The radioracemization of amino acids by ionizing radiation: Geochemical and cosmochemical implications

A number of optically active amino acids, both in the solid state and as sodium or hydrochloride salts in aqueous solution, have been exposed to ionizing radiation from a 3000 Ci⁶⁰Co -ray source to see if radioracemization might accompany their well-known radiolysis. -Ray doses causing 55–68% radiolysis of solid amino acids typically engendered 2–5% racemization, while aqueous solutions of the sodium salts of amino acids which underwent 53–66% radiolysis showed 5–11% racemization. Amino acid hydrochloride salts in aqueous solution, on the other hand, showed little or no radioracemization accompanying their radiolysis. Both radiolysis, and radioracemization were roughly proportional to -ray dose in the range studied (1–36×10⁶ rads). Mechanisms for the radioracemization of amino acids in the solid state and as aqueous sodium salts are discussed, and the absence of radioracemization for aqueous hydrochloride salts is rationalized. Isovaline, a non-protein amino acid which has been isolated from the Murchison meteorite, contains no -hydrogen atom and is therefore incapable of racemizationvia the chemical mechanisms by which ordinary amino acids racemize. Nevertheless, isovaline suffers radioracemization in the solid state to an extent comparable to that shown by ordinary amino acids, as do its sodium and hydrochloride salts in the solid state. The sodium salt of isovaline in aqueous solution, however, fails to racemize during its radiolysis. Several implicaitons of the newly described phenomenon of radiomization are pointed out for the fields of geochemistry and cosmochemistry.A portion of this research has been described previously at the 144th National Meeting of the American Association for the Advancement of Science, Washington D.C., Feb. 12–17, 1978, at the Fourth College Park Colloquium on Chemical Evolution, University of Maryland, College Park, Maryland, Oct. 18–20, 1978, and at the Carnegie Institution of Washington Conference: Advances in the Biogeochemistry of Amino Acids, Airlie House, Warrenton, Virginia, Oct. 29—Nov. 1, 1978.     

E.s.r. of spin-trapped radicals in aqueous solutions of amino acids. Reactions of the hydrated electron.

The reactions of hydrated electrons (eaq-) with amino acids were investigated by the spin-trapping method and by electron spin resonance. Tertiary nitrosobutane was used as a spin-trap to stabilize the short-lived radicals. Hydrated electrons were produced by gamma-radiolysis of de-aerated aqueous solutions of amino acids in the presence of sodium formate or tertiary butanol to scavenge OH. Radicals produced by reductive deamination of 19 amino acids were identified. Radicals formed by scission of the CH3-S- and -S-CH2- bonds of methionine as well as by deamination were observed. In the case of phenylalanine the radical formed by electron addition followed by proton transfer was identified. The reaction of proline and of hydroxyproline with eaq- resulted in the opening of the cyclic structure.     

Formation of amino acids by cobalt-60 irradiation of hydrogen cyanide solutions.

Aqueous solutions of hydrogen cyanide (0.004-0.1 M) were exposed to cobalt-60 gamma rays. Among the products formed on hydrolysis of the irradiated solution; glycine, alanine, valine, serine, threonine, aspartic acid, and glutamic acid have been identified.