bluuebunny/crossref_metadata_2025 huggingface dataset:
Copolymerization of a Germylene with Acetylene Monomers by Rhodium Catalysis
Authors: Kobayashi Shiro , Cao Shaokui
Published: March 2006

A germylene with a bulky ligand, bis[bis(trimethylsilyl)amido] germanium, was copolymerized for the first time with acetylene monomers under the catalysis of a rhodium compound, to give rise copolymers with a structure having acetylene units in excess. Among the catalysts used, a rhodium norbornadiene complex was found to be most effective for the copolymerization.
Synthesis of (±)-Nanaimoal and (±)-Nanaimool from N,N-Diethylgeranylamine
Authors: Yamada Takashi , Takabe Kunihiko
Published: March 2006

(±)-Nanaimoal and (±)-nanaimool were synthesized via Diels-Alder Reaction of 1,1-dimethyl-2,3-dimethylenecyclohexane, a novel building block for cyclic terpenoids, easily prepared from N,N-diethylgeranylamine.
Intercalative Polymerization of 3-Methyl- and 3,4-Dimethylpyrrole in the VOPO4 Interlayer Space
Authors: Matsubayashi Gen-etsu , Nakajima Hiroshi
Published: March 2006

Finely powdered VOPO4·2H2O suspended in an ethanol solution containing 3-methyl- or 3,4-dimethylpyrrole leads to the intercalative polymerization of these pyrrole derivatives through the 2,5-coupling to yield VOPO4·(H2O)1.4·(EtOH)0.2·(MeC4HNH)0.65 and VOPO4·(H2O)1.8·(EtOH)0.2·(Me2C4NH)0.6. The similar treatment of VOPO4·2H2O with pyrrole affords polypyrrole only on the VOPO4 surface.
A New Preparative Method for 1-Chloro-2,2,3-trifluoropropane (HCFC-253ca)
Authors: Arimura Takashi , Kurosawa Shigeru , Sekiya Akira
Published: March 2006

Allene was both fluorinated and chlorofluorinated with chlorine monofluoride serving as a well-known chlorofluorinating and chlorinating reagent. 1-Chloro-2,2,3-trifluoropropane was obtained as a major product in the presence of cesium fluoride.
Triple Ion Formation from Lithium and Sodium Tropolonates in Ethanol
Authors: Hojo Masashi , Fujime Chinatsu , Yoneda Hitoshi
Published: March 2006

Electrical conductivities of lithium and sodium tropolonates in ethanol were completely explained by the formation of higher ion aggregates in addition to ion pairs.
Promotion of Methane Steam Reforming Using Ruthenium-Dispersed Microporous Alumina Membrane Reactor
Authors: Chai Maorong , Machida Masato , Eguchi Koichi , Arai Hiromichi
Published: March 2006

A membrane reactor with the microporous ruthenium-dispersed alumina membrane is effective in promoting low temperature methane steam reforming. In the temperature range of 300–500 °C, the membrane reactor attained the methane conversion with a twice as large as the equilibrium value by the selective removal of hydrogen from the reaction system.
Electrochemical Behavior of Pt-modified Cobalt Oxide Electrodes in NaOH Solutions under Oxygen Atmosphere
Authors: Wada Suguru , Nishimura Katsunori , Yahikozawa Kiyochika , Enyo Michio , Takasu Yoshio
Published: March 2006

Pt-modifled cobalt oxides (Pt + Co3O4) were prepared from H2PtCl6 and Co(NO3)2 by pyrolysis. The deposited Pt species were in highly oxidized states. Glassy carbon-supported Pt + Co3O4 electrodes of ca. 10 mol%-Pt exhibited the equilibrium oxygen electrode potential and electrocatalytic activity toward the O2 reduction in O2-saturated 1 mol dm−3 NaOH solutions.
Pyrenesulfonate Solubilized in an Aerosol OT (AOT) Reversed Micelle. Location and Distribution
Authors: Mori Yoshihiro , Shinoda Hiroyuki , Kitagawa Taiji
Published: March 2006

