Cross sections for low-energy (10-50 eV) electron damage to DNA

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.     

Calculation of the proximity function of electrons

A new semianalytical method to calculate the proximity function for electrons is proposed. An integral equation for the proximity function that can be solved by using information on the spatial dose distributions is obtained. The proximity function for electrons in the energy range from 10 eV to 10 keV is calculated by solving the equation numerically, using a set of electron collision cross sections for water vapor. The results are in good agreement with those obtained using the Monte Carlo method. The proposed method can be used for electrons of high energies much more efficiently than the Monte Carlo method.     

Cross section calculations for electron scattering from DNA and RNA bases

Differential and integral cross sections for elastic electron collisions with uracil, cytosine, guanine, adenine and thymine have been calculated using the independent atom method with a static-polarization model potential for incident energies ranging from 50 to 4000 eV. Total cross sections for single electron-impact ionization of selected DNA and RNA bases have also been calculated with the binary-encounter-Bethe model from the ionization threshold up to 5000 eV. Cross sections within the investigated energy range, can be related to the molecular symmetry, the number of target electrons and molecular size; elastic and ionization processes are most efficient for guanine and adenine molecules, while the lowest cross sections were obtained for the uracil molecule. The ionization cross sections for cytosine, thymine, adenine and guanine are compared with those recently obtained with a semi-classical and binary-encounter-Bethe formalisms. No theoretical and experimental data for elastic electron scattering from DNA and RNA bases are available, but comparisons with calculations for molecules of similar size and geometry allows the validity of the theoretical approach to be verified.     

Monte Carlo simulation of strand-break induction on plasmid DNA in aqueous solution by monoenergetic electrons

The radiation-induced process of strand breaks on pBR322 plasmid DNA in aqueous solution for different energy electrons was studied by Monte Carlo simulation. Assumptions of induction mechanisms of single- and double-strand breaks (SSBs and DSBs) used in the simulation are that SSB is induced by OH or H reaction with DNA and that DSB is induced by two SSBs on the opposite strands within 10 bp. Dose-response relationships of SSBs and DSBs were demonstrated for monoenergetic electrons of 100 eV, 10 keV, 1 keV and 1 MeV, and the yields of SSB and DSB were calculated. The dose-response relationships of SSBs and DSBs can be fitted by linear and linear-quadratic functions, respectively. The ratio of quadratic to linear components of DSB induction changes due to the electron energy. A high contribution of the linear component is observed for 1 keV electrons in the dose range below 160 Gy. The yields of SSBs and DSBs for all examined electron energies lie well within the experimental data when the probability of strand-break induction by OH and H is assumed to be around 0.1-0.2. The yield of SSBs has a minimum at 1 keV, while the yield of DSBs has a maximum at 1 keV in the examined energies. The strand breaks are formed most densely for 1 keV electrons.     

Energy spectra of secondary electrons in water vapour

The purpose of this work is to present a method for the calculation of secondary electron spectra generated by photons in water vapour in the energy region from 10 eV to 10 MeV. The cross sections below and above 1 keV have been treated separately. Examples are given for secondary electron spectra for low-energy photons, <100 eV, in which all electrons are photoelectrons, and at higher energy regions, such as for ⁶⁰Co photons. The spectrum of the first generation of secondary electrons, produced by ⁶⁰Co photons, which are mainly due to incoherent scattering, was fitted with a set of polynomial functions which can be used as input for electron radiation action calculations.     

Low-energy electron penetration range in liquid water

Monte Carlo simulations of electron tracks in liquid water are performed to calculate the energy dependence of the electron penetration range at initial electron energies between 0.2 eV and 150 keV, including the subexcitation electron region (<7.3 eV). Our calculated electron penetration distances are compared with available experimental data and earlier calculations as well as with the results of simulations using newly reported amorphous ice electron scattering cross sections in the range approximately 1-100 eV.     

