Solvent- and Light-Sensitive AIEE-Active Azo Dye: From Spherical to 1D and 2D Assemblies

Fluorescent molecular assembly systems provide an exciting platform for creating stimuli-responsive nano- and microstructured materials with optical, electronic, and sensing functions. To understand the relationship between (i) the plausible molecular structures preferentially adopted depending on the solvent polarity (such as N,N-dimethylformamide [DMF], tetrahydrofuran [THF], and toluene), (ii) the resulting spectroscopic features, and (iii) self-assembled nano-, micro-, and macrostructures, we chose a sterically crowded triangular azo dye (3Bu) composed of a polar molecular core and three peripheral biphenyl wings. The chromophore changed the solution color from yellow to pink-red depending on the solvent polarity. In a yellow DMF solution, a considerable amount of the twisted azo form could be kept stable with the help of favorable intermolecular interactions with the solvent molecules. By varying the concentration of the DMF solution, the morphology of self-assembled structures was transformed from nanoparticles to micrometer-sized one-dimensional (1D) structures such as sticks and fibers. In a pink-red toluene solution, the periphery of the central ring became more planar. The resulting significant amount of the keto-hydrazone tautomer grew into micro- and millimeter-sized 1D structures. Interestingly, when THF-H₂O (1:1) mixtures were stored at a low temperature, elongated fibers were stacked sideways and eventually developed into anisotropic two-dimensional (2D) sheets. Notably, subsequent exposure of visible-light-irradiated sphere samples to solvent vapor resulted in reversible fluorescence off↔on switching accompanied by morphological restoration. These findings suggest that rational selection of organic dyes, solvents, and light is important for developing reusable fluorescent materials.     

Fabrication of Functionally Graded SiO2‐Mo Material by Centrifugation and Floc‐Casting of Highly Concentrated Slurry

To fabricate functionally graded materials, a highly concentrated slurry of SiO₂‐Mo system was prepared and centrifugal force was applied in an attempt to achieve a graded composition. Subsequently, we formed a homogeneous green body with compositional gradation by floc‐casting at 80°C, which was then fired at 1750°C for 10 min in Ar. The sintered body had compositional ratios of SiO₂ and Mo as well as electrical conductivities that changed gradually along the direction of centrifugal force. The results demonstrate that centrifugation and control of slurry characteristics such as flocculation are effective in fabricating functionally graded SiO₂‐Mo materials.     

Low-Friction Coatings of Zinc Oxide Synthesized by Optimization of Crystal Preferred Orientation

The crystal preferred orientation of zinc oxide (ZnO) coatings on stainless steel substrates was precisely controlled by a combinatorial sputter-coating system. ZnO coatings were analyzed by X-ray diffraction spectroscopy, and surface and interfacial cutting analysis methods. The frictional properties of the coatings in a vacuum, the atmosphere, oil of n-hexadecane, and oil doped with palmitic acid molecules were observed. Different frictional behaviors of the ZnO coatings were observed by varying the crystal preferred orientation. A low-friction coefficient as less as 0.2 was realized by ZnO coatings with uni- and multi-crystal orientation in all of those conditions. Inverse proportion of the friction coefficient to normal load was observed on ZnO coatings with bi-orientation of (002) and (103) in pure and palmitic acid doped oil.     

Low Frictional Coating of Copper Oxide with Preferred Crystal Orientation

Coating films of copper oxide were synthesized on stainless steel substrates with a r.f. magnetron sputter. The composition of the films could be controlled by changing a gas ratio of oxygen and argon in sputter plasma, which was analyzed with X-ray diffraction spectroscopy. Frictional property of the films in an atmospheric pressure and in an ultra high vacuum (UHV) was measured with a pin-on-disk vacuum tribometer. Frictional coefficients of the film as low as 0.03 and 0.05 were achieved in an atmospheric pressure and in UHV, respectively. It is therefore, expected that the films are applicable to smooth-drive movable materials for ultimate conditions such as UHV and high temperature.     

Suppression of Bone Necrosis around Tooth Extraction Socket in a MRONJ-like Mouse Model by E-rhBMP-2 Containing Artificial Bone Graft Administration