Pyrenesulfonate (PSA−) solubilized in an AOT reversed micelle was found to exist both in the water pool and in the surfactant phase by analyzing decay profiles of laser-induced transient species. Relative abundance in the two phases strongly depends on the molar ratio of [H2O]/[AOT].
Dansyl and Indolyl Groups as a Probing Pair for Intersegmental Arrangement in Four α-Helix Bundle Structure of a Polypeptide
Authors: Nishino Norikazu , Mihara Hisakazu , Uchida Toshiharu , Fujimoto Tsutomu
Published: March 2006

Dansylaminoalanine and tryptophan were separately incorporated into the α-helical segments of the four α-helix bundle structure of a 53-peptide. The perfect transfer of fluorescence energy of the indolyl group to the dansyl moiety was observed in aqueous solution by the emission at 480 nm upon excitation at 280 nm. The addition of MeOH unfolded the bundle structure and resulted in the interruption of the efficient energy transfer.
Decomposition of Chlorinated Hydrocarbons in Aqueous Solutions by Ultrasonic Irradiation
Authors: Inazu Koji , Nagata Yoshio , Maeda Yasuaki
Published: March 2006

Trichloroethylene, tetrachloroethylene, 1,1,1-trichloroethane, chloroform and carbon tetrachloride in dilute aqueous solutions were rapidly decomposed to chloride anions, hydrogen, carbon monoxide and carbon dioxide by ultrasonic irradiation.
Tryptophan 2,3-dioxygenase-like Activity of Monoclonal Antibody Anchored by a Manganese(III) Porphyrin Complex
Authors: Ohkubo Katsutoshi , Ishida Hitoshi , Sagawa Takashi , Urabe Kenji , Seri Kei-ichi , Suga Mamoru
Published: March 2006

Anchoring of a manganese(III) porphyrin complex to monoclonal (or polyclonal) antibody performed with the p-nitrophenylamino moiety of the complex, and this antibody anchored by the metal complex showed efficient catalytic activity and stereoselective ability for tryptophan 2,3-dioxygenase like dioxygenolyses of N-acetyl- L(and/or D)-tryptophan methyl esters in THF/H2O (pH 8.0) under atmospheric O2 at 25 °C.
Crystal Structures of Cation-Radical Salts of a Bis(1,3-dithiole) Donor Containing a 1,2,5-Thiadiazole Unit
Authors: Yamashita Yoshiro , Tanaka Shoji
Published: March 2006

X-Ray analyses of PF6 and BF4 cation-radical salts of 4,7-bis(4,5-dimethyl-1,3-dithiol-2-ylidene)-4,7-dihydro-2,1,3-benzothiadiazole reveal that the PF6 salt showing a metallic behavior has a uniform stacking of donor molecules, while the BF4 salt showing a semiconducting behavior has a dimeric structure.
Infrared Spectra of Frozen Clay-Water System
Authors: Mizoguchi Masaru , Low Philip F
Published: March 2006

Infrared spectra of 0.12 mm thick frozen clay-water system were obtained at sub-zero temperature with a FTIR spectrometer. The absorbances at the frequency of 2700 cm−1 decreased gradually with increasing temperature. The freezing point depression determined by the absorbance increased with clay and salt concentrations.
Acid-catalyzed Facile Racemization of Axially Dissymmetric 2′-Hydroxy-1,1′-binaphthyl-2-carboxylic Acid
Authors: Oi Shuichi , Kawagoe Kazumasa , Miyano Sotaro
Published: March 2006

Axially dissymmetric 2′-hydroxy-1,1′-binaphthyl-2-carboxylic acid was synthesized and shown to rapidly racemize in 1 mol dm−3 sulfuric acid in dioxane at 100 °C. The lactone obtained from enantiomerically pure (S)-3 gave racemic 3 on hydrolysis, showing that the first example of a facile atropisomerization of 2,2′-disubstituted 1,1′-binaphthyls was ascribed to lactonization-ring opening.
Utility of 3,4-Dimethoxybenzyl (DMPM) Glycosides. A New Glycosylation Triggered by 2,3-Dichloro-5,6-dicyano-p-benzoquinone (DDQ) Oxidation
Authors: Inanaga Junji , Yokoyama Yasuo , Hanamoto Takeshi
Published: March 2006

