The odor removing fibers having biomimetic functions have been developed applying the enzymelike catalytic functions of iron (III) or cobalt (II) phthalocyanine (Fe (III)-, Co (II)-pc) derivatives and their polymers. The oxidoreductase role as antidote against poisonous substance invading the body by activating oxygen in the blood. We have studied the kinetics of model reaction of Fe (III)- or Co (II)-pc derivatives and their polymers, which have similar structure to active center, hematoporphirine IX, of oxidation-reduction enzymes. The Fe (III)- or Co (II)-pc derivatives and remarkably effective catalyst for the metal complexes. Next, various kinds of new odor removing materials by supporting Fe (III)-, Co (II) -octacarboxyphthalocyanines [M-oapc, M = Fe (III), Co (II) ] on various polymer materials and fiber have been developed.
The kinetics of odor removing mechanism of Mt-oapc supporting on porous and amorphous enriched rayon stable fiber have been also investigated.
It was found that the foul oder su bstances such as thiols, amines, etc. can be removed by the enzymelike reaction of Mt-oapc supporting on the rayon fibers. Further, the odor-removing abilities of these fibers by the room for bedridden patients, waste water treatment place and lavatory were evaluated. These results showed trace amount sulfur compounds which are main compound in odor were effectively removed less than 0.1 ppb using the fiber containing Mt-oapc. The fiber eliminated more quantity of the foul oder substances by 20 to 100 times than did activated carbon, and can withstand 50 times of washing.
Applying these properties, new types of odor-removers such as mattress, quilt, blanket, wad, woven, and nonwoven materials produced from odor-removing fibers have been developed.

View full abstract

Mizumoto-cho, Muroran-shi 050 Japan The reproducibility of electrode performance was tested from electrode to electrode using platinumethyl cellulose-xylene ternary pastes sintered on yttria-stabilized zirconia electrolytes. A data scattering over an appreciable range was observed, which was attributed to changes of electrode-electrolyte contact area (geometric factor) and those of non-geometric factor such as catalytic activity and diffusivity for adsorbed oxygen. The geometric factor was measured from the area of cathodic peak of cyclic voltammogram, which was calibrated by the actual contact area obtained from the optical micrographs of the electrode-electrolyte interface. The non-geometric factor was obtained from the slope of decay curve. It was found that the data scattering observed owed to both the geometric and non-geometric factors in an almost equal weight.

View full abstract

The behavior of a silver-silver oxide electrode in KOH solution containing zirconium (IV) chloride was investigated by potentiostatic and galvanostatic methods as well as by observation using a scanning electron microscope (SEM), electron prove micro analysis (EPMA), and X-ray diffraction (XRD)The following results were obtained.
(1) The potential of the initial stage on a discharge process measured by the galvanostatic method disappeared completely in the solutions with more than 1×10^-1 mol/l (4.7 mol/l KOH), and the potential of the secondary stage kept the plateau potential throughout the discharge.
(2) Only the two oxidation-reduction peaks among the four oxidation-reduction peaks on the cyclic voltammograms measured by the potentiostatic method disappeared completely in the solutions with more than 1×10^-1mol/l (4.7 mol/l KOH).
(3) The charge-discharge capacity of the electrode measured by the galvanostatic method was obviously increased by the additinon of zirconium (IV ) chloride. Consequently, zirconium (IV) chloride 1×10^-1m ol/l (4.7 mol/l KOH) solution was more effective than the solution of other concentrations. (4) It was observed by the SEM that the active materials of the electrode grew to be branch-like fine crystals in the presence of zirconium (IV) chloride.

