RESUMO
In this work, through a combination of photoluminescence spectroscopy, X-ray powder diffraction and magnetic measurements, it is determined that ZnO rods, made hydrothermally using a combination of magnetic field with respect to the force of gravity, exhibit superparamagnetic properties which emerge from Zn defects. These Zn defects result in a size-dependent superparamagnetic property of the rods. Red emissions, characteristic of Zn vacancies, and magnetic susceptibility both increased with decreasing rod size. The ZnO rods have significantly larger superparamagnetic cluster sizes (one order of magnitude) and lower fluctuation rates when compared to other superparamagnetic particles.
RESUMO
The purpose of the present work was to study how chemical reactions and the electronic structure of atoms are affected by confinement at the sub-nanometer scale. To reach this goal, we studied the H atom in talc, a layered clay mineral. Talc is a highly 2D-confining material with the width of its interlayer space close to angstrom. We investigated talc with a particle accelerator-based spectroscopic method that uses elementary particles. This technique generates an exotic atom, muonium (Mu), which can be considered as an isotope of the H atom. Moreover, the technique allows us to probe a single atom (H atom) at any time and explore the effects of the layered clay on a single ion (proton) or atom. The cation/electron recombination happens in two time windows: one faster than a nanosecond and the other one at longer than microseconds. This result suggests that two types of electron transfer processes take place in these clay minerals. Calculations demonstrated that the interlayer space acts as a catalytic surface and is the primary location of cation/electron recombination in talc. Moreover, the studies of the temperature dependence of Mu decay rates, due to the formation of the surrogate of H2, is suggestive of an "H2" formation reaction that is thermally activated above 25 K, but governed by quantum diffusion below 25 K. The experimental and computational studies of the hyperfine coupling constant of Mu suggest that it is formed in the interlayer space of talc and that its electronic structure is extremely changed due to confinement. All these results imply that the chemistry could be strongly affected by confinement in the interlayer space of clays.
RESUMO
The ionizing radiation in aqueous solutions of gold nanoparticles, stabilized by electrostatic non-covalent intermolecular forces and steric interactions, with antimicrobial compounds, are investigated with picosecond pulse radiolysis techniques. Upon pulse radiolysis of an aqueous solution containing very low concentrations of gold nanoparticles with naked surfaces available in water (not obstructed by chemical bonds), a change to Cerenkov spectrum over a large range of wavelengths are observed and pre-solvated electrons are captured by gold nanoparticles exclusively (not by ionic liquid surfactants used to stabilize the nanoparticles). The solvated electrons are also found to decay rapidly compared with the decay kinetics in water. These very fast reactions with electrons in water could provide an enhanced oxidizing zone around gold nanoparticles and this could be the reason for radio sensitizing behavior of gold nanoparticles in radiation therapy.
