Abstracts of Papers

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Department of Chemistry for Materials* nonmember
Composite Polymer Electrolytes Based on Poly(ethylene oxide), Hyperbranched Polymer, BaTiO3 and
LiN(CF3SO2)2, Takahito ITOH, Yoshiaki ICHIKAWA, Takahiro UNO, Masataka KUBO, and Osamu
YAMAMOTO*: Solid State Ionics, 156, pp. 393-399, 2003.
Composite polymer electrolytes based on poly(ethylene oxide) (PEO) with hyperbranched polymer(poly[bis(triethylene glycol)benzoate] capped with an acetyl group) (HBP), ceramic filler (BaTiO3), and lithium
salt (LiN(CF3SO2)2) were examined as the electrolyte for all solid-state lithium polymer batteries and optimized
to achieve high ionic conductivity. The ionic conductivity of the optimized composite polymer electrolyte,[(PEO−20 wt.% HBP)12(LiN(CF3SO2)2)]−10 wt.% BaTiO3, where the PEO with number-average molecularweights (Mn) of 60×104, HBP with Mn of 15,000 and BaTiO3 with a particle size of 0.5 µm were used, wasfound to be 2.6×10-4 S/cm at 30 ºC and 5.2×10-3 S/cm at 80 ºC, respectively. The optimized composite
polymer electrolyte showed an electrochemical stability window of 4.0 V and was stable until 312 ºC under air.
Spontaneous Polymerization Mechanism of Electron-Accepting Substituted Quinodimethane with
p-Methoxystyrene, Yukihiro MITSUDA, Takashige FUJIKAWA, Takahiro UNO, Masataka KUBO, and Takahito
ITOH: Macromolecules, 36, pp. 1028-1033, 2003.
Spontaneous reactions of 1-(2,2-dimethyl-1,3-dioxane-4,6-dione-5-ylidene)-4-(dicyanomethylene)2,5-cyclohexadiene (QM1) with p-methoxystyrene (MeOSt) were investigated in chloroform at room
temperature at different monomer feed ratios. The hexane-insoluble products were to be copolymers of
7-(4-methoxyphenyl)-8,8-dicyanoquinodimethane (QM2) with small amounts (3-6 mol%) of the QM1, and thereaction product in the hexane-soluble fractions was to be the one-to-one adduct (Cycloadduct) of methylene
Meldrum’s acid (MM) with MeOSt. It was found that in the spontaneous reaction of the QM1 with MeOSt aside reaction involving a metathesis process took place to form new two products, QM2 and MM, and the former
polymerized and the latter underwent the cycloaddition reaction with MeOSt.
Composite Polymer Electrolytes of Poly(ethylene oxide)/BaTiO3/Li Salt with Hyperbranched Polymer, Takahito
ITOH, Yuko MIYAMURA, Yoshiaki ICHIKAWA, Takahiro UNO, Masataka KUBO, and Osamu
YAMAMOTO*: Journal of Power Sources, 119-121, pp. 403-408, 2003.
Composite polymer electrolytes composed of poly(ethylene oxide) (PEO), BaTiO3 as a ceramic filler,
LiN(CF3CF2SO2)2 as a lithium salt, and hyperbranched polymer (HBP) (poly[bis(triethylene glycol)benzoate]capped with an acetyl group) as a plasticizer were examined as the electrolyte for all solid-state lithium polymer
batteries and the ionic conductivity was optimized. The optimized 90 wt.% [(80 wt.% PEO−20 wt.%
HBP)12(LiN(CF3CF2SO2)2)]−10 wt.% BaTiO3 electrolyte, where the PEO with Mn of 60×104, HBP with Mn of
15,000 and BaTiO3 with a particle size of 0.5 µm were used, showed the ionic conductivity of 1.3×10-4 S/cm at
30 ºC and 1.6×10-3 S/cm at 80 ºC, respectively. The optimized composite polymer electrolyte has anelectrochemical stability window of 4.0 V and also it was stable until 307 ºC under air.
Effect of “Topotactic” Reduction Product of Molybdenum Disulfide on Catalytic Activity of Metallocene
Catalyst for Olefin Polymerization, Satoru YAMADA, Akihiro YANO*, Morihiko SATO*, and Takahito ITOH:
Journal of Molecular Catalysis A: Chemical, 200, pp. 239-349, 2003.
N,N-Dimethylanilinium salt of molybdenum disulfide (MoS2) was developed as a novel cocatalyst for
metallocene catalysts. The cocatalyst is composed of N,N-dimethylanilinium ion as a cationic part and“topotactic” reduction product of MoS2, obtained by acquisition of an electron by neutral host lattice of MoS2
without structural alteration, as an anionic part.
In ethylene polymerization, addition of theN,N-dimethylanilinium salt of MoS2 to the bis(indenyl)zirconium dichloride (Ind2ZrCl2)/triethylaluminum(Et3Al) catalyst improved a catalytic activity per mmol of Ind2ZrCl2. The catalytic activity for this catalyst
system activated by addition of the cocatalyst depended significantly on the amount of the cocatalyst and theN,N-dimethylanilinium ion content in the cocatalyst.

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Abstracts of Papers

Synthesis and Polymerization of Novel Quinone Methide Ketals, Ayako SENO, Takahiro UNO, Masataka
KUBO, and Takahito ITOH: Polymer Bulletin, 50, pp. 1-8, 2003.
Novel quinone methide ketals, 8-[1’-cyano-1’-(ethoxycarbonyl)methylene]-1,4-dioxaspiro[4.5]deca6,9-diene (1a) and 8-(1’,1’-dicyanomethylene)-1,4-dioxaspiro[4.5]deca-6,9-diene (1b), were synthesized, andtheir polymerization behavior was investigated. Polymerizations of 1a and 1b initiated with BPO and BF3·Et2O
gave corresponding novel ring-opening polymers, but no polymerization with BuLi. Copolymerization of 1awith St in the presence of AIBN at 60 ºC gave the monomer reactivity ratios r1(1a) = 0.50 ± 0.1 and r2(St) = 0.1 ±0.02, and Q and e values of 1a were 2.46 and +0.93, indicating that 1a is a highly conjugative,
electron-accepting monomer. Homopolymers of 1a and 1b had better thermal stability than that of
7-cyano-7-(ethoxycarbonyl)-1,4-benzoquinone methide.

Thermal, Electrical, and Mechanical Properties of Composite Polymer Electrolytes Based on Cross-Linked
Poly(ethylene oxide-co-propylene oxide) and Ceramic Filler, Zhaoyin WEN, Takahito ITOH, Takahiro UNO,
Masataka KUBO, and Osamu YAMAMOTO*: Solid State Ionics, 160, pp. 141-148, 2003.
A fully amorphous cross-linked poly(ethylene oxide-co-propylene oxide) (poly(EO/PO)) polymer
electrolyte was prepared by chemical cross-linking reaction of a macro-monomer, poly(ethyleneoxide-co-propylene oxide) with trifunctional cross-linkable acryloyl groups at the macro-monomer chain end.
The lithium salt LiN(CF3SO2)2 ([Li]/[O]=1/16) and ceramic fillers such as BaTiO3 and γ-LiAlO2 adopted in thepolymer electrolyte could maintain the fully amorphous feature of the polymer matrix. The sub-micron andnano-sized BaTiO3 fillers slightly decreased the thermal decomposition temperature of the polymer matrix, while
the nano-sized γ-LiAlO2 filler improved to some extent the thermal stability of the polymer matrix.

An Investigation of Poly(ethylene oxide)/saponite-based Composite Electrolytes, Zhaoyin WEN*, Zhonghua
GU*, Takahito ITOH, Zuxiang LIN*, and Osamu YAMAMOTO*: Journal of Power Sources, 119-121, pp.
427-431, 2003.
Two kinds of composite, based on poly(ethylene oxide) (PEO) and a mineral saponite, were prepared andtheir thermal behavior, phase composition, microstructure and electrical properties were investigated. The
results showed that PEO easily intercalates to the interlayer of saponite, replaces the interlayer water molecules,
and acts as medium for lithium ion conduction. PEO-intercalated saponite exhibited conductivity as high as 4.1
×10-3 S cm-1, a lithium ion transference number of 0.99 at 25 ºC and conductivity activation energy of 0.14 eV.
Appropriate amounts of intercalated PEO in the interlayer of saponite is important to an ideal ionic conductivity.
The PEO-intercalated saponite is thermally stable below 350 ºC. In addition, a PEO-based composite withlithium saponite as filler showed homogeneous morphology and combined properties of individual PEO andsaponite.
Polymerization by Insertion of Molecular Oxygen into Crystals of 7,7,8,8-Tetrakis(ethoxy-carbonyl)
quinodimethane, Shinji NOMURA, Takahito ITOH, Masaki OHTAKE, Takahiro UNO, Masataka KUBO,
Atsushi KAJIWARA*, Kazuki SADA*, and Mikiji MIYATA*: Angewandte Chemie International Edition, 42,
pp. 5468-5472, 2003.
7,7,8,8-Tetrakis(ethoxycarbonyl)quinodimethane (1) copolymerized with oxygen in the solid state to givea highly crystalline alternating copolymer via a radical mechanism, but in vacuo no thermal and photo solid-statepolymerizations of 1 took place. X-ray crystallographic study explained well that unique arrangement of 1 in
the crystalline state provides copolymerization with molecular oxygen.

Abstracts of Papers

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Cyclic Polyelectrolyte: Synthesis of Cyclic Poly(acrylic acid) and Cyclic Potassium Polyacrylate, Masataka
KUBO, Takeshi NISHIGAWA, Takahiro UNO, Takahito ITOH, and Hiroaki Sato*: Macromolecules, 36, pp.
9264-9266, 2003.
α-Amino, ω-carboxyl heterodifunctional poly(tert-butyl acrylate) was prepared by a living anionicpolymerization of tert-butyl acrylate using 1-phenyl-1-[4-(2,2,5,5-tetramethyl[1,2,5]azadisilolidinyl)
phenyl]hexyl lithium and succinic anhydride as an initiator and terminator, respectively. Its intramolecularcyclization was carried out to obtain cyclic poly(tert-butyl acrylate) which was converted to cyclic poly(acrylicacid) and potassium polyacrylate

Surfactant Properties of Purified Polyglycerol Monolaurates, Tomoharu KATO*, Takashi NAKAMURA*,
Masatsugu YAMASHITA*, Masami KAWAGUCHI, Tadaya KATO, and Takahito ITOH: Journal of Surfactants
and Detergents, 6, pp. 331-337, 2003.
A series of purified polyglycerol monolaurates (PGML), such as di-, tri-, tetra, and pentaglycerolmonolaurates, were synthesized, and their surfactant properties in aqueous solutions were examined. The
surfactant properties of PGML were compared with those of n-dodecyl polyoxyethylene monoethers (C12EOn) to
examine the function of the hydrophilic part of these compounds. The critical micelle concentration (CMC)
values and the surface tension at CMC of PGML and C12EOn increased linearly with an increase in the numberof glycerol and oxyethylene units, respectively; the slope of the increase was greater for PGML than C12EOn.
The minimum surface area per molecule of PGML was smaller than that of C12EOn at the air/aqueous solution
interface.