A new glycosylation which proceeds through the formation of charge transfer (CT) complex of DMPM glycosides with DDQ followed by the oxidation-triggered fragmentation of the intermediates has been developed. Primary, secondary, and tertiary alcohols are used as glycosyl acceptors for the formation of 2-deoxyglycoside derivatives.
A New Glycosphingolipid from the Red Alga Corallina pilulifera
Authors: Ishida Ryoichi , Shirahama Haruhisa , Matsumoto Takeshi
Published: March 2006

A new glycosphingolipid, named coralipid, has been isolated from a red alga and its structure has been determined to be (6E,15′Z,2S,3S,4R,2′R)-N-(2′-hydroxy-15′-tetracosenoyl)-1-O-β-galactosyl-2-amino-6-octadecene-1,3,4-triol on the basis of spectral and chemical means.
Selectivity in Oxidation of Sulfides with Hydrogen Peroxide by [π-C5H5N+(CH2)15CH3]3PM12O403− and [π-C5H5N+(CH2)15CH3]3{PO4[M(O)(O2)2]4}3− (M = Mo or W)
Authors: Ishii Yasutaka , Tanaka Hiroyuki , Nishiyama Yutaka
Published: March 2006

Dramatical difference in selectivity was observed in the hydrogen peroxide oxidation of sulfides by [π-C5H5N+(CH2)15CH3]3PW12O403− (CWP) and [π-C5H5N+(CH2)15CH3]3{PO4[W(O)(O2)2]4}3− (PCWP) under the two-phase system using chloroform as the solvent. The oxidation of sulfides with 35% H2O2 by CWP afforded the corresponding sulfoxides in high selectivity (93–99%), while the same oxidation by PCWP gave sulfones exclusively.
A Stereoselective Synthesis of a Novel Model Compound of Carzinophilin Carrying the C6-C13 Unit with Correct Stereochemistry
Authors: Hashimoto Masaru , Terashima Shiro
Published: March 2006

The title synthesis was achieved by featuring stereocontrolled elaboration of the functionalized pyrrolidine-2-thione from 2,3,5-tri-O-benzyl-β-d-arabinofuranose and base-induced construction of an aziridine ring from the 5-mesyloxymethylpyrrolidine.
A New Aerobic Oxidation System Using Pd-Cu Catalysts in the Presence of CO
Authors: Miyamoto Masanori , Minami Yumiko , Ukaji Yutaka , Kinoshita Hideki , Inomata Katsuhiko
Published: March 2006

Oxidation of benzylic ethers, tosylamides, and 9,10-dihydroanthracene could be performed efficiently under O2 and CO atmosphere in the presence of PdCl2-CuCl2 catalysts to give the corresponding esters (lactones), amides and anthraquinone, respectively.
Synthesis of Oligosilanes by Electrolysis of Hydrosilanes
Authors: Kimata Yoshinori , Suzuki Hiroshi , Satoh Shin , Kuriyama Akira
Published: March 2006

The novel electrochemical reaction of hydrosilane compounds was investigated for the synthesis of polysilanes. The product obtained by electrolysis of Methylphenylsilane 1a was an oligosilane of Mn = 454 (GPC) in 60% yield, which consisted of Si-Si bonds for the main chain. When diphenylsilane was electrolyzed in a similar manner as 1a, the major product was a dimer in 23% yield.
Reactions of Aryl Azides with Cobaltadithiolenes. Substitution Reactions via Nitrene
Authors: Katsuta Hideaki , Noguchi Naoko , Inomata Yohsuke , Kajitani Masatsugu , Akiyama Takeo , Sugimori Akira
Published: March 2006

Two types of substitution reactions occur between arylnitrene from aryl azides (1) and a cobaltadithiolene, (η5-cyclopentadienyl)(1,2-dicyano-1,2-ethenedithiolato)cobalt(III): 1) replacements of S by arylimino groups and 2) replacements of S–CX=CX moiety of a cobaltadithiolene by a biradical form of nitrene to give (η5-cyclopentadienyl)(2-imino-κN-arene-1-thiolato-κS)cobalt(III) (5). The reaction of 1 with a cluster compound [Cp4Co4S6] gives also 5.
A Novel Transamination Induced by Terpyridine Ligand Coordinated on Cobalt(III) Ion
Authors: Jitsukawa Koichiro , Hata Tomio , Yamamoto Tetsuya , Kano Keiko , Masuda Hideki , Einaga Hisahiko
Published: March 2006

