Direct Visualization of Energy-transferred Excited State in Eu Complex

Highly luminescent lanthanide (Ln) complexes have attracted much attention because Ln³⁺ ions show long-lived ff-emissions with narrow band shape. Their unique photo-optical properties are promising for the design of light-emitting materials and sensing devices. Although the ff-emissions are essentially weak because of Laporte forbidden, chelate ligands is effective to strengthen the intramolecular energy transfer from photo-excited organic ligands to Ln³⁺ ions. The direct evidence of energy transfer from ligands to Ln³⁺ and details of excited state, however, are still veiled. Here, we report direct visualization of energy-transferred excited state in Eu complex with a hexadentate ligand (L) consisting of two bipyridine moieties bridged by an ethylendiamine unit, [Eu³⁺(L)(NO₃)₂](PF₆) (Eu(L))[1] by Maximum Entropy Method (MEM) charge density[2] and electrostatic potential analysis[3] based on SR X-ray diffraction. First, we confirmed that the electron numbers of Eu and ligand L in the excited state are the same as those in the ground state, which is a direct evidence of energy transfer instead of charge transfer. Next, we observed charge re-distribution in the Eu ion and the ligand L. The electrostatic potential distributions calculated using MEM charge density give an experimental evidence for the existence of polarization of ligand L both in the ground and photo-excited states. The orientation polarization in the ground state changed during pumping at 315 nm, and the charge re-distribution are qualitatively consistent with a theoretical prediction. This characteristic luminescence behavior based on the energy relaxation process have not been detected by fundamental crystal structural analysis. We have succeeded in visualization of subtle but important change due to energy transfer in the mononuclear Europium complex with hexadentate ligand at the first time.

Structural Basis for Emergence of Superionic Conductivity by an Ion Exchange

Various superionic conductors have been examined in terms of the application to electrolytes for solid fuel cells [1]. Recently we demonstrated by impedance measurements that a simple two-step chemical reaction transformed an electronic conductor Na_xCoO₂ into a superionic one. In the present study, we performed in situ synchrotron X-ray diffraction experiments to investigate a structural mechanism for the superionic conductivity driven by the chemical treatment of the layered oxide Na_xCoO₂. We developed a temperature- and humidity-controllable capillary cell under hydrogen and helium gas flow to install in the Debye-Scherrer camera at BL44B2 of SPring-8. This cell allows us to explore a structural transformation process by reduction and humidification treatments. Structural identifications and refinements with in situ diffraction data proved that Co vacancies formed by a CoO separation suppressed the electronic conductivity. Meanwhile it turned out from charge estimation in the Na layers that the superionic conductor transition originated from an ion exchange of H₃O⁺ for Na⁺, which was confirmed by Raman spectroscopy measurements. In addition, charge densities clearly visualized the H₃O⁺ ions disordering around the Na original sites, suggesting that the H₃O⁺ behave as a carrier source. Finally it was found from electrostatic potentials that the disordering H₃O⁺ sites were coupled through shallow potential barriers to trace a honeycomb-like ion pathway. In the presentation, I will discuss what a carrier is for the superionic-conductive phase from different viewpoints such as activation energies, concentration cell tests, and molecular dynamics simulations using the experimental structure information.

Valence Electron Distributions in Ferroelectric Barium Titanate Nanopowders

Barium titanate BaTiO3 is one of the most important perovskite-type electroceramics, which undergoes the phase transition at 130 ⁰C from cubic to tetragonal, and exhibits ferroelectricity at room temperature. The phase transition depends on the particle size. BaTiO3 powders with the particle sizes less than several tens of nanometers are known to show no phase transition and hence no ferroelectricity at room temperature. The size effect of BaTiO3 is the most important issue in designing small ceramic capacitors with high capacitance. Our group has been devoted to visualizing the electron density distributions of perovskite-type oxides by analyzing the synchrotron-radiation x-ray powder diffraction (SXRD) data measured at SPring-8 using the maximum entropy method (MEM)/Rietveld method [1, 2]. In this study, the distributions of valence electrons in the outer shells of atoms are derived accurately from the SXRD data of BaTiO3 nanopowders to prove the characteristic chemical bondings which govern the ferroelectric phase transition. The powder samples used were 500 and 35 nm in particle sizes. The former showed the phase transition whereas the latter showed no phase transition. The MEM valence electron density studies at 200 ⁰C in the cubic structure revealed the clear structural variations that the Ti-O covalent bonding is found in the 500 nm sample, while all the valence electrons are localized at the O sites in the 35 nm sample exactly like an ionic crystal. Ferroelectricity originates from the balance between the long-rage Coulomb force and the short-range repulsion force. The obtained results provide direct experimental evidence that the electron orbitals hybridization on the Ti-O bonds weakens the short-range repulsion force, and causes the second-order Jahn-Teller distortion on the TiO6 octahedron in the 500 nm sample. We consider that the Ti-O bonding in the prototype structure governs the ferroelectric phase transition temperature in BaTiO3.

