Adsorption mode of ethyl pyruvate on platinum: an in situ XANES study

The adsorption of ethyl pyruvate on Pt(111) has been studied by in situ XANES measurements in the presence and absence of hydrogen. Depending on the hydrogen and ethyl pyruvate pressure, the C and O K‐edge spectra exhibit distinctly different angular dependence. Without hydrogen ethyl pyruvate is oriented preferentially perpendicular to the surface, indicating bonding via the O lone pairs. In the presence of hydrogen the mean orientation is more tilted towards the surface. Likely, ethyl pyruvate also interacts with Pt via its π system under these conditions. The observed angle‐dependent shift of the energy of the π* and σ* resonances indicates the coexistence of differently adsorbed ethyl pyruvate species. The experimental findings demonstrate the importance of the in situ approach for unraveling the adsorption mode of ethyl pyruvate in the enantioselective hydrogenation over cinchona‐alkaloid‐modified Pt. This revised version was published online in July 2006 with corrections to the Cover Date.     

Induction of DNA-double-strand breaks by auger electrons from 99mTc complexes with DNA-binding ligands

The potential of certain Auger electron emitting nuclides for systemic radiotherapeutic applications has recently gained much attention. In particular, the ability of several nuclides, including 111In, 125I, and 123I, to induce DNA double-strand breaks (dsb), a good indicator of cytotoxicity, has been extensively studied. However, this ability has never previously been shown experimentally for 99mTc, which, besides the well-known gamma radiation that is used for diagnostic applications, also emits an average of 1.1 conversion electrons and 4 Auger or Coster-Kronig electrons per decay. Owing to the short range of Auger electrons, the radionuclide needs to be located very close to the DNA for dsb to occur. We synthesized two cationic 99mTcI-tricarbonyl complexes with pendant DNA binders, pyrene and anthraquinone. The X-ray crystal structures of the two complexes could be elucidated. Linear dichroism and UV/Vis spectroscopy revealed that the complex with pyrene intercalates DNA with a stability constant, K, of 1.1 x 10(6) M(-1), while the analogous complex with anthraquinone interacts with DNA in a groove-binding mode and has an affinity value of K=8.9 x 10(4) M(-1). We showed with phiX174 double-stranded DNA that the corresponding 99mTc complexes induce a significant amount of dsb, whereas non-DNA-binding [TcO4]- and nonradioactive Re compounds did not. These results indicate that the Auger electron emitter 99mTc can induce dsb in DNA when decaying in its direct vicinity and this implies potential for systemic radiotherapy with 99mTc complexes.     

Photocatalytic mineralisation of organic compounds: a comparison of flame-made TiO2 catalysts

A comparative photocatalytic analysis was carried out on TiO₂ made in a Flame Spray Pyrolysis (FSP) process and flame-made Degussa P25. Both have similar crystallinity, phase composition, phase segregation and a non-porous surface. Hence comparison was made based on their difference in specific surface area, organic adsorption and the amount of OH• generated upon illumination. The photocatalytic activity tests were carried out using the following series of organic compounds: sucrose, glucose, fructose, maleic acid, glyoxylic acid, oxalic acid, isobutyric acid, phenol and methanol. FSP-made TiO₂ outperformed P25 for saccharides mineralisation, while for phenol and methanol mineralisation P25 was better than FSP-made TiO₂. Similar mineralisation rates were observed for both FSP-made and P25 TiO₂ for the mineralisation of carboxylic acids. This shows that the relative performance of the photocatalysts depends on the type of organic compounds to be degraded. The high surface area and possibly a more efficient interfacial charge transfer of FSP-made TiO₂ provided an efficient pathway for saccharides mineralisation. As for phenol and methanol, the mineralisation rates were higher when using P25 due to the greater amount of OH• radicals generated by this photocatalyst. The fast mineralisation rates of carboxylic acids made degradation of these organic compounds to be less affected by the TiO₂ photocatalyst properties and conditions tested in this work.     

Formation of Polymeric Lewis Acid–Lewis Base Complexes with Well-defined Organoboron Polymers

The binding of Lewis bases to organoboron polymeric Lewis acids has been studied and the parameters that determine the complexation equilibrium have been investigated, which include (i) the strength of the individual Lewis acids and Lewis bases, (ii) concentration, and (iii) temperature. While the strongly Lewis acidic borane polymers poly(4-bis(pentafluorophenyl)borylstyrene) (PS-BPf) and poly(4-(di-2-thienylboryl)styrene) (PS-BTh) form isolable complexes with strong Lewis bases such as 4-t-butylpyridine (^tPy), a temperature dependent equilibrium is established with weaker bases such as THF. Similarly, the weakly Lewis acidic boronate polymer poly(4-diethoxyborylstyrene) (PS-BOEt) undergoes a temperature dependent equilibrium with the strong Lewis base 4-dimethylaminopyridine (DMAP), while poly(4-pinacolatoborylstyrene) (PS-BPin) does not significantly bind to pyridine bases. Decomplexation of PS-BTh· ^t Py is achieved by treatment with the stronger Lewis acid, B(C₆F₅)₃, thereby confirming the reversible nature of the polymeric Lewis acid–base adducts. This paper is dedicated to Professor Ian Manners in gratitude of his guidance throughout the years and recognition of his scientific accomplishments     

Social virtual world continuance among teens: uncovering the moderating role of perceived aggregate network exposure