Novel 2-Pyrone Synthesis via the Nucleophilic Addition of Active Methine Compounds to 2-Alkynone, Iwao
HACHIYA, Hitoshi SHIBUYA, and Makoto SHIMIZU, Tetrahedron Lett., 44, pp. 2061-2063, 2003.
Novel 2-pyrone synthesis via the nucleophilic addition of active methine compounds to 2-alkynone has
been developed. The reaction of active methine compounds with 2-alkynone provided 2-pyrones in good yields.
When malonic esters were used as a nucleophile, 5-alkoxycarbonyl-2-pyrones were obtained in good to highyields. On the other hand, the use of β-ketoesters as a nucleophile instead of malonic esters gave
5-acyl-2-pyrones in good yields. Even increasing the steric bulk of the nucleophile as with a 2-allyl-β-keto ester,
the desired 2-pyrone was obtained in moderate yield. The reaction of Meldrum’s acid with 2-alkynone afforded
the decarboxylated 2-pyrone in high yield.

Tandem N-Alkylation-C-allylation Reaction of α-Imino Esters with Organoaluminums and Allyltributyltin,
Yasuki NIWA and Makoto SHIMIZU, J. Am. Chem. Soc., 125, pp. 3720-3721, 2003.
The tandem N-alkylation-C-allylation and N-alkylation-C-cyanation reactions of several α-imino esters
with organoaluminums were carried out in good to excellent yields, where two nucleophiles attacked across the
C=N double bond. The tandem reaction consists of the following three sequences: nucleophilic addition to thenitrogen atom of the imino ester, oxidation of the enolate with benzoyl peroxide, and allylation (or cyanation) to
the resulting iminium salt. The aliphatic as well as aromatic imino esters underwent the tandem
N-ethylation-C-allylation to give the addition products in moderate to good yields. To increase the utility of thetandem alkylation-allylation reaction, bis(trimethylsilyl)aluminum chloride was used as an initial N-alkylation
reagent to afford the corresponding homoallylamines in good to high yields.

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Abstracts of Papers

Design and Synthesis of 4,6-di-tert-Butyl-2,3-dihydro-5-benzofuranols as a Novel Series of Antiatherogenic
Antioxidants, Kunio TAMURA, Yoshiaki KATO*, Akikra ISHIKAWA*, Yasuharu KATO*, Motomu
HIMORI*, Mitsutaka YOSHIDA*, Yoshiaki TAKASHIMA*, Tsukasa SUZUKI*, Yoshiki KAWABE*, Osamu
CYNSHI*, Tatsuhiko KODAMA*, Etsuo NIKI*, and Makoto SHIMIZU, J. Med. Chem., 46, pp. 3083-3093,
2003.
Antioxidants have been considered as potential antiatherogenic agents by inhibiting oxidation of
low-density lipoprotein (LDL), albeit vitamin E, a natural antioxidant, has failed to show reduction on
atherosclerosis in clinical trials. A novel series of antioxidants, 4,6-di-tert-butyl-2,3-dihydro-5-benzofuranols,
were rationally designed and synthesized to overcome the clinical limitation of vitamin E. In vitro, thecompounds showed a potent inhibitory effect on lipid peroxidation detected as 2-methyl6-(p-methoxyphenyl)-3,7-dihydroimidazo[1,2-a]pyrazin-3-one (MCLA)-dependent chemiluminescence inlinoleic acid autoxidation. In vivo, 4,6-di-tert-butyl-2,3-dihydro-2,2-dipentyl-5-benzofuranoI (BO-653, 1f), an
optimal compound, showed the highest concentration in plasma and LDL fraction in Watanabe heritablehyperlipidemic rabbits, due to its high affinity to LDL.
Double Nucleophilic Addition of Ketene Silyl (Thio)acetals and Trimethylsilyl Cyanide to α,β-Unsaturated
Aldimines Promoted by Aluminum Chloride, Makoto SHIMIZU, Makiko KAMIYA, and Iwao HACHIYA,
Chem. Lett., 32, pp. 606-607, 2003.
In the presence of AlCl3, a mixture of ketene silyl (thio)acetal and trimethylsilyl cyanide underwent 1,4and subsequent 1,2-additions, respectively, with α,β-unsaturated imines to give ethyl(S-alkyl) 5-amino6-cyanopentanoates in good yields. Among the Lewis acids tested, AlCl3 and TMSI were found to be efficientpromoters. Although there was still much room for the improvement of diastereoselectivities, the use of imines
having not only aromatic group but also aliphatic group worked well. In the case of the ketene silyl acetal
derived from ethyl acetate, only 1,2-addition adduct was obtained. When ketene silyl thioacetals were used, thereaction proceeded to give 1,4-1,2-adducuts in moderate yields.

Facile Double Nucleophilic Addition of Thiols and Tetraallyltin to Latent 2-Alkynals Using in situ Hydrolysis of
the Imino Functionality Promoted by Tin(IV) Chloride Pentahydrate, Makoto SHIMIZU, Takafumi NISHI, andAkihiro YAMAMOTO, Synlett, pp.1469-1473, 2003.
In the presence of SnCl4·5H2O, a mixture of thiols and tetraallyltin underwent 1,4- and 1,2-additions,
respectively, with the imines derived from 2-alkynals to give (Z)-1-sulfenyl-1,5-alkadien-3-ols in good yield,
where the hydrolysis of the intermediary imino species was found to be crucial. Among the Lewis acids
examined, SnCl4·5H2O gave the best result. The use of a mixed solvent system was also important to increase theproduct yield, and the reaction conducted in toluene-dichloromethane gave a better result. Under the optimum
conditions found for the derivative of 3-phenylpropynal, the reactions gave the adducts with good to excellent(Z)-selectivities in good yields. The effects of acid additives are also noteworthy. The reaction conducted in thepresence of pyridinium p-toluenesulfonate or 2,4,6-collidinium p-toluenesulfonate afforded the 1,4-1,2-addition
products in higher yields, where the diastereoselectivities were somewhat lower.
Highly Chemoselective Crossed Pinacol Coupling Reaction Using the Synergetic Effect of Boron Trifluoride
Etherate and Trichloromethylsilane, Makoto SHIMIZU, Ikuhiro SUZUKI, and Hiroaki MAKINO, Synlett,pp.1635-1638, 2003.
Use of boron trifluoride etherate and trichloromethylsilane in the presence of zinc-copper couple effected acrossed imino pinacol coupling reaction to give 1,2-diamines in good yields with high diastereoselectivities. The
use of halogen as an electron-withdrawing substituent on the aromatic ring gave the unsymmetrical 1,2-diaminesin good yield with high diastereselectivities. The use of the imine possessing a 2,4-dichlorophenyl moiety gave
the crossed coupling product in low yield with low diastereoselectivity. The reaction of various imines with
N-benzylidene-p-bromophenyl aniline usually proceeded to give the crossed coupling products in good yields.
However, use of aliphatic and α,β-unsaturated aldimines did not give the desired coupling products.

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Reductive Coupling of Acid Chlorides with nitriles Promoted by Titanium Tetra iodide. A Rapid Access to
α-Imino Ketone, Makoto SHIMIZU, Nobuyuki MANABE, and Hiroshi GOTO, Chem. Lett., 32, pp. 1088-1089,
2003.
Reductive coupling reaction of carboxylic acid chlorides and alkyl nitriles were efficiently promoted bytitanium tetraiodide to give α-imino ketones in good yields. When benzoyl chloride was treated with 2.0
equivalent of titanium tetraiodide in acetonitrile or propionitrile, the corresponding α-imino ketones wereobtained in moderate yields, respectively. The reaction in isobutyronitrile gave the best yield of 61%.
Pivalonitrile, a bulky nitrile, gave a lower yield. Reactions in nitriles possessing heteroatoms, such as
chloroacetonitrile and methoxyacetonitrile, also proceeded to give the coupling products in moderate yields,
whereas trichloronitrile did not give the desired product. When unsaturated nitriles such as acrylonitrile andcrotononitrile were used, the coupling reaction did not proceed.

Photoinduced Intramolecular Electron Transfer between Carbazole and Bis(Trichloromethyl)-s-Triazine
Generating Radicals, Koichi KAWAMURA, Yoshimasa AOTANI and Hideo TOMIOKA, J. Phys. Chem. B,
107, pp. 4579-4586, 2003.
An intramolecular electron transfer and photosensitivity in dye/initiator systems, in which an electron
donating light-absorbing unit (carbazole) is tethered by methylene bonds to an electron-deficient initiator[bis(trichloromethyl)-s-triazine] was investigated. The efficient quenching of fluorescence was observed in thetethered compounds in a rigid matrix at low temperature, and the higher sensitivity of photopolymerization wasobserved in the photopolymer films containing the tethered compounds as photoinitiating systems comparedwith the films containing physical mixtures of dye and initiator. The compounds tethered by a longer
methylene chain (C6 and C11) showed a higher photosensitivity than that tethered by a shorter methylene chain(C2 and C3), despite the efficient fluorescence quenching in the latter compounds. Control of back electrontransfer after initial electron transfer or control of radiationless deactivation via exciplex formation was
suggested to be important factor to design efficient dye-linked photoinitiators.
Triplet Carbenes: From Fleeting Existence to Attractive Molecular Units, Hideo TOMIOKA, Pure Appl. Chem.,
75, pp. 1041-1047, 2003.
Attempts to stabilize the triplet state of carbenes to the extent that they can survive under normal
conditions were made, in which triplet carbenes having a half-life of 19 min are realized. A way to use theresulting persistent carbene as a unit to construct photosensitive magnetic materials is also discussed.

Photochemical Transformations of Quintet m-Phenylenedinitrenes, Sergei V. CHAPYSHEV and Hideo
TOMIOKA, Bull. Chem. Soc. Jpn., 76, pp. 2075-2089, 2003. (Best manuscript of the issue)
First photochemical transformations of quintet dinitrenes have been studied by FTIR spectroscopy during
the photolysis of 1,3-diazidobenzene and its 2-methyl- and 2,4,6-trimethyl-substituted derivatives in solid argon
at 12 K. The reactions involve two competitive processes. In the first one, the intramolecular insertion of thenitrene unit into 1,6-aromatic bond induces the ring-opening, which leads to the formation of iminoacetylenes.
The second process involves the intramolecular addition of the nitrene unit to 1,2-aromatic bond followed by thering-opening to form azirinobutadiene derivatives. Methyl groups in ortho-positions to the nitrene units ofquintet dinitrenes efficiently protect their aromatic ring from nitrene attacks, substantially increasing thephotochemical stability of such species. Thus, undesirable photochemical rearrangements of intermediate triplet
azidonitrenes at early stages of the photolysis of 1,3-diazidobenzenes are completely suppressed on introducing
the methyl group in position 2 of these azides.

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Abstracts of Papers

Photolysis of Regioisomeric Diazides of 1,2-Diphenylacetylenes Studied by Matrix-Isolation Spectroscopy and
DFT Calculations, Hideo TOMIOKA and Shinji SAWAI, Org. Biomol. Chem., 1, pp. 4441-4450, 2003.
A series of diazides of 1,2-diphenylacetylenes was photolyzed in matrices at low temperature, andtransient photoproducts were characterized by using IR, UV/vis methods combined with ESR studies.
Theoretical calculations were also used to understand the experimental findings. The introduction ofphenylethynyl groups on phenyl azides shows little effect on the photochemical pathway. In marked contrast,
azidophenylethylnyl groups exhibited a dramatic effect not only on the photochemical pathway of phenyl azides
but also on the electronic and molecular structure of photoproducts. The patterns of the effect depended upon
the relative position of azide groups in the diphenylacetylene unit.Whenever two azide groups were situated in a
conjugating position with respect to each other, the azides always resulted in the formation of a quinoidal
diimine diradical in which unpaired electrons were extensively delocalized in the π-conjugation.The m,p’-isomer
was shown to be an excellent precursor for the high-spin quintet dinitrene. Moreover, the quintet bis(nitrene)
was rather photostable under these conditions.
Triplet Carbene Surviving a Week in Solution at Room Temperature, Eri IWAMOTO, Katsuyuki HIRAI and
Hideo TOMIOKA, J. Am. Chem. Soc., 125, pp. 14664-14665, 2003.
The stability of a triplet bis(anthryl)carbene was dramatically increased simply by introducing a group at
its C10 position, where considerable spin density builds up and, hence, the carbene decays.
2,6-Dimethyl-4-tert-butylphenyl groups introduced at the C10 position of the triplet bis(anthryl)carbene are likely
to quench almost any remaining decay pathways from this portion and make the triplet survive more than one
week in solution at room temperature. This is the longest-lived triplet carbene. A light-induced generation of thestable triplet carbene opens a route to photosensitive organic magnetic materials.