The reaction of salicylidene-l-alanine with the Co(III) complex involving 2,2′:6′,2″-terpyridine (terpy) in aqueous ethanol solution afforded a peculiar transamination to form the complex, [Co(α-hydroxy salicylidene-o-hydroxybenzylamine)(terpy)]+, whose structure has been confirmed by X-ray structure analysis and positive FAB mass spectrometry.
Synthesis of σ−π Conjugated Alternating Silylene-Diacetylene Copolymers and Their Optical and Electrical Properties
Authors: Fang Mao-Ching , Watanabe Akira , Matsuda Minoru
Published: March 2006

New σ-π conjugated alternating silylene-diacetylene copolymers, –[(SiMe2)m–C≡C–C≡C]n–, m = 1, 3, 4, and 6, were synthesized by the reaction of α,ω-dichloropermethylated oligosilanes with dilithiobutadiyne, LiC≡C–C≡CLi. The IR spectra clearly indicated the presence of diyne unit in the polymer backbone. The influence of the chain length m of the dimethylsilylene unit in the –[(SiMe2)m–C≡C–C≡C]n– backbone on the optical and the electrical properties was investigated.
10,10-Dimethylanthrone-2,7-dinitrene. A Planar-Constrained, Doubly-Disjoint High-Spin Molecule with a Singlet Ground State
Authors: Ling Chris , Lahti Paul M
Published: March 2006

Photolysis of 10,10-dimethylanthrone-2,7-diazide in a glassy matrix at 77 K gives the corresponding quintet dinitrene molecule with a singlet ground state (ΔE(S → Q) = 810 J/mol). This system shows disjoint exchange behavior in a case where conjugation is assured by an enforced planar geometry.
The Selectivity of NaZnPO4 in the Dehydrogenation of Alcohols
Authors: Aramendia M Angeles , Borau Victoriano , Jimenez César , M. Marinas José , Romero F José
Published: March 2006

This paper reports on the activity and selectivity of a NaZnPO4 catalyst in the gas-phase dehydrogenation of primary and secondary alcohols. The catalyst was synthesized here for the first time and exhibited excellent selectivity in the processes studied.
Rise in Transition Temperature of γ-Fe2O3 Particles to α-Fe2O3 by SiO2 Coating
Authors: Ohmori Masahiro , Deki Shigehito
Published: March 2006

Transition temperature(Tt) of acicular γ-Fe2O3 particles to α-Fe2O3 shifted to a higher temperature by SiO2 coating. X-ray diffraction patterns and magnetic properties measured by VSM showed that γ-Fe2O3 particles still existed at more than 600 °C. The stabilized γ-Fe2O3 particles were expected to be used as recording pigments for heat-stable recording media.
The Dansyl Group as a Molecular Probe for the Histochemical Localization of a Synthetic Fibronectin-related Peptide
Authors: Yamamoto Yasuo , Katow Hideki , Sofuku Shosuke
Published: March 2006

A fibronectin-related cystine peptide was synthesized and was connected with dansyl group to locate its binding sites in sea urchin embryo. The dansyl peptide bound to the basal surface of ectoderm and the primary mesenchyme cell.
Effects of Pretreatment of Zao Zhuang and Akabira Bituminous Coals with SiCl4-NaI Reagents on Pyrolytic Behavior of Extracts
Authors: Yamamoto Akira , Murata Satoru , Nomura Masakatsu
Published: March 2006

The effects of pretreatment of Zao Zhuang and Akabira coals with SiCl4-NaI reagents (for cleavage of ether bonds) on Curie-point pyrolytic behavior of the extracts were investigated. While this treatment showed a slight increase of extraction yield, the volatile yield of extracts greatly increased along with increasing amounts of highly condensed aromatic constituents in the volatile.
Reverse Water-Gas Shift Reaction Catalyzed by Ruthenium Cluster Anions
Authors: Tominaga Ken-ichi , Sasaki Yoshiyuki , Hagihara Kohnosuke , Watanabe Taiki , Saito Masahiro
Published: March 2006

