Secondary electron-induced biomolecular fragmentation in fast heavy-ion irradiation of microdroplets of glycine solution.

The influence of secondary electrons on radiation damage of biomolecules in water was studied by fast heavy-ion irradiation of biomolecular solutions. Water microdroplets containing the amino acid glycine under vacuum were irradiated by fast carbon projectiles with energies of 0.8-8.0 MeV. A variety of fragments from the droplets were observed by time-of-flight secondary-ion mass spectrometry: methylene amine cation and formate anion originating from the cleavage of C-Cα bonds, cyanide anion generated by cleavage of multiple bonds, and protonated and deprotonated glycine. The dependence of the yield of each fragment on projectile energy was examined; different behavior was observed for positive and negative fragments. Considering that biomolecular fragmentation may be induced by secondary electrons ejected from the water molecules surrounding biomolecules, we calculated the cross section for ejection of secondary electrons from liquid water. We found that the formation of both positive and negative glycine fragment ions correlated with the predicted emission of secondary electrons at different projectile energies. The formation of [Gly-H]- fragments, typical for gas phase dissociative electron attachment to amino acids, is shown to be caused by electrons from the low-energy part of the secondary electron distribution.

Delivery of Electrons by Proton-Hole Transfer in Ice at 10 K: Role of Surface OH Radicals.

Although water ice has been widely accepted to carry a positive charge via the transfer of excess protons through a hydrogen-bonded system, ice was recently found to be a negative charge conductor upon simultaneous exposure to electrons and ultraviolet photons at temperatures below 50 K. In this work, the mechanism of electron delivery was confirmed experimentally by both measuring currents through ice and monitoring photodissociated OH radicals on ice by using a novel method. The surface OH radicals significantly decrease upon the appearance of negative current flow, indicating that the electrons are delivered by proton-hole (OH-) transfer in ice triggered by OH- production on the surface. The mechanism of proton-hole transfer was rationalized by density functional theory calculations.

UV-Induced Formation of Ice XI Observed Using an Ultra-High Vacuum Cryogenic Transmission Electron Microscope and its Implications for Planetary Science.

The occurrence of hydrogen atom-ordered form of ice Ih, ice XI, in the outer Solar System has been discussed based on laboratory experiments because its ferroelectricity influences the physical processes in the outer Solar System. However, the formation of ice XI in that region is still unknown due to a lack of formation conditions at temperatures higher than 72 K and the effect of UV-rays on the phase transition from ice I to ice XI. As a result, we observed the UV-irradiation process on ice Ih and ice Ic using a newly developed ultra-high vacuum cryogenic transmission electron microscope. We found that ice Ih transformed to ice XI at temperatures between 75 and 140 K with a relatively small UV dose. Although ice Ic partially transformed to ice XI at 83 K, the rate of transformation was slower than for ice Ih. These findings point to the formation of ice XI at temperatures greater than 72 K via UV irradiation of ice I crystals in the Solar System; icy grains and the surfaces of icy satellites in the Jovian and Saturnian regions.