Retardation Effect of Sulfonic Acid on Thermal Radical Polymerization of Styrene, Jun-ichi NAKAMIMA, Seiji
TANIZAKI and Hideo TOMIOKA, J. Japan Petroleum Institute, 46, pp. 356-367, 2003.
A new polymerization retarder was investigated as an alternative to highly toxic dinitrophenols for the
styrene distillation process. Dodecylbenzenesulfonic acid (DBS) was found to reduce the initial rate of thermal
radical polymerization of styrene. The molecular weight of polystyrene resulting from thermal polymerization
was slightly higher in the presence of DBS than in the absence of DBS. 1-Phenyltetraline (1), obviously
produced by isomerization of the initial Diels-Alder adduct of styrene (4), was also detected in the presence of
DBS. These observations suggest that DBS behaves as an acid catalyst for the isomerization of 4 to 1. The
retardation effect can be explained as the reduction of the concentration of initiate radicals generated frommolecular assisted homolysis of 4 and monomeric styrene. Although only sulfonic acid cannot completely
replace highly toxic and reactive dinitrophenols, it can reduce the amount of dinitrophenols required.

Computational Modeling of Phase Connectivity in Microstructures of Porous Materials during Sintering andGrain Growth, Masayoshi SHIMIZU, Hideaki MATSUBARA, Hiroshi NOMURA and Hideo TOMIOKA, J.
Ceram.Soc. Jpn., 111, pp. 201-211. 2003.
A Mote Carlo simulation method using a three dimensional lattice was developed to analyze theconnectivity of pores in sintered materials. The changes in porosity (fV), mean grain diameter (DS), intercept
length of pores (DV), contiguity of the solid phase (C) and fraction of connected pores (fV,C) with the number ofMonte Carlo steps (MCS) were analyzed as a function of initial porosity (fV,0) and initial grain diameter (DS,0).
In many cases fV,C decreased with MCS down to 0 %, particularly at small and intermediate values of fV,0 and DS,0.
However, in some cases of large fV,0 and DS,0, an fV,C of 100 % was maintained irrespective of MCS, which meansthat all pores may remain connected in the material. Systematic plots of DV, DS and C vs fV,0 × fV,C, whichindicate the amount (%) of connected pores, are found to be useful for designing sintering and grain growth
processes of porous materials.

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Ab Initio Molecular Orbital Study on the G-Selectivity of GGG Triplet in Copper(I)-Mediated One-Electron
Oxidation, Yasunori YOSHIOKA, Hiroko KAWAI, Tomoko SATO, Kizashi YAMAGUCHI*, and Isao SAITO*:
J. Am. Chem. Soc., 125, pp.1968–1974, 2003.
The G-selectivity for Cu(I)-mediated one-electron oxidation of 5’-TG1G2G3-3’ and 5’-CG1G2G3-3’ hasbeen examined by ab initio molecular orbital calculations. It was confirmed that G1 is selectively damaged by
Cu(I) ion for both 5’-TG1G2G3-3’ and 5’-CG1G2G3-3’, being good agreement with experimental results. The
Cu(I)-mediated G1-selectivity is primarily due to the stability of the Cu(I)-coordinated complex,[-XG1G2G3-,-Cu(I)(H2O)3]+. The Cu(I) ion coordinates selectively to N7 of G2 of 5’-G1G2G3-3’ rather than N7 of
G1. The G2-selective coordination induces the G1-selective trap of a hole that is created by one-electron oxidationand migrates to GGG triplet. Therefore, the radical cation of G1 is selectively created in both 5’-TG1G2G3-3’ and5’-CG1G2G3-3’, giving the G1-selective damage of 5’-G1G2G3-3’.

Thermal Reactions of 3-Furyl Fulgide and 3-Thienyl Fulgide. Ab Initio Molecular Orbital and CASSCF Studies,
Yasunori YOSHIOKA, Mamoru USAMI*, Masayuki WATANABE*, and Kizashi YAMAGUCHI*: J. Mol.
Struct. (THEOCHEM), 623, pp.167–178, 2003.
Thermal reactions of 3-furyl fulgide and 3-thienyl fulgide were examined at ab initio molecular orbital and
CASSCF levels. The transition states of EC and EZ-isomerizations were determined by singlet UHF methodwith 6-31G* basis set, and their activation energies were successively estimated at CASSCF level. The
geometries of the transition states of EC-isomerizations of 3-furyl fulgide and 3-thienyl fulgide are closer tothose of C-isomers than those of E-isomers. The EC-isomerization proceeds in a conrotatory mode rather than adisrotatory mode due to steric repulsion of methyl groups, in conflict with the Woodward-Hoffmann selection
rule. The activation energies of EZ-isomerizations are less by ~5 kcal/mol than those of EC-isomerizations,indicating that EZ-isomerizations are thermally preferred rather than EC-isomerizations, in harmony withthermal examinations of 3-furyl fulgide and 3-thienyl fulgide at 140 °C.
Theoretical Study of Role of H2O Molecule on Initial Stage of Reduction of O2 Molecule in Active Site of
Cytochrome c Oxidase, Yasunori YOSHIOKA, Hiroko KAWAI, and Kizashi YAMAGUCHI*: Chem. Phys. Lett.,
374, pp.45–52, 2003.
Mechanism of formation of [Fe-O-O-H, CuB] from [Fe-O-O, CuB] in active site of cytochrome c oxidase
was theoretically investigated. It was found that the H2O molecule is hydrogen-bonded to both Tyr244 andHis290, and is a key molecule to produce Fe-O-O-H. This H2O molecule plays a role as a carrier of a proton
toward Fe-O-O to yield [Fe-O-O-H, CuB]. CuB atom is formally changed from cuprous state to cupric statethrough transportation of a proton by the H2O molecule. A new reaction mechanism, which we call ‘water-protontransport’ (WPT) mechanism, is proposed for the initial stage of reduction of the O2 molecule.

Theoretical Study of Hydrogen-Bonded Network and Proton Transfer in the Active Site of Reduced Cytochromec Oxidase, Yasunori YOSHIOKA and Masaki MITANI: Internet Electron. J. Mol. Des., 2, pp.732–740, 2003.
There are many proposals of reaction mechanisms of O2-reduction catalyzed by cytochrome c oxidase(CcO) and the mechanism is not still conclusive. We have previously proposed new ‘water-proton transport’(WPT) mechanism in which H2O hydrogen-bonded to His290 and Tyr244 transports a proton to FeOO to yield
FeOOH. The path through which a proton is transferred to this H2O molecule in the active site of CcO isinvestigated from theoretical viewpoint in this work by using the hybrid B3LYP method. The H2O molecule
exists between farnesylethyl and Thr316 by hydrogen bonds and the hydrogen-bonded network, which isconnecting from Lys319 to the active site of O2-reduction, is formed in the reduced CcO. The proton necessary
for O2-reduction is provided through this hydrogen-bonded network. The proton is trapped on farnesylethyl ofheme a3, subsequently the proton is transferred to Tyr244 to give a proton to the H2O molecule between His290
and Tyr244. The energy barrier of the proton transfer is qualitatively estimated to be 12 kcal/mol.

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Abstracts of Papers

Theoretical Molecular Auger Spectra with Electron Population Analysis, Masaki MITANI, Osamu
TAKAHASHI*, Ko SAITO*, and Suehiro IWATA*: J. Electron Spectrosc. Relat. Phenom., 128, pp.103–117,
2003.
An approximation method is proposed to simulate the molecular Auger spectra. Auger transition rates are
estimated with atomic populations of valence orbitals on an excited atom by Mulliken and Löwdin population
analyses. Normal Auger energies and relative rates for H2O and NH3 molecules are evaluated using a full CI
wave functions among the valence orbitals constructed from SCF orbitals for the neutral ground state and for the
core-hole excited state. Theoretical spectra show fairly good correspondence with the experimental spectra. It isdemonstrated that the present approach is applicable for qualitative assignment and analysis of Auger spectra forlarger molecules.

Theoretical Studies on the Molecular Dependence of Bond Dissociation after Core Excitations II:
CH3CO(CH2)nCN, n = 0–3, Osamu TAKAHASHI*, Masanori JOYABU*, Masaki MITANI, Ko SAITO*, andSuehiro IWATA*: J. Comput. Chem., 24, pp.1329–1335, 2003.
Approximate theoretical normal and resonant Auger spectra for a series of methylcyano ketones were
calculated. Compared with our previous procedure, a set of initial molecular orbitals (MOs) for Auger decay
probability calculations of the normal Auger process was modified by changing from a set of ground state MOs
to a set of core-holed MOs. For the resonant Auger process, a set of MOs was also modified in the same manner.
Furthermore, the bond dissociation factor, which we introduced in the previous article, was also calculated toestimate the bond strength after Auger decay. The site-selectivity for a series of methylcyano ketones was
qualitatively explained, but a significant state-specificity was not observed. Molecular size dependence after
Auger decay was also discussed.

Theoretical Calculations of Effective Exchange Integrals by Spin Projected and Unprojected Broken-Symmetry
Methods. I. Cluster Moldels of K2NiF4-Type Solids. Taku ONISHI, Daisuke YAMAKI*, Kizashi
YAMAGUCHI*, and Yu TAKANO*: J. Chem. Phys., 118, pp. 9474-9761, 2003.
Previously, various symmetry-adapted (SA) and broken-symmetry (BS) computations have been
performed for strongly correlated transition metal species so as to examine magnetic properties in simple clustermodels. Though SA computations such as the complete active space configuration interaction (CAS CI) and
CASSCF are desirable for estimating physical constants, these computations are heavy for larger cluster models
with strongly correlated electrons. K2NiF4 is known to be the two-dimensional perovskite-type antiferromagnet
and to have the electronic configuration similar to that of La2CuO4. Here, we have examined the utility andapplicability of the BS spin-polarized hybrid-density functional theory (HUDFT) for cluster models of K2NiF4.

Theoretical Studies on the Electronic States of Electron-Doped Copper Oxides. Taku ONISHI, Daisuke Yamaki*,
and Kizashi YAMAGUCHI*: Polyhedron., 22, pp. 2191-2197, 2003.
The infinite layer copper oxides have attracted much attention in relation to high-temperature
superconductivity. Superconductivities of these species are achieved by several chemical dopings such as
hole-doping and electron-doping. In this study, we have performed spin-polarized hybrid-density functional
theory (HUDFT) calculations, in order to examine the electronic states after one electron-doping for the linear
chain cluster models. As the hole-doped electronic states have already been examined in our previous work, we
discuss the differences of the changes of the electronic states between hole-doping and electron-doping.

