Chiral Supramolecular Organogel Constructed Using Riboflavin and Melamine: Its Application in Photo-Catalyzed Colorimetric Chiral Sensing and Enantioselective Adsorption.

The synthesis of a chiral supramolecular organogel via the hierarchical helical self-assembly of optically active riboflavin and melamine derivatives is described herein. Owing to the photocatalysis of riboflavin and the supramolecular chirality induced in the helically stacked riboflavin/melamine complex, the gel is observed to act as a light-stimulated chiral sensor of optically active alcohols by detecting the change in color from yellow to green. The gel also served as an efficient chiral adsorbent, enabling optical resolution of a racemic compound with high chiral recognition ability.

Creation of a Highly Active Small Cu-Based Catalyst Derived from Copper Aluminium Layered Double Hydroxide Supported on α-Al2 O3 for Acceptorless Alcohol Dehydrogenation.

A highly dispersed carbonate-intercalated Cu2+ -Al3+ layered double hydroxide (CuAl LDH) was created on an unreactive α-Al2 O3 surface (CuAl LDH@α-Al2 O3 ) via a simple coprecipitation method of Cu2+ and Al3+ under alkaline conditions in the presence of α-Al2 O3 . A highly reducible CuO nanoparticles was generated, accompanied by the formation of CuAl2 O4 on the surface of α-Al2 O3 (CuAlO@α-Al2 O3 ) after calcination at 1073 K in air, as confirmed by powder X-ray diffraction (XRD) and Cu K-edge X-ray absorption near edge structure (XANES). The structural changes during the progressive heating process were monitored by using in-situ temperature-programmed synchrotron XRD (tp-SXRD). The layered structure of CuAl LDH@α-Al2 O3 completely disappeared at 473 K, and CuO or CuAl2 O4 phases began to appear at 823 K or 1023 K, respectively. Our synthesised CuAlO@α-Al2 O3 catalyst was highly active for the acceptorless dehydrogenation of benzylic, aliphatic, or cyclic aliphatic alcohols; the TON based on the amount of Cu increased to 163 from 3.3 of unsupported CuAlO catalyst in 1-phenylethanol dehydrogenation. The results suggested that Cu0 was obtained from the reduction of CuO in the catalyst matrix during the reaction without separate reduction procedure and acted as a catalytically active species.

Ultra-sensitive detection of pyridine in water using zinc porphyrin incorporated in a transparent hydrophobic film.

In this study, we investigated the axial coordination reaction between pyridine and zinc meso-tetra(4-sulfonatophenyl)porphyrin (ZnTPPS) incorporated in a transparent layered double hydroxide (LDH) film modified with 1-decanesulfonate (C10S) in an aqueous solution. The apparent equilibrium constant ([Formula: see text]) of the axial coordination reaction between pyridine and ZnTPPS incorporated in the transparent ZnTPPS/C10S/LDH film was approximately 260 times that of the corresponding reaction in an aqueous solution. The hydrophobisation of the LDH interlayer space by C10S, which led to the elimination of water molecules surrounding ZnTPPS and enabled the accumulation of pyridine molecules, was responsible for such a significant increase in the apparent [Formula: see text] value. The developed film can detect pyridine in aqueous solutions with ultra-high sensitivity in the order of 10-5 mol/L through changes in the colour tone, which is comparable to the molecular detection ability of insect antennae. The sensing response was also observed at pyridine concentrations as low as 10-9 mol/L.

Important Roles of Water Clusters Confined in a Nanospace as Revealed by a Synchrotron X-ray Diffraction Study.

