Laser photolysis of carboxymethylated chitin derivatives in aqueous solution. Part 1. Formation of hydrated electron and a long-lived radical.

Laser photolysis experiments on carboxymethylated chitin derivatives, such as carboxymethyl chitin (CM-chitin) and carboxymethyl chitosan (CM-chitosan), in aqueous solution by a 248 nm excimer laser were carried out for the first time. The transient absorption spectra of photolyzed CM-chitin or CM-chitosan solutions revealed a strong band with the maximum at 720 nm, which was assigned to the hydrated electron (eaq-). In the presence of argon, the eaq- decays by reacting with CM-chitin or CM-chitosan, and the rate constants are (6.1 +/- 0.1) x 10(7) M(-1) s(-1) and (3.7 +/- 0.1) x 10(7) M(-1) s(-1), respectively. Long-lived radicals with relatively weak absorption intensity were detected in the near-UV region. The absorption band was not notably characteristic and showed only an increasing absorption toward shorter wavelengths. It is similar to the signal of *CM-chitin or CM-chitosan macroradicals formed by the reaction of CM-chitin or CM-chitosan with an OH radical. It was assigned to *CM-chitin- or *CM-chitosan- macroradicals formed by eaq- + CM-chitin or CM-chitosan reaction. CM-chitin aqueous solutions were further examined by pulse radiolysis in order to confirm the site of the long-lived radical.