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RuL 3 2+ (L=2,2′-bipyridine-4,4′-diphosphonic acid) thin solid films were fabricated by three-dimensional linking between the phosphonic acid substituents of L and Zr(O)Cl2. The RuL3 chromophores in the films are electronically independent of each other in the ground state and give emission spectra essentially identical to that of RuL 3 2+ in solution, although the emission lifetime is much shorter. The films are electrochemically active, showing pseudo-reversible oxidation behavior in cyclic voltammetry. A preliminary attempt has been made to apply these films to photoelectrochemical cells.

TiO2光触媒のCO2改質性能向上を目的として，ゾルゲル・ディップコーティング法によるコーティングTiO2膜の作製条件を種々変化させて，それらがTiO2のCO2改質性能におよぼす影響を評価した．併せてコーティングTiO2膜の表面性状を観察，分析し，CO2改質性能との関係も調べた．その結果，コーティング回数を11まで増加させると，コーティングTiO2量と反応面積の増大により，CO2改質性能が向上した．高改質性能が得られたコーティング回数でコーティングTiO2膜の焼成時間を60, 300, 540 sと変化させたところ，焼成時間を長く設定すると，反応面積の増大によりCO2改質性能が向上した．TiO2ゾル溶液へのTiO2粉末混入割合を調節することで1回のコーティングあたりのTiO2量を変化させたところ，コーティング回数に応じて適切なTiO2粉末混入量を設定することで，CO2改質性能が向上することが認められた．

Polymer-dispersed liquid crystal (PDLC) films of 4-cyano-4‘-pentylbiphenyl (5CB) were fabricated between two surface-modified quartz or indium−tin-oxide (ITO) substrates that had been obtained by deposition of a boronate-terminated self-assembled monolayer, by its controlled hydrolysis, and by subsequent second-layer lamination over the completely hydrolyzed surface. It was shown that both the fluorescence from the interface layers in contact with the substrate surfaces and the electro-optic functions of PDLC devices are systematically changed with the chemical properties of the substrate surfaces (i.e., the polarity and hydroxy densities).

The fluorescence behaviour of the liquid crystal, 4-cyano-4-pentylbiphenyl (5CB), in composite thin films prepared by the photopolymerization of 5CB/diacrylate mixtures, was investigated by means of three different excitation methods, in which the total-internal-reflection or surface-limited excitation method was used for analysis of the fluorescence from an ultra-thin interface layer (100nm) in contact with the substrate surface, whereas the fluorescence from the interior bulk was analysed by the through-film excitation method. It was found that intensity ratios of the monomer and excimer emissions of 5CB are significantly lower in the interface layer than in the interior bulk, depending upon photopolymerization conditions as well as upon the structures of the diacrylates used. Scanning electron microscopic observations and light-scattering measurements of some typical composite films showed possible relationships between morphological features and fluorescence characteristics depending upon the diacryla...

For the purpose of improving the anti-asthmatic activity of 3-(imidazo[1,2-b]pyridazin-6-yl)thiopropanesulfonamide (I), the computer-assisted automated synthesis apparatus developed at Takeda was used to modify the sulfonamide moiety of I. Several kinds of sulfonamide derivatives (1-24) were easily obtained, confirming the usefulness of the automated synthesis apparatus in the laboratory. Anti-asthmatic activity of these derivatives was examined in a platelet activating factor (PAF)-induced bronchoconstriction. Among them, the piperidino-piperidine derivative (13) was found to possess comparable activity to that of I

A multilayered microchip (25 x 95 mm) used for vacuum distillation is designed, fabricated and tested by rectification of a water-methanol mixture. The polymer chip employs a cooling channel to generate a temperature gradient along a distillation channel below, which is separated into a channel (72 microm deep) for liquid phase and a channel (72 microm deep) for vapor phase by an incorporated microporous poly(tetrafluoroethylene) (PTFE) membrane. The temperature gradient is controlled by adjusting hotplate temperature and flow rate of cooling water to make the temperatures in the stripping section higher than the increasing boiling points of the water-enriched liquids and the temperatures in the rectifying section lower than the decreasing dew points of the methanol-enriched vapors. The effects of temperature gradient, feed composition, feed flow rate and membrane pore size on the micro distillation are also investigated. A theoretical plate number up to 1.8 is achieved at the optimum conditions.

