The damage induced by the impact of low energy electrons (LEE) on 
biomolecules is reviewed from a radiobiological perspective with emphasis on 
transient anion formation. The major type of experiments, which measure the 
yields of fragments produced as a function of incident electron energy 
(0.1-30 eV), are briefly described. Theoretical advances are also 
summarized. Several examples are presented from the results of recent 
experiments performed in the gas-phase and on biomolecular films bombarded 
with LEE under ultra-high vacuum conditions. These include the results 
obtained from DNA films and those obtained from the fragmentation of 
elementary components of the DNA molecule (i.e., the bases, sugar and 
phosphate group analogs and oligonucleotides) and of proteins (e.g. amino 
acids). By comparing the results from different experiments and theory, it 
is possible to determine fundamental mechanisms that are involved in the 
dissociation of the biomolecules and the production of single- and 
double-strand breaks in DNA. Below 15 eV, electron resonances (i.e., the 
formation of transient anions) play a dominant role in the fragmentation of 
all biomolecules investigated. These transient anions fragment molecules by 
decaying into dissociative electronically excited states or by dissociating 
into a stable anion and a neutral radical. These fragments can initiate 
further reactions within large biomolecules or with nearby molecules and 
thus cause more complex chemical damage. Dissociation of a transient anion 
within DNA may occur by direct electron attachment at the location of 
dissociation or by electron transfer from another subunit. Damage to DNA is 
dependent on the molecular environment, topology, type of counter ion, 
sequence context and chemical modifications.

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Low energy electron-driven damage in biomolecules

Many experimental and theoretical advances have recently allowed the study of direct and indirect effects of low-energy electrons (LEEs) on DNA damage. In an effort to explain how LEEs damage the human genome, researchers have focused efforts on LEE interactions with bacterial plasmids, DNA bases, sugar analogs, phosphate groups, and longer DNA moieties. Here, we summarize the current understanding of the fundamental mechanisms involved in LEE-induced damage of DNA and complex biomolecule films. Results obtained by several laboratories on films prepared and analyzed by different methods and irradiated with different electron-beam current densities and fluencies are presented. Despite varied conditions (e.g., film thicknesses and morphologies, intrinsic water content, substrate interactions, and extrinsic atmospheric compositions), comparisons show a striking resemblance in the types of damage produced and their yield functions. The potential of controlling this damage using molecular and nanoparticle targets with high LEE yields in targeted radiation-based cancer therapies is also discussed.

Biomolecular Damage Induced by Ionizing Radiation: The Direct and Indirect Effects of Low-Energy Electrons on DNA

We overview our recent theoretical predictions and the innovative experimental findings that inspired us concerning the mechanisms by which very low-energy (0.1-2 eV) free electrons attach to DNA and cause strong (ca. 4 eV) covalent bonds to break causing so-called single-strand breaks. Our primary conclusions are that (i) attachment of electrons in the above energy range to base pi* orbitals is more likely than attachment elsewhere and (ii) attachment to base pi* orbitals most likely results in cleavage of sugar-phosphate C-O sigma bonds. Later experimental findings that confirmed our predictions about the nature of the electron attachment event and about which bonds break when strand breaks form are also discussed. The proposed mechanism of strand break formation by low-energy electrons involves an interesting through-bond electron-transfer process.

/pdf/how-do-low-energy-0-1-2-ev-electrons-cause-dna-strand-breaks-4ycbpyp7l2.pdf

How do low-energy (0.1-2 eV) electrons cause DNA-strand breaks?

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Precursors of solvated electrons in radiobiological physics and chemistry.

Electron-induced damage of DNA and its components: Experiments and theoretical models

Collisions of 0--4 eV electrons with thin DNA films are shown to produce single strand breaks. The yield is sharply structured as a function of electron energy and indicates the involvement of ${\ensuremath{\pi}}^{*}$ shape resonances in the bond breaking process. The cross sections are comparable in magnitude to those observed in other compounds in the gas phase in which ${\ensuremath{\pi}}^{*}$ electrons are transferred through the molecule to break a remote bond. The results therefore support aspects of a theoretical study by Barrios et al. [J. Phys. B 106, 7991 (2002)] indicating that such a mechanism could produce strand breaks in DNA.

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DNA strand breaks induced by 0-4 eV electrons: the role of shape resonances.

Panajotovic, R., Martin, F., Cloutier, P., Hunting, D. and Sanche, L. Effective Cross Sections for Production of Single-Strand Breaks in Plasmid DNA by 0.1 to 4.7 eV Electrons. Radiat. Res. 165, 452–459 (2006). We determined effective cross sections for production of single-strand breaks (SSBs) in plasmid DNA [pGEM 3Zf(-)] by electrons of 10 eV and energies between 0.1 and 4.7 eV. After purification and lyophilization on a chemically clean tantalum foil, dry plasmid DNA samples were transferred into a high-vacuum chamber and bombarded by a monoenergetic electron beam. The amount of the circular relaxed DNA in the samples was separated from undamaged molecules and quantified using agarose gel electrophoresis. The effective cross sections were derived from the slope of the yield as a function of exposure and had values in the range of 10−15– 10−14 cm2, giving an effective cross section of the order of 10−18 cm2 per nucleotide. Their strong variation with incident electron energy and the resonant en...

Frédéric Martin

Papers

DNA strand breaks induced by 0-4 eV electrons: the role of shape resonances.

Effective Cross Sections for Production of Single-Strand Breaks in Plasmid DNA by 0.1 to 4.7 eV Electrons