Damage induced by 1-30 eV electrons on thymine- and bromouracil-substituted oligonucleotides

The impact of low-energy (1-30 eV) electrons on self-assembled monolayers of heterogeneous oligonucleotides chemisorbed on a gold surface has been investigated by mass spectrometry of desorbed neutral species in an attempt to understand the consequences of secondary electron damage in a short sequence of a DNA single strand. We demonstrate that the most intense observable neutral species (CN, OCN and/or H(2)NCN) desorbed from Cy(6)-Th(3) and Cy(6)-(BrdU)(3) oligos are related to primary fragmentation of the bases induced by electron impact. The dependence of the neutral species desorption on electron energy shows typical signatures of dissociative electron attachment initiated by the formation of shape- and core-excited resonances (i.e. single-electron and two-electron- one-hole transitory anions, respectively). Substitution of dTh by BrdU increases the production of neutral fragments by as much as a factor of about 3 for the entire electron energy range. When the distribution of secondary electrons along radiation tracks in H(2)O is taken into account, we show that the probability for electron damage to heterogeneous oligonucleotides is enhanced by a factor of 2.5-3 for electron energies below 20 eV for both sensitized and unsensitized strands.     

Sequence-specific damage induced by the impact of 3-30 eV electrons on oligonucleotides.

The ability of low-energy electrons to induce single- and double-strand breaks in DNA has recently been demonstrated. Here we show the propensity of 3-30 eV electrons to initiate base sequence-dependent damage to a short single DNA strand. Solid monolayer films of homogeneous thymidine (T(9)) and deoxycytidine (dCy(9)) and heterogeneous oligomers (T(6)dCy(3)) are bombarded with 1-30 eV electrons in an ultrahigh-vacuum system. CN, OCN and/or H(2)NCN are detected by a mass spectrometer as the most intense neutral fragments desorbing in vacuum. A weaker signal of CH(3)CCO is also detected, but only from oligonucleotides containing thymine. Below 17 eV, the energy dependence of the yields of CN, OCN and CH(3)CCO exhibits resonance-like structures, attributed to dissociative electron attachment (DEA). Above 17 eV, the monotonic increase in the fragment yields indicates that nonresonant processes (i.e. dipolar dissociation) control the fragmentation of these molecules. Within the energy range investigated, comparison of the magnitude of the total fragment yields produced by electron attack on dCy(9), T(6)-dCy(3) and T(9) suggests the following order in the sensitivity of single-strand DNA: dCy(9) > T(6)-dCy(3) > T(9). At 12 eV, the total fragment yields are found to be 5.8, 5.0 and 3.9 x 10(-3) fragment/electron, respectively. From the yields obtained with the two homo-oligonucleotides, we differentiate between contributions arising from the chemical nature of the base and the effect of environment (i.e. the sequence) when a thymidine unit in T(9) is replaced by dCy. The base sequence-dependent damage is found to vary with incident electron energy. These results reinforce the idea that genomic sensitivity to ionizing radiation depends on local genetic information. Furthermore, they underscore the possible role of low-energy electrons in the pathways responsible for the induction of specific genomic lesions.     

Differential and integral W-values for ionization in gaseous water under electron and proton irradiation: consistency of inelastic collision cross sections.

Differential and integral W-values for ionization in gaseous water for electron and proton irradiation have been analyzed from the theoretical point of view for consistency between ionization and total inelastic collision cross sections. For low-energy electrons, which are ubiquitous for all primary radiations, the experimental or compiled cross sections from different sources are sometimes not consistent with one another. A practical, self-consistent procedure is outlined in such cases. The high-energy asymptotic W-values for differential and integral ionization are calculated to be 33.7 and 34.7 eV, respectively, for electron irradiation and 34.6 and 32.5 eV, respectively, for proton irradiation. The computed variations of the W-values with energy are generally in good agreement with experiment. Integral primary W-values due only to the interactions between the incident particle and the water vapor are calculated to be 43.5 and 45.0 eV for electrons and protons, respectively, in the high-energy asymptotic limit.     