Reverse water-gas shift reaction (H2 + CO2 → CO + H2O) was homogeneously catalyzed by anionic Ru cluster in the presence of bis(triphenylphosphine)imminium chloride ([PPN]Cl). The catalytic reaction was estimated to proceed via dehydrogenation of hydride cluster, followed by coordination of CO2 and electrophilic attack of proton on its oxygen atom in the presence of chloride anion.
Selective Photooxidation of Propane to Propanone over Alkali-ion-modified Silica-supported Vanadium Oxides
Authors: Tanaka Tsunehiro , Takenaka Sakae , Funabiki Takuzo , Yoshida Satohiro
Published: March 2006

The addition of alkali ions (Na, K and Rb) to silica-supported vanadium oxide results in the formation of surface vanadate species which is excited by the light with wavelengths of around 400 nm. Propanone was selectively formed from propane and oxygen over alkali-ion-modified silica-supported vanadium oxides by the photoirradiation of light with wavelengths of λ > 390 nm.
Fluorescence Analysis of ANS Interacting with Individual Laser-Trapped Microspheres Having Different Surface Properties
Authors: Pfeifer-Fukumura Ursula , Misawa Hiroaki , Fukumura Hiroshi , Masuhara Hiroshi
Published: March 2006

Polystyrene microspheres were modified with polar and nonpolar groups. A fluorescent probe with spectral properties sensitive to environments was used to characterize the surface. Using the technique of laser trapping the fluorescence spectrum of the dye could be observed from a single particle dispersed in solution.
Stereoselective Synthesis of 2-Alkylamino-N-(2′-alkylphenyl)succinimide Conformers
Authors: Kishikawa Keiki , Tsuru Isao , Kohmoto Shigeo , Yamamoto Makoto , Yamada Kazutoshi
Published: March 2006

Isolable conformers of 2-alkylamino-N-(2′-alkylphenyl)succinimide were stereoselectively synthesized by amination of N-(2′-alkylphenyl)maleimides. The rotational barrier and the α-methylation of them were investigated.
Substituent Effect on Gas Phase Basicity of cis 2-Phenyl-2-butene. Intrinsic Resonance Demand of α,α-Dialkylbenzyl Carbocations
Authors: Mishima Masaaki , Nakamura Hirotaka , Nakata Kazuhide , Fujio Mizue , Tsuno Yuho
Published: March 2006

The gas phase basicities of cis 2-aryl-2-butenes have been determined by measuring proton transfer equilibria. It has been shown that the substituent effect on the stability of the conjugate acid ion of the olefin, α-ethyl-α-methylbenzyl cation, is in complete agreement with that of α-cumyl cation, suggesting that α,α-dialkyl benzyl cations seem likely to be characterized by the r value of 1.0 given by the LArSR analysis.
Construction of the C46-C55 Fragment of Ciguatoxin
Authors: Oka Takahiro , Murai Akio
Published: March 2006

The compound with all the necessary functional groups of the KLM ring system in ciguatoxin, which is one of the most complicated toxic substances of marine origin, was synthesized stereoselectively. The crucial steps involve construction of the ethynyl alcohol, the δ-valerolactone, and the natural acetals.
Ion Complex Type of Novel Chiral Smectic C* Liquid Crystal Having Chiral Hydrogentartrate Counterion
Authors: Ujiie Seiji , Iimura Kazuyoshi
Published: March 2006

A chirally ionic liquid crystal (ICLC) was prepared by the complexation of L(+)-tartaric acid and an achiral mesogenic group (NLC) with an amine unit, and its liquid crystalline behavior was examined by DSC, polarizing microscopy, and X-ray techniques. Ionic ICLC formed smectic A and chiral smectic C* phases. Due to an ionic aggregation, ionic ICLC exhibited a higher mesomorphic-isotropic phase transition temperature when compared to nonionic NLC.
Facile Synthesis of Both syn and anti Homoallylic Alcohols from Allyl Chlorides via Organosilicon Intermediates
Authors: Kobayashi Shu , Nishio Koichi
Published: March 2006