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Ln1-xSrxCo1-yFeyO3-δ(Ln=Pr, Nd, Gd; x=0.2, 0.3) for the Electrodes of Solid Oxide Fuel Cells, L. QIU, T.
ICHIKAWA, A. HIRANO, N. IMANISHI, and Y. TAKEDA: Solid State Ionics, 158, pp. 55-65, 2003.
Promising candidates of intermediate temperature electrodes for solid oxide fuel cells (SOFCs),
Ln1-xSrxCo1-yFeyO3-δ(LSCF) (Ln=Pr, Nd, Gd; x=0.2, 0.3; 0≦y≦1) were studied for their electrical conductivity,
thermal expansion rate, cathodic polarization, and reactivity with gadolinia-doped ceria (Ce0.9Gd0.1O1.95, CGO)
or yttria-stabilized zirconia (YSZ). Superiorly electrical conductivity has been demonstrated for LSCF electrodes
and all samples except Ln=Gd (y≧0.8) compositions demonstrate above 200 S/cm at 800℃. The adjustment ofthermal expansion rate to electrolyte, which is one of the main problems of Ln1-xSrxCoO3-δ, can be achieved tolower thermal expansion coefficient (TEC) values with more Fe substitution. Using CGO electrolytes, LSCF
electrodes over the composition range of y=0.0-0.8 show high cathodic activity for oxygen reduction operating
at temperatures from 700 to 900℃ and exhibit no significant dependence on the kind of lanthanide elements.
These electrode behaviors are analogous to widely used La1-xSrxCo1-yFeyO3-δ, Ln1-xSrxCo1-yFeyO3-δ (Ln=Pr, Nd,Gd) systems, however, have potential advantages in reactivity with YSZ. In Ln=Pr, Nd (y=0.8) compositions, forexample, the by-products of Ln2Zr2O7 and SrZrO3 are both suppressed when sintered at 1000℃ for 100 h. LSCF
also yield no reaction product with CGO when sintered at 1200℃ for 36 h.
Compatibility of GdxTi2O7 Pyrochlores (1.72≤x≤2.0) as Electrolytes in High-Temperature Solid Oxide Fuel Cells,
Masashi MORI*, Geoff M. TOMPSETT*, Nigel M. SAMMES*, Eisaku SUDA*, and Yasuo TAKEDA: Solid
State Ionics, 158, pp. 79-90, 2003.
The crystal structure, sintering characteristics, electrical conductivity and thermal expansion of
GdxTi2O7-δ pyrochlores (1.72 ≤ x ≤ 2.10) have been studied as potential electrolytes in high-temperature solidoxide fuel cells (SOFC). It was found that the A-site deficiency of GdxTi2O7-δ with cubic symmetry showed awide region of 1.72<x<2.03. A-site vacancies promoted the sintering characteristics of these materials. Electricalconductivity of the pyrochlores with A-site vacancies was lower than that of GdxTi2O7 in air although the reverse
was observed in reducing atmospheres, due to the appearance of electronic conduction. Average linear thermal
expansion coefficients of GdxTi2O7-δ pyrochlores decreased with increasing A-site vacancies. The difference
between the TEC in air and in a H2 atmosphere had a tendency to increase with increasing A-site vacancies.

Change in Conductivity of Yttria Stabilized Zirconia, Masatoshi HATTORI*, Yasuo TAKEDA, Satoshi
OHARA*, Jin-Ho LEE*, Kazuo MUKAI*, Takehisa FUKUI*, Yoshinori SAKAKI* and Akihiro
NAKANISHI*: Journal of the Japan Society of Powder and Powder Metallurgy, 50(4), p.297, 2003.
The change in conductivity of 8 mol% and 10 mol% yttria stabilized zirconia (8YSZ and 10YSZ,
respectively) were measured during continuous current loading at 1000℃. The conductivity of 8YSZ graduallydegraded with holding time in the test and it decreased to about 65% of the initial value after annealing for 1500
h. However, the conductivity of 10YSZ is constant under the same condition. The crystal structure of thesamples before and after annealing was investigated by X-ray diffraction techniques, Transmission electron
microscopy, and Raman spectroscopy. It was concluded that the deterioration in conductivity of 8YSZ related tothe phase transformation, such as gradual formation of fine tetragonal phase which had lower conductivity thancubic phase had.
All Solid Lithium Polymer Batteries with a Novel Composite Polymer Electrolyte, Qi LI, Takahito ITO,
Nobuyuki IMANISHI, Atsushi HIRANO, Yasuo TAKEDA, and Osamu YAMAMOTO*: Solid State Ionics, 159,
pp. 97-109, 2003.
A composite polymer electrolyte based on polyethylene oxide (PEO) with a hyperbranched polymer
poly[bis(triethylene glycol)benzoate] capped with an acetyl group (HBP) and a ceramic filler, BaTiO3, wasexamined as the electrolyte in rechargeable lithium polymer batteries. The conductivity of the composite
polymer electrolyte PEO-10 wt.% HBP with Li(CF3SO2)2N-10 wt.% LiPF6 as a lithium salt and 10 wt.% BaTiO3
was found to be 1.6×10-4 S/cm at 25℃ and 1.5×10-3 S/cm at 60℃ in a O/Li ratio of 10. The lithium
rechargeable batteries consisted of this highly conductive composite polymer electrolyte and the 4 V classcathode, LiNi0.8Co0.2O2, showed excellent charge-discharge cycling performance. The initial cathode discharge
capacity of 154 mA h/g declined only 0.1%/cycle during the first 30 cycles at 60℃.

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Abstracts of Papers

DSC Study on the Thermal Stability of Solid Polymer Electrolyte Cells, C. CAPIGLIA, J. YANG, N. IMANISHI,
A. HIRANO, Y. TAKEDA, and O. YAMAMOTO*: Journal of Power Sources, 119-121, pp. 826-832, 2003.
A novel Li-ion polymer battery (Li-IonPB) based on LiNi0.8Co0.2O2 as a cathode and an alternative
composite anode (CA) is proposed for future application in hybrid electric vehicles (HEV). A micro-Li-ion
polymer cell is prepared in situ inside the differential scanning calorimetry (DSC) sample pan, and theexothermic heat development is compared with that of the micro-lithium-solid polymer electrolyte cell. The
thermal decomposition of both cells is further investigated from a qualitative point of view.

High-Capacity Composite Anodes with SnSb and Li2.6Co0.4N for Solid Polymer Electrolyte Cells, J. YANG, Y.
TAKEDA, C. CAPIGLIA, X. D. LIU, N. IMANISHI, and O. YAMAMOTO*: Journal of Power Sources,119-121, pp. 56-59, 2003.
Composite anodes based on SnSb alloy and Li2.6Co0.4N compound can provide a reversible capacity morethan 650 mAh/g in solid polymer electrolyte. However, the capacity retention on cycling is poor at ahigh-capacity level. Limited lithium insertion (<500 mAh/g) is favorable for the cyclability. Cyclic voltammetryof the composite electrode exhibits good electrochemical reversibility. Because the nano-sized SiO1.1 host has arelatively small volume change effect and different insertion potential from SnSb and Li2.6Co0.4N, its addition ina small amount into the composite electrode can improve the mechanical and cycling stability.

Application of La0.6AE0.4MnO3 (AE=Ca and Sr) to Electric Current Collectors in High-Temperature Solid Oxide
Fuel Cells, Masashi MORI*, Nigel M. SAMMES*, Eisaku SUDA*, and Yasuo TAKEDA: Solid State Ionics,
164, pp. 1-15, 2003.
The crystallographic, mechanical, thermal and electrical properties of La0.6AE0.4MnO3 perovskites(AE=Caa and Sr) have been investigated. La0.6Ca0.4MnO3 showed an orthorhombic symmetry at room
temperature, and its symmetry changed into tetragonal at approximately 500℃ and into cubic at approximately
900℃. La0.6Sr0.4MnO3 showed tetragonal symmetry at room temperature and its symmetry changed into cubic attemperature ≥90℃. Transgranular fracture of dense La0.6AE0.4MnO3 specimens, after mechanical strength
measurements at temperatures ≤400℃, was indicated, whereas the specimens mechanically tested after themeasurement at temperatures ≥600℃ showed intergranular fracture. Thermal expansion coefficients (TECs) of
the sintered specimens in the temperature range from 50 to 1000℃ were 11.7×10-6/℃ for La0.6Ca0.4MnO3 and12.2×10-6/℃ for La0.6Sr0.4MnO3. Electrical conductivities of the dense specimens at 1000℃ were 227 S/cm forLa0.6Ca0.4MnO3 and 213 S/cm for La0.6Sr0.4MnO3. To synthesize these materials as electric current collectors inhigh-temperature solid oxide fuel cells(SOFC), La0.6AE0.4MnO3 perovskites were compounded with manganeseoxide. The TECs of the composites at around 50 vol.% Mn3O4 were almost the same as that of the Y2O3
stabilized ZrO2 (YSZ) electrolyte. Electrical conductivities of these dense specimens at 1000℃ were observed
to be between 50 and 90 S/cm. Thus, dense La0.6AE0.4MnO3- Mn3O4 composites are appropriate for the electric
current collectors in the SOFC.
Low-Temperature Sinterable Ce0.9Gd0.1O1.95 Powder Synthesized through Newly-Devised Heat-Treatment in the
Coprecipitation Process, Eisaku SUDA*, Bernard PACAUD*, Yvan MONTARDI*, Masashi MORI*, Masakuni
OZAWA*, and Yasuo TAKEDA: Electrochemistry, 71(10), pp. 866-872, 2003.
The low-temperature sinterable Ce0.9Gd0.1O1.95 (CGO) Powder has been synthesized through a
newly-devised heat-treatment process in the coprecipitation method. The precipitate obtained by the
coprecipitation method, namely cerium-gadolinium carbonate slurry, was stirred at 80℃ for 3 h. After filtrating
this slurry, the precipitate was washed using pure water and was calcined at 700℃ for 5 h in air. From theresults of transmission electron microscopy and X-ray diffraction analysis, the CGO powder showed uniform
particle size of approximately 100 nm and its crystallite size was calculated to be approximately 20 nm. For thetablet of the powder, the relative densities reached ≥ 94% at temperatures ≥ 1000℃ for holding time ≥ 5 h.

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Laser Vaporization Synthesis of Polyhedral Graphite, Fumio KOKAI, Kunimitsu TAKAHASHI*, Daisuke
KASUYA*, Atsuko NAKAYAMA*, Yoshinori KOGA*, Masako YUDASAKA* and Sumio IIJIMA*: Appl.
Phys. A , 77, pp. 69-71, 2003.
Polyhedral graphite (PG) particles have been synthesized by CO2 laser vaporization of graphite inhigh-pressure Ar gas (8x105 Pa). Faceted PG particles, ranging in size from 110 to 500 nm, have a turbostratic
structure. The yield of PG is more than 90 %. This synthesis is based on the condensation of hot carbon species
confined by an Ar-gas atmosphere.