Low-energy (5-40 eV) electron-stimulated desorption of anions from physisorbed DNA bases

We present the results of experiments on anion desorption from the physisorbed DNA bases adenine, thymine, guanine and cytosine induced by the impact of low-energy (5-40 eV) electrons. Electron bombardment of DNA base films induces ring fragmentation and desorption of H(-), O(-), OH(-), CN(-), OCN(- ) and CH(2)(-) anions through either single or complex multibond dissociation. We designate the variation of the yield of an anion with electron energy as the yield function. Below 15 eV incident electron energy, bond cleavage is controlled mainly by dissociative electron attachment. Above 15 eV, the portion of a yield function that increases linearly is attributed to nonresonant processes, such as dipolar dissociation. A resonant structure is superimposed on this signal around 20 eV in the anion yield functions. This structure implicates dissociative electron attachment and/or resonant decay of the transient anion into the dipolar dissociation channel, with a minimal contribution from multiple inelastic electron scattering. The yields of all desorbing anions clearly show that electron resonances contribute to the damage of all DNA bases bombarded with 5-40 eV electrons. Comparison of the ion yields indicates that adenine is the least sensitive base to slow electron attack. Electron-irradiated guanine films exhibit the largest yields of desorbed anions.     

Analysis of low-energy electron track structure in liquid water

An implementation is presented of interaction cross sections for non-relativistic electron track structure simulations. The model, incorporating liquid-phase cross sections for inelastic interactions and improved algorithms for elastic scattering, is applied to Monte Carlo simulation of the track structure of low-energy electrons. Benchmark distributions and mean values are presented for several measures of penetration distances that characterize the general physical extent of the track structure. The results indicate that, except for the last approximately 500 eV of energy loss, electron tracks have a quasi-linear character; this suggests that a major part of an electron track may be reasonably described by a lineal-energy-like characterization.     

Concepts on charge transfer through naturally vibrating DNA molecule

Delocalization of charges thorough DNA occurs due to the natural and continuous movements of molecule which stimulates the charge transfer through the molecule. A model is presented showing that the mechanism of electrical conduction occurs mainly by thermally-activated drift motion of holes under control of the localized carriers; where electrons are localized in the conduction band. These localized (stationary-trapped) electrons control the movements of the positive charges and do not play an effective role in the electrical conduction itself. It is found that the localized charge-carriers in the bands have characteristic relaxation times at 5×10(^-2)s, 1.94×10(^-4)s, 5×10(^-7)s, and 2×10(^-11)s respectively which are corresponding to four intrinsic thermal activation energies 0.56eV, 0.33eV, 0.24eV, and 0.05eV respectively. The ac-conductivity of some published data are well fitted with the presented model and the total charge density in DNA molecule is calculated to be n=1.88×10(^19)cm(^-3) at 300K which is corresponding to a linear electron density n=8.66×10(^3)cm(^-1) at 300K. The model shed light on the role of transfer and/or localization of charges through DNA which has multiple applications in medical, nano-technical, bio-sensing and different domains. So, repair DNA by adjusting the charge transport through the molecule is future challenges to new medical applications.     

Radiosensitization of DNA by gold nanoparticles irradiated with high-energy electrons

Zheng, Y., Hunting, D. J., Ayotte, P. and Sanche, L. Radiosensitization of DNA by Gold Nanoparticles Irradiated with High-Energy Electrons. Radiat. Res. 168, 19-27 (2008). Thin films of pGEM-3Zf(-) plasmid DNA were bombarded by 60 keV electrons with and without gold nanoparticles. DNA single- and double-strand breaks (SSBs and DSBs) were measured by agarose gel electrophoresis. From transmission electron micrographs, the gold nanoparticles were found to be closely linked to DNA scaffolds, probably as a result of electrostatic binding. The probabilities for formation of SSBs and DSBs from exposure of 1:1 and 2:1 gold nanoparticle:plasmid mixtures to fast electrons increase by a factor of about 2.5 compared to neat DNA samples. For monolayer DNA adsorbed on a thick gold substrate, the damage increases by an order of magnitude. The results suggest that the enhancement of radiosensitivity is due to the production of additional low-energy secondary electrons caused by the increased absorption of ionizing radiation energy by the metal, in the form of gold nanoparticles or of a thick gold substrate. Since short-range low-energy secondary electrons are produced in large amounts by any type of ionizing radiation, and since on average only one gold nanoparticle per DNA molecule is needed to increase damage considerably, targeting the DNA of cancer cells with gold nanoparticles may offer a novel approach that is generally applicable to radiotherapy treatments.     

