DNA Nucleobase under Ionizing Radiation: Unexpected Proton Transfer by Thymine Cation in Water Nanodroplets

The effect of ionizing radiation on DNA constituents is a widely studied fundamental process using experimental and computational techniques. In particular, radiation effects on nucleobases are usually tackled by mass spectrometry in which the nucleobase is embedded in a water nanodroplet. Here, we present a multiscale theoretical study revealing the effects and the dynamics of water droplets towards neutral and ionized thymine. In particular, by using both hybrid quantum mechanics/molecular mechanics and full ab initio molecular dynamics, we reveal an unexpected proton transfer from thymine cation to a nearby water molecule. This leads to the formation of a neutral radical thymine and a Zundel structure, while the hydrated proton localizes at the interface between the deprotonated thymine and the water droplet. This observation opens entirely novel perspectives concerning the reactivity and further fragmentation of ionized nucleobases.     

Inelastic interactions of protons and electrons with biologically relevant molecules

Ionization and fragmentation of water and uracil molecules was studied both by electron and proton impact. A special coincidence technique allows on an event by event basis the investigation of product ions formed upon the collision of protons with neutral molecules including the identification of the charge state of the projectile. This enables the characterization of the ionization processes occurring, i.e. direct ionization, single electron capture or double electron capture for 0, 1 or 2 electrons that are transferred from the target to the projectile, respectively. For uracil the fragmentation patterns obtained by electron and proton impact ionization reveal close similarities and indicate a comparable amount of excitation for the two different ionization mechanisms at high enough projectile energies. Received 25 February 2002 Published online 13 September 2002     

Multiple H 3 + fragment production in single collision of fast H n + clusters with He atoms

The production of H ₃ ⁺ ions resulting from single collisions of mass-selected ionic hydrogen clusters, H _n ⁺ (n=9, 25, 31), with helium at high velocity (1.55 times the Bohr velocity) has been studied. A strong double H ₃ ⁺ ion production resulting from one incident cluster is observed. Moreover, evidence for a triple H ₃ ⁺ fragment production is presented forn=25 and 31. Thus, in this energy range, the collision gives rise to multifragmentation processes. The formation of H ₃ ⁺ ions takes place in the fragmentation of the multicharged cluster resulting from the collision.     

Silver Metallic Nanoparticles with Surface Plasmon Resonance: Synthesis and Characterizations

Silver nanoparticles were synthesized by the reduction of the silver nitrate (AgNO₃) using the latex copolymer in ethanol solution under microwave (MW) heating. The reaction parameters such as silver precursor concentration (from 0.005 to 0.1 g/l) and MW power (200–800 W) significantly affect the formation rate, shape, size and distribution of the silver nanoparticles. A significant reduction of irradiation time was observed when the MW energy is compared to conventional thermal reduction processes. The prepared silver nanoparticles show uniform and stable sizes from 5 to 11 nm, which can be stored at room temperature for approximately 12 months without any visible change. These peculiarities indicate that the latex copolymer is a good stabilizer for the silver nanoparticles. The optical properties, morphology, and crystalline structure of the silver-latex copolymer nanocomposites were characterized by the Ultraviolet–Visible spectroscopy, transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The study of the TEM images at high magnifications identified the silver nanoparticles as face-centered cubic (fcc) structure with spherical and hexagonal shapes.     

Ab Initio Study of the Stepwise versus Concerted Fragmentation Pathways in Microhydrated Thymine Radical Cations

Thymine radiation-induced fragmentation is characterised by ring opening and the loss of HNCO/NCO. These pathways have been investigated using DFT calculations in the presence of zero, one and two water molecules. In addition to the already characterised stepwise fragmentation mechanism, we propose a novel concerted pathway reported here for the first time. We show that both the stepwise and concerted mechanisms are competitive with activation energies of 2.05 eV and 2.00 eV, respectively, in the gas phase. The effect of microhydration on these mechanisms are examined based on the most stable conformations found by an exploration of the potential energy surface performed by using DFT-based ab initio molecular dynamics. Microhydration is also accompanied by an increase in the activation energies, with respect to gas phase, amounting to 0.47 eV—an increase that is associated to a stabilising effect of water in agreement with recent experimental studies. However, we also point out that this effect is greatly dependent on the specific water arrangement around thymine and could be limited to only 0.13 eV for some configurations.     

Rapid Synthesis of Silver Nanoparticles by Microwave-Polyol Method with the Assistance of Latex Copolymer

Highly stable and monodispersed silver nanoparticles with uniform morphology have been successfully prepared by microwave (MW) irradiation within a few seconds from the mixture of silver nitrate, ethanol and latex copolymer. The aqueous emulsion of latex copolymer acts as both reducing and stabilizing agent. To the best of our knowledge, it was the first time that the effect of MW irradiation time and latex concentration on the silver nanoparticle preparation and properties was analyzed. The formation of silver nanoparticles was confirmed by Ultraviolet–visible spectroscopy and transmission electron microscopy (TEM). The UV–Vis spectra are marked by the characteristic surface plasmon absorption band in the range 410–420 nm. From TEM images, silver nanoparticles were observed to be spherical with sizes ranging from 4 to 10 nm. Electron diffraction patterns on selected area, indicated that the silver nanoparticles are crystalline with face centered cubic structure.