Raman Scattering Study of Cubic–Tetragonal Phase Transition in Zr1−xCexO2 Solid Solution

A structural phase transition between the cubic (space group, Fm 3 m) and tetragonal (space group, P 4₂ /nmc) phases in a zirconia–ceria solid solution (Zr_1−xCe_xO₂) has been observed by Raman spectroscopy. The cubic–tetragonal ( c–t" ) phase boundary in compositionally homogeneous samples exists at a composition X₀ (0.8 < X₀ < 0.9) at room temperature, where t " is defined as a tetragonal phase whose axial ratio c/a equals unity. The axial ratio c/a decreases with an increase of ceria concentration and becomes 1 at a composition X'₀ (0.65 < X'₀ < 0.7) at room temperature. The sample with a composition between X₀ and X'₀ is t " ZrO₂. By Raman scattering measurements at high temperatures, the tetragonal ( t" ) → cubic and cubic → tetragonal phase transitions occur above 400°C in Zr_0.2 Ce_0.8O₂ solid solution.     

Room-Temperature Preparation of Highly Crystallized Luminescent SrWO4 Film by an Electrochemical Method

Highly crystallized luminescent SrWO₄ film has been prepared on a tungsten substrate in an alkaline solution containing strontlum ions by an electrochemical method using constant direct current of 1 mA/cm² at room temperature (25°C). This film showed only a single blue emission at 461 nm with the excitation of 248 nm at liquid nitrogen temperature (- 196°C), strongly suggesting it consists of well-crystallized defect-free crystals.     

Tetragonal—Monoclinic Phase Transition Enthalpy and Temperature of ZrO2-CeO2 Solid Solutions

DSC (differential scanning calorimeter) measurements were performed to investigate the tetragonal-monoclinic ( t-m ) transition enthalpy of the compositionally homogeneous ZrO₂- X mol% CeO₂ solid solution of X = 0, 4, 8, and 12. The transition enthalpy decreases linearly with an increase of CeO₂ content. The m → t transition enthalpy on heating agreed well with the inverse t → m one obtained during cooling. With increasing X , the DSC peak broadens and the transition temperature distribution of each sample increases, while the thermal hysteresis is almost independent of X .     

Detection of Lymph Node Metastases in Human Colorectal Cancer by Using 5-Aminolevulinic Acid-Induced Protoporphyrin IX Fluorescence with Spectral Unmixing

Accurate evaluation of metastatic lymph nodes (LNs) is indispensable for adequate treatment of colorectal cancer (CRC) patients. Here, we demonstrate detection of metastases of human CRC in removed fresh LNs using 5-aminolevulinic acid (ALA)-induced protoporphyrin IX (PpIX) fluorescence. A spectral unmixing method was employed to reduce the overlap of collagen autofluorescence on PpIX fluorescence. A total of 17 surgery patients with advanced CRC were included in this study. After 5-ALA at a dose of 15 mg/kg of body weight was applied orally 2 h prior to surgery, 87 LNs were subjected to spectral fluorescence imaging and histopathological diagnosis, and statistical analysis was performed. No apparent side effect was observed to be associated with 5-ALA administration. The spectral unmixing fluorescence intensity of PpIX in metastatic LNs was 10.2-fold greater than that in nonmetastaic LNs. The receiver-operating-characteristic (ROC) analysis showed that the area under the curve (AUC) was calculated as 0.95. Our results show the potential of 5-ALA-induced PpIX fluorescence processed by spectral unmixing for detecting metastases in excised fresh LNs from patients with CRC, suggesting that this rapid and feasible method is applicable to gross evaluation of resected LN samples in pathology laboratories.     

In Situ Observations of Phase Transition Using High-Temperature Neutron and Synchrotron X-ray Powder Diffractometry

It is of vital importance for the study of phase diagrams to investigate in situ diffusionless phase transition points at high temperatures. We have developed high-temperature techniques to measure in situ neutron and synchrotron X-ray powder diffractometry profiles. This paper reviews our recent studies obtained using these methods. The new furnace for high-temperature neutron diffraction study yields no extra peaks caused by heaters and refractory; thus, we have been able to measure very small neutron signals from the sample. Quality neutron diffraction data at high temperatures up to ∼1590°C have been analyzed using the Rietveld method for various materials, such as zirconia solid solutions and calcium titanate. High-resolution synchrotron X-ray diffractometry enables exact determination of the phase transition temperatures of perovskite-related materials.     