Preparation of Lithium Niobate Thin Films on Diamond-Coated Silicon Substrate for Surface Acoustic Devices,
Masatou ISHIHARA*, Takako NAKAMURA*, Fumio KOKAI and Yoshinori KOGA*: Diamond RelatedMaterials, 12, pp. 1809-1813, 2003.
Lithium niobate (LiNbO3) has a piezoelectric property, which makes it an ideal material for the fabricationof surface acoustic wave (SAW) devices. When highly oriented LiNbO3 films are deposited on a diamondsubstrate, a LiNbO3/diamond-layered structure is produced that can be used for wide-bandwidth applications in
SAW devices at high frequencies. The LiNbO3 thin films were deposited on diamond-coated silicon substrate by
the radio-frequency reactive sputtering system. When a stoichiometric LiNbO3 target was used as the sputteringtarget and the cooling efficiency of the target was poor, only LiNbO3 reflections appeared in X-ray diffraction
patterns. It is suggested that the appearance of the Li-deficient phase of LiNbO3 is caused by the dissociation oflithium and oxygen from LiNbO3 during deposition. When an Li-enriched LiNbO3 target was used as the
sputtering target and the cooling efficiency of the target was good, stoichiometric LiNbO3 films were preparedand the preferential orientation was (110). It was found that the use of the Li-enriched target and the cooling of
the target suppressed the dissociation of lithium.
Determination of Antimony in Waters by Electrothermal Atomic Absorption Spectrometry with Preconcentration
on a Tantalum Wire, Md. Nurul AMIN, Satoshi KANECO, Ken NOMURA, Tohru SUZUKI and Kiyohisa
OHTA: Mikrochim. Acta, 141, pp. 87–91, 2003.
A preconcentration method for antimony in waters involving adsorption on a tantalum wire, followed byelectrothermal atomic absorption spectrometry with a tungsten tube atomizer is described. The best pH for theadsorption of antimony was 2. The optimal immersing time was 120 s. Under the optimal conditions, thedetection limit for antimony by the tantalum wire preconcentration method was 50 pg/mL (3S/N) and the relative
standard deviation was 9.4%. The effects of large amounts of concomitants on the preconcentration of antimony
were evaluated. Even though 103-104 fold excess of matrix elements existed in water, the antimony response
was not significantly affected by the matrix elements. The method with preconcentration on a tantalum wire wasapplied to the determination of antimony in waters and proved to be sensitive, simple, and convenient. This
adsorption method can be utilized in in-situ sampling of ultra-trace antimony in environmental samples (water).
Furthermore, after sampling it is easy to carry and store the tantalum wire without contamination for a long time.
The technique developed was shown to be useful for the determination of Sb in waste waters at the 1-5 µg/L
level.
High-Efficiency Electrochemical CO2-to-Methane Reduction Method Using Aqueous KHCO3 Media at Less
Than 273 K, Satoshi KANECO, Nobuhide HIEI, Yue XING, Hideyuki KATSUMATA, Hisanori OHNISHI,
Tohru SUZUKI and Kiyohisa OHTA: J. Solid State Electrochem., 7, pp. 152–156, 2003.
The electrochemical reduction of CO2 with a Cu electrode in a KHCO3 aqueous solution was investigatedat low temperature. A divided H-type cell was employed; the electrolyte was a 1.1 mol dm-3 KHCO3 aqueous
solution. The temperature during the electrolysis of CO2 was reduced to 269 K. Methane, ethylene, and formic
acid were obtained from CO2 as the main products. The maximum faradaic efficiency of methane was 44% at a
relatively negative potential and 269 K. The efficiency of hydrogen formation, as the competition against CO2
reduction, significantly decreased with lowering the temperature. On the basis of this work, the high-efficiency
electrochemical CO2 to methane conversion method appears to be achieved.

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Abstracts of Papers

Removal of Natural Organic Polyelectrolytes by Adsorption onto Tobermorite, Satoshi KANECO, Kumiko
ITOH, Hideyuki KATSUMATA, Tohru SUZUKI, Kazuaki MASUYAMA*, Kunihiro FUNASAKA*, Kazuyuki
HATANO* and Kiyohisa OHTA: Environ. Sci. Technol. (American Chemical Society), 37, pp. 1448–1451,
2003.
Natural organic polyelectrolytes, such as humic and fulvic acids, were removed by adsorption onto
silicate rocks. Tobermorite, zeolite, and molecular sieves 5A were used as the adsorbents. Tobermorite wasmore efficient by 40‑50% in the removal of fulvic acids, and by 30〜50% for humic acid than zeolite ormolecular sieves, respectively. Humic acid removal from the solution by adsorption onto silicate rocks took
place more readily than fulvic acid removal. From the determined heat of adsorption, the adsorption process inthe present study may be chemisorption (ligand exchange). Metal/humic acid complexes was effectively
removed by adsorption onto tobermorite. Since tobermorite (a silicate rock) can be easily synthesized andobtained commercially, the adsorption method of fulvic and humic acids is superior to their precipitation.
Sunlight Photocatalytic Degradation of Bisphenol A in Water with Titanium Dioxide, Satoshi KANECO,
Yasumasa FUJIWARA, Tohru SUZUKI, Hideyuki KATSUMATA, Kunihiro FUNASAKA* and Kiyohisa
OHTA: ITE Lett. Batt. New Technol. Med., 4, pp. 211–214, 2003.
The photocatalytic degradation of 4,4’-isopropylidenediphenol (bisphenol A) in aqueous solutions with
TiO2 semiconductors was investigated under sunlight illumination. It was found that the primary
photocatalytic decomposition reaction follows a pseudo first-order kinetic law. During the photocatalytic
degradation, the first-order rate constant k was 0.025 min-1. The present detoxification method will be able tobe applied to various endocrine-disrupting chemicals.

Carbon Dioxide Sequestration Technology by Electrochemical Conversion at Cadmium Electrode in Methanol
under Mild Conditions, Satoshi KANECO, Ryosuke IWAO, Hideyuki KATSUMATA, Tohru SUZUKI andKiyohisa OHTA: Photo/Electrochem. Photobiol. Environ. Energy Fuel, 2, pp. 181−189, 2003.
The electrochemical reduction of CO2 in a KOH/methanol-based electrolyte was investigated with acadmium wire electrode at ambient temperature and pressure. Carbon monoxide, formic acid and methane werethe main products from the CO2. The Faradaic efficiency of formic acid increased as the potential became
negative, however in contrast the formation efficiency of CO deceased. Under the optimum experimental
conditions, 64 % Faradaic efficiency formic acid, 48 % CO and 0.2 % methane were produced from CO2 by theelectrochemical reduction. Hydrogen evolution in competition with CO2 reduction was observed at only a 0.9 %Faradaic efficiency. The partial current density for the CO2 reduction was more than 109 times greater than thatfor hydrogen evolution. Future work to advance this technology may include the use of solar energy as theelectric energy source. This research can contribute to applications of the conversion of CO2-saturated methanol
into useful products and the large-scale removal of CO2 from the atmosphere.
Continuous Degradation of Chlorodibromomethane in a Flow System Using Zinc Powder under Mild Conditions,
Ahmed H.A. DABWAN, Tohru SUZUKI, Satoshi KANECO, Hideyuki KATSUMATA and Kiyohisa OHTA:
Photo/Electrochem. Photobiol. Environ. Energy Fuel, 2, pp. 163−171, 2003.
The continuous destruction of chlorodibromomethane in a flow system using zinc metallic powder wasinvestigated under mild conditions. The dechlorination efficiency increased with increasing temperature up to 35o
C. Consequently, it was found that chlorodibromomethane could be almost completely degraded in thecontinuous flow system using the zinc powder above 35 oC. The continuous complete decomposition treatmentof chlorodibromomethane could be performed for 12 h. This research will be able to contribute to the treatment
technology of chlorodibromomethane-contaminated ground water.

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Slurry Sampling Electrothermal Atomic Absorption Spectrometric Determination of Copper in Herbal Medicine
Samples with a Molybdenum Tube Atomizer, Md. Nurul AMIN, Satoshi KANECO, Tohru SUZUKI andKiyohisa OHTA: Microchim. J., 74, pp. 181-186, 2003.
An ultrasonic slurry sampling electrothermal atomic absorption spectrometric method with amolybdenum tube atomizer has been developed for the determination of copper in herbal medicine samples.
Glycerol solution (10%) was used as the slurry medium. The optimum pyrolysis temperature was 760 °C. The
detection limit was 72 fg (3×S/N ratio). Matrix element interference was investigated and it was found thatglycerol as a chemical modifier eliminated the interference. The amounts of copper in herbal medicines
determined by the method proposed are in good accordance with those measured in dissolved acid-digested
samples. The method enables rapid calibration, and simple and rapid analysis of copper in herbal medicine
samples at low cost.

Degradation of CHBrCl2 in a Continuous Flow System Using Metal Powder under Mild Condition, Ahmed H.A.
DABWAN, Tohru SUZUKI, Satoshi KANECO, Hideyuki KATSUMATA and Kiyohisa OHTA: ITE Lett. Batt.
New Technol. Med, 4, pp. 461–464, 2003.
The continuous destruction of bromodichloromethane in a flow system using nickel, zinc and Ag/Zn
bimetal powders was investigated under mild conditions. Bimetallic Ag/Zn was very effective for the continuous
degradation of bromodichloromethane. The yields for bromide and chloride ions were greater than 70 and 96%
in the continuous degradation using bimetallic Ag/Zn, respectively. The continuous decomposition treatment of
bromodichloromethane could be performed with a relatively high efficiency for 12 h. This research will be able
to contribute to the treatment technology of bromodichloromethane-contaminated ground water.

Size Distributions and Characteristics of Atmospheric Inorganic Particles by Regional Comparative Study in
Urban Osaka, Japan, Kunihiro FUNASAKA*, Mamoru SAKAI*, Masanao SHINYA*, Takeji MIYAZAKI*,
Toshikazu KAMIURA*, Satoshi KANECO, Kiyohisa OHTA and Tadao FUJITA: Atmos. Environ., 37, pp.
4597–4605, 2003.
Size distributions and characteristics of atmospheric inorganic particles at two different monitoring sites
were statistically compared in order to survey site-specific original sources of the particulate constituents. The
average concentration difference of fine and coarse particles between the sites was, respectively, 1.4 and 4.7µg/m3, and coarse particulate Fe, Mn, Zn and Pb were significantly high at the heavy traffic-flow site. Coarse
particulate Zn and Pb form a closely related cluster group but Mn belongs to another independent group together
with Fe. Comparative study for the Zn/Pb ratio possibly suggested that the regional differences of Zn and Pb
were derived from road dust components and this might be caused essentially by tire wears and previous lead
additives, respectively. On the contrary, the differences of coarse particulate Fe and Mn might be commonly anddirectly affected by industrial sources such as iron–steel factories close to the heavy traffic-flow site.
Electrothermal Atomic Absorption Spectrometric Determination of Cadmium in Bangladeshi Vegetables with a
Metal Tube Atomizer And Slurry Sampling Technique, Md. Nurul AMIN, Satoshi KANECO, Tohru SUZUKI
and Kiyohisa OHTA: Int. J. Environ. Anal. Chem., 83, pp. 1035−1044, 2003.
Ultrasonic slurry sampling electrothermal atomic absorption spectrometry with a molybdenum tube
atomizer has been applied for the determination of cadmium in vegetable samples in Bangladesh. The
suspension-stabilizing medium was 10% glycerol solution. The optimum pyrolysis temperature was 300 °C. The
detection limit was 13 fg (3S/N). Matrix element interference was studied and it was found that thiourea as achemical modifier eliminated the interference. The results for the determination of cadmium in vegetablesamples by the proposed method were in good agreement with those measured in dissolved acid-digested
samples. The method enables rapid calibration, and simple and rapid analysis of cadmium in vegetable samples
at low cost.