View full abstract

The non-stoichiometric dissolution of hydroxyapatite (HAP) in aqueous solutions of NaCl, Na₂SO₄, and sodium dodecyl sulfate (SDS) was studied. Molar ratios of Ca²⁺ to phosphate ion (Pi) released from HAP varied depending on species and concentration of an added salt. The order of salts inc reasing [Pi] was SDS >Na₂SO₄>NaCl, while that increasing [Ca²⁺] was NaCl> Na₂SO₄ > SDS, where the concentration of SDS was lower than its cmc (critical micellization concentration). These results were explained as follows: Pion the surface of HAP is more easily replaced by SO₄^2- than Cl- through a mechanism of ion exchange with isomorphic substitution, because the ion size of SO₄^2- is quite similar to that of PO₄^3--. On the other hand, the chemical structure of dodecyl sulfate ion (DS-) is made u p by a covalent bond between -SO₄- and a hydrocarbon chain (-C₁₂H₂₅). The adsorption of organic DS-, therefore, was enhanced more than that of inorganic SO₄^2- by both the hydrophobic/cooperative e ffect of the hydrocarbon chains and the isomorphous replacement of the terminal -SO₄- with PO₄^3- on the surface of HAP. Excess amounts of negative charge due to the adsorbed DS- accelerate the release of Pi from HAP in order to relax the high electrochemical potential of the surface. This mechanism result s in more release of Pi in the presence of SDS than in the presence of Na₂SO₄. The sequence of th e salts for the Ca²⁺ releasing was in t he reverse of that for the Pi releasing by virtue of restriction of the solu bility product of HAP.

View full abstract

Alkoxide techniques were employed to control the particle size of rhodium dispersed on silica. It was confirmed from the TEM observations that the particles in the reduced catalyst were in a uniform size level and the mean particle size could be adjusted in the range of 25-80 Å by changing the rhodium loading from 0.5 to 20.0 wt%. The EXAFS results showed that the rhodium ions were homogeneously dispersed in the gels obtained by a hydrolysis of the mixed solution of rhodium (III) nitrate dissolved in trimethylene glycol and tetraethyl orthosilicate, leading to a high uniformity of the particle size of rhodium. It was also found that the small metal particles were formed by drying and calcining the gels and grew by reduction with hydrogen. The turnover number of the gas phase hydroformylation of ethylene over the catalyst remarkably increased with a decrease in the metal particle size. Deposition of carbons onto the surface of the catalyst was observed during the reaction, resulting in a significant reduction of the number of the active site for the reaction.

View full abstract

The cobalt (III) and rhodium (III) complexes containing a terdentate ligand (bis (3-aminopropyl)amine, abbreviated as dpt) which forms two six-membered chelate rings, and a bidentate ligand (2, 2'bipyridine or 1, 10-phenanthroline, abbreviated as bpy or phen, respectively) forms a plane five-membered chelate ring, [CoC1(bpy) (dpt) ]²⁺, [CoCl (phen) (dpt) ]²⁺, [RhC1 (bpy) (dpt) ]²⁺, and [RhCl(phen) (dpt)]²⁺, were prepared. The crystal structures of the perchlorate salts were determin ed by X-ray diffraction method as mer-endo(Cl, NH)-isomer (Fig.1 (a)) for two cobalt (III) complexes, and as mer-exo (Cl, NH)-isomer (Fig.1 (b) ) for two rhodium (III) ones. All the six-membered chelate rings formed by dpt ligand adopted chair conformation. The analogous cobalt (III) complexes containing a terdentate rigand (N-(2-aminoethyl)-1, 3-propanediamine, abbreviated as aepn) which forms a five- and a six-membered chelate rings, [CoCl(bpy) (aepn) ]²⁺ and [CoCl(phen) (aepn)]²⁺, were also prepared. The structures of the complexes were identified on the basis of the spectroscopic data as the mer-type. For all the complexes prepared in this work, no fac-isomers were obtained or detected.

View full abstract

The synthesis and properties of 7-isopropyl-4-methyl-1-azulenemethanol (1) have been studied in detail. As a result, compound (1) is considerably stable in a solution such as hexane or ethanol, but it is very sensitive to air at neat state. Autoxidation of compound (1), which was allowed to stand at 10∼16°C for 100 h under aerobic conditions, gave the following compounds. These compounds were is olated and purified by silica-gel column chromatography, and confirmed by spectroscopic (UV-vis, IR, ¹H-1NMR and MS) data. They are: a) Hydrocarbon compounds: 7, 7'-diisopropyl-4, 4'-dimethyl-1, 1"methylenediazulene (1A₁), 7-isopropyl-4-methyl-1, 3-bis[ (7-isopropyl-4-methyl-1-azulenyl) methyl]azulene (1A₂) and guaiazulene tetramers (1A₃) (as mixture of (1A₃₁) and (1A₃₂); b) Ether compounds: 7, 7'-diisopropyl-4, 4"-dimethyl-1, 1'-oxydimethylenediazulene (1B₁), 7, 7'-diisopropyl-4, 4'dimethyl-3- (7-isopropyl-4-methyl-1-azulenyl)methyl-1, 1'-oxydimethylenediazulene (1B₂); c) Sidechain oxidized compound: 7-isopropyl-4-methyl-1-azulenecarbaldehyde (1C); d) An alcoholic compound: 7-isopropy1-4-methyl-3-(7-isopropyl-4-methyl-1-azulenyl)methyl-1-azulenemethanol (1D). All of them are found to be novel ones besides compound (1C).