A RaPID Macrocyclic Peptide That Inhibits the Formation of α-Synuclein Amyloid Fibrils

There is considerable interest in drug discovery targeting the aggregation of α-synuclein (αSyn) since this molecular process is closely associated with Parkinson's disease. However, inhibiting αSyn aggregation remains a major challenge because of its highly dynamic nature which makes it difficult to form a stable binding complex with a drug molecule. Here, by exploiting Random non-standard Peptides Integrated Discovery (RaPID) system, we identified a macrocyclic peptide, BD1, that could interact with immobilized αSyn and inhibit the formation of fibrils. Furthermore, improving the solubility of BD1 suppresses the co-aggregation with αSyn fibrils while it kinetically inhibits more effectively without change in their morphology. We also revealed the molecular mechanism of kinetic inhibition, where peptides bind to fibril ends of αSyn, thereby preventing further growth of fibrils. These results suggest that our approach for generating non-standard macrocyclic peptides is a promising approach for developing potential therapeutics against neurodegeneration.     

A Compact Furnace for Synchrotron Powder Diffraction Experiments up to 1800 K

A new electric furnace has been designed and fabricated for measurements of the high-resolution synchrotron radiation powder diffraction profiles from materials at high temperatures up to 1807 K in air, suitable for the multiple-detector system installed at the BL-4B₂ experimental station of the Photon Factory, Tsukuba, Japan. In the present study, at 1703 K in air, the whole powder pattern of National Institute of Standard and Technology ceria powder was step scanned at a step interval of 0.004° in 2θ, by the counting time of 1.5 s/step and with a monochromatized 1.205363(5) Å X-ray, in just 7 h. The full width at half-maximum of the 111 reflection of the ceria was narrow (0.0139°). The δ d / d resolution of the ceria ranged from 0.058% to 0.126% at 1703 K, where d and δ d are the lattice spacing and peak width, respectively. Precise unit-cell parameter 5.51259(1) Å and the atomic displacement parameters were refined by the Rietveld analysis of the powder data measured at 1703 K. An electron-density map of ceria at 1703 K was obtained by the maximum-entropy method.     

Effect of Water on Adsorption Behavior at Polymer/γ-Fe2O3 Interface

The adsorption behavior of a hydroxylated polymer onto γ-Fe₂O₃ particles in a tetrahydrofuran/water solvent system was investigated. The saturation adsorption of the polymer decreased with an increase in the water content of the solvent system, and the degree of dispersion of the magnetic particles in the paint also decreased. It was shown that the water located not at the interface between the particles and the solution but in the solution. Water interacted with the polymer and increased the radius of gyration of the polymer in solution. Thus, the polymer did not interact with the particles, and the particles were prevented from having a high dispersion.     

Low-Temperature Phase Equilibria by the Flux Method and the Metastable–Stable Phase Diagram in the ZrO2–CeO2 System

Low-temperature phase equilibria ranging from 1000° to 1200°C in the ZrO₂–CeO₂ system were investigated by annealing compositionally homogeneous ZrO₂–CeO₂ solid solutions in a Na₂B₂O₇.1 NaF flux. The 5 mol% CeO₂ samples decomposed into monoclinic ( m ) and tetragonal ( t ) phases during annealing at 1100°2 and 1120°C, and the t -phase transformed diffusionlessly into monoclinic ( m ') symmetry during quenching. A eutectoid reaction, t → ( m + c ), was confirmed to occur at 1055°± 10°C, where the equilibrium compositions of the t -, m -, and c -phases were 11.2 ± 2.8, 0.9 ± 0.9, and 84 ± 1 mol% CeO₂, respectively. The equilibrium phase boundaries were almost independent of the annealing time and/or the flux:sample ratio, which indicates that the flux accelerates the reaction rate withouts affecting the equilibration. The previous data are discussed using metastable–stable phase diagrams. The discrepancies of the low-temperature phase diagram in the literature are attributable to either regarding the metastable phase boundaries as stable ones or ignoring the sluggish kinetics.