Oxygen attachment on alkanethiolate SAMs induced by low-energy electron irradiation.

Reactions of (18)O2 with self-assembled monolayer (SAM) films of 1-dodecanethiol, 1-octadecanethiol, 1-butanethiol, and benzyl mercaptan chemisorbed on gold were studied by the electron stimulated desorption (ESD) of anionic fragments over the incident electron energy range 2-20 eV. Dosing the SAMs with (18)O2 at 50 K results in the ESD of (18)O(-) and (18)OH(-). Electron irradiation of samples prior to (18)O2 deposition demonstrates that intensity of subsequent (18)O(-) and (18)OH(-) desorption signals increase with electron fluence and that in the absence of electron preirradiation, no (18)O(-) and (18)OH(-) ESD signals are observed, since oxygen is unable to bind to the SAMs. A minimum incident electron energy of 6-7 eV is required to initiate the binding of (18)O2 to the SAMs. O2 binding is proposed to proceed by the formation of CHx-1(•) radicals via resonant dissociative electron attachment and nonresonant C-H dissociation processes. The weaker signals of (18)O(-) and (18)OH(-) from short-chain SAMs are related to the latter's resistance to electron-induced damage, due to the charge-image dipole quenching and electron delocalization. Comparison between the present results and those for DNA oligonucleotides self-assembled on Au (Mirsaleh-Kohan, N. et al. J. Chem. Phys. 2012, 136, 235104) indicates that the oxygen binding mechanism is common to both systems.

Low energy electron stimulated desorption from DNA films dosed with oxygen.

Desorption of anions stimulated by 1-18 eV electron impact on self-assembled monolayer (SAM) films of single DNA strands is measured as a function of film temperature (50-250 K). The SAMs, composed of 10 nucleotides, are dosed with O(2). The OH(-) desorption yields increase markedly with exposure to O(2) at 50 K and are further enhanced upon heating. In contrast, the desorption yields of O(-), attributable to dissociative electron attachment to trapped O(2) molecules decrease with heating. Irradiation of the DNA films prior to the deposition of O(2) shows that this surprising increase in OH(-) desorption, at elevated temperatures, arises from the reaction of O(2) with damaged DNA sites. These results thus appear to be a manifestation of the so-called "oxygen fixation" effect, well known in radiobiology.