States of water molecules confined in a nanospace designed by montmorillonite (negatively charged silicate layer) and charge compensating benzylammonium were investigated. Caffeine was used as a probe because of its compatibility for the fine structure of the interlayer water. Powder synchrotron radiation X-ray diffraction (SXRD) and adsorption isotherms of the water vapor revealed a metastable structure of bimolecular water layers (2WLs) in the interlayer space. Water molecules readily penetrated to expand the interlayer space to 0.56 nm. The interlayer space did not increase further even in the presence of excess water. According to the isosteric heat of water, the expansion was limited because of moderate hydration as forming 2WLs. Caffeine molecules replaced a part of the water molecules in the 2WLs to expand the interlayer space to 0.65 nm. Time-resolved SXRD with an accumulation time of 500 ms revealed that the interlayer expansion reached a steady state within a few minutes. The caffeine intercalation proceeded, involving a change in the molecular orientation that increased the contact area of the caffeine molecules. The interlayer expansion was limited in all the solvents examined (mixtures of water with methanol, ethanol, acetone, and tetrahydrofuran), while the packing density of the incorporated caffeine was maximized in the absence of an organic solvent. The water molecules confined in the interlayer space acted as an actuator to accommodate a large quantity of amphiphilic molecules by adapting the nanostructure, which was achieved by releasing the confined water molecules.

Radiation exposure dose outside the irradiation field due to differences in pediatric head computed tomography scanning methods.

The use of pediatric computed tomography (CT), a valuable imaging tool, has been increasing rapidly. The present study examined radiation exposure in non-irradiated fields of CT scans in pediatric patients using a 7-year-old child phantom. Radio-photoluminescence glass dosimeters were placed in the insertion ports of the phantom corresponding to the organs. For the helical and the non-helical scans, the doses to the head in the irradiation field were 54.6 mGy and 53.4 mGy, respectively. The dose measured for the helical scan was 2.3% higher than that for the non-helical scan. The largest dose was in the thyroid gland, and the doses for helical and non-helical scans were 5.37 mGy and 3.58 mGy, respectively. The difference in the dose between helical and non-helical scans was 1.79 mGy. The dose measured for the helical scan was 50% higher than that for the non-helical scan. The dose to which the thyroid gland was exposed outside the irradiation field in the head CT scan was 5.37 mGy using the helical scan method. The excess relative risk per gray increased by 3-5.5% if the excess relative risk per gray was 5-10. Decreasing the dose to the thyroid gland, which has a high risk of cancer after radiation exposure, is desirable. The dose to the thyroid gland was higher in the helical scan than in the non-helical scan. This is probably because overscanning, which is unique to helical scanning, increases the exposure dose outside the irradiation field.

Photocatalytic Hydrogen Evolution over Exfoliated Rh-Doped Titanate Nanosheets.

Various amounts of Rh-doped titanate nanosheets (Ti3NS:Rh(x), where x is doped amount) were prepared to develop a new nanostructured photocatalyst based on metal oxide compounds that can split water to produce H2 under sunlight. Ti3NS:Rh(x) was obtained by acid exchange, intercalation, and exfoliation of Rh-doped layered sodium titanate compound (Na2Ti3-x Rh x O7). A new energy gap was found in the diffuse reflection spectrum of the Ti3NS:Rh(x) colloidal suspension solution; this new energy gap corresponds to electrons in the 4d level of Rh3+ or Rh4+, which are doped in the Ti4+ site. A photocatalyst activity of Ti3NS:Rh(x) for H2 evolution in water with triethylamine (TEA) as an electron donor was investigated. The appropriate amount of Rh doping can improve the photocatalytic activity of Ti3NS for H2 evolution from water using triethylamine (TEA) as a sacrifice agent. The reason was related to the rich state of Rh3+ or Rh4+ doped in the Ti4+ site of Ti3NS. Doping Rh 1 mol % of Ti, Ti3NS:Rh(0.03) shows the H2 evolution rates up to 1040 nmol/h, which is about 25 times larger than that of nondoped Ti3NS under UV irradiation (>220 nm) and 302 nmol/h under near-UV irradiation (>340 nm). These results show that the development of new nanostructured photocatalyst based on Rh-doped titanate compounds that can produce H2 under near-UV irradiation present in sunlight was a success.

Why Do Carbonate Anions Have Extremely High Stability in the Interlayer Space of Layered Double Hydroxides? Case Study of Layered Double Hydroxide Consisting of Mg and Al (Mg/Al = 2).