View full abstract

Photocyclization of diphenylamine (DPA) to carbazole has been known to proceed via dihydrocarbazole (M) produced from the excited triplet state (T). The quantum yield (φc. ) for the formation of carbazole is markedly affected by the addition of chloromethanes (Q): φc, represented as a function of [Q], φc (Q), shows a convex curvature; i. e. Q causes both acceleration and retardation of the photocyclization reaction. The present study was carried out in order to elucidate the role of Q in the photocyclization reaction of diphenylamines.
Fluorescence of DPA is quenched markedly by the addition of Q. The rate constant of fluorescence quenching (k₂) increases with the increase in electron affinity of Q, indicating that the quenching of the lowest excited singlet state (S₁) is caused by the electron transfer from Sistate of the amine to Q. However, the quenching of S₁ by Q cannot fully explain the variation of φc, n the whole range of [Q] studied.
Computer simulation of φc (Q) revealed that dehydrogenation of M by Q accelerates the photocyclization, while the quenching of Si and T by Q retards the photocyclization. In this simulation process of Oc, we introduced acceleration and retardation facters, Fa and Fr, which depend on the nature of Q. The plot of both log Fa and log Frvslf, gave straight lines, suggesting that the electrontransfer processes play an important role in both acceleration and retardation in the photocyclization as well as quenching of fluorescence. Detailed discussions on the chemical mechanism of acceleration and retardation were made. The differences between the Nsubstituted and Nunsubstituted amine were also discussed.

View full abstract

Reaction of bifunctional molecules having two α, β-unsaturated carbonyl groups with lanthanoid reagents (Yb, YbCl₃/Zn, SmI₂) has been investigated. Reaction of 1, 2-bis[ (E)-3-oxo-3-phenyl-1propenyl]benzene (1) with lanthanoid reagents results in various intramolecular cyclization under mild conditions to give 1, 4-dihydronaphthalenes (3) and indan derivatives (4, 5a-b) in moderate yields, independent of varieties of lanthanoid reagents. This cyclization is induced by single electron transfer (SET) to carbonyl group from lanthanoid metals, followed by radical addition to an internal olefin. Stereochemical cource of this radical cyclization for 1 is determined to be cis. Furthermore, the reaction of (2E, 7E)-1, 9-dipheny1-2, 7-nonadiene-1, 9-dione (2) with Yb metal gives bicyclo[3.3.0]octanes (6)and tricyclo[11.3.0.0^5.9]1hexadecane derivatives (7) in moderate yields via double cyclization processes. First, anion radical generated by SET from Yb metal adds to the internal C-C double bond followed by the aldol condensation of the Yb enolate. These cyclizations proceed regio- and stereoselectively under mild conditions. In the case of the reaction of 2 with 2 molar equiv. of SmI2, cyclopentane derivative (8)is formed.

View full abstract

Acrylic acid was grafted onto a polyethylene film by preirradiation grafting. The resulting hydrophilic membrane was evaluated on i ts water selective separation of ethanol-water mixtures based o n pervaporation method. The separation factor and permeation rate increased when the concentration of the carboxyl groups in the grafted membrane increased. For instance, the separation factor and permeation rate of 30 wt% aqueous ethanol solution through a membrane with 220% of degree of grafti ng were 6and 4.6 kg/ (m²⋅h ), respectively. Moreover, the effect of radiation crosslinking on the water selective separation was also examined. In the comparison of crosslinking before and after the introdu ction of graft chains, the latter designated effective selective separation of water from the ethanol-water mix ture. The separation performance of the noncrosslinked and after crosslinked membrane with 220% of degree of grafting was compared using 70 wt% aqueous ethanol solution, and the separation factor of the after crosslinked membrane was 10 times larger than that of the noncrosslinked membrane.

