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Department of Chemistry for Materials* nonmember

Effect of “Topotactic” Reduction Product of Tungsten Disulfide on Catalytic Activity of Metallocene
Catalyst for Olefin Polymerization, Satoru YAMADA, Akihiro YANO*, Morihiko SATO*, Takahito
ITOH : Journal of Molecular Catalysis A: Chemical 208, pp. 55-65, 2004

N,N-Dimethylanilinium (Ph(Me)2NH+) salt of tungsten disulfide (WS2) was developed as anovel cocatalyst for metallocene catalysts. The cocatalyst is composed of N,N-dimethylanilinium ion asa cationic part and "topotactic" reduction product of WS2, obtained by acquisition of an electron by theneutral host lattice of WS2 without structural alteration, as an anionic part. Notable improvement of
the catalytic activity for ethylene polymerization using the bis(indenyl)zirconium dichloride(Ind2ZrCl2)/triethylaluminum (Et3Al) catalyst was observed upon the addition of the Ph(Me)2NH+ saltof WS2. The addition of the corresponding molybdenum disulfide (MoS2) one that had smaller
crystallite size than the Ph(Me)2NH+ salt of WS2 showed the lower catalytic activity. The resultant
poly(ethylene) prepared by the Ind2ZrCl2/Et3Al/Ph(Me)2NH+ salt of WS2 possessed similar properties
like narrow polydispersity to that prepared by conventional metallocene type catalysts. The Zr
loadings on the precipitate of the Ind2ZrCl2/Et3Al catalyst activated by the Ph(Me)2NH+ salt of WS2
increased with a decrease in the crystallite size of the Ph(Me)2NH+ salt of WS2. However, the catalytic
activities in ethylene polymerization decreased drastically, indicating that the decrease of thecrystallite size led to the significant increase of inactive species for ethylene polymerization.

Spontaneous Polymerization Mechanism of 7,7-Dicyanobenzoquinone Methide with
p-Methoxystyrene, Yukihiro MITSUDA, Shuji KAWAGUCHI, Takahiro UNO, Masataka KUBO,
Takahito ITOH : Macromolecules 37, pp. 1251-1256, 2004
Spontaneous polymerization of 7,7-dicyanobenzoquinone methide (CQM) with
p-methoxystyrene (MeOSt) was investigated. An alternating copolymer of CQM with MeOSt was
obtained as the hexane-insoluble product, and a small amount of a 1:2 cycloadduct of CQM:MeOSt in
addition to large amounts of unreacted CQM and MeOSt was obtained as the hexane-soluble product.
To clarify an active intermediate in this reaction, spontaneous polymerizations of CQM with MeOSt
were carried out in the presence of additives such as 2,2,6,6-tetramethylpiperidine-1-oxy (TEMPO)
and acetic acid and in three solvents with different polarity. The spontaneous reaction in the presenceof the TEMPO did not afford any products trapped by TEMPO. On the other hand, the reaction in thepresence of acetic acid gave a 1:1:1 adduct of CQM:MeOSt:acetic acid in a quantitative yield. It was
concluded from these results that the spontaneous polymerization of CQM with MeOSt might proceed
via a zwitterionic intermediate, which has gauche and trans forms.

Crystal
Structures
andTopochemical
Polymerizationsof
7,7,8,8-Tetrakis(alkoxycarbonyl)quinodimethanes, Shinji NOMURA, Takahito ITOH, Hirofumi
NAKASHO, Takahiro UNO, Masataka KUBO, Kazuki SODA*, Katsunari INOUE*, Mikiji
MIYATA* : Journal of American Chemical Society 126, pp. 2035-2041, 2004

A―25

Highly conjugated monomers, 7,7,8,8-tetrakis(alkoxycarbonyl)quinodimethanes (methoxy(1a), ethoxy (1b), isopropoxy (1c), benzyloxy (1d), chloroethoxy (1e), and bromoethoxy (1f)), weresynthesized. Recrystallizations of 1a, 1c, 1e, and 1f yielded two crystal forms (prisms (1a-A) andneedles (1a-B), needles (1c-A) and plates (1c-B), prisms (1e-A) and plates (1e-B), and prisms (1f-A) andneedles (1f-B)), which have different molecular packing modes by X-ray crystal structure analysis,
indicating that the crystals are polymorphic. In the photopolymerizations of these monomer crystals
in the solid state, 1a-A, 1e-A, and 1f-A polymerized topochemically to give crystalline polymers. For
their thermal polymerizations in the solid state, in addition to 1a-A, 1e-A, and 1f-A, 1e-B and 1f-B
polymerized, but polymers formed from the 1e-B and 1f-B were amorphous. The packing of
quinodimethane molecules in the crystals was defined by four kinds of parameters, stacking distance(ds), the distance between the reacting exomethylene carbon atoms (dcc), the angles formed between
the stacking axis and longer axis of the monomer molecule (θ1), and the shorter axis of the monomer
molecule (θ2), and then the polymerization reactivity of these quinodimethanes in the solid state wasdiscussed on the basis of these parameters.

Ionic Conductivity and Mechanical Property of Cross-linked Hyperbranched Polymer Electrolytes for
Lithium Secondary Batteries, Takahito ITOH, Seiji HORII, Shinya HASHIMOTO, Takahiro UNO,
Masataka KUBO, Osamu YAMAMOTO* : Transaction of the Materials Research Society of Japan 29,
pp. 1025-1030, 2004
Composite polymer electrolytes composed of cross-linkable hyperbranched polymer (HBP),
poly[bis(triethylene glycol)benzoate] capped with acetyl and/or acryloyl groups in various ratios,poly(ethylene oxide), BaTiO3 as an inorganic filler, and LiN(CF3SO2)2 as a lithium salt were preparedby solvent casting, followed by thermal cross-linking, and their ionic conductivities and mechanicalproperties were investigated.

