Deep Red Photoluminescence from Cr3+ in Fluorine-Doped Lithium Aluminate Host Material.

Deep red phosphors have attracted much attention for their applications in lighting, medical diagnosis, health monitoring, agriculture, etc. A new phosphor host material based on fluorine-doped lithium aluminate (ALFO) was proposed and deep red emission from Cr3+ in this host material was demonstrated. Cr3+ in ALFO was excited by blue (~410 nm) and green (~570 nm) rays and covered the deep red to near-infrared region from 650 nm to 900 nm with peaks around 700 nm. ALFO was a fluorine-doped form of the spinel-type compound LiAl5O8 with slightly Li-richer compositions. The composition depended on the preparation conditions, and the contents of Li and F tended to decrease with preparation temperature, such as Al4.69Li1.31F0.28O7.55 at 1100 °C, Al4.73Li1.27F0.17O7.65 at 1200 °C, and Al4.83Li1.17F0.10O7.78 at 1300 °C. The Rietveld analysis revealed that ALFO and LiAl5O8 were isostructural with respect to the spinel-type lattice and in a disorder-order relationship in the arrangement of Li+ and Al3+. The emission peak of Cr3+ in LiAl5O8 resided at 716 nm, while Cr3+ in ALFO showed a rather broad doublet peak with the tops at 708 nm and 716 nm when prepared at 1200 °C. The broad emission peak indicated that the local environment around Cr3+ in ALFO was distorted, which was also supported by electron spin resonance spectra, suggesting that the local environment around Cr3+ in ALFO was more inhomogeneous than expected from the diffraction-based structural analysis. It was demonstrated that even a small amount of dopant (in this case fluorine) could affect the local environment around luminescent centers, and thus the luminescence properties.

Crystal structure of silver carbonate iodide Ag10(CO3)3I4.

The title silver carbonate iodide, Ag10(CO3)3I4, deca-silver(I) tris-(carbonate) tetra-iodide, was recently reported as a precursor of the new superionic conductor Ag17(CO3)3I11. Ag10(CO3)3I4, was prepared by heating a stoichiometric powder mixture of AgI and Ag2CO3 at 430 K. A single-crystal suitable for X-ray diffraction analysis was obtained by slow cooling of a melt with an AgI-rich composition down from 453 K. Ag10(CO3)3I4 exhibits a layered crystal structure packed along [10], in which Ag atoms are inter-calated between the layers of hexa-gonally close-packed I atoms, and CO3 groups. Up to now, Cs3Pb2(CO3)3I is the only other compound containing carbonate groups and iodide ions registered in the Inorganic Crystal Structure Database.

Superionic Ag+ Conductor Ag17(CO3)3I11.

A new superionic Ag+ conductor with a nominal composition Ag17(CO3)3I11 (11AgI-3Ag2CO3) was found in the AgI-Ag2CO3 system. The conductor, which was formed at temperatures from 100 to 170 °C, is a metastable phase that gradually decomposes into AgI and Ag10(CO3)I4 over a period of a few weeks at room temperature (RT). A Ag+ ionic conductivity of 0.16 S/cm was measured at RT, and an activation energy of 0.33 eV was evaluated in the temperature range from -9 to 19 °C. Single-crystal X-ray analysis revealed that Ag17(CO3)3I11 crystallized in a rhombohedral unit cell with hexagonal parameters of a = 15.8831(6) Å and c = 30.0730(13) Å at -183 °C and space group R3c. The Ag atoms were distributed over 53 sites in the asymmetry unit, with a maximum occupancy of 0.33(8). The continuous distribution of the partially occupied Ag sites was associated with the conduction paths of the Ag+ ions in the structure.

Enhanced bone formation in the vicinity of porous ß-TCP scaffolds exhibiting slow release of collagen-derived tripeptides.