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Abstracts of Papers

Biodegradation of Phthalic Acid Esters by Bakery Yeast Saccharomyces cerevisiae, Aleya BEGUM, Hideyuki
KATSUMATA, Satoshi KANECO, Tohru SUZUKI and Kiyohisa OHTA: Bull. Environ. Contam. Toxicol., 70,
pp. 255–261, 2003.
Biodegradation of phthalic acid esters (PAEs), namely diethyl phthalate (DEP), di-n-butyl phthalate(DBP) and butylbenzyl phthalate (BBP) was performed by Saccharomyces cerevisiae. The degradation reactionof PAEs followed a first order kinetic law and the degradation rate was DBP>BBP>DEP. The half-lives of DEP,
DBP and BBP were 56, 16, 22 h, respectively.

Removal of Organic Polyelectrolytes and Their Metal Complexes by Adsorption onto Xonotlite, Hideyuki
KATSUMATA, Satoshi KANECO, Rika MATSUNO, Kumiko ITOH, Kazuaki MASUYAMA*, Tohru SUZUKI,
Kunihiro FUNASAKA* and Kiyohisa OHTA: Chemosphere, 52, pp. 909–915, 2003.
Natural organic polyelectrolytes (humic and fulvic acids) and their metal complexes were removed byadsorption onto xonotlite. The removal percentages of humic and fulvic acids by xonotlite were ca. 80 and 30%,
respectively. Humic acid removal from solution by adsorption onto xonotlite took place more readily than fulvic
acid removal. The molecular weight distributions of the humic substances remaining in solution after adsorption
with the xonotlite were measured with size exclusion chromatography. A comparison of molecular weight
distributions demonstrated conclusively that large molecular weight components were adsorbed preferentially,
indicating that adsorption efficiency depends on the number of functional groups of humic substances.
Furthermore, the surface topography of the adsorbent was observed before and after adsorption by scanningelectron microscopy. The calculated heat of adsorption was of 330 kJ mol–1 which was evaluated from theClapeyron-Clausius equation. Therefore, the adsorption type can be considered chemical. Since xonotlite can beeasily synthesized and obtained at low cost, the adsorption method of humic and fulvic acids is superior to theirprecipitation.
Formation of Dioxins from Newspaper Combustion in the Presence of Sodium Chloride and Poly (Vinylidene
Chloride), Hideyuki KATSUMATA, Makoto YABUUCHI, Satoshi KANECO, Tohru SUZUKI and Kiyohisa
OHTA: Fresenius Environ. Bull., 12, pp. 406–412, 2003.
Exhaust gases from the combustion of newspapers alone, from newspapers impregnated sodium chloride(NaCl), and from newspapers mixed with poly (vinylidene chloride) (PVDC) were collected. The samples wereanalyzed for dioxins by high-resolution gas chromatography/mass spectrometry. Total amounts of dioxins foundin the samples were 21.6 pg g–1 from newspapers alone, 51.9 pg g–1 from newspapers with NaCl, and 1525 pg g–1
from newspapers with PVDC. It is postulated that there is a correlation between dioxin formation and chloride
content. Formation of total PCDFs was considerably higher than that of total PCDDs, except in the case ofnewspapers alone. The total PCDF/total PCDD ranged from 0.16 (newspaper alone) to 16.4 (newspaper with
PVDC). These results indicate that NaCl and PVDC contribute significantly to dioxin formation from wastematerials combusted in incinerators.
Air Pollution by Dioxins at Various Locations Using Polyurethane Foam as A Monitoring Indicator, Hideyuki
KATSUMATA, Hidetoshi OKADA, Satoshi KANECO, Tohru SUZUKI and Kiyohisa OHTA:
Photo/Electrochem. Photobiol. Environ. Energy Fuel, 2, pp. 173−180, 2003.
Evaluation method of air pollution by dioxins was proposed by using polyurethane foam as a monitoring
indicator. This sampling method is based on the adsorption of dioxins in atmosphere to the polyurethane.
Collection of dioxins by the polyurethane foam was performed at three sites in Hisai City, Mie Prefecture, where
are near the incinerator, for two to four weeks. In the sampling period of two weeks, adsorption amounts ofdioxins on the polyurethane at Site 1, 2 and 3 were 4.47, 25.9 and 3.52 pg cm–2, respectively. 4CDD/F isomers
predominantly adsorbed at all sites and it was observed that the adsorption amount of PCDD/Fs was decreased
with increasing the number of chloride. Furthermore, the distribution pattern of 4CDD isomers at Site 2 wasinvestigated. The 1,3,6,8- and 1,3,7,9-isomers composed over 75% of the total isomers of 4CDD. This patternmight show that the 4CDD was mainly derived from chloronitrophene, which is a kind of pesticides.

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Removal of Heavy Metals in Rinsing Wastewater from Plating Factory by Adsorption with Economical Viable
Materials, Hideyuki KATSUMATA, Satoshi KANECO, Kentaro INOMATA, Kumiko ITOH, Kunihiro
FUNASAKA*, Kazuaki MASUYAMA*, Tohru SUZUKI and Kiyohisa OHTA: J. Environ. Manage., 69, pp.
187–191, 2003.
The removal of heavy metals from plating factory wastewater with economical materials was investigatedby the column method. Montmorillonite, kaolin, tobermorite, magnetite, silica gel and alumina were used as the
economical adsorbents to wastewater containing Cd(II), Cr(VI), Cu(II) and Pb(II). This removal method ofheavy metals proved highly effective as removal efficiency tended to increase with increasing pH and decrease
with increasing metal concentration. The removal percentages by adsorption onto montmorillonite, tobermorite,
magnetite, and silica gel showed high values for all metals. From the results for the heat of adsorption, theadsorption process in the present study might be chemisorption. The proposed method was successfully applied
to the removal of Cd(II), Cr(VI) and Cu(II) in rinsing wastewater from plating factory in Nagoya City, Aichi
Prefecture, Japan. Since the economical adsorbents used can be obtained commercially because they are easily
synthesized, the wastewater treatment system developed is rapid, simple and cheap for the removal of heavy
metals.
Removal of Di-n-butyl Phthalate from Aqueous Solution by Adsorption with Bakers’ Yeast Saccharomyces
cerevisiae, Aleya BEGUM, Hideyuki KATSUMATA, Nozomu SAKUMA, Satoshi KANECO, Tohru SUZUKI
and Kiyohisa OHTA: Photo/Electrochem. Photobiol. Environ. Energy Fuel, 2, pp. 155−162, 2003.
The adsorption behavior of two phthalic acid esters (PAEs) namely, diethyl phthalate (DEP) and di-n-butyl
phthalate (DBP) from aqueous solution to baker’s yeast (Saccharomyces cerevisiae) was quantitatively
characterized in this work. The effects of yeast amounts, pH values, culture time, temperature and initial PAEs
concentrations were studied. The experimental results showed that the adsorption efficiency of DBP was muchhigher than that of DEP. Therefore, the present method could be selectively adsorb the DBP to S. cerevisiae.
Clausius-Clapeyron equation was applied to estimate the heat of adsorption. The heat of adsorption of DBP was
373 kJ mol–1, indicating that the adsorption behavior seemed to be chemical adsorption.
Microbial Metabolism of Phthalic Acid Esters by Bakers’ Yeast Saccharomyces cerevisiae, Aleya BEGUM,
Hideyuki KATSUMATA, Satoshi KANECO, Tohru SUZUKI and Kiyohisa OHTA: Fresenius Environ. Bull., 12,
pp. 1309–1314, 2003.
Microbial metabolism behavior of two phthalic acid esters (PAEs) namely, diethyl phthalate (DEP) andbutylbenzyl phthalate (BBP) from aqueous solution by bakers' yeast Saccharomyces cerevisiae wasquantitatively characterized by high performance liquid chromatography (HPLC). The optimal culture
temperature, amount of yeast, yeast growth time, and ammonium dihydrogen phosphate (ADP) amount, that can
influence on biodegradation of PAEs were 30 0C, 2.0 mg mL-1, 30 min, and 0.5 mg mL-1, respectively. Under the
optimal conditions, the degradation percentage of DEP and BBP were 19% and 43%, respectively after 24 hcultivation. The metabolites of DEP degradation as identified by gas chromatography-mass spectrometry(GC/MS) appeared to be ethyl methyl phthalate (EMP), dimethyl phthalate (DMP) and phthalic acid (PA),whereas monobutyl phthalate (MBP), diethyl phthalate (DEP) and phthalic acid (PA) were identified as
metabolites of BBP. Therefore, it can be considered that one of the degradation pathways involves sequential
cleavage of the ester bond to yield PA.
Two-Dimensional High Performance Liquid Chromatography Mapping of Sugar Chains Demonstrated the
Biantennary, Complex N-Glycan Addition to the Recombinant Glycoprotein Produced by Baculovirus-Infected
Antheraea pernyi Insect Cells, Masahiro NAGAYA, Jun KOBAYASHI, Noriko TAKAHASHI*, Koichi KATO*
and Tetsuro YOSHIMURA: Journal of Insect Biotechnol. & Sericol., 72, pp. 79-86, 2003.
To evaluate the N-glycosylation property of an insect cell line, AnPe, which was derived from embryos of
the Chinese oak silkworm Antheraea pernyi and used in a newly developed baculovirus expression vector
system, N-glycans of purified PTTH produced by AnPe cells infected with a recombinant AnpeNPV, weredigested with glycoaminase A, reductively aminated with 2-aminopyridine, and identified by 2D-HPLC mapping
technique, and the result that a reaction catalyzed by GlcNAc transferase II, a key enzyme to form biantennary,complex N-glycans, occurs more efficiently in AnPe than in Sf9 was obtained, suggesting that the proportion ofcomplex N-glycans in AnPe cells may be largely enhanced by inhibiting the N-acetylglucosaminidase activity
and/or supplying sufficient amounts of enzymes and substrates required for the sugar chain extension in the
Golgi.

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Abstracts of Papers

Antheraea pernyi Nucleopolyhedrovirus p143 Gene: Nucleotide Sequence and Ineffectiveness in Host Range
Expansion of Autographa californica Nucleopolyhedrovirus. Ken-ichi MAEGAWA, Jun KOBAYASHI and
Tetsuro YOSHIMURA: Int. J. Wild Silkmoth & Silk, 8, pp. 29-41, 2003
The nucleotide sequences of 3.2- and 4.9-kbp PstI P and H fragments of the AnpeNPV containing the p143
gene were determined. A putative DNA helicase of 1212 amino acids was encoded by the gene and exhibitedhigh sequence identities of 58% to 78% with the p143 gene products of other group I NPVs. Seven conserved
helicase motifs, a leucine zipper motif, and two nuclear localization signals, which are conserved among thebaculovirus DNA helicases, were also found in the AnpeNPV p143 gene product. The AnpeNPV p143 gene
introduced in the AcNPV genome were co-expressed with the AcNPV p143 at early phase of infection, but did
not enhance either BV production at late phase or recombinant protein production at very late phase in AnPecells. Thus, the AnpeNPV p143 gene was not effective in host range expansion of AcNPV to semipermissive
AnPe cells, although the results was not conclusive.
Efficient Production of Monoclonal Antibodies Specific to Aimed Epitope Sequences by a B Cell TargetingTechnique. Masahiro TOMITA, Takanobu TANIGUCHI, Jun-ichiro TANAKA, Hana SAWADA*, Norikazu
NISHINO* and Tetsuro YOSHIMURA: Peptide Science 2002, pp.397-400, 2003.
Human insulin consists of 51 amino acid residues, and has been shown to harbor several differences inamino acid residues from mouse insulin. When the mouse immune system recognizes human insulin as aforeign antigen, such regions must play an important role in humoral immunity for producing antibodies specificto human insulin. A BLAST (Basic Local Alignment Search Tool) analysis is one of the simplest and the mostavailable methods for predicting epitope sequences in an antigen of interest. We focused on generating
monoclonal antibodies specific to desired epitope sequences of human insulin by a B cell targeting technique.
The hybridoma cells secreting monoclonal antibodies against the aimed peptide sequences were successfully
obtained, although the specificity was rather polyreactive.