Preparation of Mechanically Cross-Linked Polystyrenes, Masataka KUBO, Naoki KATO, Takahiro
UNO, Takahito ITOH : Macromolecules 37, pp. 2762-2765, 2004
This paper reports preparation of mechanically cross-linked polystyrenes using cyclic
macromonomer as a nonbonding cross-linking agent. Emulsion and thermal self-initiatedcopolymerizations of styrene with a well-defined cyclic macromonomer based on a cyclic polystyrene
were carried out to obtain mechanically cross-linked polystyrenes with high swellability. Mechanicallycross-linked chloromethylated polystyrene was prepared by thermal self-initiated terpolymerization of
the cyclic macromonomer, styrene, and 4-vinylbenzyl chloride.

Spontaneous Polymerization Mechanism of 7,7-Dicyanobenzoquinone Methide with 1,3-Cyclohexane,
Shuji KAWAGUCHI, Yukihiro MITSUDA, Takahiro UNO, Masataka KUBO, Takahito ITOH :Kobunshi Ronbunshu 61, pp. 263-268, 2004
Spontaneous polymerization of 7,7-dicyanobenzoquinone methide (CQM) with
1,3-cyclohexane (CHD) was investigated. The spontaneous reactions gave alternating copolymers of
CQM with CHD, where CHD units were incorporated in 1,2- and 1,4-addition structures, asA―26

hexane-insoluble products and a Diels-Alder adduct of CQM with CHD as hexane-soluble product.
Addition of acetic acid to the spontaneous polymerization system did not affect the composition anddistribution of products. On the other hand, the spontaneous polymerization in the presence of
2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) gave a low molecular weight alternating copolymer
with TEMPO at the terminal end as hexane-insoluble product and a 1:1:1 adduct as hexane-soluble
product. It was concluded from these results that the spontaneous polymerization of COM with CHD
proceeds via a diradical intermediate.

Influence of Hyperbranched Polymer Structure on Ionic Conductivity in Composite Polymer
Electrolytes of PEO/Hyperbranched Polymer/BaTiO3/Li Salt System, Takahito ITOH, Seiji HORII,
Takahiro UNO, Masataka KUBO, Osamu YAMAMOTO* : Electrochimica Acta 50, pp. 271-274, 2004
The influence of the hyperbranched polymer (HBP) structure such as molecular weights,
molecular weight distribution, chain-end, ethylene oxide (EO) chain lengths on the ionic conductivityof the composite polymer electrolytes composed of poly(ethylene oxide) (PEO), BaTiO3 as a ceramicfiller, LiN(CF3SO2)2 as a lithium salt, and HBP as a plasticizer were investigated. The difference in themolecular weights of the HBP did not affect significantly the ionic conductivity. However, molecularweight distribution of the HBP might affect the ionic conductivity of the composite polymer electrolyte,
which decreased with broadening of the molecular weight distribution. Further branching at the
chain-end structure in the HBP led to a decrease in the ionic conductivity. The HBP with a longer EO
chain length was effective to an enhancement of the ionic conductivity.

Spontaneous Polymerization Mechanism of Electron-Accepting Substituted Quinodimethane withVinyl Ether and Cyclic Ketene Acetal, Yukihiro MITSUDA, Takashige FUJIKAWA, Katsumi
NAKASAKA, Takahiro UNO, Masataka KUBO, Takahito ITOH, Journal of Polymer Science: Part A:
Polymer Chemistry 42, pp. 3800-3811, 2004
The spontaneous reactions of 1-(2,2-dimethyl-1,3-dioxane-4,6-dione-5-ylidene)-4-(dicyanomethylene)-2,5-cyclohexadiene (QM-1) with a vinyl ether, butyl vinyl ether (BVE), and a cyclic keteneacetal, 2-methylene- 1,3-dioxepane (MDOP), were investigated. The reaction of QM-1 with BVE
produced a terpolymer composed of QM-1, 7-butoxy-8,8-dicyanoquinodimethane, and BVE units as ahexane-insoluble product and a one-to-one adduct of methylene Meldrum's acid and BVE as ahexane-soluble product. The spontaneous reaction of QM-1 with BVE produced, in the presence of
2,2,6,6-tetramethylpiperidine-1-oxy (TEMPO), a terpolymer carrying TEMPO units in the chain ends,
and in the presence of methanol, a one-to-one-to-one adduct of QM-1, BVE, and methanol was isolated.
The spontaneous reaction with bulkier, electron-donating MDOP produced a low-molecular-weight
alternating cooligomer of QM-1 with MDOP. The spontaneous polymerization was proposed toproceed via a zwitterionic intermediate taking two forms, gauche and trans, depending on the
bulkiness of the comonomer.

Asymmetric Anionic Polymerization of 2,6-Dimethyl-7-phenyl-1,4-benzoquinone Methide, Takahiro
UNO, Masaya MINARI, Masataka KUBO, Takahito ITOH : Journal of Polymer Science: Part A:
Polymer Chemistry 42, pp. 4548-4555, 2004

A―27

Asymmetric anionic polymerizations of 2,6-dimethyl-7-phenyl-1,4-benzoquinone methide (1)were performed with various chiral anionic initiators, and the specific rotations of the obtained
polymers were investigated. Optically active poly(1)s with configurational chirality were obtained withall the initiators, and a complex of fluorenyllithium (FlLi) with (-)-sparteine [(-)-Sp] produced poly(1)with the largest negative specific rotation ([α]435 = -26.8°). The specific rotations of poly(1)s obtainedwith FlLi/(-)-Sp depended on the initiator concentration and the solvent polarity. The maximum
specific rotations were obtained at an almost constant initiator concentration (ca. 0.03 mol/L),
regardless of the monomer concentration, in toluene, whereas a higher initiator concentration was
required in more polar solvents. These results suggested that the aggregation state of the propagating
chain end significantly affected the specific rotation of poly(1).