Phase transitions and critical phenomena of ice under high pressure

Water distributes ubiquitously among the solar system and outer space in a wide variety of solid forms, i.e. more than ten kinds of crystalline ice, two types of amorphous ice, and clathrate hydrates. These polymorphs often play crucial roles in the planetary geology. Diversity of the stable ices and hydrates also suggests the existence of the various kinds of stable and metastable phases yet to be discovered [1]. Computer simulations and the theoretical treatments are useful to explore them. In this talk, we introduce the phase transitions of ice VII, which is one of the highest-pressure ice phases. The melting curve of ice VII to high-pressure liquid water has not been settled by experiments. We have proposed the intervention of a plastic phase of ice (plastic ice) between ice VII and liquid water, based on molecular dynamics (MD) simulations and the free energy calculations [2], which enables to account for large gaps among the various experimental curves of ice VII. In plastic ice, the water molecules are fixed at the lattice points, while they rotate freely. Interestingly, our additional survey by large-scale MD simulations elucidates that the phase transition between ice VII and plastic ice is first-order at low pressure as it was already predicted, while it is found to be second-order at higher pressures, where a tricritical point joins these phase boundaries together [3]. The critical fluctuations may give a clue for determining the phase boundary experimentally. We also argue about the phase transition dynamics of liquid water to ice VII at their direct phase boundary where metastable plastic ice phase plays an important role.

Crystal Structure analyses of dipeptidyl aminopeptidase BII from P. mexicana WO24.

The peptidase family S46 that contains the dipeptidyl aminopeptidase BII (DAP BII) from Pseudoxanthomonas mexicana WO24 is the only exopeptidase family in clan PA peptidases. Our present phylogenetic and experimental studies indicated that the catalytic triad of DAP BII is composed of His 86, Asp 224 and Ser 657 and implied that unknown large helical domains involved in exopeptidase activity[1]. However, three-dimensional structure of a family S46 peptidase has not yet been reported. Thus, the crystal structure of DAP BII is essential not only to understand the catalytic mechanism of family S46 peptidases but also to clarify the structural origin of the exo-type peptidase activities of these enzymes. Recently, we have successfully crystallized the DAP BII and collected X-ray diffraction data to 2.3 Å resolution from the crystal. This crystal belonging to space group P2₁2₁2₁, with unit-cell parameters a = 76.55 Å, b = 130.86 Å, c = 170.87 Å[2]. Structural analysis by the multi-wavelength anomalous diffraction method is underway[3]. Here, we report the first crystallization and structural analysis of the DAP BII from P. mexicana WO24 as family S46 peptidase. Other enzymes that belong to this family are DPP7 and DPP11 from Porphyromonas gingivalis, DPP11 from Porphyromonas endodontalis (periodontal pathogen) and DPP11 from Shewanella putrefaciens (multidrug resistance associated opportunistic pathogen). These gram-negative bacterial pathogens are known to asaccharolytic. Especially, Porphyromonas gingivalis is known to utilize dipeptides, instead of free amino acids, as energy source and cellular material. Since S46 peptidases are not found in mammals, we expect our study will be useful for the discovery of specific inhibitors to S46 peptidases from these pathogens.

In situ synchrotron powder diffraction for an ionic conductor transition

In situ synchrotron X-ray powder diffraction can be one of the most powerful probes to investigate the structure evolution by a chemical reaction thanks to simultaneity of data collection. It is not, however, with ease to produce a homogeneous chemical reaction in the limited spaces, which is essential to see an atomic-scale structure evolution. We have developed an in situ capillary cell for both high-temperature H₂ reduction and precise humidity control at the SPring-8 BL44B2. We successfully applied this in situ system to an electronic conductor LaSr₃Fe₃O₁₀, which is transformed into an ionic conductor by the two-step chemical treatments [1]. LaSr₃Fe₃O₁₀ has a triple-layer structure with a FeO₆ octahedral unit. One triple layer is bonded with another layer through van der Waals interaction. Structure refinements with in situ synchrotron powder diffraction data revealed that the H₂ reduction at 613 K produced in-plane oxygen vacancies, which resulted in suppression of the interlayer interaction. We found from charge density studies and Raman spectroscopy measurements that the following humidification intercalated H₂O and OH^- into the interlayer and intralayer, respectively. That means that H₂O plays a role for suppression of three-dimensional electronic conductivity, stabilizing the intercalation structure. On the other hand, the OH^- ions behave as carriers for ionic conductivity, maintaining the charge neutrality in the intralayer. Finally we determined the composition of the ionic conductor to be LaSr₃Fe₃O_8.0 (OH) _1.2·2H₂O, which indicates a transformation of LaSr₃Fe₃O₁₀ into an OH^- ionic conductor. In the presentation, I will discuss the OH^- ionic conduction channel based on electrostatic potentials obtained from charge densities.

Nanoporous Structural Science Developed by the MEM/Rietveld Method

Wide-spread functionalization research of Metal Organic Frameworks(MOFs) has brought rapid increase in variety of materials since the beginning of structural study in nanoporous of MOFs were made by SR(Synchrotron Radiation) powder diffraction using the MEM(Maximum Entropy Method)/Rietveld Method(Kitaura et al, 2002). The MEM/Rietveld method has successfully applied to refine the structural position of absorbed molecules and to investigate a bonding nature between the molecules and MOF's pore walls. Noise-resistance electron density mapping with incomplete data set was a key advantage of MEM to visualize unmodeled feature of molecules in nanoporous. Since then, the charge density studies by the MEM/Rietveld Method have uncovered various ordering structure of absorbed molecules into nanoporous more and more(Takata, 2008). Those findings ignited trends to design the nanoporous as the space to be functionalized. Recently, the MEM/Rietveld method has been further developed as the method to map an electrostatic potential and electric field(Tanaka 2006). This technique is making a progress in structural science of MOFs since the visualized electrostatic potential in the nanoporous ought to provide information of interplay between the molecule and the pore walls. The talk will present the recent progress and challenges of the MEM/Rietveld method to the structural science of the MOFs.