On the Mechanism of the Steady-State Gamma Radiolysis-Induced Scissions of the Phenyl-Vinyl Polyester-Based Resins

The major societal problem of polymeric waste necessitates new approaches to break down especially challenging discarded waste streams. Gamma radiation was utilized in conjunction with varying solvent environments in an attempt to discern the efficacy of radiolysis as a tool for the deliberate degradation of model network polyesters. Our EPR results demonstrated that gamma radiolysis of neat resin and in the presence of four widely used solvents induces glycosidic scissions on the backbone of the polyester chains. EPR results clearly show the formation of alkoxy radicals and C-centered radicals as primary intermediate radiolytic products. Despite the protective role of the phenyl groups on the backbone of the radiation-induced polyester chains, the radiolytic-glycosidic scissions predominate. Among the following three solvents used in this study (water, isopropyl alcohol, and dichloromethane), the highest radiolytic yield of glycosidic scission was achieved using water. The •OH radicals produced in the radiolysis of phenyl unsaturated polyester aqueous suspensions very rapidly abstract H atoms from the methylene group, which is followed by a very rapid glycosidic scission. The lowest glycosidic yield was found in the dichloromethane solutions of these polyester resins due to scavenging by the fast electron capture reactions.

Gamma Irradiation of Aqueos Solution of L-Aspartic Acid, L-Aspartic Acid in Solid State, and L-Aspartic Acid Adsorbed into Na-Montmorillonite: Its Relevance in Chemistry Prebiotic

Aspartic acid is an amino acid present in the modern proteins, however, is considered a primitive amino acid hence its importance in prebiotic chemistry experiments studies. In some works of prebiotic chemistry have been studied the synthesis and the stability of organic matter under high energy sources, and the role of clays has been highlighted due to clays that can affect the reaction mechanisms in the radiolytic processes. The present work is focused on the study of the role of Namontmorillonite in the gamma radiolysis processes of L-aspartic acid. Gamma radiolysis processes were carried out in three different systems a) L-aspartic acid in aqueous solution; b) L-aspartic acid in solid-state; and c) L-aspartic acid adsorbed into Na-montmorillonite. L-aspartic acid was analyzed by high-performance liquid chromatography−electrospray ionization−mass spectrometry (HPLCESI-MS). The results showed that the decomposition of L-aspartic acid considerably decreased in the presence of clay thus highlighting the protector role of clays and favors the stability of organic matter even under the possible high energy conditions of primitive environments. The principal product ofgamma radiolysis of L-aspartic acid was succinic acid produced by deamination reaction. On the other hand, when aspartic acid was irradiated in solid-state the main product was the L-aspartic acid dimer. Both radiolysis products are important for chemical evolution processes for L-aspartic acid in primitive environments.