Solid-State Polymerization of 7-Alkoxycarbonyl-7-cyano-1,4-benzoquinone Methides, Takahito ITOH,
Shinji NOMURA, Nagisa SAITOH, Takahiro UNO, Masataka KUBO, Kazuki SODA*, Katsunari
INOUE*, Mikiji MIYATA* : Macromolecules 37, pp. 7938-7944, 2004
Thermalpolymerizations
andphotopolymerizationsof
7-alkoxycarbonyl-7-cyano-1,4-benzoquinone methides (methoxy (2a), ethoxy (2b), propoxy (2c),isopropoxy (2d), butoxy (2e), and sec-butoxy (2f)) were investigated in the solid state. In the thermal
polymerization in the solid state, 2a, 2c, 2d, and 2e polymerized to give glassy solids or a mass of
crystals, but both 2b and 2f did not polymerize. In the photopolymerization in the solid state, allmonomer crystals except for 2a polymerized to give corresponding polymers as needlelike solids. The
needlelike polymer obtained by photopolymerization of highly reactive 2c was amorphous by powder
X-ray diffraction measurement. Crystal structure of 2c was determined by single-crystal X-ray
structure analysis, and the molecular packing in the crystals was discussed.

Molecular
OxygenInsertion
Polymerization
into
CrystalsofTetrakis(alkoxycarbonyl)quino-dimethanes, Takahito ITOH, Shinji NOMURA, Masaki OHTAKE,
Takafumi YOSHIDA, Takahiro UNO, Masataka KUBO, Atsushi KAJIWARA*, Kazuki SODA*,
Mikiji MIYATA* : Macromolecules 37, pp. 8230-8238, 2004
Solid-state alternating copolymerization took place by molecular oxygen insertion in the
crystalsof
7,7,8,8-tetrakis(ethoxycarbonyl)quinodimethane(1a)and
7,7-bis(ethoxycarbonyl)-8,8-bis(methoxycarbonyl) quinodimethane (1b) to form highly crystalline
needlelike white solids for 1a and amorphous ones for 1b. The polymer structures were confirmed by
1H NMR, 13C NMR, IR, elemental analysis, powder XRD, and TGA measurements. However, in vacuo
polymerizations of 1a and 1b in the solid state with heating and photoirradiation did not take place.
7,7,8,8-Tetrakis(methoxycarbonyl)quinodimethane (1c) did not undergo solid-state alternating
copolymerization with oxygen even in the presence of oxygen, but instead it homopolymerized to form
highly crystalline homopolymer. The difference in the solid-state polymerization reactivity was
discussed on the basis of molecular packing in the crystals obtained by X-ray crystallography. In
addition, it was found by ESR measurement that the solid-state alternating copolymerizations withmolecular oxygen proceed by means of a radical mechanism.

A―28

Preparation of Mechanically Cross-Linked Poly(vinyl alcohol), Masataka KUBO, Naoki HAYAKAWA,
Yuya MINAMI, Masashi TAMURA, Takahiro UNO, Takahito ITOH: Polymer Bulletin 52, pp.
201-207, 2004
A novel cyclic macromonomer based on a cyclic polystyrene was prepared. Its radical
copolymerization with vinyl acetate was carried out to give a mechanically cross-linked poly(vinyl
acetate) which was converted to a mechanically cross-linked poly(vinyl alcohol) with high swellability.

Polymer Electrolytes Plasticized With Hyperbranched Polymer For Lithium Polymer Batteries,
Takahito ITOH, Seiji HORII, Shinya HASHIMOTO, Takahiro UNO, Masataka KUBO: Ionics 10, pp.
450-457, 2004
Hyperbranched polymers (HBPs) with different terminal groups and different ethyleneoxide (EO) chain lengths were prepared, and the influence of the HBP structures including molecularweights and molecular weight distribution on the ionic conductivity and the mechanical property of
the composite polymer electrolytes composed of poly(ethylene oxide) (PEO), HBP, BaTiO3 as a ceramicfiller, and Li(CF3SO2)2 as a lithium salt were investigated. It was found that the molecular weights ofthe HBP do not affect significantly the ionic conductivity, but the molecular weight distribution might
affect it, and also further branching at the terminals of the HBP led to decrease in the ionic
conductivity. The HBP with longer EO chain length was effective for enhancement of the ionic
conductivity in comparison with the HBP with shorter one. The increase in cross-linkable groups(acryloyl group) at the terminals of the HBP improved the tensile strength, but caused the ionic
conductivity to decrease. Loosely cross-linked composite polymer electrolyte showed higher ionic
conductivity and higher tensile strength than no cross-linked one.

Double Nucleophilic Addition of Azide and Tetraallyltin to the Latent α,β-Unsaturated Aldehydes
Using in situ Hydrolysis of the Imino Functionality Promoted by Tin(IV) Chloride Pentahydrate,
Makoto SHIMIZU, Takafumi NISHI: Synlett, pp. 889-891, 2004

Double Nucleophilic Addition of Azide and Tetramethallyltin to α,β-Unsaturated Aldimines Promoted
by Aluminum Chloride, Makoto SHIMIZU, Chiaki YAMAUCHI, Toshiki OGAWA: Chem. Lett. 33 (5),pp. 606-607, 2004

Synthesis of 5-Acetyl-2-pyridones via Nucleophilic Addition of β-Keto Esters to Alkynyl Imines, Iwao
HACHIYA, Kana OGURA, Makoto SHIMIZU: Synthesis, pp. 1349-1352, 2004

Stereodivergent Synthesis of (2R)-2,3-Diricinolein by Lipase-catalyzed Hydrolysis of Triricinolein,
Iwao HACHIYA, Akihisa MAKINO, Makoto, SHIMIZU, Masatsugu AKITA*, Takashi
HAMAGUCHI*: Tetrahedron: Asymmetry 15 (16), pp. 2451-2454, 2004

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Aza-Reformatsky-type Reaction of α-Iodomethyl Ketone O-Alkyl Oximes Promoted by Titanium
Tetraiodide, Makoto SHIMIZU, Tadahiro TOYODA: Org. Bio. Chem. 2 (20), pp. 2891-2892, 2004