A new strategy based on polymerization-induced phase separation (PIPS) techniques was proposed for fabricating palladium nanoparticles (PdNPs) captured in a microporous network polymer. Pd(OAc)(2) was premixed with a monomer having a poly(amidoamine)-based dendrimer ligand, and subsequently this was thermally polymerized with an excess amount of ethylene glycol dimethacrylate under PIPS conditions. In this system, the formation of PdNPs occurred concurrently with the polymer synthesis in a one-pot process, even with no additional reducing reagent. The resultant microporous polymer was found to have a mesoporosity; the nitrogen sorption analysis gave a specific-surface area of 511 m(2) g(-1), an average pore diameter of 9.9 nm, and a total pore volume of 1.01 mL g(-1). The TEM images of the polymer revealed that the created PdNPs were very small with a diameter of mainly ca. 2.0 nm; the high-resolution images were lattice-resolvable, showing the crystalline nature of the PdNPs (Pd(111) facets). Catalytic performances of the PdNP-containing microporous polymers were investigated for a heterogeneous Suzuki-Miyaura reaction of 4'-bromoacetophenone and phenylboronic acid in water. In the presence of 10(-2) molar equiv of the polymer, the reaction efficiently proceeded at 80 degrees C and gave the desired product, 4-acetylbiphenyl, in >90% yield after 2 h. On the basis of the ICP-AES analysis, the Pd content released into the solution phase was estimated to be only 0.27% of the initial charge. Thereby, this polymer was successfully recovered by simple filtration and reused with only a minimal loss of activity (yield >90% even at the eighth run). When the catalytic reaction was examined with a low amount of the polymer catalyst, the turnover number (TON) reached 8.5 x 10(4) while maintaining a good yield. Finally, the dendrimer template effect of the polymer catalyst was discussed by referring to the catalytic performances of a control polymer prepared with nonintegrated ligand monomers.

Planar bilayer membranes were obtained from polymerized double-chain ammonium amphiphiles. Their properties were closely related to those of the corresponding aqueous bilayers, and a life time longer than one day was observed for a well-organized polymer sample.

Direct measurements of forces between stable hydrophobic monolayers are performed, revealing very long-range attraction which extends to a separation of 300 nm in pure water. The attraction decreases in the presence of NaBr, while the pull-off force changes only moderately.

Se-Alkynyl selenocarboxylates (1) were found to readily react with alcohols and amines to give O-alkyl selenocarboxylates (4) and selenoamides (6) in moderate to good yields, respectively. The formation mechanisms of 4 and 6 via selenoketene and ammonium alkyneselenolate, respectively, are proposed.

A calcium-binding protein, regucalcin, was isolated from rat liver cytosol. Rabbit-anti-regucalcin antiserum, which was raised against regucalcin conjugated by glutaraldehyde to bovine serum albumin, was applied to glutaraldehyde-fixed whole mounts and subsequently visualized using the peroxidase-antiperoxidase methods. Rat hepatic regucalcin immunoreactivity was most pronounced in the liver and brain of rats, while it was not seen in the duodenum, testicle, spleen, lung and smooth muscle (bladder), and appeared only slightly in the kidney and heart. Control experiments using non-immune sera or adsorbed anti-rat liver regucalcin antiserum showed no staining. The present finding suggests that regucalcin localizes in the liver and brain of rats.

We have developed a methodology for the two-dimensional multilayer formation of polypyridine ruthenium complexes on solid surfaces under mild conditions. The alternate multilayers of the ruthenium ...