Investigation of the electron energy distribution function in hollow-cathode glow discharges in nitrogen and oxygen

The mechanism for the formation of the inverse electron distribution function is proposed and realized experimentally in a nitrogen plasma of a hollow-cathode glow discharge. It is shown theoretically and experimentally that, for a broad range of the parameters of an N₂ discharge, it is possible to form a significant dip in the profile of the electron distribution function in the energy range ε=2–4 eV and, accordingly, to produce the inverse distribution with df(ε)/d?>0. The formation of a dip is associated with both the vibrational excitation of N₂ molecules and the characteristic features of a hollow-cathode glow discharge. In such a discharge, the applied voltage drops preferentially across a narrow cathode sheath. In the main discharge region, the electric field E is weak (E<0.1 V/cm at a pressure of about p～0.1 torr) and does not heat the discharge plasma. The gas is ionized and the ionization-produced electrons are heated by a beam of fast electrons (with an energy of about 400 eV) emitted from the cathode. A high-energy electron beam plays an important role in the formation of a dip in the profile of the electron distribution function in the energy range in which the cross section for the vibrational excitation of nitrogen molecules is maximum. A plasma with an inverted electron distribution function can be used to create a population inversion in which more impurity molecules and atoms will exist in electronically excited states.     

Calculation on spectrum of direct DNA damage induced by low-energy electrons including dissociative electron attachment

In this work, direct DNA damage induced by low-energy electrons (sub-keV) is simulated using a Monte Carlo method. The characteristics of the present simulation are to consider the new mechanism of DNA damage due to dissociative electron attachment (DEA) and to allow determining damage to specific bases (i.e., adenine, thymine, guanine, or cytosine). The electron track structure in liquid water is generated, based on the dielectric response model for describing electron inelastic scattering and on a free-parameter theoretical model and the NIST database for calculating electron elastic scattering. Ionization cross sections of DNA bases are used to generate base radicals, and available DEA cross sections of DNA components are applied for determining DNA-strand breaks and base damage induced by sub-ionization electrons. The electron elastic scattering from DNA components is simulated using cross sections from different theoretical calculations. The resulting yields of various strand breaks and base damage in cellular environment are given. Especially, the contributions of sub-ionization electrons to various strand breaks and base damage are quantitatively presented, and the correlation between complex clustered DNA damage and the corresponding damaged bases is explored. This work shows that the contribution of sub-ionization electrons to strand breaks is substantial, up to about 40–70%, and this contribution is mainly focused on single-strand break. In addition, the base damage induced by sub-ionization electrons contributes to about 20–40% of the total base damage, and there is an evident correlation between single-strand break and damaged base pair A–T.     

Alteration of protein structure induced by low-energy (<18 eV) electrons. I. The peptide and disulfide bridges

