Hydroperoxyl radical and formic acid formation from common DNA stabilizers upon low energy electron attachment.

2-Amino-2-(hydroxymethyl)-1,3-propanediol (TRIS) and ethylenediaminetetraacetic acid (EDTA) are key components of biological buffers and are frequently used as DNA stabilizers in irradiation studies. Such surface or liquid phase studies are done with the aim to understand the fundamental mechanisms of DNA radiation damage and to improve cancer radiotherapy. When ionizing radiation is used, abundant secondary electrons are formed during the irradiation process, which are able to attach to the molecular compounds present on the surface. In the present study we experimentally investigate low energy electron attachment to TRIS and methyliminodiacetic acid (MIDA), an analogue of EDTA, supported by quantum chemical calculations. The most prominent dissociation channel for TRIS is through hydroperoxyl radical formation, whereas the dissociation of MIDA results in the formation of formic and acetic acid. These compounds are well-known to cause DNA modifications, like strand breaks. The present results indicate that buffer compounds may not have an exclusive protecting effect on DNA as suggested previously.

High-Resolution Electron Attachment to the Water Dimer Embedded in Helium Droplets: Direct Observation of the Electronic Conduction Band Formation.

For bulk liquid helium the bottom of the conduction band (V0) is above the vacuum level. In this case the surface of the liquid represents an electronic surface barrier for an electron to be injected into the liquid. Here we study the electronic conduction band for doped helium droplets of different sizes. Utilizing an electron monochromator, the onset of the (H2O)2- ion yield corresponding to V0 is determined for helium droplets doped with the water dimer. While for larger droplets the onset approaches the well-known bulk value of about 1 eV, the barrier does not continuously decrease with smaller droplet size. A minimum value of V0 = 0.76 ± 0.10 eV is observed, which corresponds to a droplet size of Nmin = 1600 ± 900. For droplet sizes below Nmin, a peak at ∼0 eV appears, which is well-known from neat H2O clusters. Hence, we interpret Nmin as the smallest droplet size in which the electronic band structure is formed in liquid helium droplets.

Study of Electron Ionization and Fragmentation of Non-hydrated and Hydrated Tetrahydrofuran Clusters.

Mass spectroscopic investigations on tetrahydrofuran (THF, C4H8O), a common model molecule of the DNA-backbone, have been carried out. We irradiated isolated THF and (hydrated) THF clusters with low energy electrons (electron energy ~70 eV) in order to study electron ionization and ionic fragmentation. For elucidation of fragmentation pathways, deuterated TDF (C4D8O) was investigated as well. One major observation is that the cluster environment shows overall a protective behavior on THF. However, also new fragmentation channels open in the cluster. In this context, we were able to solve a discrepancy in the literature about the fragment ion peak at mass 55 u in the electron ionization mass spectrum of THF. We ascribe this ion yield to the fragmentation of ionized THF clusters. Graphical Abstract ᅟ.

Electron interactions with the focused electron beam induced processing (FEBID) precursor tungsten hexachloride.

RATIONALE: Secondary electrons with an energy distribution below 100 eV are formed when high-energy particles interact with matter. In the focused electron beam induced deposition, high-energy beams are used to decompose organometallic compounds on surfaces. We investigated the electron ionisation of WCl6 and dissociative electron attachment to WCl6 in the gas phase in order to better understand the decomposition mechanism driven by secondary electrons. METHODS: A double-focusing mass spectrometer coupled with a Nier-type ion source was used to perform the present studies. The electron ionisation studies were performed with an electron energy of 70 eV and dissociative electron attachment studies in the energy range of ~0-14 eV. RESULTS: Tungsten hexachloride rapidly oxidises, leading to the formation of a mixture of pure WCl6 and WCl4 O together with WCl2 O2 species. The fragmentation of the three chlorinated compounds is effective, although electron ionisation to WCl6 leads to W(+) in contrast with WCl2 O2 and WCl4 O leading to WO2 (+) and WO(+) , respectively, as lighter fragments. With regard to electron attachment, decomposition of the precursor molecules is observed; however, W(-) was not detected within the detection limit of the instrument. CONCLUSIONS: Electron ionisation and dissociative electron attachment (DEA) to WCl6 , WCl4 O and WCl2 O2 lead to strong fragmentation. In electron ionisation, the fragmentation by loss of chlorine atoms was observed for both WCl6 and the oxidised species. Additionally, the loss of all chlorine ligands is observable for WCl6 as well as the oxidised species. The DEA results have shown dissociation by the scission of chlorine atoms as well as by the scission of an oxygen atom. The formation of chlorine and oxygen anions was observed, indicating the formation of a neutral counterpart containing the metal atom, free to be attacked by the next electron.

Complete ligand loss in electron ionization of the weakly bound organometallic tungsten hexacarbonyl dimer.

We observed the bare W2(+) metal cation upon electron ionization of the weakly bound W(CO)6 dimer. This metal cation can be only observed due to the fast conversion of the weak cluster bond into a strong covalent bond between the metal moieties.

The Effect of Solvation on Electron Attachment to Pure and Hydrated Pyrimidine Clusters.

The interaction of low-energy electrons with biomolecules plays an important role in the radiation-induced alteration of biological tissue at the molecular level. At electron energies below 15 eV, dissociative electron attachment is one of the most important processes in terms of the chemical transformation of molecules. So far, a common approach to study processes at the molecular level has been to carry out investigations with single biomolecular building blocks like pyrimidine as model molecules. Electron attachment to single pyrimidine, as well as to pure clusters and hydrated clusters, was investigated in this study. In striking contrast to the situation with isolated molecules and hydrated clusters, where no anionic monomer is detectable, we were able to observe the molecular anion for the pure clusters. Furthermore, there is evidence that solvation effectively prevents the ring fragmentation of pyrimidine after electron capture.