Most of the energy deposited in cells by ionizing radiation is channeled into the production of abundant free secondary electrons with ballistic energies between 1 and 20 electron volts. Here it is shown that reactions of such electrons, even at energies well below ionization thresholds, induce substantial yields of single- and double-strand breaks in DNA, which are caused by rapid decays of transient molecular resonances localized on the DNA's basic components. This finding presents a fundamental challenge to the traditional notion that genotoxic damage by secondary electrons can only occur at energies above the onset of ionization, or upon solvation when they become a slowly reacting chemical species.

Nonthermal secondary electrons with initial kinetic energies below 100 eV are an abundant transient species created in irradiated cells and thermalize within picoseconds through successive multiple energy loss events. Here we show that below 15 eV such low-energy electrons induce single (SSB) and double (DSB) strand breaks in plasmid DNA exclusively via formation and decay of molecular resonances involving DNA components (base, sugar, hydration water, etc.). Furthermore, the strand break quantum yields (per incident electron) due to resonances occur with intensities similar to those that appear between 25 and 100 eV electron energy, where nonresonant mechanisms related to excitation/ionizations/dissociations are shown to dominate the yields, although with some contribution from multiple scattering electron energy loss events. We also present the first measurements of the electron energy dependence of multiple double strand breaks (MDSB) induced in DNA by electrons with energies below 100 eV. Unlike the SSB and DSB yields, which remain relatively constant above 25 eV, the MDSB yields show a strong monotonic increase above 30 eV, however with intensities at least 1 order of magnitude smaller than the combined SSB and DSB yields. The observation of MDSB above 30 eV is attributed to strand break clusters (nano-tracks) involving multiple successive interactions of one single electron at sites that are distant in primary sequence along the DNA double strand, but are in close contact; such regions exist in supercoiled DNA (as well as cellular DNA) where the double helix crosses itself or is in close proximity to another part of the same DNA molecule.

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We have measured the electron energy dependence for production of a great variety of anion fragments, induced by resonant attachment of subionization electrons to thymine (T) and cytosine (C) within femto-second time scales. At the lowest electron energies we also observe stable molecular anions of these bases, viz., T− and C−. Our measurements suggest that this resonant mechanism may relate to critical damage of irradiated cellular DNA by subionization electrons prior to thermalization.

We report direct measurements of the formation of single-, double- and multiple strand breaks in pure plasmid DNA as a function of exposure to 10-50 eV electrons. The effective cross sections to produce these different types of DNA strand breaks were determined and were found to range from approximately 10(-17) to 3 x 10(-15) cm(2). The total effective cross section and the effective range for destruction of supercoiled DNA extend from 3.4 to 4.4 x 10(-15) cm(2) and 12 to 14 nm, respectively, over the range 10-50 eV. The variation of the effective cross sections with electron energy is discussed in terms of the electron's inelastic mean free path, penetration depth, and dissociation mechanisms, including resonant electron capture; the latter is found to dominate the effective cross sections for single- and double-strand breaks at 10 eV. The most striking observations are that (1) supercoiled DNA is approximately one order of magnitude more sensitive to the formation of double-strand breaks by low-energy electrons than is relaxed circular DNA, and (2) the dependence of the effective cross sections on the incident electron energy is unrelated to the corresponding ionization cross sections. This finding suggests that the traditional notion that radiobiological damage is related to the number of ionization events would not apply at very low energies.

Electron stimulated desorption of neutral molecular fragments is used to study degradation of ordered organic thin films under low-energy (0–18 eV) electron impact, and total electron doses ranging between 180–550 μC/cm2. Different saturated linear thiols HS(CH2)nX (n=2 or 15, and X=CH3 or COOH) are adsorbed from solution onto a gold surface to produce a self-assembled monolayer (SAM). Here, we present yield function measurements for electron stimulated desorption of moities such as H2, CH3, CH3CH2, CH3CH2CH2, CO, and CO2 from such thin chemisorbed films. For CH3-terminated SAMs, neutral fragment desorption thresholds lie between 5–7 eV, whereas for COOH-terminated SAMs, desorption thresholds as low as 0.2 and 3–5 eV are observed. The results suggest that the incident electrons interact with functional groups localized at the film–vacuum interface, which then leads to predominantly methyl group C–H, and C–COOH bond cleavage. In addition to nonresonant degradation mechanisms, which vary monotonically from threshold with increasing incident electron energy, structures in the neutral fragment desorption yield functions are related to resonant electron attachment. Particularly for Au–S(CH2)15COOH monolayers, this mechanism leads to a desorption peak of CO fragments at incident electron energies near 1.0 eV.

We report measurements of dissociative electron attachment (DEA) to gaseous 5-bromouracil (BrU) for incident electron energies between 0 and 16 eV. Low energy electron impact on BrU leads not only to the formation of a long lived parent anion BrU−, but also various anion fragments resulting from endo- and exo-cyclic bond ruptures, such as Br−, uracil-yl anions, i.e., (U-yl)−, OCN−, and a 68 amu anion tentatively attributed to H2C3NO−. The incident electron energy dependent signatures of either the Br− and (U-yl)− yields (at 0, 1.4, and 6 eV), or the OCN− and H2C3NO− yields (at 1.6 and 5.0 eV) suggests competing DEA channels for anion fragment formation. The production cross sections, at 0 eV incident electron energy, for BrU−, Br−, and (U-yl)− are estimated to be about 6×10−15, 6×10−14, and 1.0×10−15 cm2, respectively.

Dissociative electron attachment to pentaerythritol tetranitrate: Significant fragmentation near 0 eV Absolute partial cross sections for electron-impact ionization of CH4 from threshold to 1000 eV We have measured the formation of anion fragments in gas phase glycine (H 2 NCH 2 COOH) via dissociative electron attachment ͑DEA͒ reactions in the 0-15 eV electron energy range, using a monochromatic electron beam and mass spectrometric detection of the negative ions. By far the most intense product observed is the closed shell glycine anion (H 2 NCH 2 COO) Ϫ which appears from a low-energy resonance with a peak located at 1.4 eV and a cross section in the range 10 Ϫ16 cm 2 . The corresponding precursor ion can be characterized by electron attachment into the empty * orbital of the ϪCOOH group as recently assigned from electron transmission experiments and ab initio self-consistent field calculations ͓Aflatooni, Hitt, Gallup, and Burrow, J. Chem. Phys. 115, 6489 ͑2001͔͒. This precursor state is also observed to decompose ͑with much lower intensity͒ yielding a negative ion fragment with 58 amu, which is attributed to anions of the stoichiometric composition H 2 C 2 O 2Ϫ or H 4 C 2 NO Ϫ . A further prominent DEA peak is observed at 6 eV, which is likely associated with a core excited resonance, and leads to formation of at least six different negative ion fragment species with the following mass numbers: 16 amu (O Ϫ /NH 2 Ϫ ), 17 amu (OH Ϫ ), 26 amu (CN Ϫ ), 28 amu (H 2 CN Ϫ ), 45 amu (HCO 2 Ϫ ), 56 amu (H 2 C 2 NO Ϫ ).