A Cation-Exchange Resin Promoted Imino Aldol Reaction, Leading to the Synthesis of 2-Isocephem
and 2-Oxa-isocephem , Makoto SHIMIZU, Masanori TACHI, Iwao HACHIYA: Chem. Lett. 33 (10), pp.
1394-1395, 2004

An Improved Process for the Large-Scale Preparation of Antirheumatic Agent MX-68, Noriaki
MARUYAMA, Hirohito SHIMIZU*, Takashi SUGIYAMA*, Masashi WATANABE*, Masahiro KATO*,
Makoto SHIMIZU: Organic Process Research & Development 8 (6), pp. 883-888, 2004

Reductive Coupling of Aldehydes with Nitriles Promoted by Titanium Tetraiodide, Makoto SHIMIZU,
Hiroshi GOTO: Lett. Org. Chem. 1 (4), pp. 346-348, 2004

3,4,6-Trisubstituted-2-pyrone Synthesis via the Nucleophilic Addition of 2-Alkyl Meldrum’s Acid to
Alkynyl Ketone, Iwao HACHIYA, Hitoshi SHIBUYA, Kazuma HANAI, Makoto SHIMIZU: Lett. Org.
Chem. 1 (4), pp. 349-352, 2004
Double Nucleophilic Addition of Ketene Silyl Acetals to α,β-Unsaturated Imines: Factors Controlling
the Regioselectivity, Makoto SHIMIZU, Hiroshi KUROKAWA, Atsushi TAKAHASHI: Lett. Org.
Chem. 1 (4), pp. 353-356, 2004.

New Synthetic Reactions Using the Reducing Ability of Titanium Tetraiodide [in Japanese], Makoto
SHIMIZU: J. Synth. Org. Chem., Jpn. 62 (3), pp. 205-213, 2004

Elimination-Addition Mechanism for Nucleophilic Substitution Reaction of Cyclohexenyl Iodonium
Salts and Regioselectivity of Nucleophilic Addition to the Cyclohexyne Intermediate, Morifumi
FUJITA*, Wan Hyeok KIM*, Yuichi SAKANISHI*, Koji FUJIWARA*, Sayaka HIRAYAMA*, Tadashi
OKUYAMA*, Yasuhiro OHKI*, Kazuyuki TATSUMI*, Yasunori YOSHIOKA : J. Am. Chem. Soc. 126(24), pp.7548-7558, 2004
The reaction of 4-substituted cyclohex-1-enyl(phenyl)iodonium tetrafluoroborate withtetrabutylammonium acetate gives both the ipso and cine acetate-substitution products in aprotic
solvents. The isomeric 5-substituted iodonium salt also gives the same mixture of the isomeric acetateproducts. The reaction is best explained by an elimination-addition mechanism with 4-substituted
cyclohexyne as a common intermediate. The cyclohexyne formation was confirmed by deuterium
labeling and trapping to lead to [4 + 2] cycloadducts and a platinum-cyclohexyne complex.
Cyclohexyne can also be generated in the presence of some other mild bases such as fluoride ion,alkoxides, and amines, though amines are less effective bases for the elimination. Kinetic deuterium
isotope effects show that the anionic bases induce the E2 elimination (kH/kD > 2), while the amines

A―30

allow formation of a cyclohexenyl cation in chloroform to lead to E1 as well as SN1 reactions (kH/kD ≈1). Bases are much less effective in methanol, and methoxide was the only base to efficiently afford thecyclohexyne intermediate. Nucleophiles react with the cyclohexyne to give regioisomeric products in
the ratio dependent on the ring substituent. The observed regioselectivity of nucleophilic addition to
substituted cyclohexynes is rationalized from calculated LUMO populations, which are governed by
the bond angles at the acetylenic carbons: The less deformed carbon has a higher LUMO populationand is preferentially attacked by the nucleophile.

Vibrational Analysis with the Symmetrically Combined Morse Potential Model for AntisymmetricStretching in [ClDCl] Formed by Photodissociation of (DCl)2, Masaki MITANI, Yasunori YOSHIOKA,
Dock–Chil CHE*, Toshio KASAI* : J. Phys. Chem. A 108 (24), pp.5220-5225, 2004
We estimate the line spacing between vibrational levels for the antisymmetric stretching in[ClDCl] to elucidate the origin of the oscillating structure on the translational energy distribution of
the terminal D atom released by the photodissociation of (DCl)2. The vibrational analysis with thesymmetrically combined Morse potential model is performed for linear hydrogen-bonding [ClDCl] andthe dependence of change in vibrational levels on the Cl–Cl distance is examined. It is found that thecalculated assignment and observed spacing show good correspondence for RClCl = 3.65 or 3.70 Å, and
it is therefore strongly suggested that the oscillation of dissociated D translational energy reflects theantisymmetric stretching vibration in the [ClDCl] counterpart.

Effect of Aging on Conductivity of Yttria Stabilized Zirconia, Masatoshi HATTORI*, Yasuo TAKEDA,
Yoshinori SAKAKI*, Akihiro NAKANISHI*, Satoshi OHAR*, Kazuo MUKAI*, Jin-Ho LEE*,
Takehisa FUKUI*: Journal of Power Sources 126, pp.23-27, 2004
Effect of Annealing on the Electrical Conductivity of the Y2O3-ZrO2 System, M. HATTORI*, Y.
TAKEDA, J. –H. LEE*, S. OHARA*, K. MUKAI*,T. FUKUI*, S. TAKAHASHI*, Y. SAKAKI*, A.
NAKANISHI*: Journal of Power Sources 131, pp.247-250, 2004

The Effect of Doped Elementals on the Electrochemical Behavior of Hexagonal Li2.6Co0.4N, Yu LIU,
Kumi HORIKAWA, Minako FUJIYOSHI, Nobuyuki IMANISHIi, Atsushi HIRANO, Yasuo TAKEDA:
Journal of the Electrochemical Society 151(9), pp. A1450-A1455, 2004

