Robust Molecular Anodes for Electrocatalytic Water Oxidation Based on Electropolymerized Molecular Cu Complexes.

A multistep synthesis of a new tetra-amidate macrocyclic ligand functionalized with alkyl-thiophene moieties, 15,15-bis(6-(thiophen-3-yl)hexyl)-8,13-dihydro-5H-dibenzo[b,h][1,4,7,10]tetraazacyclotridecine-6,7,14,16(15H,17H)-tetraone, H L, is reported. The reaction of the deprotonated ligand, L , and Cu(II) generates the complex [LCu] , that can be further oxidized to Cu(III) with iodine to generate [LCu] . The H L ligand and their Cu complexes have been thoroughly characterized by analytic and spectroscopic techniques (including X-ray Absorption Spectroscopy, XAS).

Role of cerium oxide in bioactive glasses during catalytic dissociation of hydrogen peroxide.

The addition of cerium oxide to bioactive glasses, important materials for bone tissue regeneration, has been shown to induce multifunctionality, combining a significant bioactivity with antioxidant properties. We provide a real time investigation of the evolution of the electronic properties of highly diluted cerium ions in a liquid environment containing hydrogen peroxide - the most abundant reactive oxygen species in living cells. This challenging task is undertaken by means of high-energy resolution fluorescence detected by X-ray absorption near-edge spectroscopy at the Ce L3 edge.

XANES study of vanadium and nitrogen dopants in photocatalytic TiO thin films.

We report an X-ray absorption near edge structure (XANES) study of vanadium (V) and nitrogen (N) dopants in anatase TiO thin films deposited by radio-frequency magnetron sputtering. Measurements at the Ti K and V K edges were combined with soft X-ray experiments at the Ti L, O K and N K edges. Full potential ab initio spectral simulations of the V, O and N K-edges were carried out for different possible configurations of substitutional and interstitial dopant-related point defects in the anatase structure.

Contraction, cation oxidation state and size effects in cerium oxide nanoparticles.

An accurate description of the structural and chemical modifications of cerium oxide nanoparticles (NPs) is mandatory for understanding their functionality in applications. In this work we investigate the relation between local atomic structure, oxidation state, defectivity and size in cerium oxide NPs with variable diameter below 10 nm, using x-ray absorption fine structure analysis in the near and extended energy range. The NPs are prepared by physical methods under controlled conditions and analyzed in morphology and crystalline quality by high resolution transmission electron microscopy.

Electronic properties of epitaxial cerium oxide films during controlled reduction and oxidation studied by resonant inelastic X-ray scattering.

We investigated the evolution of the electronic structure of cerium oxide ultrathin epitaxial films during reduction and oxidation processes using resonant inelastic X-ray scattering at the Ce L3 absorption edge, a technique sensitive to the electronic configurations at the 4f levels and in the 5d band thanks to its high energy resolution. We used thermal treatments in high vacuum and in oxygen partial pressure to induce a controlled and reversible degree of reduction in cerium oxide ultrathin epitaxial films of different thicknesses. Two dominant spectral components contribute to the measured spectra at the different degrees of oxidation/reduction.

Probing long-lived plasmonic-generated charges in TiO2 /Au by high-resolution X-ray absorption spectroscopy.

Exploiting plasmonic Au nanoparticles to sensitize TiO2 to visible light is a widely employed route to produce efficient photocatalysts. However, a description of the atomic and electronic structure of the semiconductor sites in which charges are injected is still not available. Such a description is of great importance in understanding the underlying physical mechanisms and to improve the design of catalysts with enhanced photoactivity.

Oxygen vacancy induced room temperature ferromagnetism in Pr-doped CeO2 thin films on silicon.

Integration of functional oxides on Si substrates could open a pathway to integrate diverse devices on Si-based technology. Oxygen vacancies (Vo(··)) can strongly affect solid state properties of oxides, including the room temperature ferromagnetism (RTFM) in diluted magnetic oxides. Here, we report a systematical study on the RTFM of oxygen vacancy engineered (by Pr(3+) doping) CeO2 epitaxial thin films on Si substrates.

X-ray absorption studies of Zn(2+)-binding sites in Escherichia coli transhydrogenase and its betaH91K mutant.

Transhydrogenase couples hydride transfer between NADH and NADP(+) to proton translocation across a membrane. The binding of Zn(2+) to the enzyme was shown previously to inhibit steps associated with proton transfer. Using Zn K-edge X-ray absorption fine structure (XAFS), we report here on the local structure of Zn(2+) bound to Escherichia coli transhydrogenase.

Synergic approach to XAFS analysis for the identification of most probable binding motifs for mononuclear zinc sites in metalloproteins.

In the present work a data analysis approach, based on XAFS data, is proposed for the identification of most probable binding motifs of unknown mononuclear zinc sites in metalloproteins. This approach combines multiple-scattering EXAFS analysis performed within the rigid-body refinement scheme, non-muffin-tin ab initio XANES simulations, average structural information on amino acids and metal binding clusters provided by the Protein Data Bank, and Debye-Waller factor calculations based on density functional theory. The efficiency of the method is tested by using three reference zinc proteins for which the local structure around the metal is already known from protein crystallography.