It has been experimentally proven that orally ingested collagen-derived tripeptides (Ctp) are quickly absorbed in the body and effectively promote the regeneration of connective tissues including bone and skin. Ctp are capable to activate osteoblasts and fibroblasts, which eventually promotes tissue regeneration. Based on these findings, a hypothesis was formulated in this study that direct delivery of Ctp to bone defect would also facilitate tissue regeneration as well as oral administration. To test the hypothesis, we prepared a bone augmentation material with the ability to slowly release Ctp, and investigated its in vivo bone regeneration efficacy. The implant material was porous ß-tricalcium phosphate (ß-TCP) scaffold which was coated with a co-precipitated layer of bone-like hydroxyapatite and Ctp. The ß-TCP was impregnated with approximately 0.8%(w/w) Ctp. Then, the Ctp-modified ß-TCP was implanted into bone defects of Wistar rats to evaluate in vivo efficacy of Ctp directly delivered from the material to the bone defects. The control was pristine porous ß-TCP. In vitro tests showed that Ctp were steadily released from the co-precipitated layer for approximately two weeks. The Ctp-modified scaffolds significantly promoted new bone formation in vivo in their vicinity as compared with pristine ß-TCP scaffolds; 6 weeks after the implantation, Ctp-modified scaffolds promoted twice as much bone formation as the control implants. Consequently, we achieved the slow and steady release of Ctp, and found that direct delivery of Ctp from implant materials was effective for bone regeneration as well as oral administration. A ß-TCP scaffold capable of slowly releasing bone-enhancing substances significantly promoted bone formation.

Effect of the up-front heat treatment of gelatin particles dispersed in calcium phosphate cements on the in vivo material resorption and concomitant bone formation.

Calcium phosphate cements (CPCs), consisting of a mixture of calcium phosphate powders and setting liquid, have been widely used in orthopedic applications. One of the drawbacks of CPCs is their poor resorbability in the living body, which hinders substitution with natural bones. One of the strategies to facilitate the resorption of CPCs is the incorporation of bioresorbable or water-soluble pore-generating particles (porogens), such as gelatin, in the CPC matrices. In spite of numerous reports, however, little is known about the effect of the dissolution/resorption rate of the porogens on concomitant bone regeneration. In the present study, we prepared preset CPCs dispersed with 10 mass% of low-endotoxin gelatin particles 200-500 µm in diameter having different heat-treatment histories, therefore exhibiting different dissolution rate, and then the obtained CPC/gelatin composites were evaluated for in vivo resorption and concomitant in vivo bone formation behaviors. As the results, the dispersion of gelatin particles markedly promoted in vivo resorption of CPC, and enhanced concomitant bone formation, connective tissue formation, osteoblast proliferation, and vascularization. The dissolution/resorption rate was able to be controlled by changing the up-front heat-treatment temperature. In particular, when CPC/gelatin composites were implanted in distal metaphysis of rabbits, the optimum dissolution/resorption was attained by heat-treating gelatin particles at 383 K for 24 h before dispersing in CPC. Quick resorption of calcium phosphate cement and concomitant bone formation by dispersing properly heat-treated with gelatin particles.

Enhancement of mechanical strength and in vivo cytocompatibility of porous ß-tricalcium phosphate ceramics by gelatin coating.

BACKGROUND: In an attempt to prepare scaffolds with porosity and compressive strength as high as possible, we prepared porous ß-tricalcium phosphate (TCP) scaffolds and coated them with regenerative medicine-grade gelatin. The effects of the gelatin coating on the compressive strength and in vivo osteoblast compatibility were investigated. METHODS: Porous ß-TCP scaffolds were prepared and coated with up to 3 mass% gelatin, and then subjected to thermal cross-linking. The gelatin-coated and uncoated scaffolds were then subjected to compressive strength tests and implantation tests into bone defects of Wistar rats. RESULTS: The compressive strength increased by one order of magnitude from 0.45 MPa for uncoated to 5.1 MPa for gelatin-coated scaffolds. The osteoblast density in the internal space of the scaffold increased by 40 % through gelatin coating. CONCLUSIONS: Coating porous bone graft materials with gelatin is a promising measure to enhance both mechanical strength and biomedical efficacy at the same time.