Diffusion-reaction model of positron annihilation for complex defect pattern.

The increasing structural complexity in modern material science is often associated with grain sizes in theµm- and the sub-µm-regime. Therefore, when positron annihilation is applied for studying free-volume type defects in such materials, positron trapping at grain boundaries (GBs) cannot be neglected, even when other defect types are in the primary focus. For this purpose, the available diffusion-reaction model for positron trapping and annihilation at GBs is extended to competitive trapping at two different types of intragranular defects. Closed-form expressions for the mean positron lifetime and the relative intensities of the defect-specific positron lifetime components are given. The model is presented for cylindrical-shaped crystallites, but is valid in the general sense for spherical symmetry as well with appropriate replacements. The model yields the basis for properly determining defect concentrations, even for the inconvenient but common case that one intragranular defect type exhibits a lifetime component similar to that in GBs. It turns out, that positron trapping at GBs matters even forµm-sized crystallites and should not be neglected for precise studies of intragranular defects.

Positronium chemistry of a Fe2+/3+ solution under electrochemical control.

The positronium chemistry of a Fe2+/3+ solution is studied under full electrochemical control. For this novel approach to positronium electrochemistry, a suitable cell setup is used, which allows simultaneously both electrochemical measurements and positron annihilation spectroscopy. For the Fe2+/3+ redox couple, positronium serves as an ideally suited atomic probe owing to the rather different positronium chemistry of Fe2+ (spin conversion) and Fe3+ (total positronium inhibition and oxidation). This enabled the precise in situ monitoring of oxidation and reduction by means of positron lifetime upon slow cycling voltammetry or galvanostatic charging. The variation of the mean positron lifetime with the Fe2+/3+ concentration ratio could be quantitatively described by a reaction rate model for positronium formation and annihilation. An asymmetric behavior of the variation of the mean positron lifetime with applied potential, as compared to the simultaneously recorded symmetric current-potential curve, could be explained by the stronger influence of Fe3+ on the characteristics of positronium formation and annihilation. The highly reversible galvanostatic charging behavior monitored by positron lifetime underlines the attractive application potentials of positronium electrochemistry for in situ studies of iron-based redox-flow battery electrolytes.

Electrochemical switching of positronium triplet quenching.

Switching of positronium triplet quenching could successfully be demonstrated by electrochemical means in an aqueous K3[Fe(CN)6] electrolyte. For this purpose a suitable cell was designed to combine positron annihilation with electrochemical measurements. Highly reversible substantial variations of the mean positron lifetime τm could be observed upon electrochemical switching between the oxidation states Fe(CN)63- and Fe(CN)64-, arising from oxidation of positronium by Fe(CN)63-. Dynamic in situ measurements in dependence of potential exhibit a hysteresis like behavior of τm which perfectly correlates with the shift between the reduction and oxidation peaks simultaneously monitored by cyclic voltametry.

Nanoporous gold electrodes modified with self-assembled monolayers for electrochemical control of the surface charge.

The electrochemical behaviour of nanoporous gold modified with self-assembled monolayers is investigated with regard to its point of zero charge (pzc) and proton transfer reaction. Due to their high surface-to-volume ratio and conductivity, nanoporous electrodes represent promising materials for numerous applications, including the immobilization of biomolecules in biotechnology and biosensing. Therefore, the fundamental understanding and controllability of the surface state of the electrode is essential. To achieve a precise surface charge control, nanoporous gold (npAu) is modified with self-assembled monolayers (SAMs) of different lengths (3-mercaptopropionic acid (MPA) and 16-mercaptohexadecanoic acid (MHDA)). Cyclic voltammetry and impedance spectroscopy are used to determine the pzc. The most distinct pzc, and thus the most precise charge control, is found for the long-chain MHDA. Subsequently, the proton transfer reaction was investigated as a function of pH and scan rate. The observed protonation/deprotonation reaction was qualitatively well in line with the literature for planar gold electrodes, albeit the fraction of electrochemical controllable SAMs increased by a factor of 10 compared to planar electrodes indicating attractive application potential.

Influence of high-pressure torsion deformation on the corrosion behaviour of a bioresorbable Mg-based alloy studied by positron annihilation.

The effect of high-pressure torsion (HPT) on the corrosion behavior of extruded ZX00 (Mg-0.45wt%Zn-0.45wt%Ca) in phosphate buffered saline solution is investigated. MgCaZn alloys are promising candidates for the use as bioresorbable implant materials and, therefore, are in the focus of current research. To improve their strength, severe plastic deformation, e.g. via the technique of HPT, can be used. Positron lifetime spectroscopy (PLS) is applied as sensitive tool for studying open-volume defects which evolve during HPT processing and subsequent corrosion. The studies were complemented by electrochemical impedance spectroscopy (EIS). In the uncorroded state, grain boundaries are the major type of positron trap as quantitatively analysed by means of diffusion-reaction models for positron trapping and annihilation in fine-grained alloys. Upon corrosion, positronium formation and annihilation indicate larger open-volume structures, such as pores and cracks, in the emerging corrosion product and oxide layers. Both PLS and EIS clearly show that HPT-deformation strongly reduces the resistance against corrosion. Evidence is found for corrosion-induced open-volume defects, presumably related to hydrogen, in deeper parts of the material below the corrosion layer.

Induction of stilbene phytoalexins in grapevine (Vitis vinifera) and transgenic stilbene synthase-apple plants (Malus domestica) by a culture filtrate of Aureobasidium pullulans.

Products containing the epiphytic yeast Aureobasidium pullulans are commercially available and applied by fruit growers to prevent several fungal and bacterial diseases of fruit trees. The proposed beneficial mechanisms relate to limitations of space and nutrients for the pathogens in presence of the rapidly proliferating yeast cells. These explanations ignore the potential of yeasts to elicit the plant's defense. Our experiments aim at clarifying if an autoclaved and centrifuged suspension of A. pullulans may induce defense mechanisms. As a model system, the biosynthesis and accumulation of stilbene phytoalexins in callus and shoots of grapevine Vitis vinifera grown in vitro was used. Yeast application to the plant tissue stimulated stilbene biosynthesis, sometimes at the cost of flavonoids. The expression of the gene encoding stilbene synthase was enhanced and the enzyme showed higher activity while chalcone synthase activity and expression was reduced in some cases. An accumulation of stilbenes was also found in transgenic apple trees (Malus domestica cv. Holsteiner Cox) harboring the stilbene synthase-gene under control of its own promoter. These results clearly show that the application of A. pullulans may induce defense mechanisms of the treated plants.