This paper reports on fabrication of water-compatible palladium nanoparticle (PdNP) catalysts supported on microporous polymers, which show high activity and extremely low Pd leaching behaviour in the usage for carbon cross-coupling reactions. The supported PdNP catalysts were fabricated by utilizing the polymerization-induced phase separation (PIPS) method. An outstanding point of the present study is to use a small molecule ligand monomer (D-m) based on N,N-dimethyl ethylenediamine, instead of the PAMAM dendrimer-based monomer used previously having integrated ligand sites. When D-m that had been complexed with Pd2+ was copolymerized with excess 1,6-hexanediol dimethacrylate (HX) in the PIPS setup, a highly active catalytic polymer (D-HX) having extremely low Pd leaching characteristics was successfully obtained. The TEM images of D-HX revealed that the created PdNPs were small with a diameter of mainly ca. 5.0 nm. Catalytic performances of D-HX were investigated for a heterogeneous Suzuki–Miyaura reaction in water. In the presence of 10−2 molar equiv. of the polymer, the reaction efficiently proceeded at 80 °C and gave the desired product in ca. 90% yield after 2 h. D-HX could be easily recovered by simple filtration and reused with only a minimal loss of activity. Intriguingly, the hot filtration test indicated that nearly no Pd species was thermally released from D-HX, which is in large contrast with the results of other polymers tested herein leading to a lot of Pd leaching. Through this study, it was demonstrated that the microscopic structure of the polymer supports could be well-controlled by changing the structure of monomers and it was closely related to the Pd leaching behaviour of the present heterogeneous catalysis systems.

Inspired by naturally occurring superhydrophobic surfaces, a number of approaches have been attempted to create specific surfaces having both micro- and nanoscale textures. To bring the artificial superhydrophobic surfaces closer to practical applications, a widely usable and simpler method that is systematically derived is required. Here, we describe a unique UV light-triggered micro/nanofabrication system for creating superhydrophobic surfaces, where the basic idea underlying this method comes from polymerization-induced phase separation (PIPS) phenomena. The operation consists of a three-step sequence and can be quickly performed within several minutes under an open-air condition: (1) coating of a precursor mixture for PIPS on a substrate, (2) UV curing to induce phase separation between the growing polymers and solvents, and (3) ethanol flushing to remove solvents to leave a specific texture at the surface. By selecting appropriate components of the PIPS mixture (cross-linkable monomers, solvents, and soluble polymer additives), phase separation rapidly and effectively occurred even in the film UV-polymerization format through the increasing thermodynamic instability; thereby specialized surfaces having micro- and nanoscale textures could be logically constructed. On the basis of the systematic investigation, this method was thus proved to be versatile and applicable for rational design of creating both transparent superhydrophobic films and water repellent fabric textiles.

A multilayered microfluidic chip used for vacuum membrane distillation is designed, fabricated and tested by rectification of a water-methanol mixture.

Hybrid multilayers of phthalocyanines (Pc) and titanium oxide (TiOx) have been effectively fabricated on the surfaces of quartz and indium-tin-oxide (ITO) according to the following layer-by-layer sequence; (i) the formation of a titanium butoxide layer (Ti(OBu)m) grafted onto the substrate surface by immersion of a substrate into a solution of Ti(OBu)4, (ii) hydrolysis of Ti(OBu)m to a TiOx layer with a Ti–OH surface, (iii) dipping of the treated substrate into a solution of Pc1–Pc3 bearing four or eight (triethoxysilyl)alkoxy substituents to form a Pc layer on the TiOx surface, presumably through Ti–O–Si bonding, (iv) hydrolysis of excess Si(OEt)3 groups in the Pc layer to form a silanol surface and (v) cyclic repetition of steps (i)–(iv). Atomic force microscopy (AFM) has shown that the multilayer surfaces are smooth, with surface roughnesses similar to that of a pristine substrate. The ratios of Ti atoms/Pc molecule for three different multilayers determined by X-ray photoelectron spectroscopy (XPS) were found to be roughly constant (3.8–4.3). For hole-only diodes of ITO/N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine/Au, it has been found that the surface modification of ITO with the hybrid multilayers of Pc1 causes remarkable current enhancements at low applied biases depending on the cycle number of the layer-by-layer deposition.

