Fullerene-based ruthenium catalysts: a novel approach for anchoring metal to carbonaceous supports. I. Structure

The influence of fullerenes and related support materials on the structural and catalytic properties of ruthenium was investigated. Catalysts based on C₆₀, raw fullerene black, extracted fullerene black, cathode deposit and graphite were prepared by an impregnation/activation procedure with Ru₃CO₁₂. The local co-ordination sphere of the resulting highly dispersed X-ray amorphous ruthenium was investigated by means of EXAFS. The dominating role of the presence of non-six-membered carbon rings on the structure and the stability of the Ru particles will be illustrated. This revised version was published online in July 2006 with corrections to the Cover Date.     

Method for characterization of triacylglycerols and fat-soluble vitamins in edible oils and fats by supercritical fluid chromatography

This study demonstrates the usefulness of capillary supercritical fluid chromatography (SFC) for the characterization of triacylglycerols of edible oils and fats. Triacylglycerols were separated according to the acyl carbon number and the degree of unsaturation on a 25% cyanopropyl/25% phenyl/50% methylpolysiloxane stationary phase. Valuable information concerning the triacylglycerol composition of berry oils was obtained, despite the overlapping of certain triacylglycerol peaks. Simultaneous analysis of fat-soluble vitamins and triacylglycerols is not practical by capillary SFC with flame-ionization detection because of the low concentration of naturally-occurring fat-soluble vitamins in edible oils. Therefore, higher loading of the sample, which led to overloading of triacylglycerols, was required to get reasonable peaks for fat-soluble vitamins. The method was applied to the characterization of triacylglycerols and tocopherols in sea buckthorn pulp and seed oil, and cloudberry seed oil without any sample purification prior to SFC. In addition, the stationary phase proved useful for separating the more complex mixtures of triacylglycerols found in milk fat and in fish oil.     

Activity and Selectivity of a Nanostructured CuO/ZrO2 Catalyst in the Steam Reforming of Methanol

Steam reforming of methanol for production of hydrogen can be carried out over copper based catalyst. In the work presented here, the catalytic properties of a CuO/ZrO₂ catalyst (8.5wt%) synthesised by a templating technique were investigated with respect to activity, long term stability, CO formation, and response to oxygen addition to the feed. The results were obtained using a fixed bed reactor and compared to a commercial methanol synthesis catalyst CuO/ZnO/Al₂O₃. It is shown that, depending on the time on stream, the temporary addition of oxygen to the feed has a beneficial effect on the activity of the CuO/ZrO₂ catalyst. After activation, the CuO/ZrO₂ catalyst is found to be more active (per copper mass) than the CuO/ZnO/Al₂O₃ system, more stable during time on stream (measured up to 250h), and to produce less CO. Structural characterisation by means of X-ray powder diffraction (XRD) and X-ray absorption spectroscopy (XAS) reveals that the catalyst (as prepared) consists of crystalline, tetragonal zirconia with small domain sizes (about 60Å) and small/disordered crystallites of CuO.     

Electrolytical fission at mercury cathodes of an NO single bond in ethers derived from 1-hydroxybenzo(d)-1,2,3-triazoles

The single NO bond in various ethers derived from 1-hydroxybenzo(d)-1,2,3-triazoles is reduced at mercury cathodes in a 2-electron process giving rise to the non-substituted benzotriazole and a corresponding primary alcohol. Controlled-potential electrolysis actually resulted in isolating the products of the above type eg benzotriazole and 2-piperidinoethanol. Cathodic reduction of non-substituted benzotriazole in acid media proceeds evidently via a chemical reaction between benzotriazole and hydrogen obtained by the catalytic reduction of hydrogen ions at the mercury electrode.     

Hydrogenation of Citral Over a Polymer Fibre Catalyst

A polymer-supported Pd catalyst was investigated in hydrogenation of citral (3,7-dimethyl-2,6-octadienal), which is a stereoisomer with an isolated and a conjugated double bond as well as a carbonyl group. The catalyst was a fibrous polymer-supported catalyst modified with functional groups and immobilized metals. A comparison of the polymer-supported catalyst with conventional catalysts was made.     

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.