Thermal and photochemical reactivity of oxygen atoms on gold nanocluster surfaces

Reduction of oxidized gold nanoclusters by exposures to foreign gases and irradiation of UV photons has been investigated using X-ray photoelectron spectroscopy. Gold nanoclusters with narrow size distributions protected by alkanethiolate ligands were deposited on a TiO₂(1 1 0) surface with dip coating. Oxygen plasma etching was used for removal of alkanethiolate ligands and oxidization of gold clusters. The oxidized gold clusters were exposed to CO, C₂H₂, C₂H₄, H₂, and hydrogen atoms. Although, C₂H₄ and H₂ did not show any indications of reduction of oxidized gold clusters, CO, C₂H₂, and hydrogen atoms reduced the oxides on gold cluster surfaces. Among them, hydrogen atoms were most effective for reduction. Irradiation of UV photons around 400 nm could also reduce the oxidized gold clusters. The photochemical reduction mechanism was proposed as follows. The photo-reduction was initiated by electronic excitation of gold clusters and oxygen atoms activated reacted with carbon atoms at the surfaces of gold clusters. Carbon species were likely absorbed in gold clusters or remained at the boundaries between gold clusters when gold clusters agglomerated during oxygen plasma exposures. As the photochemical reduction progressed, carbon atoms segregated to the surfaces of gold clusters.     

On the way to sol–gels: an analysis of the intra‐ and intermolecular hydrogen bonding in [Ba(OH)I(H2O)4]

We have been able, via a new synthetic route, to obtain a complete crystal structure of the title compound, tetra­aqua­barium hydro­xide iodide, [Ba(OH)I(H₂O)₄], for which the heavy atoms only were characterized by Kellersohn, ­Beckenkamp & Lutz [Z. Naturforsch. TeilB (1991), 46 , 1279–1286]. In the present results, the H‐atom positions could be located using X‐ray data collection at low temperature. A three‐dimensional network is built up via hydrogen bonds. It was also observed that the title compound undergoes hy­drolysis and might therefore be regarded as an intermediate in the formation of sol–gels, starting from BaI₂ and leading to [Ba(OH)₂(H₂O)_x].     

Monitoring the heterogeneity in single cell responses to drugs using electrochemical impedance and electrochemical noise

Impedance spectroscopy is a widely used technique for monitoring cell–surface interactions and morphological changes, typically based on averaged signals from thousands of cells. However, acquiring impedance data at the single cell level, can potentially reveal cell-to-cell heterogeneity for example in response to chemotherapeutic agents such as doxorubicin. Here, we present a generic platform where light is used to define and localize the electroactive area, thus enabling the impedance measurements for selected single cells. We firstly tested the platform to assess phenotypic changes in breast cancer cells, at the single cell level, using the change in the cell impedance. We next show that changes in electrochemical noise reflects instantaneous responses of the cells to drugs, prior to any phenotypical changes. We used doxorubicin and monensin as model drugs and found that both drug influx and efflux events affect the impedance noise signals. Finally, we show how the electrochemical noise signal can be combined with fluorescence microscopy, to show that the noise provides information on cell susceptibility and resistance to drugs at the single cell level. Together the combination of electrochemical impedance and electrochemical noise with fluorescence microscopy provides a unique approach to understanding the heterogeneity in the response of single cells to stimuli where there is not phenotypic change.

A light addressable single-cell impedance technique for cell adhesion monitoring and measurement of a cell''s drug response based on electrochemical noise is introduced.     

Risk-neutral valuation of participating life insurance contracts in a stochastic interest rate environment

Over the last years, the valuation of life insurance contracts using concepts from financial mathematics has become a popular research area for actuaries as well as financial economists. In particular, several methods have been proposed of how to model and price participating policies, which are characterized by an annual interest rate guarantee and some bonus distribution rules. However, despite the long terms of life insurance products, most valuation models allowing for sophisticated bonus distribution rules and the inclusion of frequently offered options assume a simple Black–Scholes setup and, more specifically, deterministic or even constant interest rates.We present a framework in which participating life insurance contracts including predominant kinds of guarantees and options can be valuated and analyzed in a stochastic interest rate environment. In particular, the different option elements can be priced and analyzed separately. We use Monte Carlo and discretization methods to derive the respective values.The sensitivity of the contract and guarantee values with respect to multiple parameters is studied using the bonus distribution schemes as introduced in [Bauer, D., Kiesel, R., Kling, A., Ruß, J., 2006. Risk-neutral valuation of participating life insurance contracts. Insurance: Math. Econom. 39, 171–183]. Surprisingly, even though the value of the contract as a whole is only moderately affected by the stochasticity of the short rate of interest, the value of the different embedded options is altered considerably in comparison to the value under constant interest rates. Furthermore, using a simplified asset portfolio and empirical parameter estimations, we show that the proportion of stock within the insurer’s asset portfolio substantially affects the value of the contract.     

On the chemical synthesis of titanium nanoparticles from ionic liquids

Abstract  

We report on attempts towards the synthesis of titanium nanoparticles using a wet chemical approach in imidazolium-based ionic liquids (ILs) under reducing conditions. Transmission electron microscopy finds nanoparticles in all cases. UV/Vis spectroscopy confirms the nanoparticulate nature of the precipitate, as in all cases an absorption band between ca. 280 and 300 nm is visible. IR spectroscopy shows that even after extensive washing and drying, some IL remains adsorbed on the nanoparticles. Raman spectroscopy suggests the formation of anatase nanoparticles, but X-ray diffraction reveals that, possibly, amorphous titania forms or that the nanoparticles are so small that a clear structure assignment is not possible. The report thus shows that (possibly amorphous) titanium oxides even form under reducing conditions and that the chemical synthesis of titanium nanoparticles in ILs remains elusive.