Generation of Monoclonal Antibodies Directed against Peptide Sequences by a B Cell Targeting Technique.
Masahiro TOMITA, Takanobu TANIGUCHI, Jun-ichiro TANAKA, Hana SAWADA*, Norikazu NISHINO*,
Tian Yow TSONG* and Tetsuro YOSHIMURA: Human Antibodies, 12, pp.37-39, 2003.
Two putative eiptope sequences in human insulin that are VNQHLCG and FFYTPKT were constructedbased on a BLAST (Basic Local Alignment Search Tool) analysis. Firstly, the targeting of B lymphocytes bythese epitope sequences after in vitro immunization was immunofluorescently confirmed, and then the
peptide-selected B lymphocytes were combined with myeloma cells by exploiting the specificity and strength of
the interaction between biotin and avidin. These cell complexes were selectively fused by an electrical pulse.
Several clones secreting monoclonal antibodies against each peptide sequence were successfully obtained,
although they showed rather polyreactive specificities. We suggest that the targeting technique have driven
efficient production of monoclonal antibodies against the peptide sequences even after short immunization.

NTP Concentration Switches Transcriptional Activity by Changing the Large-Scale Structure of DNA, Tatsuo
AKITAYA*, Kanta TSUMOTO, Ayako YAMADA*, Naoko MAKITA*, Koji KUBO* and Kenichi
YOSHIKAWA*: Biomacromolecules, 4, pp. 1121-1125, 2003.
It is becoming clearer that genetic activity is closely associated with the intracellular energy state.
However, the mechanisms of this association are still unclear. In this study, we focused on large-scale changes inthe structure of DNA to examine the effect of the NTP concentration on the transcription reaction with T7 RNApolymerase and compared the results with long duplex DNA to those with a short persistent-length fragment.
The transcriptional activity dramatically changed only for long duplex DNA within a narrow range of NTP
concentrations associated with changes in the large-scale structure of DNA. This result suggests that the energy
state may play an essential role in regulating ON/OFF switching on transcriptional activity.

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Giant DNA Molecules Exhibit On/Off Switching of Transcriptional Activity through Conformational Transition,
Kanta TSUMOTO, François LUCKEL* and Kenichi YOSHIKAWA*: Biophys. Chem., 106, pp. 23-29, 2003.
We found that the transcriptional activity of large DNAs (40 kbp) can be completely inhibited by adding
condensing agents, spermine and poly(ethylene glycol), whereas under the same conditions short fragments (140bp) still show active transcription. Fluorescence microscopic observations of large DNAs revealed clear
correlation between the higher-order structure of templates and their transcriptional activity. The steep decreasein transcriptional activity leading to complete inhibition, or on/off switching, is interpreted in terms ofconformational transition of the ensemble of DNA molecules.

Gene Expression within Cell-Sized Lipid Vesicles, Shin-ichiro M. NOMURA*, Kanta TSUMOTO, Tsutomu
HAMADA*, Kazunari AKIYOSHI*, Yoichi NAKATANI* and Kenichi YOSHIKAWA*: ChemBioChem, 4, pp.
1172-1175, 2003.
Functional protein synthesis was observed in cell-sized lipid vesicles following encapsulation of agene-expression system. Expression of rsGFP (red-shifted green fluorescent protein) within individual vesicles
was observed by fluorescence microscopy. Interestingly, at the early stage of the reaction, the expression
efficiency inside the vesicle was remarkably higher than that in the solution outside. The synthesized rsGFP in
individual vesicles is safe from attack by proteinase K added to the external aqueous solution. Studies oncell-sized vesicles expressing protein should contribute to a fundamental understanding of certain aspects ofliving systems and will be useful for practical applications, such as the construction of microreactors.

Surfactant Properties of Purified Polyglycerol Monolaurates, Tomoharu KATO, Takeshi NAKAMURA*,
Masatsugu YAMASHITA*, Masami KAWAGUCHI, Tadaya KATO, and Takahito ITOH: J. Surfactants
Detergents, 6, pp 331 – 337, 2003.
A series of purified polyglycerol monolaurates (PGML), such as di-, tri-, tetra, and pentaglycerolmonolaurates, were synthesized, and their surfactant properties in aqueous solutions were examined. The
surfactant properties of PGML were compared with those of n-dodecyl polyoxyethylene monoethers (C12EOn) to
examine the function of the hydrophilic part of these compounds.
The critical micelle concentration (CMC)
values and the surface tension at CMC of PGML and C12EOn increased linearly with an increase in the numberof glycerol and oxyethylene units, respectively.
The initial foam heights of the surfactants at the CMC
increased with an increase in the number of glycerol and oxyethylene units. and the foam heights of PGML wereconsistently higher and more stable than those of C12EOn.
Triglycerol monolaurate showed the lowest
interfacial tension and the highest detergency among all of the surfactants tested. Therefore, the PGML
showed better performance in all the surfactant properties tested than C12EOn.
Structural Regulation of Peptide-Conjugated Graft Copolymer: A Simple Model for Amyloid Formation,
Tomoyuki KOGA*, Kazuhiro. TAGUCHI*, Yoshiaki KOBUKE*, Takatoshi KINOSHITA*, and Masahiro
HIGUCHI, Chem. Eur. J., 9, pp. 1145-1156, 2003.
We successfully synthesized a novel artificial protein model, polyglutamate-grafted polyallylamine (1),and described its structural and conformational properties in solutions. The secondary and quaternary
structures of the peptide 1 can be easily controlled by manipulating the pH, solution composition, and salt
concentration. Only under the condition of low pH (< 8) or that of low salt concentration (< 30 mM) did theelectrostatic repulsive force based on the protonated amino groups permit the controlled growth of 1-aggregates
and the tight packing of hydrophobic PMLG chains, resulting in induction of highly-ordered fibril formation
with α-to-β structural transition. These findings strongly suggest that the formation of fibril structure is not
restricted to specific protein sequences but is, rather, a common property of polypeptides. The ability to control
the distribution of high-order structures of the model peptide formed by manipulating environmental conditions
or intermolecular interaction should provides important insights not only for understanding the assembly
mechanism of peptides and proteins, but also for developing novel peptide-based material with well-definednanostructures.

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Abstracts of Papers

The Formation of Gold Metal Fibers During the Production of E-Glass Fibers, Hiroshi ASAO and Kanichi
KAMIYA: Adv. Composite Mater., 12, pp.1-12, 2003.
We first examined the relation between the solubility of gold and the reduction-oxidation (redox) conditionof E-glass, but it was difficult to find a universal relation between the gold solubility and the redox of the glasses.
Next, we examined the relation between the solubility of gold and the theoretical optical basicity of the glass andfound that the theoretical optical basicity of the glasses was closely related to the gold solubility. We discussed
the mechanism of increasing the solubility of the gold, probably through the formation of some complex withoxide ions. In the industrial process, no metal fiber was formed when glass composition of theoretical opticalbasicity larger than about 0.60l was spun.

Surface Properties of Polydimethylsilloxane-Based Inorganic/Organic Hybrid Films Deposited on Polyimide
Sheets by the Sol-Gel Method, Takuya SHINDOU, Shingo KATAYAMA*, Noriko YAMADA* and Kanichi
KAMIYA: J. Sol-Gel Science and Technology, 27, pp. 15-21, 2003.
Polydimethylsiloxane (PDMS)-based inorganic/organic hybrids films were prepared on polyimide sheetsby the sol-gel method using silanol-terminated PDMS and titanium tetraisopropoxide as starting materials. The
effect of heat-treatment temperature on the surface property of the hybrid films was examined in terms of contact
angle of water and Tapping-Mode Atomic Force Microscopy (AFM). AFM phase images showed the presenceof domains, 200-500 nm in size, on the surface of these films after heat-treatment below 300°C. These regions
were more hydrophilic than the rest of the area. The domains disappeared at 300°C and the surface became
homogeneous surface of the peak to valley value about 10 nm. The films were hydrophobic, and a maximum
contact angle (about 115°C) was obtained.

Photoinduced Phenomena in Na2S-GeS2 Glasses, Keiji TANAKA*, Noriyuki NEMOTO* and Hiroyuki NASU:
Jpn. J. Appl. Phys., 42, pp. 6748-6752, 2003.
Composition dependence of physical properties and photoinduced phenomena in ionic chalcogenide
glasses, Na2S-GeS2, has been studied. The density, optical gap, and photoinduced phenomena show
characteristic changes at around 10Na2S-90GeS2. In the glasses with greater Na2S contents, photoenhanced
hydration occurs. Photoinduced birefringence is maximal at 20Na2S-80GeS2. Origins of these features are
discussed on the bases of atomic and electronic models.

Non-Linear Optical Properties of Li2O-TiO2-P2O5 Glasses, Nobuhiro SHIMOJI, Tadanori HASHIMOTO,
Hiroyuki NASU and Kanichi KAMIYA: J. Non-Cryst. Solids, 324, pp. 50-57, 2003.
The non-linear optical properties of Li2O-TiO2-P2O5 glasses were measured by Z-scan technique using anano-second pulsed laser. The non-linear refractive index (γZ) estimated from Z-scan normalized transmittancewas considered to include the optical Kerr effect (γK), the thermo-optic effect (γT) and the resonant non-linearity(γR) related to Ti3+ ions of which content was increased with TiO2 content. The sign of γZ for glasses with 5 and10mol% TiO2 was positive, whereas for glasses with 15 and 20 mol% TiO2 it was negative. The γT of all theglasses in the present work was negative due to the negative temperature coefficient of linear refractive index(dn/dΤ), and decreased with increasing TiO2 content, and was considered to be dominated by the two-photon
absorption. For Ti3+-containing 50Li2O･15TiO2･35P2O5 glass with negative γZ (-1.78 × 10-18 m2W-1), each ofthese three contributions was evaluated. The thermo-optic γT was determined to be –22.11 × 10-18 m2W-1, theoptical Kerr γK was positive (11.87 × 10-18 m2W-1), and the resonant γR was positive (8.46 × 10-18 m2W-1).

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Second Harmonic Generation from YAl3(BO3)4-Containing Glass-Ceramics Prepared by Thermal Poling of
Y2O3-Al2O3-B2O3 Glasses, Yoshitsugu YAMAMOTO, Tadanori HASHIMOTO, Hiroyuki NASU and Kanichi
KAMIYA: Jpn. J. Appl. Phys., 42, pp. 5043-5047, 2003.
Transparent glass-ceramics containg YAl3(BO3)4 crystals were prepared by thermal poling of theY2O3-Al2O3-B2O3 glasses. Second harmonic generation coluld be measured from both the glass-ceramics
prepared with/without applied voltage, however, intensity is markedly enhanced in the samples prepared withapplied voltage. In the thermally poled samples, the preferred orientaion of precipitated YAl3(BO3)4 crystals
was observed, which may be attributed to the enhancement of second harmonic intensity.