Layered double hydroxides (LDHs) are promising compounds in a wide range of fields. However, exchange of CO32- anions with other anions is necessary, because the CO32- anions are strongly affixed in the LDH interlayer space. To elucidate the reason for the extremely high stability of CO32- anions intercalated in LDHs, we investigated in detail the chemical states of CO32- anions and hydrated water molecules in the LDH interlayer space by synchrotron radiation X-ray diffraction, solid-state NMR spectroscopy, and Raman spectroscopy. We found the rigidity of the network structure formed between the CO32- anions, hydrated water molecules, and the hydroxyl groups on the metal hydroxide layer surface to be a crucial factor underlying the stability of CO32- anions in the LDH interlayer space.

Which types of clay minerals fix cesium ions effectively? the "cavity-charge matching effect".

How can radioactive Cs+ ions be removed from aqueous solution? From this perspective, the adsorption of Cs+ was investigated by using five types of clay minerals possessing different charge exchange capacities. The fixation ability for Cs+ depended on the charge exchange capacity of the clay minerals. Phlogopite and vermiculite, where the number of charges is almost equal to half the number of siloxane ditrigonal cavities in the structure, exhibited a strong Cs+ fixation ability among these clay minerals. In these clay minerals, effective interlayer collapse, which leads to quasi-irreversible adsorption of Cs+, is expected from the introduction of Cs+ into the layer space. This is named the "cavity-charge matching effect". This study clarifies why only phlogopite and vermiculite can fix Cs+ quite strongly among various types of clay minerals. These findings are beneficial for removing radioactive Cs+ ions from the environment using clay minerals through the cavity-charge matching effect.

Synthesis, photodynamic activities, and cytotoxicity of new water-soluble cationic gallium(III) and zinc(II) phthalocyanines.

The cationic Ga(III) and Zn(II) phthalocyanines carrying N-methyl-pyridinium groups at eight peripheral ß-positionshave been synthesized. These complexes are highly soluble in dimethyl sulfoxide (DMSO) and moderately soluble in water and phosphate buffered saline (PBS); both Ga(III)Cl and Zn(II) complexes have shown no aggregation in water up to 1.2 × 10-4 and 1.5 × 10-5 M, respectively. A higher water-solubility of Ga(III)Cl complex as compared to Zn(II) complex is ascribed to the presence of an axially coordinated chloride. The spectroscopic properties, photogeneration of singlet oxygen (1O2), and cytotoxicity of these complexes have been investigated. The absolute quantum yields (ΦΔabsolute) for the photogeneration of singlet oxygen using Ga(III)Cl and Zn(II) complexes have been determined to be 4.4 and 5.3%, respectively, in DMSO solution. The cytotoxicity and intracellular sites of localization of Ga(III)Cl and Zn(II) complexes have been evaluated in human HEp2 cells. Both complexes, localized intracellularly in multiple organelles, have shown no cytotoxicity in the dark. Upon exposure to a low light dose (1.5 J/cm2), however, Zn(II) complex has exhibited a high photocytotoxicity. The result suggests that Zn(II) complex can be considered as a potential photosensitizer for Photodynamic therapy (PDT).

Optical Humidity Sensing Using Transparent Hybrid Film Composed of Cationic Magnesium Porphyrin and Clay Mineral.

A transparent hybrid film composed of cationic magnesium porphyrin and clay mineral was developed, and its chromic behavior depending on relative humidity (RH) was investigated. The hybrid film was obtained via intercalation of magnesium porphyrin into clay film; magnesium porphyrin was intercalated into the interlayer spaces of the clay mineral without aggregation. The absorption spectra of the hybrid film showed red shifts compared to the aqueous solution of magnesium porphyrin because of the π-conjugated system extension with coplanarization of the meso-substituted pyridinium group and porphyrin ring. The absorption maximum of the hybrid film was gradually shifted to a shorter wavelength, and the color of the hybrid film was changed with increasing RH. The X-ray diffraction measurement suggested that the basal space of clay was expanded with increasing RH, indicating that the interlayer space of clay was expanded by water adsorption, and the spectral shift was induced by the change in coplanarization degree between the porphyrin ring and meso-substituted pyridinium groups.