We present measurements of low-energy (<18 eV) electron-stimulated desorption of anions from acetamide (CH(3)CONH(2)) and dimethyl disulfide [DMDS: (CH(3)S)(2)] films. Electron irradiation of physisorbed CH(3)CONH(2) produces H(-), CH(3)(-) and O(-) anions, whereas the H(-), CH(2)(-), CH(3)(-), S(-), SH(-) and SCH(3)(-) anions are observed to desorb from the DMDS film. Below 12 eV, the dependence of the anion yields on the incident electron energy exhibits structures that indicate that a resonant process (i.e. dissociative electron attachment) is responsible for molecular fragmentation. Within the range of 1-18 eV, it is found that (1.7 and 1.4) x 10(7) H(-) ions/incident electron and (7.8 x 10(-11) and 4.3 x 10(-8)) of the other ions/incident electron are desorbed from acetamide and DMDS films, respectively. These results suggest that, within proteins, the disulfide bond is more sensitive to low-energy electron attack than the peptide bond. In biological cells, some proteins interact closely with nucleic acid. Therefore, the observed fragments, when produced from secondary low-energy electrons generated by high-energy radiation, not only may denature proteins, but may also induce reactions with the nearby nucleic acid and damage DNA.     

Cross sections for low-energy (1-100 eV) electron elastic and inelastic scattering in amorphous ice

We report the integral cross sections per scatterer (i.e. elastic collision, phonon excitations, vibrational excitations, electronic excitations and ionization) for 1-100 eV electron scattering in an amorphous film of ice condensed at a temperature of 14 K. The integral cross sections are determined relative to the total from a two-stream multiple-scattering analysis of the electron energy distribution backscattered from the film. Their energy dependence is obtained from both the analysis of the elastic electron reflectivity as a function of the film thickness and the vibrational electron energy-loss spectra measured for several incident energies and large film thickness. The magnitude and various features found in the energy dependence of the cross sections are discussed, whenever possible, by comparison with data and with scattering mechanisms available in the gas phase. Microcospic effects, which are implicitly included in cross sections determined in this way, are discussed in terms of interference and coherent multiple-scattering contributions among the scattering sites as well as interactions of the scattering sites with their neighbors in the condensed phase.     

A Monte Carlo code for the simulation of heavy-ion tracks in water

TILDA, a new Monte Carlo track structure code for ions in gaseous water that is valid for both high-LET (approximately 10(4) keV/microm) and low-LET ions, is presented. It is specially designed for a comparison of the patterns of energy deposited by a large range of ions. Low-LET ions are described in a perturbative frame, whereas heavy ions with a very high stopping power are treated using the Lindhard local density approximation and the Russek and Meli statistical method. Ionization cross sections singly differential with energy compare well with the experiment. As an illustration of the non-perturbative interaction of high-LET ions, a comparison between the ion tracks of light and heavy ions with the same specific energy is presented (1.4 MeV/nucleon helium and uranium ions). The mean energy for ejected electrons was found to be approximately four times larger for uranium than for helium, leading to a much larger track radius in the first case. For electrons, except for the excitation cross sections that are deduced from experimental fits, cross sections are derived analytically. For any orientation of the target molecule, the code calculates multiple differential cross sections as a function of the ejection and scattering angles and of the energy transfer. The corresponding singly differential and total ionization cross sections are in good agreement with experimental data. The angular distribution of secondary electrons is shown to depend strongly on the orientation of the water molecule.     

Monte Carlo calculations of energy deposition distributions of electrons below 20 keV in protein

The distributions of energy depositions of electrons in semi-infinite bulk protein and the radial dose distributions of point-isotropic mono-energetic electron sources [i.e., the so-called dose point kernel (DPK)] in protein have been systematically calculated in the energy range below 20 keV, based on Monte Carlo methods. The ranges of electrons have been evaluated by extrapolating two calculated distributions, respectively, and the evaluated ranges of electrons are compared with the electron mean path length in protein which has been calculated by using electron inelastic cross sections described in this work in the continuous-slowing-down approximation. It has been found that for a given energy, the electron mean path length is smaller than the electron range evaluated from DPK, but it is large compared to the electron range obtained from the energy deposition distributions of electrons in semi-infinite bulk protein. The energy dependences of the extrapolated electron ranges based on the two investigated distributions are given, respectively, in a power-law form. In addition, the DPK in protein has also been compared with that in liquid water. An evident difference between the two DPKs is observed. The calculations presented in this work may be useful in studies of radiation effects on proteins.