The effect of regucalcin, a calcium-binding protein isolaetd from rat liver cytosol, on (Ca2+-Mg2+)-adenosine triphosphatase (ATPase) activity in the plasma membranes of rat liver was investigated. 125I-Regucalcin bound to the plasma membranes in the presence or absence of 0.1 mM Ca2+. Regucalcin (0.35 μM) increased the plasma membrane (Ca2+-Mg2+)-ATPase activity about 15% (p M), glucagon (10-6 and 10-5M) or norepinephrine (10-7-10 M), suggesting that the regucalcin effect is not linked to guanosine triphosphate (GTP)-binding protein in the plasma membranes. Vanadium (10 and 10 μM), which inhibits the phosphorylation of liver plasma membrane (Ca2+-Mg2+)-ATPase, decreased the enzyme activity about 20% (p

Polymeric adsorbents containing an azobenzene moiety as a ligand were prepared, and the photoinduced adsorption behavior of proteins to the adsorbent was studied. This method regulates by light the adsorption/desorption of proteins in hydrophobic chromatography. In the dark, the amount of protein adsorbed onto the adsorbent increased with increasing hydrophobicity of either adsorbent or protein. On irradiation with UV light, the amount of protein adsorbed decreased. Such a photoinduced change of the adsorption of protein was considered to be caused by the change of the hydrophobic interaction between the adsorbent and the protein due to the photoisomerization of the azobenzene moiety accompanying the polarity change of the adsorbent. It is also found that the desorption of protein was dependent on the balance of the hydrophobicity between the adsorbents and proteins. When column chromatography was carried out, the proteins were adsorbed in the dark and could be eluted after photoirradiation, with water as the single solvent. Furthermore, mixture of proteins could be separated by using a hydrophobic gradient column which was constituted by two polymeric adsorbents having different hydrophobicity.

Radiation-induced reaction of thiamine monochloride with di-1-adamantyl tetrasulfide gave two products, 3-(4-amino-2-methyl-5-pyrimidinylmethyl)-6a-(1-adamantyldithio)-3a-methylperhydrofuro[2,3-d]thiazole and 2-(1-hydroxymethyl)-3-(4-amino-2-methyl-5-pyrimidinylmethyl)-6a-(1-adamantyldithio)-3a-methylperhydrofuro[2,3-d]thiazole.

The photocurrents of the substituted anthracenes, 1, 5-diacetylanthracene (2), 1-acetylanthracene (3), 9-acetylanthracene (4), 1, 5-dichloroanthracene(5), 1, 5-diethylanthracene (6), 1, 5-dimethoxyanthracene (7), 9-cyanoanthracene (8) and anthracene (1), were measured by using their "surface-type" cells in nitrogen. The compounds of (1), (5), (6), (7)and (8) showed the photocurrent spectra which corresponded to the absorption spectra of their evaporated films (Fig.1). In the cases of (2) and (3), however, the anomalous photocurrent apPeared in the threshold region of their absorption spectra. Especially, the anomalous photocurrent of (2) became larger (Fig.2). The appearance of the anomalous photocurrent was characteristic of anthracenes having the acetyl group at 1- and/or 5-position. The magnitude of the photocurrents of the 1, 5-disubstituted anthracenes was similar to that of (1). On the other hand, the photocurrents of the monosubstituted anthracenes were smaller than that of (1). Among the monosubstituted anthracenes, the compound (4) showed no photocurrent under the same conditions. Contrary to the results obtained in the cases of phenazines, the photoconductivities of the anthracene derivatives became better in air.

It was found that benzenesulfinic acid reacted with N-substituted maleimides in aqueous ethanol to give sulfoneimides in good yields. The rate for the reaction was determined by the use of the neutralization titration, the effect of a substituent in N-substituted maleimides on the rate was studied, and the reaction route of benzenesulfinic acid with N-substituted maleimide was deduced.

The effects of hetero atoms and substituents on the photocurrents of the parent compounds were investigated by comparison of the photocurrents of 52 specimens of the aza-benzenoid and oxa-benzenoid compounds.