COMPARISON OF THE PERIPHERAL DOSES FROM DIFFERENT IMRT TECHNIQUES FOR PEDIATRIC HEAD AND NECK RADIATION THERAPY.

Intensity-modulated radiation therapy (IMRT) can deliver high and homogeneous doses to the target area while limiting doses to organs at risk. We used a pediatric phantom to simulate the treatment of a head and neck tumor in a child. The peripheral doses were examined for three different IMRT techniques [dynamic multileaf collimator (DMLC), segmental multileaf collimator (SMLC) and volumetric modulated arc therapy (VMAT)]. Peripheral doses were evaluated taking thyroid, breast, ovary and testis as the points of interest. Doses were determined using a radio-photoluminescence glass dosemeter, and the COMPASS system was used for three-dimensional dose evaluation. VMAT achieved the lowest peripheral doses because it had the highest monitor unit efficiency. However, doses in the vicinity of the irradiated field, i.e. the thyroid, could be relatively high, depending on the VMAT collimator angle. DMLC and SMLC had a large area of relatively high peripheral doses in the breast region.

Sequential energy and electron transfer in a three-component system aligned on a clay nanosheet.

To achieve the goal of energy transfer and subsequent electron transfer across three molecules, a phenomenon often utilized in artificial light harvesting systems, we have assembled a light absorber (that also serves as an energy donor), an energy acceptor (that also serves as an electron donor) and an electron acceptor on the surface of an anionic clay nanosheet. Since neutral organic molecules have no tendency to adsorb onto the anionic surface of clay, a positively charged water-soluble organic capsule was used to hold neutral light absorbers on the above surface. A three-component assembly was prepared by the co-adsorption of a cationic bipyridinium derivative, cationic zinc porphyrin and cationic octaamine encapsulated 2-acetylanthracene on an exfoliated anionic clay surface in water. Energy and electron transfer phenomena were monitored by steady state fluorescence and picosecond time resolved fluorescence decay. The excitation of 2-acetylanthracene in the three-component system resulted in energy transfer from 2-acetylanthracene to zinc porphyrin with 71% efficiency. Very little loss due to electron transfer from 2-acetylanthracene in the cavitand to the bipyridinium derivative was noticed. Energy transfer was followed by electron transfer from the zinc porphyrin to the cationic bipyridinium derivative with 81% efficiency. Analyses of fluorescence decay profiles confirmed the occurrence of energy transfer and subsequent electron transfer. Merging the concepts of supramolecular chemistry and surface chemistry we realized sequential energy and electron transfer between three hydrophobic molecules in water. Exfoliated transparent saponite clay served as a matrix to align the three photoactive molecules at a close distance in aqueous solutions.

Dense Deposition of Gold Nanoclusters Utilizing a Porphyrin/Inorganic Layered Material Complex as the Template.

We examined the deposition of gold clusters through the reduction of a gold precursor sensitized by nonaggregated, assembled porphyrin molecules on an inorganic layered material surface in order to develop a novel strategy for constructing assemblies of gold clusters. Visible light irradiation on nonaggregated, assembled porphyrin on the inorganic surface in the presence of the gold precursor and an electron donor induced the deposition of gold NPs on the surface of the inorganic layered material. Uniform gold clusters, with an average diameter of 1.5 nm, were deposited on the surface without aggregation. The average interparticle distance between adjacent gold clusters (center to center) was 2.3 nm, which agrees well with the average intermolecular distance of the nonaggregated, assembled porphyrin molecules on the inorganic surface. Thus, the generated gold clusters appear to reflect the nonaggregated, assembled structure of the porphyrin molecules on the inorganic surface. This method, termed the photosensitized template reduction (PTR) method, is a useful and novel technique for the deposition of metal nanoparticles on the surfaces of supporting materials.

High density intercalation of porphyrin into transparent clay membrane without aggregation.

Cationic porphyrin was successfully intercalated into transparent clay membrane by developing the new strategy for the sample preparation conditions. When water:ethanol = 1:2 (v:v) was used as solvent for porphyrin penetration process, high density intercalation of porphyrin into the clay membrane was achieved. In the interlayer space, porphyrin molecules do not aggregate owing to intercharge distance matching effect (size-matching effect), even at high density condition. Judging from XRD and absorption measurements, the orientations of the porphyrins in the clay layers should be almost parallel to the clay nanosheet as monolayer. Because the fluorescence quantum yield did not depend on its loading level, it is turned out that intercalated TMPyP in the clay film keeps the photoactivity even under the high density conditions.

