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.     

Synthesis of copolymers of tert‐butyl vinyl ether with maleic and citraconic anhydrides

In the present study, the effects of charge‐transfer complex formation and intramolecular fragmentation (side‐chain lactonization) in radical copolymerization of tert‐butyl vinyl ether (t‐BVE) with anhydrides of maleic (MA) and citraconic (CA) acids and the structure–thermal behavior relationships of the resulting copolymers were examined using the ¹H‐NMR, FTIR, DSC, and TGA analysis methods. It was shown that copolymerization under the chosen conditions proceeded through intramolecular fragmentation with the formation of γ‐lactone units. Side‐chain fragmentation of t‐BVE–MA and t‐BVE–CA copolymers also was confirmed by TGA and DSC analysis. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2455–2463, 2006 2006     

Combined Ozone Pretreatment and Anaerobic Digestion for the Reduction of Biological Sludge Production in Wastewater Treatment

The ever-increasing amount of solid waste generated by wastewater treatment plants highlights emerging economic and environmental issues. In order to develop new processes producing less sludge, the use of ozone combined with anaerobic digestion was investigated for waste activated sludge treatment. This paper was aimed at evaluating the impact of ozone pretreatment on anaerobic digestion and particularly the enhancement of biogas production. Sludge solubilization was estimated in terms of modification of chemical oxygen demand, solids and nitrogen. Batch anaerobic digestion highlighted the enhancement of ozonated sludge biodegradability. Ozonation led to an increase in biogas production. The ozone dose of 0.15 g O₃/g total solids resulted in a considerable increase in the soluble COD ratio from 4% to 37%. This ozone dose achieved the highest increase in biogas production: 2.4 times greater than without chemical pretreatment.     

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     

Uncooperative gait recognition by learning to rank

Gait is a useful biometric because it can operate from a distance and without subject cooperation. However, it is affected by changes in covariate conditions (carrying, clothing, view angle, etc.). Existing methods suffer from lack of training samples, can only cope with changes in a subset of conditions with limited success, and implicitly assume subject cooperation. We propose a novel approach which casts gait recognition as a bipartite ranking problem and leverages training samples from different people and even from different datasets. By exploiting learning to rank, the problem of model over-fitting caused by under-sampled training data is effectively addressed. This makes our approach suitable under a genuine uncooperative setting and robust against changes in any covariate conditions. Extensive experiments demonstrate that our approach drastically outperforms existing methods, achieving up to 14-fold increase in recognition rate under the most difficult uncooperative settings.     

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.     

Optimizing BRDF orientations for the manipulation of anisotropic highlights

This paper introduces a system for the direct editing of highlights produced by anisotropic BRDFs, which we call anisotropic highlights. We first provide a comprehensive analysis of the link between the direction of anisotropy and the shape of highlight curves for arbitrary object surfaces. The gained insights provide the required ingredients to infer BRDF orientations from a prescribed highlight tangent field. This amounts to a non‐linear optimization problem, which is solved at interactive framerates during manipulation. Taking inspiration from sculpting software, we provide tools that give the impression of manipulating highlight curves while actually modifying their tangents. Our solver produces desired highlight shapes for a host of lighting environments and anisotropic BRDFs.     

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.