Fabrication of octacalcium phosphate block through a dissolution-precipitation reaction using a calcium sulphate hemihydrate block as a precursor

Although octacalcium phosphate (OCP) powder and a collagen/gelatin composite demonstrate good potential as bone substitutes, an OCP block has not been fabricated to date. In this study, the feasibility of fabricating an OCP block was evaluated through a dissolution-precipitation reaction using a calcium sulfate hemihydrate (CSH) block as a precursor. When the block was immersed in a phosphate salt solution, its composition changed to that of OCP, while its structure was maintained. The diametral tensile strength (DTS) of the OCP block was 1.0?±?0.2?MPa. The macroporosity and microporosity of the OCP block were 33.4?±?4.5% and, 69.0?±?1.6%, respectively. New bone attached well to the OCP block, and this block was partially replaced by bone 2 weeks after implantation. Four weeks after implantation, the surface of the OCP block was nearly covered with new bone and ~30% of the block was replaced by new bone, while no replacement by bone was observed in the case of a hydroxyapatite (HAp) block used as a control. It is concluded that OCP blocks are potentially suitable for their use as artificial bone substitutes.     

Modeling of quantitative relationships between physicochemical properties of active pharmaceutical ingredients and tensile strength of tablets using a boosted tree

Objectives: The aim of this study was to explore the potential of boosted tree (BT) to develop a correlation model between active pharmaceutical ingredient (API) characteristics and a tensile strength (TS) of tablets as critical quality attributes.

Methods: First, we evaluated 81 kinds of API characteristics, such as particle size distribution, bulk density, tapped density, Hausner ratio, moisture content, elastic recovery, molecular weight, and partition coefficient. Next, we prepared tablets containing 50% API, 49% microcrystalline cellulose, and 1% magnesium stearate using direct compression at 6, 8, and 10?kN, and measured TS. Then, we applied BT to our dataset to develop a correlation model. Finally, the constructed BT model was validated using k-fold cross-validation.

Results: Results showed that the BT model achieved high-performance statistics, whereas multiple regression analysis resulted in poor estimations. Sensitivity analysis of the BT model revealed that diameter of powder particles at the 10th percentile of the cumulative percentage size distribution was the most crucial factor for TS. In addition, the influences of moisture content, partition coefficients, and modal diameter were appreciably meaningful factors.

Conclusions: This study demonstrates that BT model could provide comprehensive understanding of the latent structure underlying APIs and TS of tablets.     

Colored amorphous silica-based powder with TiN nanocrystals precipitated by ammonolysis of Ti–Si–O ternary glass

Coloration of amorphous silica powder containing titania was investigated by nitridation in an ammonia flow. The oxide precursors were obtained by the hydrolysis of a mixture of tetraethyl orthosilicate (TEOS) and tetrabutoxy titanium (TBT). The color changed with the amount of TBT in the mixture, the hydrolysis pH and the ammonolysis temperature. The original white color of the 8 mol% TBT powder hydrolyzed under basic pH conditions changed to pale goldenrod at 700°C, then to dark olive green at 800°C, and further darkened with increasing ammonolysis temperature. A steel-blue color appeared at 900°C for the powder obtained with 3 mol% TBT, and increased in darkness at 1000°C. A similar bluish color was observed for powders obtained by acidic hydrolysis after ammonolysis above 900°C, and this was independent of the amount of titania, although the chroma decreased with increasing firing temperature for the powder with 3 mol% TBT. The ammonolysis powder products were characterized using X-ray diffraction (XRD), electron probe micro analysis (EPMA), transmission electron microscopy-electron energy-loss spectroscopy (TEM-EELS), scanning transmission electron microscopy-high-angle annular dark-field imaging (STEM-HAADF) and Ti–K edge X-ray absorption fine structure (XAFS). The color change was related to both precipitated TiN nanocrystals and residual titanium in the amorphous silica matrix. The TiN exhibited a goldish reflection and also plasmonic absorption from light blue to gray depending on the TiN crystallite size. The plasmonic absorption and resonance of nanocrystalline TiN will be useful similarly to that of gold in nanotechnology for various kinds of energy application.     

