the glyoxalase enzyme system. J Am Chem Soc 100:5934–5939

  21. Handschuh GJ, Lohrmann R, Orgel LE (1973) The effect of Mg2+ and Ca2+ on urea-catalyzed phosphorylation reactions. J Mol Evol 2:251–262

  22. hartman H (1975) Speculations on the origin and evolution of metabolism. J Mol Evol 4:359–370

  23. Hong JH, Becker RS (1979) Hydrogen atom initiated chemistry. J Mol Evol 13:15–26

  24. Hubbard JS, Hardy JP, Horowitz NH (1971) Photocatalytic production of organic compounds from CO and H2O in a simulated Martian atmosphere. Proc Natl Acad Sci USA 68:574–578

  25. Hulshof J, Ponnamperuma C (1976) Prebiotic condensation reactions in an aqueous medium: a review of condensing agents. Orig Life 7:197–224

  26. Isbell HS (1976) A diradical mechanism for the degradation of reducing sugars by oxygen. Carbohydr Res 49:C1-C4

  27. Jencks WP (1976) Free energies of hydrolysis and decarboxylation. In: Fasman GD (ed), Handbook of biochemistry and molecular biology, 3rd edn. Physical and chemical data, vol 1. CRC Press, Cleveland, p 296

  28. Kanchuger MS, Byers LD (1979) Acyl substituent effects on thiohemiacetal equilibria. J Am Chem Soc 101:3005–3010

  29. Konigstein J, Fedoronko M (1975) Kinetic study of aldolization reactions of trioses. Coll Czech Chem Commun 40:1183–1192

  30. Lederer E, Lederer M (1957) Chromatography. Elsevier, New York, p. 184

  31. Levine JS, Augustsson TR, Natarajan M (1982) The prebiological paleoatmosphere: stability and composition. Orig Life 12:245–259

  32. Lynen F (1951) Quantitative Bestimmung von Acyl-Mercaptanen mittels der Nitroprussid-Reaktion. Annalen 574:33–37

  33. Miller SL (1957) The formation of organic compounds on the primitive Earth. Ann NY Acad Sci 69:260–275

  34. Miller SL, Parris M (1964) Synthesis of pyrophosphate under primitive Earth conditions. Nature 204:1248–1250

  35. Mizuno T, Weiss AH (1974) Synthesis and utilization of formose sugars. Adv Carbohydr Chem Biochem 29:173

  36. Oro J, Stephen-Sherwood E (1976) Abiotic origin of biopolymers. Orig Life 7:37–47

  37. Osterberg R, Orgel LE (1972) Polyphosphate and trimetaphosphate formation under potentially prebiotic conditions. J Mol Evol 1:241–248

  38. Perlin AS (1962) Trioses:D-, l-, andDl-glyceraldehyde, oxidative degradation of ketohexoses. In: Whistler RL, Wolfrom ML (eds) Methods in carbohydrate chemistry, vol 1. Academic Press, New York, p 61

  39. Pigman W, Anet EFLJ (1972) Mutarotations and actions of acids and bases. In: Pigman W, Horton D (eds) The carbohydrates, vol 1A. Academic Press, New York, p 165

  40. Putnam EW (1957) Paper chromatography of sugars. In: Colowick SP, Kaplan NO (eds) Methods in enzymology, vol III. Academic Press, New York, p 62

  41. Rabinowitz J, Chang S, Ponnamperuma C (1968) Phosphorylation on the primitive Earth: phosphorylation by way of inorganic phosphate as a potential prebiotic process. Nature 218:442–443

  42. Reid C, Orgel LE (1967) Synthesis of sugars in potentially prebiotic conditions. Nature 216:455

  43. Reynolds SJ, Yates DW, Pogson CI (1971) Dihydroxyacetone phosphate: its structure and reactivity with α-glycerophosphate dehydrogenase, aldolase and triose phosphate isomerase and some possible metabolic implications. Biochem J 122:285–297

  44. Riddle V, Lorenz FW (1968) Nonenzymic, polyvalent anioncatalyzed formation of methylglyoxal as an explanation of its presence in physiological systems. J Biol Chem 243:2718–2724

  45. Sagan C, Khare BN (1971) Long-wavelength ultraviolet photoproduction of amino acids on the primitive earth. Science 173:417–420

  46. Speck JC (1958) The Lobry de Bruyn-Alberda van Ekenstein transformation. Adv Carbohydr Chem 13:63

  47. Stadtman ER (1957) Preparation and assay of acyl coenzyme A and other thiol esters; use of hydroxylamine. In: Colowick SP, Kaplan NO (eds) Methods in enzymology, vol III. Academic Press, New York, p 931

  48. Stahl E (1965) Thin-layer chromatography. Academic Press, New York, p 499

  49. Steinman G, Lemmon RM, Calvin M (1964) Cyanamide: a possible key compound in chemical evolution. Proc Natl Acad Sci USA 52:27–30

  50. Thauer RK, Jungermann K, Decker K (1977) Energy conservation in chemotrophic anaerobic bacteria. Bacteriol Rev 41:100–180

  51. Thompson AR (1951) Separation of saturated mono-hydroxamic acids by partition chromatography on paper. Aust J Sci Res Ser B 4:181–186

  52. Vander Jagt DL, Han LB, Lehman CH (1972) Kinetic evaluation of substrate specificity in the glyoxalase-I-catalyzed disproportionation of α-ketoaldehydes. Biochemistry 11:3735–3740

  53. Vince R, Wadd WB (1969) Glyoxalase inhibitors as potential anticancer agents. Biochem Biophys Res Commun 35:593–598

  54. Warshowsky B, Sandstrom WM (1952) The action of oxygen on glucose in the presence of potassium hydroxide. Arch Biochem Biophys 37:46–55

  55. Weber AL (1981a) Formation of the thioester, N,S-diacetylcysteine, from acetaldehyde and N,N′-diacetylcystine in aqueous solution with ultraviolet light. J Mol Evol 17:103–107

  56. Weber AL (1981b) Formation of pyrophosphate, tripolyphosphate, and phosphorylimidazole with the thioester, N,S-diacetylcysteamine, as the condensing agent. J Mol Evol 18:24–29

  57. Weber AL (1982a) Formation of the thioester, N-acetyl, S-lactoylcysteine, by reaction of N-acetylcysteine with pyruvaldehyde in aqueous solution. J Mol Evol 18:354–359

  58. Weber AL (1982b) Formation of pyrophosphate on hydroxyapatite with thioesters as condensing agents. Biosystems 15:183–189

  59. Weber AL (1983) Thiol-catalyzed formation of lactate and glycerate from glyceraldehyde. J Mol Evol 19:237–243

  60. Weber AL, Orgel LE (1979) The formation of peptides from glycine thioesters. J Mol Evol 13:193–202

  61. Wedmid Y, Baumann WJ (1977) Long chain stereomeric 2-alkyl-4-methoxycarbonyl-1,3-dioxolanes in glycerol acetal synthesis. J Org Chem 42:3624–3626

  62. Zahler WL, Cleland WW (1968) A specific and sensitive assay for disulfides. J Biol Chem 243:716–719

Download references

Author information

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Weber, A.L. Nonenzymatic formation of “energy-rich” lactoyl and glyceroyl thioesters from glyceraldehyde and a thiol. J Mol Evol 20, 157–166 (1984). https://doi.org/10.1007/BF02257376

Download citation

Key words

  • Glyceraldehyde
  • Intramolecular rearrangement
  • Oxidation
  • Lactoyl thioester
  • Glyceroyl thioester
  • Prebiotic