Medication-related osteonecrosis of the jaw (MRONJ) is related to impaired bone healing conditions in the maxillomandibular bone region as a complication of bisphosphonate intake. Although there are several hypotheses for the onset of MRONJ symptoms, one of the possible causes is the inhibition of bone turnover and blood supply leading to bone necrosis. The optimal treatment strategy for MRONJ has not been established either. BMP-2, a member of the TGF-β superfamily, is well known for regulating bone remodeling and homeostasis prenatally and postnatally. Therefore, the objectives of this study were to evaluate whether cyclophosphamide/zoledronate (CY/ZA) induces necrosis of the bone surrounding the tooth extraction socket, and to examine the therapeutic potential of BMP-2 in combination with the hard osteoinductive biomaterial, β-tricalcium phosphate (β-TCP), in the prevention and treatment of alveolar bone loss around the tooth extraction socket in MRONJ-like mice models. First, CY/ZA was intraperitoneally administered for three weeks, and alveolar bone necrosis was evaluated before and after tooth extraction. Next, the effect of BMP-2/β-TCP was investigated in both MRONJ-like prevention and treatment models. In the prevention model, CY/ZA was continuously administered for four weeks after BMP-2/β-TCP transplantation. In the treatment model, CY/ZA administration was suspended after transplantation of BMP-2/β-TCP. The results showed that CY/ZA induced a significant decrease in the number of empty lacunae, a sign of bone necrosis, in the alveolar bone around the tooth extraction socket after tooth extraction. Histological analysis showed a significant decrease in the necrotic alveolar bone around tooth extraction sockets in the BMP-2/β-TCP transplantation group compared to the non-transplanted control group in both MRONJ-like prevention and treatment models. However, bone mineral density, determined by micro-CT analysis, was significantly higher in the BMP-2/β-TCP transplanted group than in the control group in the prevention model only. These results clarified that alveolar bone necrosis around tooth extraction sockets can be induced after surgical intervention under CY/ZA administration. In addition, transplantation of BMP-2/β-TCP reduced the necrotic alveolar bone around the tooth extraction socket. Therefore, a combination of BMP-2/β-TCP could be an alternative approach for both prevention and treatment of MRONJ-like symptoms.     

Photocatalytic properties of titanium dioxide sputtered on a nanostructured substrate

The effective one-step physical approach is demonstrated for the fabrication of anatase titanium dioxide nanotubes through r.f. magnetron sputtering of TiO₂ on a highly ordered nanoporous anodic alumina template. The nanostructured TiO₂ benefited from the combination of unique properties of both the sputtering technique that provided well-controlled environment for the fabrication of anatase phase TiO₂ and the porous anodic alumina (PAA) that provided uniform and ordered nanopores. The photocatalytic properties of TiO₂ films were characterized following the degradation of methylene blue molecules under UV light irradiation. The photocatalytic activity of the nanostructured TiO₂ films has been found to be approximately twice higher in comparison with the flat TiO₂ films fabricated at the same conditions.     

Prevention of Cracks in Functionally Graded SiO2‐Mo Materials Fabricated by Uniaxial Compression Casting and Pressureless Sintering

In industrial high‐intensity discharge lamps, cracks and delaminations occasionally develop at the interface between SiO₂ and the Mo foil in the seal. Here, functionally graded SiO₂‐Mo materials for use in these lamps were fabricated by uniaxial compression casting and pressureless sintering. Consequently, vertical cracks developed across the sintered body layers, and interfacial cracks developed between the 100 wt% SiO₂ and 90 wt% SiO₂‐Mo layers. Therefore, the effects of residual stress, difference in the coefficient of thermal expansion (CTE), and difference in the volume shrinkage on these cracks were investigated. Vertical cracks were suppressed when residual stress was relaxed by annealing near the annealing point of silica glass during the cooling step in the sintering process. Interfacial cracks were suppressed when the difference in the CTE of the interface between the 100 wt% SiO₂ and 90 wt% SiO₂‐Mo layers was relaxed by inserting layers of 95 wt% SiO₂‐Mo between them. Furthermore, the suppression effect became stronger when the difference in the volume shrinkage of the layers was relaxed by sintering to join the separately sintered monolayers. Thus, the development of these cracks was influenced by the residual stress, CTE, and volume shrinkage. Therefore, these cracks can be prevented by optimizing these factors.     

Development of a genetic transfer system in selenate-respiring bacterium Citrobacter sp. strain JSA which was isolated from natural freshwater sediment

Conjugative mating between the selenate-reducing bacterium Citrobacter sp. strain JSA and Escherichia coli S17-1 harboring the broad-host-range plasmid pKT230 or pKT240 (IncQ) allowed genetic transfer to strain JSA at a maximum frequency of 2.5×10(-5) (pKT230) and 5.1×10(-6) (pKT240) per recipient JSA cell. Kanamycin-resistant (selection marker of pKT230 and pKT240) transconjugants were routinely obtained with this method, and we confirmed that both vectors were also successfully transferred and replicated in strain JSA without alteration of the replicon. Furthermore, an electroporation method has also allowed transformation of JSA at a frequency of 10(-7) to 10(-6) transformants per μg vector DNA (per recipient cell), and PCR and hybridization analyses revealed that pKT230 and pKT240 are stably maintained in transformed JSA cells. These results indicated that both InQ plasmids can be used as vectors for gene transfer to selenate-reducing strain JSA. This is the first study to demonstrate an effective method for genetic transfer in a selenate-reducing Citrobacter bacterium and will aid in the elucidation of the selenium oxyanion reduction mechanism in this genus of environmental selenate-respiring isolates.