Lithium Transition Metal Nitrides with the Modified Morphology Characteristics as Advanced AnodeMaterials for Lithium Ion Batteries, Y. LIU, T. MATSUURA, N. IMANISHI, T. ICHIKAWA, A.
HIRANO, Y. TAKEDA: Electrochemistry Communication 6, pp.632-636, 2004

Silicon/Carbon Composites as Anode Materials for Li-Ion Batteries, Y. LIU, K. HANAI, J. YANG*, N.
IMANISHI, A. HIRANO, Y. TAKEDA: Electrochemical and Solid-State Letters 7(10), pp.A369-A372,
2004

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Study of the Capacity Fading Mechanism for Fe-Substituted LiCoO2 Positive Electrode, Victoria L.
MCLAREN*, Anthony R. WEST*, Mitsuharu TABUCHI*, Akiko NAKASHIMA*, Hikari
TAKAHARA*, Hironori KOBAYASHI*, Hikari SAKAEBE*, Hiroyuki KAGEYAMA*, Atsushi
HIRANO, Yasuo TAKEDA: Journal of the Electrochemical Society 151(5), pp. A672-A681, 2004

Novel Composite Anodes Based on Layered Lithium Transition Metal Nitrides for Lithium Secondary
Batteries, Y. LIU, K. HORIKAWA, M. FUJIYOSHI, T. MATSUURA, N. IMANISHI, Y. TAKEDA:
Solid State Ionics 172, pp.69-72, 2004

Electrical and Thermal Properties of Dense Ce1-xRExO2-δ Electrolyte Using Low-Temperature
Sinterable Powder (0 ≤ x ≤ 0.2, RE=Y, Sm, Gd), Eisaku SUDA*, Bernard PACAUD*, Yvan
MONTARDI*, Masashi MORI*, Yasuo TAKEDA: Transactions of the Materials Research Society ofJapan 29(5), pp.2317-2320, 2004

Impedance Spectroscopy of Perovskite Air Electrodes for SOFC Prepared by Laser Ablation Method,
N. IMANISHI, T. MATSUURA, Y. SUMIYA, K. YOSHIMURA, A. HIRANO, Y. TAKEDA, D. MORI*,
R. KANNO*: Solid State Ionics 174, pp.245-252, 2004

Effects of Charge Disproportionation on the Phonon Density of State in Fe Perovskites, Jobu
MATSUO*, Makoto SETO*, Shinji KITAO*, Yasuhiro KOBAYASHI*, Rie HARUKI*, Takaya
MITSUI*, Atsushi FUJIMORI*, Yasuo TAKEDA, Shuji KAWASAKI*, Mikio TAKANO*: Journal of
the Physical Society of Japan 73 (10), pp.2768-2770, 2004

Modification of Carbon Nanotubes by Laser Ablation of Copper, Akira. KOSHIO, Mitsuru SHIRAISHI,
Yuuji KOBAYASHI, Masatou ISHIHARA*, Yoshinori KOGA*, Syunji BANDOW*, Sumio IIJIMA*,
Fumio KOKAI: Chem. Phys. Lett. 396, pp.410-414, 2004
Multi-wall carbon nanotubes (MWNTs) were modified by laser ablation of Cu in thepresence of He gas. Quasi-spherical particles with diameters of 200 nm to 2 µm were sparsely
deposited on as-grown MWNTs. Agglomerated nanoparticles with sizes of 1-10 nm covered
ultrasonically-treated MWNTs. Both particles were oxidized. The interaction of nanoparticles with thesurface of the ultrasonicated MWNTs, due to small charge transfer to carbon atoms of the MWNTs
upon adsorption of Cu, was suggested. We discuss the size distribution and morphology of theparticles from cluster and particle formation in gas-phase and the surface properties of the two
MWNTs.

Compression of Polyhedral Graphite up to 43 GPa and X-ray Diffraction Study on Elasticity andStability of the Graphite Phase, Atsuko NAKAYAMA*, Sumio IIJIMA*, Yoshinori KOGA*, Katsuya
SHIMIZU*, Kaori HIRAHARA*, Fumio KOKAI: Appl. Phys. Lett. 84, pp. 5112-5114, 2004

A―32

The crystal structure of polyhedral graphite particles (“G balls”) has been investigated underpressure up to 43 GPa and at room temperature by x-ray powder diffraction measurements. The
polyhedra maintain the graphite phase under pressure higher than 40 GPa. A 29% compression involume at 43 GPa involves an unusual decrease in the interlayer distance of 25%. The polyhedra
recover their original crystal structure by releasing the pressure. A closed and solid structure of thepolyhedra, suppressing a transition into another phase, causes them to become metallic underpressure higher than 20 GPa.

Three Nanostructured Graphitic Particles and their Growth Mechanisms from High-Temperature
Carbon Vapor Confined by Ar Gas, Fumio KOKAI, Akira KOSHIO, Daisuke KASUYA*, KaoriHIRAHARA*, Kunimitsu TAKAHASHI*, Atsuko NAKAYAMA*, Masatou ISHIHARA*, Yoshinori
KOGA*, Sumio IIJIMA*: Carbon, 42, pp.2515-2520, 2004
CO2 laser vaporization of graphite was carried out in the presence of high pressure Ar gas
up to 0.8 MPa. We compared transmission electron microscope images and Raman spectra ofdeposited particles and luminous laser plumes of vaporized and clustered carbon species. We discuss
the growth mechanisms of three graphitic carbon particles, a single-wall carbon nanohorn aggregate,a platelet graphite particle, and a polyhedral graphite particle, grown depending on the confinementof the Ar atmosphere. The formation of graphitic sheet or shell structures, dependent on resident
carbon densities and their temperature gradient, is thought to begin from supersaturated hot carbon
vapor up to about 3000°C and lead to the growth of the three graphitic particles.

