Kinetics of Organic Transformations Under Mild Aqueous Conditions: Implications for the Origin of Life and Its Metabolism

Overview

Journal Orig Life Evol Biosph

Specialties Biology
Molecular Biology

Date 2004 Dec 3

PMID 15573498

Citations 10

Authors

Arthur L Weber

Affiliations

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Abstract

The rates of thermal transformation of organic molecules containing carbon, hydrogen, and oxygen were systematically examined in order to identify the kinetic constraints that governed origin-of-life organic chemistry under mild aqueous conditions. Arrhenius plots of the kinetic data were used to estimate the reaction of half-lifes at 50 degrees C. This survey showed that hydrocarbons and organic substances containing a single oxygenated group were kinetically the most stable; whereas organic substances containing two oxygenated groups in which one group was an alpha- or beta-positioned carbonyl group were the most reactive. Compounds with an alpha- or beta-positioned carbonyl group (aldehyde or ketone) had rates of reaction that were up to 10(24)-times faster than rates of similar molecules lacking the carbonyl group. This survey of organic reactivity, together with estimates of the molecular containment properties of lipid vesicles and liquid spherules, indicates that an origins process in a small domain that used C,H,O-intermediates had to be catalytic and use the most reactive organic molecules to prevent escape of its reaction intermediates.

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References

Weber A . Formation of the thioester, N-acetyl, S-lactoylcysteine, by reaction of N-acetylcysteine with pyruvaldehyde in aqueous solution. J Mol Evol. 1982; 18(5):354-9. DOI: 10.1007/BF01733903. View

Siskin M, Katritzky A . Reactivity of organic compounds in superheated water: general background. Chem Rev. 2001; 101(4):825-35. DOI: 10.1021/cr000088z. View

Chittenden G, Schwartz A . Prebiotic photosynthetic reactions. Biosystems. 1981; 14(1):15-32. DOI: 10.1016/0303-2647(81)90018-6. View

Morowitz H, Kostelnik J, Yang J, Cody G . The origin of intermediary metabolism. Proc Natl Acad Sci U S A. 2000; 97(14):7704-8. PMC: 16608. DOI: 10.1073/pnas.110153997. View

Luijkx G, van Rantwijk F, van Bekkum H, Antal Jr M . The role of deoxyhexonic acids in the hydrothermal decarboxylation of carbohydrates. Carbohydr Res. 1995; 272(2):191-202. DOI: 10.1016/0008-6215(95)00098-e. View

Wachtershauser G . Groundworks for an evolutionary biochemistry: the iron-sulphur world. Prog Biophys Mol Biol. 1992; 58(2):85-201. DOI: 10.1016/0079-6107(92)90022-x. View

de Gier J, Mandersloot J, Hupkes J, McElhaney R, van Beek W . On the mechanism of non-electrolyte permeation through lipid bilayers and through biomembranes. Biochim Biophys Acta. 1971; 233(3):610-8. DOI: 10.1016/0005-2736(71)90160-x. View

Radzicka A, Wolfenden R . A proficient enzyme. Science. 1995; 267(5194):90-3. DOI: 10.1126/science.7809611. View

Waddell T, Heinrich R, MONTERO F . Theoretical approaches to the evolutionary optimization of glycolysis--chemical analysis. Eur J Biochem. 1997; 244(2):527-43. DOI: 10.1111/j.1432-1033.1997.t01-1-00527.x. View

10.

Kasting J, Pollack J . Effects of high CO2 levels on surface temperature and atmospheric oxidation state of the early Earth. J Atmos Chem. 1984; 1:403-28. DOI: 10.1007/BF00053803. View

11.

Larralde R, Robertson M, Miller S . Rates of decomposition of ribose and other sugars: implications for chemical evolution. Proc Natl Acad Sci U S A. 1995; 92(18):8158-60. PMC: 41115. DOI: 10.1073/pnas.92.18.8158. View

12.

WESTHEIMER F . Why nature chose phosphates. Science. 1987; 235(4793):1173-8. DOI: 10.1126/science.2434996. View

13.

Chakrabarti A, Deamer D . Permeability of lipid bilayers to amino acids and phosphate. Biochim Biophys Acta. 1992; 1111(2):171-7. DOI: 10.1016/0005-2736(92)90308-9. View

14.

Weber A . Origin of fatty acid synthesis: thermodynamics and kinetics of reaction pathways. J Mol Evol. 1991; 32:93-100. DOI: 10.1007/BF02515381. View

15.

Antal Jr M, Mok W, Richards G . Mechanism of formation of 5-(hydroxymethyl)-2-furaldehyde from D-fructose an sucrose. Carbohydr Res. 1990; 199(1):91-109. DOI: 10.1016/0008-6215(90)84096-d. View

16.

DEUTICKE B . Properties and structural basis of simple diffusion pathways in the erythrocyte membrane. Rev Physiol Biochem Pharmacol. 1977; 78:1-97. DOI: 10.1007/BFb0027721. View

17.

Hargreaves W, Deamer D . Liposomes from ionic, single-chain amphiphiles. Biochemistry. 1978; 17(18):3759-68. DOI: 10.1021/bi00611a014. View

18.

Kallen R, Jencks W . Equilibria for the reaction of amines with formaldehyde and protons in aqueous solution. A re-examination of the formol titration. J Biol Chem. 1966; 241(24):5864-78. View

19.

Enoch H, STRITTMATTER P . Formation and properties of 1000-A-diameter, single-bilayer phospholipid vesicles. Proc Natl Acad Sci U S A. 1979; 76(1):145-9. PMC: 382893. DOI: 10.1073/pnas.76.1.145. View

20.

Halliwell B, Butt V . Flavin mononucleotide-sensitized photo-oxidation of glyoxylate in Good's buffers. Biochem J. 1972; 129(5):1157-8. PMC: 1174274. DOI: 10.1042/bj1291157. View