Skills (5)
Publications (110) View all
-
Article: Effects of copper and vanadium deposition in multi-walled hydrogen trititanate and mixed-phase anatase/trititanate nanotubes.
[show abstract] [hide abstract]
ABSTRACT: Metal incorporation and doping is one of the routes commonly explored to improve visible light photocatalytic activity of titania and related materials. In this work, we explore the effect of copper and vanadium deposition and incorporation in multi-walled hydrogen trititanate and mixed-phase anatase/trititanate nanotubes. The molecular designed dispersion method is used to introduce the metals in the materials. Electron paramagnetic resonance facilitates a full characterization of the metal sites before and after calcination and allows determining the UV- and visible-light-induced formation of paramagnetic intermediates. Vanadium or copper deposition on the tubes leads to increased formation of F(+) centres under visible or UV illumination. The EPR results are linked to the activity towards rhodamine 6G photobleaching of the different materials.Dalton Transactions 04/2013; · 3.84 Impact Factor -
Article: Is the heme pocket region modulated by disulfide-bridge formation in fish and amphibian neuroglobins as in humans?
[show abstract] [hide abstract]
ABSTRACT: Neuroglobin, a globin characterized by a bis-histidine ligation of the heme iron, has been identified in mammalian and non-mammalian vertebrates, including fish, amphibians and reptiles. In human neuroglobin, the presence of an internal disulfide bond in the CD loop (CD7-D5) is found to modulate the ligand binding through a change in the heme pocket structure. Although the neuroglobin sequences mostly display conserved Cys at positions CD7, D5 and G18/19, a number of exceptions are known. In this study, neuroglobins from amphibian (Xenopus tropicalis) and fish (Chaenocephalus aceratus, Dissostichus mawsoni and Danio rerio) are investigated using electron paramagnetic resonance and optical absorption spectroscopy. All these neuroglobins differ from human neuroglobin in their Cys-positions. It is demonstrated that if disulfide bonds are formed in fish and amphibian neuroglobins, the reduction of these bonds does not result in alteration of the heme pocket in these globins (proteins). Furthermore, it is shown that mutagenesis of the Cys residues of X. tropicalis neuroglobin influences the protein structure. The amphibian neuroglobin is also found to be more resistant to H(2)O(2)-induced denaturation than the other neuroglobins under study, although all show an overall large stability in high concentrations of this oxidant. This article is part of a Special Issue entitled: Oxygen Binding and Sensing Proteins.Biochimica et Biophysica Acta 02/2013; · 4.66 Impact Factor -
Article: Photocatalytic Removal of Soot: Unravelling of the Reaction Mechanism by EPR and in situ FTIR Spectroscopy.
[show abstract] [hide abstract]
ABSTRACT: Photocatalytic soot oxidation is studied on P25 TiO(2) as an important model reaction for self-cleaning processes by means of electron paramagnetic resonance (EPR) and Fourier transform infrared (FTIR) spectroscopy. Contacting of carbon black with P25 leads on the one hand to a reduction of the local dioxygen concentration in the powder. On the other hand, the weakly adsorbed radicals on the carbon particles are likely to act as alternative traps for the photogenerated conduction-band electrons. We find furthermore that the presence of dioxygen and oxygen-related radicals is vital for the photocatalytic soot degradation. The complete oxidation of soot to CO(2) is evidenced by in situ FTIR spectroscopy, no intermediate CO is detected during the photocatalytic process.ChemPhysChem 11/2012; · 3.41 Impact Factor -
Article: V(6)O(13) films by control of the oxidation state from aqueous precursor to crystalline phase.
[show abstract] [hide abstract]
ABSTRACT: An aqueous deposition process for V(6)O(13) films is developed whereby the vanadium oxidation state is continuously controlled throughout the entire process. In the precursor stage, a controlled wet chemical reduction of the vanadium(v) source with oxalic acid is achieved and monitored by (51)Vanadium Nuclear Magnetic Resonance ((51)V-NMR) and Ultraviolet-Visible (UV-Vis) spectroscopy. The resulting vanadium(iv) species in the aqueous solution are identified as mononuclear citrato-oxovanadate(iv) complexes by Electron Paramagnetic Resonance (EPR) and Fourier Transform Infra-Red (FTIR) spectroscopy. This precursor is successfully employed for the deposition of uniform, thin films. The optimal deposition and annealing conditions for the formation of crystalline V(6)O(13), including the control of the vanadium oxidation state, are determined through an elaborate study of processing temperature and O(2) partial pressure. To ensure a sub 100 nm adjustable film thickness, a non-oxidative intermediate thermal treatment is carried out at the end of each deposition cycle, allowing maximal precursor decomposition while still avoiding V(iv) oxidation. The resulting surface hydrophilicity, indispensable for the homogeneous deposition of the next layer, is explained by an increased surface roughness and the increased availability of surface vanadyl groups. Crystalline V(6)O(13) with a preferential (002) orientation is obtained after a post deposition annealing in a 0.1% O(2) ambient for thin films with a thickness of 20 nm.Dalton Transactions 10/2012; · 3.84 Impact Factor -
Article: Charge transfer in the weak driving force limit in blends of MDMO-PPV and dithienylthiazolo[5,4-d]thiazoles towards organic photovoltaics with high V(OC).
[show abstract] [hide abstract]
ABSTRACT: A series of three 5'-aryl-2,5-dithienylthiazolo[5,4-d]thiazole (DTTzTz) semiconducting molecules with different aryl substituents has been investigated as alternative acceptor materials in combination with the donor polymer poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylene vinylene] () in order to evaluate the photoinduced charge transfer (CT) efficiency in the resulting blends, designed towards possible application in organic photovoltaics. Photoluminescence quenching together with polaron detection by electron paramagnetic resonance and photoinduced absorption (PIA) demonstrate an increasing charge transfer efficiency when the DTTzTz substituents are varied from thien-2-yl to 4-trifluoromethylphenyl and 4-cyanophenyl groups, correlating well with the increasing acceptor strength in this series of molecules. In line with this observation, there is a decrease in the effective optical bandgap relative to pure that becomes more pronounced along this series of acceptor compounds, reaching 0.12 eV in the blend with . Intermolecular interactions between the blend components lead to lower energy transitions which are found to contribute significantly to the device external quantum efficiency. The high V(OC) reached in devices based on blends meets the expectations for such a donor:acceptor combination. However, thermal activation of charge carrier recombination occurs because of the weak driving force for charge transfer, as shown by time-dependent PIA measurements, and this is suggested as a cause for the observed low photovoltaic performance.Physical Chemistry Chemical Physics 10/2012; · 3.57 Impact Factor