Optimization of Solar Photocatalytic Degradation Conditions of Bisphenol A in Water Using Titanium
Dioxide, Satoshi KANECO, Mohammad A. RAHMAN, Tohru SUZUKI, Hideyuki KATSUMATA,
Kiyohisa OHTA: J. Photochem. Photobiol. A: Chem. 163, pp. 419–424, 2004

Solar Photocatalytic Degradation of Bisphenol A in Water with ZnO, Mohammad A. RAHMAN,
Satoshi KANECO, Tohru SUZUKI, Hideyuki KATSUMATA, Kiyohisa OHTA: Photo/Electrochem.
Photobiol. Environ. Energy Fuel 3, pp. 199–205, 2004

Determination of Silver in Waters by Tungsten Wire Preconcentration Method - Electrothermal
Atomic Absorption Spectrometry, Mohammad A. RAHMAN, Satoshi KANECO, Md N. AMIN, Tohru
SUZUKI, Kiyohisa OHTA: Talanta 62, pp. 1047–1050, 2004

Separation of Zinc Compounds by Sequential Metal Vapor Elution Analysis with Atomic Absorption
Detection, Mohammad A. RAHMAN, Satoshi KANECO, Tohru SUZUKI, Hideyuki KATSUMATA,
Kiyohisa OHTA: Talanta 64, pp. 989–992, 2004

Slurry Sampling for Direct Analysis of Lead in Bangladeshi Vegetable Samples by Molybdenum
Electrothermal Atomizer Atomic Absorption Spectrometry, Mohammad A. RAHMAN, Satoshi

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KANECO, Tohru SUZUKI, Hideyuki KATSUMATA, Kiyohisa OHTA: ITE Lett. Batt. New Technol.
Med. 5, pp. 363–368, 2004

Leaching Behavior of Lead Compounds in Atmosphere Fine and Coarse Particles, Kunihiro
FUNASAKA*, Takeji MIYAZAKI*, Toshikazu KAMIURA*, Joji FUKUYAMA*, Hideyuki
KATSUMATA, Satoshi KANECO, Tohru SUZUKI, Kiyohisa OHTA: ITE Lett. Batt. New Technol.
Med. 5, pp. 577–580, 2004
Development of Sintering Preparation Technology of Porous Materials from Sea Bottom Sediments for
Waste Water Treatment, Satoshi KANECO, Takuya HARADA, Ahmed H.A. DABWAN, Tohru
SUZUKI, Hideyuki KATSUMATA, Kiyohisa OHTA: ITE Lett. Batt. New Technol. Med. 5, pp.
467–471, 2004

Electrochemical Reduction of CO2 at Alloy Electrode in Methanol, Satoshi KANECO, Hiroki
YAMAUCHI, Hideyuki KATSUMATA, Tohru SUZUKI, Kiyohisa OHTA: Stud. Surf. Sci. Catal. 153,
pp. 277–282, 2004

Reduction of Carbon Dioxide Using Metal Powders, Hideyuki KATSUMATA, Kouichirou
MATSUSHITA, Satoshi KANECO, Tohru SUZUKI, Kiyohisa OHTA: Stud. Surf. Sci. Catal. 153, pp.
55–60, 2004

Long Term Sampling Method for PCDD/Fs in Atmosphere by Adsorption onto Economical Materials,
Hideyuki KATSUMATA, Satoshi KANECO, Tohru SUZUKI, Kiyohisa OHTA: Chem. Lett. 33, pp.
1618–1619, 2004

Effect of Metal Nitrates on the Formation of PCDD/Fs during Newspaper Combustion, Hideyuki
KATSUMATA, Satoshi KANECO, Tohru SUZUKI, Kiyohisa OHTA: Bull. Environ. Contamn. Toxicol.
73, pp. 479–486, 2004

Removal of Humic Substances and Their Metal Complexes by Adsorption with Bone Char, Hideyuki
KATSUMATA, Satoshi KANECO, Haruna KASAI, Kumiko ITOH, Kazuaki MASUYAMA*, Tohru
SUZUKI, Kunihiro FUNASAKA*, Kiyohisa OHTA: Environ. Eng. Sci. 21, pp. 341–348, 2004

Microbial Metabolism of Di-n-Butyl Phthalate by Bacterium Bacillus Natto, Aleya BEGUM, Hideyuki
KATSUMATA, Satoshi KANECO, Tohru SUZUKI, Kiyohisa OHTA: Chem. Lett. 33, pp. 682–683,
2004

Removal of Heavy Metals in Aqueous Solution by Adsorption onto Oyster Shell, Hideyuki

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KATSUMATA, Satoshi KANECO, Tohru SUZUKI, Kiyohisa OHTA, Yoshihiro YOBIKO:
Photo/Electrochem. Photobiol. Environ. Energy Fuel 3, pp. 165–172, 2004

Removal of Heavy Metals in Water by Adsorption onto Sintering Porous Materials from Sea Bottom
Sediments, Hideyuki KATSUMATA, Takuya HARADA, Satoshi KANECO, Ahmed H.A. DABWAN,
Tohru SUZUKI, Kiyohisa OHTA: ITE Lett. Batt. New Technol. Med. 5, pp. 573– 576, 2004

Preconcentration of Phthalic Acid Esters in Water Samples by Saccharomyces cerevisiae Immobilizedon Silica Gel, Hideyuki KATSUMATA, Aleya BEGUM, Satoshi KANECO, Tohru SUZUKI, Kiyohisa
OHTA: Anal. Chim. Acta 502, pp. 167–172, 2004

Degradation of Bisphenol A in Water by the Photo-Fenton Reaction, Hideyuki KATSUMATA,
Shinsuke KAWABE, Satoshi KANECO, Tohru SUZUKI, Kiyohisa OHTA: J. Photochem. Photobiol. A:
Chem. 162, pp. 297–305, 2004

Nucleotide Sequence Analysis of p10 Gene of Antheraea pernyi Nucleopolyhedrovirus andConstruction of Two Transfer Vector Plasmids, Kenichi MAEGAWA, Xie T. WANG*, Jun
KOBAYASHI*, Tetsuro YOSHIMURA: International Journal of Wild Silkmoth and Silk 9, pp. 53-60,
2004

