Radiolysis of aqueous solutions of sugar phosphates

The mechanism of the radiation-induced dephosphorylation reaction was investigated by studying the γ-radiolysis of 10mM solutions of D-glucopyranosyl phosphate, D-glucose 6-phosphate (Glc-6-P), and d-ribose 5-phosphate (Rib-5-P). Dephosphorylation occurred with OH-radical participation, since G(H₃PO₄) values for nitrous oxide-saturated solutions were 4.1, 1.7, and 2.3, and for nitrogen-saturated solutions 2.6, 1.1, and 1.6, respectively. The formation of phosphate-free compounds accompanied the release of inorganic phosphate. The main, neutral products of the radiolysis of Glc-6-P were 6-deoxyhexos-5-ulose (G = 0.2) and D-gluco-hexodialdose (G = 0.3). Irradiation of Rib-5-P gave ribo-pentodialdose and 5-deoxypentos-4-ulose as the main, neutral products. A scheme for the dephosphorylation process is proposed.     

Radiolysis of human gastric glycopolypeptides in aqueous solution

The degradation of human gastric glycopolypeptides by hydroxyl radicals formed in irradiated N2O-saturated aqueous solution has been investigated. Gel exclusion chromatography shows the formation of lower molecular weight degradation products after irradiation and the appearance of unsaturated carbonyl-containing products which absorb in the ultra-violet. The radiation-induced destruction of individual monosaccharides in three human glycopolypeptides having different oligosaccharide chains has been measured. The results indicate that the structure of the oligosaccharide chain determines the extent of destruction of each type of monosaccharide present.     

Radiolysis of poly(U) in oxygenated solution

Aqueous N2O/O2-saturated solutions of poly(U) were irradiated at 0 degrees C and the release of unaltered uracil determined. Immediately after irradiation G(uracil release) was 1.5 which increased to a value of 5.3 +/- 0.3 upon heating to 95 degrees C. Thereby all of the organic hydroperoxides (G = 6.8 +/- 0.7) and some of the hydrogen peroxide (G = 1.7 +/- 0.2) was destroyed leaving G(peroxidic material; mainly hydrogen peroxide) = 1.0 +/- 0.7. G(chromophore loss) = 8-11 was measured immediately after irradiation, but no increase was observed upon heating. Addition of iodide destroyed the hydroperoxides and caused immediate base release to rise to G = 4 and further heating brought the value to that observed in the absence of iodide. In contrast, on reducing the hydroperoxides with NaBH4, immediate uracil release rose to only G = 2.8 and no further increase was observed on heating. A major product (G = 2.7) is carbon dioxide. There are also osazone-forming compounds produced (G = 2.7), all of which are originally bound to poly(U). Heating in acid solutions, as is required for this test, releases glycoladehyde-derived osazone (G = 0.8) and further unidentified low molecular weight material (G = 0.9). It is concluded that the primary radicals which cause these lesions are the base OH adduct radicals. In the presence of oxygen these are converted into the corresponding peroxyl radicals which abstract an H atom from the sugar moiety. In the course of this reaction base-hydroperoxides are formed. However, such base hydroperoxides cannot be the only organic hydroperoxides, but some (G congruent to 2.5) sugar-hydroperoxides must be formed as indicated by the increase in base release by the addition of iodide. It is speculated that a sugar-hydroperoxide located at C(3') is reduced by iodide to a carbonyl function at C(3'), a lesion that releases the base, while reduction with NaBH4 reduces it to an alcohol function at C(3') thus preventing base release.     

Radiolysis,racemization, and the origin of optical activity

An investigation has been undertaken to determine whether ionizing radiation might engender racemization (radioracemization) of optically active amino acids, along with their well-known radiolysis. We have exposed a number of solid and dissolved optically active amino acids to the ionizing radiation from a 3000-Ci ⁶⁰Co γ-ray source for periods of time which would engender substantial, but not total radiolysis. γ-Ray doses which caused 55–68% radiolysis of solid amino acids typically engendered 2–5% racemization. Aqueous solutions of the sodium salts of amino acids which underwent 53–66% radiolysis typically showed 5–11% racemization. The corresponding hydrochloride salts in aqueous solution, however, underwent little or no racemization. In aqueous solution both percentage degradation and percentage racemization were approximately proportional to γ-ray dosage within the range employed (1–36 × 10⁶ rads). Mechanisms for the radioracemization of amino acids in the solid state and as dissolved sodium salts are proposed, and the absence of racemization for dissolved hydrochloride salts is rationalized. Implications of these observations with regard to the origin of optical activity by the Vester-Ulbricht β-decay mechanism are discussed, as are their implications regarding the use of diagenetic racemization rates of ancient amino acid samples as criteria for geochronological and geothermometric calculations.