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8-oxo-Guanine is a mutagenic lesion produced by reactions involving reactive oxygen species and guanine in DNA. Its production induces mispairing between the canonical nucleobases during DNA replication such that various types of cancers are associated with the DNA lesion. Since radiation therapy is used in some cases, the interaction of low-energy electrons with 8-oxo-guanine can in turn produce other reactive species, which in principle could have either a detrimental or protective effect on the organism. Motivated by these facts, we report a comparative experimental study of electron-induced fragmentation of guanine and 8-oxo-guanine, along with a theoretical study of the π* shape resonances and bound anion states, which may trigger those dissociation reactions. The electron-induced fragmentation of 8-oxo-guanine is remarkably distinct from the native form. More complex reactions were observed for the oxidized species, which may produce several anion fragments at very low energies (∼0 eV). The dehydrogenated parent anion, which is already a minor fragment in guanine, was completely suppressed in 8-oxo-guanine. The calculated thermodynamical thresholds also suggest that NH 2 elimination in guanine, at sub-excitation energies, proceeds via a complex reaction involving rearrangement steps.

We report a computational study of the anion states of the resveratrol (RV) and resorcinol (RS) molecules, also investigating dissociative electron attachment (DEA) pathways. RV has well-known beneficial effects in human health, and its antioxidant activity was previously associated with DEA reactions producing H 2 . Our calculations indicate a valence bound state ( π 1 * ) and four resonances ( π 2 * to π 5 * ) for that system. While the computed thermodynamic thresholds are compatible with DEA reactions producing H 2 at 0 eV, the well-known mechanism involving vibrational Feshbach resonances built on a dipole bound state should not be present in RV. Our results suggest that the shallow π 1 * valence bound state is expected to account for H 2 elimination, probably involving π 1 * / σ OH * couplings along the vibration dynamics. The RS molecule is also an oxidant and a subunit of RV. Because two close-lying hydroxyl groups are found in the RS moiety, the H 2 -elimination reaction in RV should take place at the RS site. Our calculations point out a correspondence between the anion states of RV and RS and even between the thresholds. Nevertheless, the absence of bound anion states in RS, indicated by our calculations, is expected to suppress the H 2 -formation channel at 0 eV. One is led to conclude that the ethene and phenol subunits in RV stabilize the π 1 * state, thus switching on the DEA mechanism producing H 2 .

Low-energy electrons (LEEs) can very efficiently induce bond breaking via dissociative electron attachment (DEA). While DEA is ubiquitous, the importance of other reactions initiated by LEEs remains much more elusive. Here, we looked into this question by measuring highly accurate total cross sections for electron scattering from 1-methyl-5-nitroimidazole (1M5NI), a model radiosensitizer. The small uncertainty and high energy resolution allow us to identify many resonant features related to the formation of transient anions. In addition to novel insights about DEA reactions through the lower-lying resonances, our key finding is that the higher-lying resonances do not undergo DEA, implying alternative decay channels with significant cross sections. In particular, dissociation into two neutral fragments is probably involved in the case of 1M5NI. This finding has direct implications for the understanding of LEE-induced chemistry, particularly in the fundamental processes underlying the radiosensitization activity.

We report cross sections for elastic electron scattering by gas phase glycine (neutral form), obtained with the Schwinger multichannel method. The present results are the first obtained with a new implementation that combines parallelization with OpenMP directives and pseudopotentials. The position of the well known π* shape resonance ranged from 2.3 eV to 2.8 eV depending on the polarization model and conformer. For the most stable isomer, the present result (2.4 eV) is in fair agreement with electron transmission spectroscopy assignments (1.93 ± 0.05 eV) and available calculations. Our results also point out a shape resonance around 9.5 eV in the A' symmetry that would be weakly coupled to vibrations of the hydroxyl group. Since electron attachment to a broad and lower lying σ* orbital located on the OH bond has been suggested the underlying mechanism leading to dissociative electron attachment at low energies, we sought for a shape resonance around ~4 eV. Though we obtained cross sections with the target molecule at the equilibrium geometry and with stretched OH bond lengths, least-squares fits to the calculated eigenphase sums did not point out signatures of this anion state (though, in principle, it could be hidden in the large background). The low energy (~1 eV) integral cross section strongly scales as the bond length is stretched, and this could indicate a virtual state pole, since dipole supported bound states are not expected at the geometries addressed here.

We report cross sections for low-energy elastic electron scattering by pyrrole, obtained with the Schwinger multichannel method implemented with pseudopotentials. Our calculations indicate pi( *) shape resonances in the B(1) and A(2) symmetries, and two sigma( *) resonances in the A(1) symmetry (the system belongs to the C(2v) point group). The present assignments of pi( *) resonances are very close to those previously reported for the isoelectronic furan molecule, in agreement with electron transmission spectra. The lowest-lying sigma( *) anion is localized on the N-H bond and provides a dissociation coordinate similar to those found in the hydroxyl groups of organic acids and alcohols. This sigma(NH) ( *) resonance overlaps the higher-lying pi( *) resonance (possibly both pi( *) states) and could give rise to direct and indirect dissociation pathways, which arise from electron attachment to sigma( *) and pi( *) orbitals, respectively. The photochemistry of pyrrole and 9-H adenine is similar, in particular with respect to the photostability mechanism that allows for the dissipation of the photon energy, and we believe pyrrole would also be a suitable prototype for studies of dissociative electron attachment (DEA) to DNA bases. We point out the connection between the mechanisms of photostability and DEA since both arise from the occupation of sigma( *) and pi( *) orbitals in neutral excited states and in anion states, respectively.

The development of new alternative routes for production of second generation ethanol from sugarcane biomass poses a challenge to the scientific community. Current research in this field addresses the use of a plasma-based pretreatment of the lignocellulosic raw material. With the aim to provide a theoretical background for this experimental technique we investigate the role of low-energy electrons from the plasma in the rupture of the matrix of cellulosic chains. In this paper, we report calculated cross sections for elastic scattering of low-energy electrons by the alpha- and beta-D-glucose monomers. The calculations employed the Schwinger multichannel method with pseudopotentials and were carried out at the static-exchange and static-exchange plus polarization levels of approximation. Through the comparison of the results obtained with inclusion of polarization effects we discuss the influence of the different conformations of the hydroxyl group linked to the anomeric carbon on the resonance spectra of these molecules. Resonant structures appearing at different energies for alpha- and beta-glucose at the low-energy regime of impact energies can be understood as a fingerprint of an "isomeric effect" and suggest that distinct fragmentation mechanisms proceeding via sigma* shape resonances may become operative depending on the glucose anomer under consideration. For energies above 15 eV the integral elastic cross sections are very similar for both monomers. Differential cross sections for the glucopyranose anomers considered in this work are typically dominated by a strong forward scattering due to the molecules' large electric dipole moments and, for energies close to the resonances' positions, they display particular features at the intermediate angular region, notably a pronounced f-wave scattering pattern, that are probably associated with the presence of those structures.