Development of Orally Administrated Liposome Vaccines against Bacteria- and Virus-Infectious
Diseases in Cultured Fishes: Tetsuro YOSHIMURA, Takeyoshi TAKAGI, Kanta TSUMOTO,
Masayuki SHONO, Teruo MIYAZAKI: Immunology 2004, pp. 225-228, 2004

Ligand-Printed Ion Pore Composed of Polypeptide Assembly in a Lipid Bilayer Membrane, Masahiro
HIGUCHI, Tomoyuki KOGA*, Yoshiaki KOBUKE*, Takatoshi KINOSHITA*, Masami
KAWAGUCHI: Trans. MRS-J. 29, pp. 3143-3146, 2004
A simple and novel approach for the preparation of a synthetic ligand-gated ion channel wasinvestigated. The ligand-induced formation of an amphiphilic polypeptide assembly acts as an ion
channel in lipid bilayer membrane. Various functional groups, which bind to the specific site on theligand (X), were introduced at the amino terminal of α-helical polypeptide. The interaction between
the ligand (X) and the terminal groups of the polypeptides induced the specific location of the α-helicalpolypeptide rods. Removing of the ligand (X) provided the ligand-printed ion pore in the membrane,
while re-binding of the ligand (X) closed the pore. Another ligand (Y) was inactive to the ligand(X)-printed ion pore, i.e., it did not close the channel. This ligand-printed polypeptide assembly may
permit a novel and easier production of the ligand-gated ion channel, which will give a novel approachfor the construction of signal transduction molecular devices.

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Viscous Fingering of Silica Suspensions Dispersed in Polymer Fluids, Masami KAWAGUCHI: ACS
Symposium Series No. 869 Nonlinear Dynamics in Polymeric Systems, pp. 250-261, 2004
Experimental studies of the viscous fingering of shear shinning silica suspensions in a radial
Hele-Shaw cell and shear thickening silica suspensions in a linear Hele-Shaw cell were performed by
the injection of air. For the shear thinning silica suspensions, the instability, namely changes in theviscous fingering pattern, was strongly related to the polymer concentration in the dispersant rather
than the silica concentration. For the shear thickening silica suspensions, the imposed shear rate at
which the instability was first observed, was close to the critical shear rate of the corresponding silica
suspension. The finger velocities of the shear thinning silica suspensions were in agreement with themodified Darcy’s law, while those of the shear thickening silica suspensions with the silica
concentrations higher than 7.5 wt% were much lower than the prediction of the modified Darcy’s law.
Rheo-Optical Properties of Silicone Oil Emulsions in the Presence of Polymer Emulsifiers, Masami
KAWAGUCHI, Kenji KUBOTA: Langmuir 20 (4), pp. 1126-1129, 2004
Oil in water emulsions were prepared by dispersion of silicone oils into an aqueous solutionof hydroxylpropyl methyl cellulose (HPMC) or poly(ethylene oxide) (PEO)-poly(propylene oxide)(PPO)-PEO block copolymers. The emulsions were characterized by measurements of steady-state
shear viscosities, dynamic moduli, and stress-strain sweep curves coupled with optical microscopeobservation. The emulsions emulsified by HPMC showed solid-like viscoelastic responses, while theemulsions prepared by the block copolymers indicated liquid-like viscoelastic behavior. The
simultaneous optical microscopic observation showed that the emulsions stabilized by HPMC did not
flow below the yield stress, while those by the block copolymers did flow.

Viscous Fingering Instabilities in an Oil in Water Emulsion, Masami KAWAGUCGHI, Sayaka
YAMAZAKI, Tadaya KATO: Phys. Fluids 16 (6), pp. 1908-1914, 2004
Viscous fingering of silicone oil emulsion stabilized by hydroxylpropyl methyl cellulose (HPMC)
in water was performed by the injection of water and an aqueous solution of HPMC as a function of
the injection rate. The pressure imposed at the finger tip was simultaneously monitored. Changes
in the viscous fingering patterns from a crack-like pattern to a ramified one through a cups-like one
were observed with an increase of the injection rate, irrespective of the injected fluid. Such a patterntransition was strongly related to rheological properties of the emulsion. Moreover, the finger
velocities of the emulsion were in agreement with the modified Darcy’s law

Structure Study of Binary Titanophosphate Glasses Prepared by Sol-Gel and Melting Methods,
Anjiang TANG, Tadanori HASHIMOTO, Tetsuya NISHIDA, Hiroyuki NASU, Kanichi KAMIYA:
Journal of the Ceramic Society of Japan 112(9), pp. 496-501, 2004
The 70TiO2･30P2O5 (mol%) glass was prepared by the sol-gel method. Its structure was
examined by means of IR, Raman spectroscopy and X-ray radial distribution function analysis, andwas compared with the corresponding melt-derived glass. It was found that average coordination
number of Ti4+ ions was almost 6 and Ti4+ ions formed predominantly TiO6 octahedra in theA―36

sol-gel-derived glass, while Ti4+ ions were present in the 4, 5 and / or 6-fold coordination states to give
average coordination number in-between 4 and 5 in the melt-glass. The preference of highcoordination state of Ti4+ ions in the sol-gel glass was consistent with higher refractive index anddensity than the melt-glass.

Effective Deposition of Nano-Sized Silver Particles on Silica to Develop a Sensitive Local
Plasmon-Based SPR Sensor, Noritsugu HASIMOTO*, Tadanori HASHIMOTO, Koichi MORI,
Hiroyuki NASU, Kanichi KAMIYA: Journal of the Ceramic Society of Japan, Supplement 112-1,
PacRim5 Special Issue 112(5), pp. S576-S578, 2004
Nano-sized silver particles-deposited silicas were prepared by (a) the sol-gel method, theevaporation-condensation of silver on (b) silica glass and (c) sol-gel derived silica film. Opticalabsorption peak due to surface plasmon resonance (SPR) of silver particles was measured using
UV-VIS spectrophotometer. When the films were immersed in liquid, SPR absorption peak of thefilms (b) and (c) was shifted toward longer wavelength with the increase of the refractive index of theliquid, suggesting that these films can be used as optical sensors. On the other hand, SPR absorption
peak of the film (a) was little shifted. The sensitivity to the refractive index change for the film (b)was 81.4 nm, and that of the film (c) made by depositing silver particles on the sol-gel silica was large
as 90.2 nm, which may be attributed to less coverage of silver particles with silica matrix than the film(a) and less aggregate of them than the film (b).