The Influence of Matrix on Quantum Size Confinement of Semiconductor Microcrystals Doped in Glass Thin
Films Prepared by RF-Sputtering, Hiroyuki NASU, Hiroshi IWATANI, Takafumi IWANO, Tadanori
HASHIMOTO and Kanichi KAMIYA: Jpn. J. Appl. Phys., 42, pp. 270-273, 2003.
Various types of semiconductor microcrystal-doped glass thin films were successfully prepared by
RF-sputtering. The blue shift of the absorption edge in the visible light region, caused by the quantum
confinement effect, was observed in all the thin films. The amount of the blue shift was found to depend
significantly not only on the types of semiconductor dopants and the microcrystal radius but also on the type ofmatrix. The blue shift of semiconductor microcrystals with a small exciton Bohr radius, such as CuCl, showed
an exciton confinement effect. On the other hand, the blue shift of microcrystals with a large Bohr radius, suchas CdSe, has been expected to follow the electron-hole independent confinement model. But it was found todeviate significantly from the theoretical curve. This deviation was explained in terms of the Coulombinteraction between electron and hole, size-dependent dielectric constants of the dopants and the dielectric
constant of matrix.
Development of Nonlinear Optical Materials Dispersed with Ultra-Fine Silver Particles [in Japanese], Noritsugu
HASHIMOTO, Tadanori HASHIMOTO, Hiroyuki NASU and Kanichi KAMIYA: Reports of the Mie
Prefectural Science and Technology Promotion Center Industrial Research Division, 27, pp. 71-76, 2003.
Ag aerosol particles generated by the evaporation-condensation method were deposited on a glass
substrate. Thin film thus obtained consists of nano-sized Ag particles. Absorption spectrum shows a peak due
to surface plasmon resonance, and absorption peak wavelength of as-deposited samples was shifted toward
longer wavelength with increasing particle diameter. In the case of annealed samples, absorption peakwavelength was much shorter than that of as-deposited samples. Nonlinear refractive index and nonlinear
absorption coefficient determined by Z-scan technique were negative, and its absolute value for as-deposited
samples was increased as the absorption peak wavelength became close to the laser wavelength used in themeasurement. Nonlinear refractive index for annealed sample was increased with decreasing particle diameter
due to quantum confinement effects.
Glucose Degradation Products (GDP) Retard Remesothelialization Independently of D-Glucose Concentration,
Llinos W MORGAN*, Anders WIESLANDER*, Malcolm DAVIES*, Takashi HORIUCHI, Yuji OHTA*, M
Janine BEAVIS*, Kathryn J. CRAIG*, John D. WILLIAMS* and Nicholas TOPLEY*: Kidney Int., 64,
pp.1854-1866, 2003.
To examine the effects of specific GDP on the remesothelialization process, the impact of conventional
and low GDP peritoneal dialysis solutions, D-glucose, and individual GDP in a scratch-wounding model wasassessed. In untreated HPMC, the rate of wound closure was linear and the process was complete by 18 +- 3.6hours(N=16). In wounded HPMC exposed to dilutions of heat-sterilized but not filtered laboratory solutions(1.5% or 4.0% glucose,pH7.4), remesothelialization was significantly retarded (P=0.04 and P=0.009 vs. M199,
respectively). In Gambrosol, remesothelialization was significantly retarded in both 1.5% and 4.0% solutions.
Remesothelialization was dose-dependently retarded in HPMC exposed to 3,4-DGE (>10 μ mol/L),
formaldehyde (>5μmol/L) but not by exposure to the other GDP tested even at 5 times the concentration present
in low glucose solutions. These data identify that the formaldehyde and 3,4-DGE present in heat-sterilized
peritoneal dialysis solutions are important in reducing mesothelial cell regeneration. Specifically targeting theirremoval may have major benefits in preserving the mesothelium during long-term peritoneal dialysis.

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Abstracts of Papers

Image Analysis of Remesothelialization Following Chemical Wounding of Cultured Human Peritoneal
Mesothelial Cells: The Role of Hyaluronan Synthesis, Takashi HORIUCHI, Keiichi MIYAMOTO, Sunao
MIYAMOTO*, Mika FUJITA*, Nami SANO*, Kyoko MINAMIYAMA*, Yuichirou FUJIMURA*, Koichi
NAGASAWA*, Chie OTSUKA* and Yuji OHTA*: Kidney Int., 64, pp.2280-2290, 2003.
To understand what happens during the wound healing process of the mesothelium, we have developed an
in vitro wounding model of cultured human peritoneal mesothelial cells (HPMCs) utilizing an image acquisition
and analysis system. Using this system, cell mobility and hyaluronan synthesis were quantified and theirinterrelationship discussed. Centripetal migration of the HPMCs into the wound area was the predominant
process involved in wound repair with proliferation playing a secondary role. Staining for B-HABP was confinedto the remesothelialized area when wound closure was complete at 24 hours. At 48 hours after wound closure,the stained area was even more visible, although somewhat diffuse; thereafter, staining was reduced to almost
background levels. The cell culture model of wound healing used in our study has enabled us to demonstratequantitative image data of the cellular processes that occur during wound healing. Synthesis and subsequentdecomposition of hyaluronan appears to be related to the mobility of the wounded and intact HPMCs in thismodel system.
Expression of mRNA for Growth Factors and Extracellular Matrix Proteins after Injury to Cultured Peritoneal
Cells: Does the Healing Process Contribute to Peritoneal Ultrastructural Alteration?, Takashi HORIUCHI, Koki
FUJIKAWA*, Kimio TAKAI*, Akinobu SUGA*, Katsusuke NAITO*, Atsushi OHATA*, Shinya
NAKASONE*: J. Artif. Organs, 6, pp. 253-259, 2003.
To test a possible mechanism for peritoneal membrane alteration, we investigated whether chemicallyinjured peritoneal mesothelial cells and fibroblasts upregulate their production of growth factors and ECM as aconsequence of the healing process. A significant increase was only observed for TGF-β1, while VEGF showed
the least change with time. For RPFB, HGF, b-FGF, VEGF, and FN mRNA expression were slightly suppressedcompared to control levels up to 72h postwounding. TGF-β1, however, increased markedly above control
expression levels by the end of the wound healing process. The production of profibrotic growth factors bymesothelial cells in response to injury may represent a mechanism whereby fibroblast activation, resulting infibroblast hyperplasia and excessive extracellular matrix accumulation, culminates in alteration of the peritoneal
membrane ultrastructure.
Inhibition of Cryogelation by the Novel Synthetic Peptide (Gly-Arg-Lys-Lys-Thr): Recognition Site of Extra
Domain A Containing Fibronectin for Heparin in Cryogelation, Keiichi MIYAMOTO, Daisuke KOBAYASHI,
Rizu MAEDA, Takaharu ITO, Takashi KOMAI: Int. J. Biol. Macromol. 31, pp. 207-15, 2003.
Cryogel is a physical gel formed by the heterophilic aggregation of extra domain A (EDA) containing
fibronectin [EDA(+)FN], plasma fibronectin (pFN), fibrinogen (Fbg) and heparin (Hep) in the blood ofrheumatoid arthritis (RA) patients. In cryogelation EDA(+)FN cross-links to form an interaggregate of cryogelwith Hep. In the present study, we determined the recognition structure of Hep for EDA(+)FN by using oligoand desulfonated-Hep. We also determined the recognition structure of EDA(+)FN for Hep by an inhibition
experiment on the heparin binding domain II (HepII) in EDA(+)FN with the synthetic peptides,
Arg-Arg-Ala-Arg(RRAR),
Asp-Gln-Ala-Arg(DNAR),
Ile-Lys-Tyr-Glu-Lys(IKYEK),
and
Gly-Arg-Lys-Lys-Try (GRKKT). The GRKKT sequence clearly inhibited bonding between EDA(+)FN and
Heps containing oligo- and desulfonated-Hep. These results demonstrated that inhibition of cryogelation inplasma could progress to a novel treatment for RA.
Preparation of Polyion Complex Capsule and Fiber of Chitosan and Gellan-Sulfate at Aqueous Interface,
Hiroyuki YAMAMOTO*, Kousaku OHKAWA*, Emi NAKAMURA*, Keiichi MIYAMOTO, Takashi KOMAI:
Bull. Chem. Soc. Jpn., 76, pp. 2053-2057, 2003.
The electrostatic interaction between polysaccharides has been studied. Different characteristic surface
structures, such as true spheres and fibrous forms, are made front gellan-sulfate (GS) and chitosan via polyion
complex (PIC) formation. When a chitosan solution is added dropwise into a GS solution, spherical droplets
form in the GS solution. The procedure makes true spherical capsules with various diameters, which are stableenough for finger pinching or magnetic stirring in distilled water. The soft droplet capsule is acid resistant, alkali
resistant, and stable in boiling water. When an aqueous GS solution is added into an aqueous chitosan solution
without mixing, a film of PIC is formed at the interface. When this PIC film is withdrawn from the interface, afiber line forms in the wet states. After the intact wet fiber is dried in air, a strong fiber forms. The tensile
strength of the strongest fiber created is 196 MPa.

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Release of (1 → 3)- β -D-Glucan from Depth-type Membrane Filters and Their In Vitro Effects on
Proinflammatory Cytokine Production, Takashi HORIUCHI, Atsushi OHATA*, Makoto USAMI*, Koichi
NAGASAWA*, Keiko KINOSHITA*: Artificial Organs, 27(8), pp.728-735, 2003.
To clarify the origin of (1→3)-β-D-glucan in blood products and assess the biological activity of filter
extracts, we evaluated (1→3)-β-D-glucan extraction from depth filters used to process blood products and theirin vitro effects on proinflammatory cytokine production from macrophages. Cellulose or nylon filters wereanalyzed for (1→3)-β-D-glucan using the Fungitec G test. To evaluate the biological activity of the filter
extracts, Mono Mac 6 cells (a human macrophage cell line) were cultured with filter extracts with or without
lipopolysaccharide, and tumor necrosis factor-alpha (TNF-α) and interleukin-1 beta (IL-1β) concentrationsin the culture media were measured. (1→3)-β-D-glucan was released from seven cellulose filters but the nylon
filter level was undetectable. Proinflammatory cytokine production ranged from 74.3% to 119.0% of the control
for TNF-α and 81.2% to 115.9% for IL-1β. TNF-α and IL-1β levels were low without lipopolysaccharide.
The data indicate that (1→3)-β-D-glucan in blood products is contaminated with the depth filters and that thesefilter extracts modulate proinflammatory cytokine production from macrophages.
Experimental Proof of Contamination of Blood Components by (1→3)-β-D-Glucan Caused by Filtration with
Cellulose Filters in the Manufacturing Process, Takashi HORIUCHI, Koichi NAGASAWA*, Tatsuyuki YANO*,
Go KITABAYASHI*, Hiroaki MORIMOTO*, Yuji YAMADA*, Atsushi OHATA*, Makoto USAMI*: J. Artif.
Organs, 6, pp. 49-54, 2003.
To investigate the contamination of blood components by (1→3)-β-D-glucan from cellulose filters, invitro experiments were performed by using six cellulose filters and a nylon filter. Human serum albumin (HSA)
solution (100ml) was flowed through each filter after rinsing with 100ml of distilled water, and (1→3)-β-D-glucan in each fraction was determined by Fungitec G test MK. The concentration of (1→3)-β-D-glucan
eluted from cellulose filter in 100-ml distilled water fractions ranged from 6 to 207pg/ml, and that of HSA
fractions ranged from 33 to 20,784pg/ml. These date showed that remarkably higher (1→3)-β-D-glucan levels
were detected in HSA fractions flowed through cellulose filter in spite of advance rinsing with 100ml of distilledwater. In the case if a nylon filter, (1→3)-β-D-glucan was not eluted in either fraction. These results indicatethat (1→3)-β-D-glucan contamination in blood components is caused by filtration with cellulose filters in the
manufacturing process.