View full abstract

A methodology of fuzzy clustering was applied to a classification of common solvents. The data used here are based on the interaction between certain solutes and a solvent, representing the characteristi cs of dipole, proton acceptor and proton-donor of solvents. In case of cluster number being 7, almost the same classification was obtained as that of a qualitative classification by Snyder. In addition, when the grade of membership of each solvent is interpreted as a set funcion which is a measure of sets, an additiv ity between measures holds good. So, a function of each solvent can be predicted by Lebesgue integration with a probabilitiy variable being a function of a representative solvent.

View full abstract

There has been a great deal of interest in the electro-optical properties of composite systems consisting of side chain type liquid crystalline polymer (SCLCP) and low molecular weight liquid crystal (LMWLC). Adding a photoisomerizable molecule to the composite systems gives a rewritable optical storage effect. This paper will focus on two experimental results; 1) to strengthen the aggregation of the ternary system by developing an induced smectic component system in order to realize a high contrast and improved memory characteristics, 2) to achieve fast optical write by using the third harmonic of a YAG laser. Poly [ [6- [4-[ (4-methoxyphenyl) oxycarbonyl]phenoxy]hexyllmethylsiloxane] (PS6EM), 4-butyl- (4-methoxyphenylazo) benzene (MPABB) and 4-cyano-4'-pentyloxybiphenyl (50CB) were used as the SCLCP, photoisomerizable molecule with weak polar end and the LMWLC with strong polar end, respectively. The PS6EM/MPABB/5OCB (40/10/50 mol%) composite system revealed a reading contrast ratio of 300. Optical write time was reduced from over 10 m in to few seconds by using the YAG laser with a Q-SW (Continuun, NY-60).

View full abstract

The reduction of racemic ethyl 2-oxocyclohexanecarboxylate (1) by the use of normal dry bakers'yeast (Free BY) or calcium alginate-immobilized bakers' yeast (IM-Alg) gave ( + )-1R, 2S-2-hydroxy ester (2) exclusively, while considerable amount of the corresponding ( + )-1S, 2S-2- hydroxy ester (2)was obtained together with ( + )-1R, 2S-2-hydroxy ester (2) in the presence of allyl alcohol. The ratio of the cis isomer (1R, 2S) to the trans isomer (1S, 2S) was about 7:3∼6:4 and the enantiomeric purity of each isomer was very high. In contrast, the reduction of 1 by the use of polyurethane-immobilized bakers' yeast (IM-PU) gave a mixture of ( + )-1R, 2S- and ( + )-15, 2S-2-hydroxy esters (7: 3) in the absence of allyl alcohol.

View full abstract

A titanium-containing organic thin film was prepared from titanium tetraisopropoxide (TIPP) by plasma polymerization. The effects of photoirradiation (visible light) on the electric conductivity of the film in the presence of organic vapors such as ethanol, acetaldehyde, formaldehyde, and benzaldehyde were investigated at various temperatures. The film showed electric current changes as large as 6-20 μA when exposed to ethanol and acetaldehyde under visible light irradiation. These results indicated the possibility of an organic gas sensor operable below 100°C.

View full abstract

Microviscosity of water-pool, nw, in reversed micellar cores of sodium 1, 2-bis (2-ethylhexyloxycarbonyl)ethanesulfonate (AOT) and metal 1, 2-bis (3-ethylheptanoyl) ethanesulfonic acid (MOT) was determined with a viscosity-sensitive probe, Auramine 0 (AuO). AuO aqueous solutions were solubilized in AOT or MOT reversed micelles. The detemined by the measurement of the fluorescence intensity and absorbance of the solutions was depicted as a function of R_{W, A} (=[H₂O[MOT] and R_{W, M} (= [H₂O]/n[MOT], in which the number n shows metal valence).
The relation between ηw, and R_{W, M} for MOT solutions coincided wi th that for AOT solutions. With the increase in R_W( R_{W, A} and R_{W, M}), the ηw rapidly decreased in the region of R<10, and leveled off at about R = 20. The level off values of r7, were higher than the value of bulk water. This shows the localizatio n of Au0 molecules in the vicinity of anionic polar head of AOT or MOT surfactant molecules.

View full abstract