Size-matching effect on inorganic nanosheets: control of distance, alignment, and orientation of molecular adsorption as a bottom-up methodology for nanomaterials.

We have been investigating complexes composed of nanolayered materials with anionic charges such as clay nanosheets and dye molecules such as cationic porphyrins. It was found that the structure of dye assembly on the layered materials can be effectively controlled by the use of electrostatic host-guest interaction. The intermolecular distance, the molecular orientation angle, the segregation/integration behavior, and the immobilization strength of the dyes can be controlled in the clay-dye complexes. The mechanism to control these structural factors has been discussed and was established as a size-matching effect. Unique photochemical reactions such as energy transfer through the use of this methodology have been examined. Almost 100% efficiency of the energy-transfer reaction was achieved in the clay-porphyrin complexes as a typical example for an artificial light-harvesting system. Control of the molecular orientation angle is found to be useful in regulating the energy-transfer efficiency and in preparing photofunctional materials exhibiting solvatochromic behavior. Through our study, clay minerals turned out to serve as protein-like media to control the molecular position, modify the properties of the molecule, and provide a unique environment for chemical reactions.

Novel methodology to control the adsorption structure of cationic porphyrins on the clay surface using the "size-matching rule".

Saponite-type clays that have different cation exchange capacities were successfully synthesized by hydrothermal synthesis. The structure and properties were analyzed by X-ray diffraction, X-ray fluorescence, (27)Al NMR, FT-IR, thermogravimetric and differential thermal analysis, atomic force microscopy, and cation exchange capacity measurement. The intercharge distances on the synthetic saponite (SS) surfaces were calculated to be 0.8-1.9 nm on the basis of a hexagonal array. The complex formation behavior between SS and cationic porphyrins was examined. It turns out that the average intermolecular distance between porphyrin molecules on the SS surface can be controlled, depending on the charge density of the SS. In the case of tetrakis(1-methylpyridinium-4-yl)porphyrin (H(2)TMPyP(4+)), the average intermolecular distances on the SS surface can be controlled from 2.3 to 3.0 nm on the basis of a hexagonal array. It was also found that absorption maxima of porphyrins depend on the charge density of the SS. The adsorption behavior of porphyrin on the SS surface can be rationally understood by the previously reported "size-matching rule". This methodology using host-guest interaction can realize a unique adsorption structure control of the porphyrin molecule on the SS surface, where the gap distance between guest porphyrin molecules is rather large. These findings will be highly valuable to construct photochemical reaction systems such as energy transfer in the complexes.

Indications of total ankle arthroplasty for rheumatoid arthritis: evaluation at 5 years or more after the operation.

Abstract The postoperative results of total ankle arthroplasty (TAA) were surveyed, and the indications of TAA for rheumatoid arthritis (RA) were examined. We have performed TAA in properly selected patients with indication of ankle joint destruction due to RA. The subjects were 18 RA patients (20 joints) who underwent TAA between April 1988 and April 1996. Type-ND or type-TNK Bioceram was used without cement for possible revision of TAA. No destruction of large joints was found in 8 patients, and TAA was used as part of multiple arthroplasty in 10 patients. After the operation, decrease in or disappearance of joint pain was obtained, and range of motion and improved ability to walk were secured. The clinical results were superior to those obtained for 17 joints of 17 patients who underwent ankle arthrodesis during the same period. However, a radiolucent zone was observed an X-ray examination in every case, after 8 years on average (range 5-12 years) after operation. Under present conditions, ankle arthrodesis should be used for younger patients. When no destruction of the hip or knee joint is found and the patient is 65 years of age or older, we believe TAA is indicated. In cases of multiple arthroplasty or with bilateral ankle joint destruction, TAA appears to be useful if patients are young, considering their better life expectancy and quality of life.