Engagement in virtual worlds has become pervasive, particularly among the young. At the same time, the number of virtual environments has increased rapidly. Due to intensifying competition, promoting sustained usage, i.e. continuance, has become a top priority for virtual world operators. Prior research has shown that network externalities play a key role in the adoption of communication technologies. However, a small amount of research has examined the role of network externalities in continued IT usage in general or with respect to the virtual world participation in particular. To fill in this gap, we examine how perceived network externalities affect the continuance of social virtual worlds. To this end, we introduce the concept of perceived aggregate network exposure (PANE). We extend the original information systems (IS) continuance model with perceived enjoyment and position PANE as a moderator. We test the model with data collected from 2134 Finnish Habbo Hotel users and employ structural equation modelling in the analysis. The results demonstrate that PANE moderates the influence of motivational factors on continued use intention and satisfaction.     

Tailoring of Surfaces with Ultrathin Layers for Controlled Binding of Biopolymers and Adhesion and Guidance of Cells

Various strategies are described for the bio-functionalization of solid substrates by design of interfacial architectures. The first approach is based on the self-assembly process of long-chain thiol molecules from solution to a (noble) metal surface. If some of these building blocks carry a binding site (ligand) for proteins (receptors, antibodies, etc.) the metal surface can be tailored for maximum specific binding while simultaneously minimizing nonspecific adsorption. The second concept is based on polymers that are covalently attached to (oxide) surfaces. The preparation of these (end-) grafted functional polymers involves either the binding of preformed macromolecules to corresponding sites at the surface of the support or the recently introduced “grafting-from” method, by which an initiator molecule is first covalently bound to the surface and then activated — either by heat or light — in the presence of suitable monomer units such that a polymer chain grows from the solid/solution interface. Finally, the functionalization of patterned surfaces by peptide chains that mimic the binding domains of cell adhesion proteins is summarized. It is demonstrated that not only the selective adhesion of neuronal cells can then be controlled, but also their development with the outgrowth of dendrites and axons.     

Evaluation of UF and RO in a cellulose saccharification process

The applications of membrane separation within the bioconversion of lignocellulosic materials to ethanol are studied, and this paper reports on cellulolytic enzyme recovery, and reduction of the product inhibition. The conversion of cellulose and hemicellulose to hexoses and pentoses is carried out in a laboratory scale UF-membrane reactor, and the sugars, which have an inhibiting effect on the enzymes, are continuously removed with the permeate. By optimizing the space velocity, the enzyme inhibition is minimized and the rate of hydrolysis is significantly increased.The recovery of the enzymes has also been investigated with regard to their mechanical stability and adsorption on the substrate. Prior to enzymatic hydrolysis, the raw material is subjected to a pretreatment to make the cellulose more accessible to the enzymes, and the effect of the pretreatment can easily be evaluated in the UF-membrane reactor.As a result of the continuous removal of products formed in the hydrolysis, the permeate has a low content of fermentable sugars, and to give the optimal conditions for the fermentation a concentration step is needed. Different RO-membranes are tested in a laboratory scale batch cell to be able to choose a membrane material, fit for filtration in larger modules.     

Influence of OSC material on the behaviour of metallic Pd catalysts in C2H4 and CO oxidation as well as in NO reduction

Topics in Catalysis - The interaction of CO, C2H4, O2, and NO reaction gas compounds over the metallic Pd/Al2O3 and Pd/OSC/Al2O3 monoliths was investigated in order to understand the behaviour of...     

Application of a multiline material characterization method to inkjet printed electronics

Material characterization has become increasingly important with the adoption of simulation‐based workflow for microwave electronics design. This article focuses on the characterization of printable electronics materials using transmission‐line measurements and demonstrates the capability of the multiline characterization method to separate dielectric and conductor losses when line geometry and material properties vary between the lines. The effects of multiline algorithm, number of line standards, and methods for selecting optimal line lengths are demonstrated. Consistent characterization results are obtained from inkjet‐printed transmission lines on two different substrate materials. In addition, local conductor thickness variations are demonstrated as an effective way to decrease losses. Finally, the simulation‐based procedure for determining the material properties is outlined and applied to printable electronics characterization. © 2013 Wiley Periodicals, Inc. Int J RF and Microwave CAE 24:177–183, 2014.     

Are test cases needed? Replicated comparison between exploratory and test-case-based software testing

Manual software testing is a widely practiced verification and validation method that is unlikely to fade away despite the advances in test automation. In the domain of manual testing, many practitioners advocate exploratory testing (ET), i.e., creative, experience-based testing without predesigned test cases, and they claim that it is more efficient than testing with detailed test cases. This paper reports a replicated experiment comparing effectiveness, efficiency, and perceived differences between ET and test-case-based testing (TCT) using 51 students as subjects, who performed manual functional testing on the jEdit text editor. Our results confirm the findings of the original study: 1) there is no difference in the defect detection effectiveness between ET and TCT, 2) ET is more efficient by requiring less design effort, and 3) TCT produces more false-positive defect reports than ET. Based on the small differences in the experimental design, we also put forward a hypothesis that the effectiveness of the TCT approach would suffer more than ET from time pressure. We also found that both approaches had distinctive issues: in TCT, the problems were related to correct abstraction levels of test cases, and the problems in ET were related to test design and logging of the test execution and results. Finally, we recognize that TCT has other benefits over ET in managing and controlling testing in large organizations.