Multifunctional Composites of Chiral Valine Derivative Schiff Base Cu(II) Complexes and TiO2

We have prepared four new Cu(II) complexes containing valine moieties with imidazole ligands at the fourth coordination sites and examined their photo-induced reactions with TiO₂ in order of understanding the reaction mechanisms. Under a nitrogen atmosphere, the intermolecular electron transfer reactions (essentially supramolecular interactions) of these systems, which resulted in the reduction of Cu(II) species to Cu(I) ones, occurred after UV light irradiation. In this study, we have investigated the conditions of the redox reactions in view of substituent effects of aldehyde moieties. The results of cyclic voltammetry (CV) on an rotating ring-disk electrode (RRDE) suggested that the substitution effects and redox potentials were correlated. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations were also performed to simulate the UV–Vis and circular dichroism (CD) spectra; the results revealed a reasonably good correlation between the substituent effects and the highest occupied molecular orbitals and the lowest unoccupied molecular orbitals (HOMO-LUMO) gaps associated with the most intense transition bands. In addition, we summarized the substitution effects of Cu(II) complexes for their corresponding UV light-induced reactions.     

Controllable 1D Patterned Assembly of Colloidal Quantum Dots on PbSO4 Nanoribbons

Control of the 1D self‐assembly pattern of colloidal quantum dots (QDs) on PbSO₄ nanoribbon (NRb) templates is achieved. The internal structure of the NRbs is investigated by X‐ray diffraction, revealing the isotropic packing of the PbSO₄ nanoclusters in the NRbs. Colloidal QDs in a chloroform/hexane mixture are adsorbed onto the region close to the edges of the NRbs and form a 1D assembly of straight single line or double lines by controlling the amount of OAm. This is the first demonstration of a densely packed 1D self‐assembly of colloidal QDs with a straight line pattern without the use of any molecular bridge or adhesive. Atomic force microscopy measurements of the NRbs show depressions in the phase profile along the width of the NRbs, corresponding to the position of the 1D QD chain. The amount of adsorbed QDs on the NRbs in solution decreases as the addition of OAm increases, suggesting that additional OAm prevents interaction between the QDs and NRbs but facilitates the uniform adsorption of the 1D assembly. The low‐dimensional self‐assembly of colloidal QDs in this study opens up the possibility for the creation of anisotropically assembled QD superstructures.     

Development of Sensor and Control Systems of a Wearable Robot to Walk on a Step

The goal of our study is to develop a system for walking on a step using a wearable robot. Our system consists of (1) sensing of a step from the movement of the walker, (2) detection of the foot placement state related to the step, and (3) generation of gait patterns of climbing and stepping down for the step. In the generation of gait patterns for the step, toe trajectories are generated according to the height of the step to avoid collision of the swinging leg with the step. The hip trajectory is generated by an optimization technique that minimizes the sum of the joint angular jerk of the robot subject to constraints on the hip position and the velocity at toe liftoff. Each joint angle trajectory is calculated from the generated trajectories by means of inverse kinematic equations. We investigated the feasibility of the proposed sensor and control systems for two steps with different heights.     

Reversible Reaction with CO2 and Control of CO2 Absorption/Desorption Properties of Ba2(Fe1−xInx)2O5 Solid Solutions

Ba₂(Fe_1?xIn_x)₂O₅ was prepared by a solid‐state reaction under a N₂ flow. It was revealed that the solid solutions had a cubic perovskite structure with disordered oxygen vacancies at room temperature. Thermogravimetry and X‐ray diffraction measurements revealed that Ba₂(Fe_1?xIn_x)₂O₅ can reversibly react with CO_2. It was found that the equilibrium temperature of the reaction could be controlled by preparing solid solution.     

Adiabatic photo-steering theory in topological insulators

Feasible external control of material properties is a crucial issue in condensed matter physics. A new approach to achieving this aim, named adiabatic photo-steering, is reviewed. The core principle of this scheme is that several material constants are effectively turned into externally tunable variables by irradiation of monochromatic laser light. Two-dimensional topological insulators are selected as the optimal systems that exhibit a prominent change in their properties following the application of this method. Two specific examples of photo-steered quantum phenomena, which reflect topological aspects of the electronic systems at hand, are presented. One is the integer quantum Hall effect described by the Haldane model, and the other is the quantum spin Hall effect described by the Kane–Mele model. The topological quantities associated with these phenomena are the conventional Chern number and spin Chern number, respectively. A recent interesting idea, time-reversal symmetry breaking via a temporary periodic external stimulation, is also discussed.