Radiation Chemistry of Carbohydrates, X* γ-Radiolysis of Crystalline D-Glucose and D-Fructose

Abstract

α-D-Glucose and β-D-fructose were γ-irratiated in the solid (polycrystalline) state at room temperature at doses of 3.5 · 1020-4.2 · 1021 eV g-1 (dose rate 1.16 · 1018 eV g-1 min-1). Carbohydrate products containing ≤ 6 carbon atoms were identified and their G-values (in parentheses) measured. Glucose: Dihydroxyacetone (1) (0.05), 3-deoxy-tetrose (2) (0.015), 1,4-dideoxy-2-pentulose (3) (0.05), 2,4-dideoxy-pentose (4) (0.085), 2,4-dideoxy-pentonic acid (5), 2,3-dideoxypentos-4-ulose (6) (together 0.035), threose (7), erythrulose (8), erythrose (9), erythronic acid (10) (together 0.04), 1-deoxy-2-pentulose (11) (0.005), 2-deoxy-ribose (12) (0.25), 3-deoxy-pentosulose (18) (0.02), 3,5-dideoxy-hexonic acid (14) (0.02), 2,3-dideoxy-hexonic acid (15) (0.01), arabinose (16) (0.25), ribose (17), ribonic acid (18) (together 0.02), 2-deoxy-2-C-hydroxymethyl-pentonic acid (19) (0.06), 5-deoxy-gluconic acid (20), 2deoxy-5-keto-glucose (21), 2-deoxy-gluconic acid (22), 2-deoxy-3-keto-glucose (28), 3-deoxy-glucosone (24), 3-deoxy-gluconic acid (25), 3-deoxy-4-keto-glucose (26), 3-deoxymannonic acid (27) (together 0.4). Identified but nor measured quantitatively were glucosone (28), 3-keto-glucose (29), 4-keto-glucose (30), 5-keto-glucose (31) and gluconic acid (82). G(H2) = 5.75; G(CO2) = 0.7. Fructose: 7-9 (together 0.65), 3-deoxy-pentonic acids (37), 3-deoxy-pentosulose (88) (together 0.3), arabonic acid (89) (0.1), 18 (0.05), 6-deoxy-2,5-hexodiulose (40) (40). Identified but not measured quantitatively were glyceraldehyde (34), butanone-(3)-diol-(1,2) (35) and 2- and 3-deoxy-hexodiuloses. G(H2) = 4.75, G(CO2) = 0.05. Reaction schemes are proposed to account for the formation of the products. The scission of the hemiacetal bond and of the C-Η and C-C bonds next to it appears to be typical for solid state irradiations. The formation of deoxy-compounds is observed both in the solid state and in aqueous solution. The formation of dideoxy-compounds is only prominent in the solid state. In polycrystalline fructose a chain reaction is induced leading to 6-deoxy-2,5-hexodiulose (40).