Optical Properties of Ti3+-Free Ternary Titanophosphate Glasses, Tadanori HASHIMOTO, Hiroyuki
NASU, Kanichi KAMIYA: Proceedings of the XX ICG in Kyoto, Sep.27th-Oct.1st, O-07-085, 2004
The Ti3+-free binary TiO2-P2O5 glasses containing TiO2 up to 74 mol% prepared by themelt-quenching and a long-term post-annealing around the glass transition temperature in the air
possess high transparency, high-index, high-dispersion and low density, and are expected as novel
eco-optical glasses. In the present study, the effect of third and fourth components on the time ofpost-annealing to remove Ti3+ ions, and linear and nonlinear optical properties was examined. The
substitution of K2O for P2O5 in binary glasses shortened the post-annealing time and decreased thethermo-optic coefficient. The addition of a small amount of SnO2 to binary glasses was found to beeffective for removing Ti3+ ions, or decoloration of glasses with maintaining high-index, and also forstabilizing laser pulses. In addition, quaternary Li2O-ZnO-TiO2-P2O5 glasses were expected as
high-index molding glasses.

Structure Study of TiO2-P2O5 Glasses Prepared by Sol-Gel Method, Anjiang TANG, Tadanori
HASHIMOTO, Hiroyuki NASU, Kanichi KAMIYA: Proceedings of the XX ICG in Kyoto,Sep.27th-Oct.1st, O-10-021, 2004
The xTiO2･(100-x)P2O5 (x = 70-95 mol%) glasses with refractive indicies as high as 2.1-2.3
were prepared by the sol-gel method. The refractive index was higher in the sol-gel-glass than in themelt-glass at x = 70. Heat-treated compositions with x = 90 and 95 were considered to be compositesof 13-15 mass% nano-sized anatase and glass matrices with x slightly smaller than nominal values,A―37

but were highly transparent. It was found by IR and Raman techniques that 6-fold coordinated Ti4+
ions are predominant in the glass phase, while 4 or 5, and 6-fold ones are coexisting in the melt-glassof x = 70. These results were consistent with very high refractive index of the sol-gel glasses.

Influences of Nanocrystal-Size and Matrix on Third-Order Optical Nonlinearity for Thin Films
Prepared by RF-Sputtering, Hiroyuki NASU, Akimasa TANAKA, Tadanori HASHIMOTO, Kanichi
KAMIYA, Kenji KAMADA*: Proceedings of the XX ICG in Kyoto, Sep.27th-Oct.1st, O-16-017, 2004
CdSe microcrystals with various size was successfully embedded in various glass matrices
by magnetron Rf sputtering technique. The mean size of microcrystals was controllable by changing
the relative surface ratio of CdSe pellets to the matrix in the target, and increased with increasing therelative area. The negative real part of the third-order optical susceptibility was seen for the allpresent films, and magnitude of the absolute value of real part in the same glass matrix increased
with decreasing microcrystal size. On the other hand, the increase of the dielectric constant of thematrix increase the magnitude. Therefore it is interpreted that the strengthening the quantum size
effect increase the magnitude of the real part of the third-order optical nonlinearity. Furthermore,even taking account of the imaginary part, it is evident that the strengthening the quantum size effectincreases total third-order optical nonlinearity.

Electroluminescence from CdSe Nanocrystal-Doped ITO Films on SiO2 Glass Substrates, Hiroyuki
NASU, Yasuhiro Matsuzaki, Tadanori HASHIMOTO, Kanichi KAMIYA: Proceedings of the XX ICG
in Kyoto, Sep.27th-Oct.1st, O-16-025, 2004
Electroluminescence was observed in CdSe microcrystal-doped indium tin oxide (ITO) thinfilms on SiO2 glass substrates by Rf-sputtering method. The size of CdSe microcrystals was changedby altering the relative surface area of the CdSe pellets on the ITO target. ITO was well crystallizedon SiO2 glass substrates. Emission spectra shifted from red to yellow with decreasing CdSe
microcrystal size. The shift was considered to result from the blue shift of the absorption edge causedby the quantum confinement effect of CdSe microcrystals.

Review of Combination of Peritoneal Dialysis and Hemodialysis as a Modality of Treatment for
End-stage Renal Disease, H. FUKUI*, S. HARA*, Y. HASHIMOTO*, T. HORIUCHI, M. IKEZOE*, N.
ITAMI*, M. KAWABE*, H. KAWANISHI*, Y. KIMURA*: Ther Apher Dial 8, pp. 56-61, 2004
Because the contribution of residual renal function (RRF) to total solute clearance is often
significant in continuous ambulatory peritoneal dialysis (CAPD), loss of RPF over time can lead toinadequate dialysis if appropriate prescription management strategies are not pursued. Additionally,
declines in ultrafiltration caused by increases in peritoneal permeability may limit continuation of
CAPD therapy. Peritoneal dialysis and hemodialysis (PD＋HD) combination therapy (complementary
dialysis therapy) is an alternative method. This therapy allows the patient to maintain daily
activities, as with CAPD, while undergoing once-a-week HD supplements for the insufficient removalof solutes and water. This therapy allows for the continuation of PD without shifting to total HD in PD
patients who continue to have uremic symptoms even after individualization of the PD prescription.

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This treatment option is psychologically more acceptable to patients and may be expected to provide
such accompanying beneficial effects as peritoneal resting, impravement of QOL and reduction in
medical cost.