The fe2+ site of photosynthetic reaction centers probed by multiple scattering x-ray absorption fine structure spectroscopy: improving structure resolution in dry matrices.

We report on the x-ray absorption fine structure of the Fe(2+) site in photosynthetic reaction centers from Rhodobacter sphaeroides. Crystallographic studies show that Fe(2+) is ligated with four N(epsilon) atoms from four histidine (His) residues and two O(epsilon) atoms from a Glu residue. By considering multiple scattering contributions to the x-ray absorption fine structure function, we improved the structural resolution of the site: His residues were split into two groups, characterized by different Fe-N(epsilon) distances, and two distinct Fe-O(epsilon) bond lengths resolved.

X-Ray absorption studies of Zn2+ binding sites in bacterial, avian, and bovine cytochrome bc1 complexes.

Binding of Zn2+ has been shown previously to inhibit the ubiquinol cytochrome c oxidoreductase (cyt bc1 complex). X-ray diffraction data in Zn-treated crystals of the avian cyt bc1 complex identified two binding sites located close to the catalytic Qo site of the enzyme. One of them (Zn01) might interfere with the egress of protons from the Qo site to the aqueous phase.

The inhibitory binding site(s) of Zn2+ in cytochrome c oxidase.

EXAFS analysis of Zn binding site(s) in bovine-heart cytochrome c oxidase and characterization of the inhibitory effect of internal zinc on respiratory activity and proton pumping of the liposome reconstituted oxidase are presented. EXAFS identifies tetrahedral coordination site(s) for Zn(2+) with two N-histidine imidazoles, one N-histidine imidazol or N-lysine and one O-COOH (glutamate or aspartate), possibly located at the entry site of the proton conducting D pathway in the oxidase and involved in inhibition of the oxygen reduction catalysis and proton pumping by internally trapped zinc.

Cytochrome C in a dry trehalose matrix: structural and dynamical effects probed by x-ray absorption spectroscopy.

We report on the structure and dynamics of the Fe ligand cluster of reduced horse heart cytochrome c in solution, in a dried polyvinyl alcohol (PVA) film, and in two trehalose matrices characterized by different contents of residual water. The effect of the solvent/matrix environment was studied at room temperature using Fe K-edge x-ray absorption fine structure (XAFS) spectroscopy. XAFS data were analyzed by combining ab initio simulations and multi-parameter fitting in an attempt to disentangle structural from disorder parameters.

Manganese-induced growth of GaAs nanowires.

GaAs nanowires have been grown on SiO2 and GaAs by molecular beam epitaxy using manganese as growth catalyst. Transmission electron microscopy shows that the wires have a wurtzite-type lattice and that alpha-Mn particles are found at the free end of the wires. X-ray absorption fine structure measurements reveal the presence of a significant fraction of Mn-As bonds, suggesting Mn diffusion and incorporation during wire growth.

Direct observation of nitrogen location in molecular beam epitaxy grown nitrogen-doped ZnO.

ZnO is a wide band gap, naturally n-type semiconductor with great promise for optoelectronic applications; the main obstacle yet to be overcome is p-type doping. Nitrogen, the most promising candidate currently being pursued as a dopant, has been predicted to preferentially incorporate into the ZnO lattice in the form of a N-2 molecule at an O site when a plasma source is used, leading to compensation rather than p-type doping. We demonstrate this to be incorrect by using N K-edge x-ray absorption spectra and comparing them with first-principles calculations showing that nitrogen, in fact, incorporates substitutionally at O sites where it is expected to act as an acceptor.

Multiple scattering x-ray absorption studies of Zn2+ binding sites in bacterial photosynthetic reaction centers.

Binding of transition metal ions to the reaction center (RC) protein of the photosynthetic bacterium Rhodobacter sphaeroides has been previously shown to slow light-induced electron and proton transfer to the secondary quinone acceptor molecule, Q(B). On the basis of x-ray diffraction at 2.5 angstroms resolution a site, formed by AspH124, HisH126, and HisH128, has been identified at the protein surface which binds Cd(2+) or Zn(2+).

Electron transfer kinetics in photosynthetic reaction centers embedded in polyvinyl alcohol films.

The coupling between electron transfer and protein dynamics has been studied at room temperature in isolated reaction centers (RCs) from the photosynthetic bacterium Rhodobacter sphaeroides by incorporating the protein in polyvinyl alcohol (PVA) films of different water/RC ratios. The kinetic analysis of charge recombination shows that dehydration of RC-containing PVA films causes reversible, inhomogeneous inhibition of electron transfer from the reduced primary quinone acceptor (Q(A)(-)) to the secondary quinone Q(B). A more extensive dehydration of solid PVA matrices accelerates electron transfer from Q(A)(-) to the primary photooxidized electron donor P(+).

Treatment of EXAFS data taken in the fluorescence mode in non-linear conditions.

The aim of this work is to investigate the possibility of extracting correct structural parameters from fluorescence EXAFS data taken at high count rates with an energy-resolving detector. This situation is often encountered on third-generation synchrotron radiation sources which provide a high flux on the sample. Errors caused by pulse pile-up in the extraction of structural information have been quantified in a real experiment, and different approaches to the problem of data correction have been elaborated.