Highly regio- and diastereoselective synthesis of homoallylic alcohols from allyl chlorides via organosilicon intermediates are attained. While syn homoallylic alcohols were prepared from (Z)-allyl chlorides, anti homoallylic alcohols were obtained from (E)-allyl chlorides. 1-Chloro-2,4-pentadiene reacted at the γ position of the diene system regioselectively.
2-Amino-1-phenyl-1,3-propanediol Derivatives. New Ligands for Asymmetric 1,4-Addition of Organozinc Reagents to Enones
Authors: Fujisawa Tamotsu , Itoh Satoru , Shimizu Makoto
Published: March 2006

In the presence of (1S,2S)-3-benzyloxy-2-morpholino-1-phenylpropanol derived readily from (1S,2S)-2-amino-1-phenyl-1,3-propanediol and nickel acetylacetonate, diethylzinc added to α,β-unsaturated ketones to give alkylated product in high optical purity (up to 95%ee). The effects of solvents and additives and the use of such ligands as a chiral catalyst were also investigated.
A New Synthetic Method of Macrocylic Lactones from ω-Iodoalkylacrylates
Authors: Abe Motoji , Hayashikoshi Takaoki , Kurata Takeo
Published: March 2006

When the photostimulated cyclization reaction of ω-iodoalkylacrylates was performed in the presence of metal hydride complexes such as sodium cyanoborohydride(NaBH3CN), sodium borohydride(NaBH4) and potassium borohydride(KBH4), the corresponding macrocyclic lactones were produced. The use of NaBH3CN led to the highest yield of lactones.
Quantitative Analysis of Ethanol in Water Solution by a Heterocontact-type Sensor of CuO/ZnO
Authors: Hirota Koitsu , Miyayama Masaru , Nakamura Yoshinobu , Yanagida Hiroaki
Published: March 2006

Methods of quantitative analysis in the system of ethanol-water were investigated using a heterocontact-type sensor consisted of semiconducting ceramics of copper oxide (CuO) and zinc oxide (ZnO). The current-voltage (I-V) characteristics of the heterocontact in the solutions changed depending on the ethanol concentration when measured at AC 50 Hz at room temperature. It was found that the ethanol concentration can be determined quantitatively by analyzing the shape of I-V hysteresis loop.
The Oxidation of Dimethyl 2-Hydroxy-5-isopropylazulene-1,3-dicarboxylat and Its 6-Isopropyl Isomer with Lead Dioxide - The First Formation of a Diethenodicyclopenta[ef:kl]heptalene Derivative -
Authors: Lin Yun-Shan , Lin Shih Jue , Huang Tian-Chyuan , Chen Fa-Ching , Morita Tadayoshi , Kurihara Teruo , Nozoe Tetsuo
Published: March 2006

Oxidation of dimethyl 2-hydroxy-6-isopropylazulene-1,3-dicarboxylate (1a) with lead dioxide in acetic acid gave a 1,1′-bi-[2(1H)azulenone] derivative in good yield. The similar reaction of 5-isopropyl isomer of 1a gave two 1,1′-bi-[2(1H)azulenone] and a novel diethenoazupyrene derivative, as the first example, through 1,6′-coupling reaction followed by intramolecular Diels-Alder type cyclization.
Mg2+-Selective Electrode Comprising Double-Helical DNA as Receptive Entity
Authors: Maeda Mizuo , Nakano Koji , Uchida shinji , Takagi Makoto
Published: March 2006

Cyclic voltammograms of ferrocyanide/ferricyanide redox couple with a DNA-immobilized electrode gave the peak currents due to the reversible electrode reaction, which were significantly enhanced on adding Mg2+. The electrode responded also to Ca2+ and Ba2+, although the onset concentrations of the electrode response were 50-times larger than that for Mg2+. The selectivity in the order of Mg2+ > Ca2+, Ba2+ >> Na+, K+ seems consistent with the binding affinity of the metal ions with double-helical DNA.
A New Alkoxyiodination and Nitratoiodination of α,β-Unsaturated Ketone and Ester Using Iodine-Cerium(IV) Ammonium Nitrate
Authors: Horiuchi C Akira , Ochiai Keiko , Fukunishi Hirotada
Published: March 2006

Reaction of α,β-unsaturated ketones and electron-deficent unsaturated esters with iodine-cerium(IV) ammonium nitrate in alcohols (methanol, ethanol, or 1-propanol) under 0 °C-reflux gave the corresponding β-alkoxy-α-iodoketones and esters in good yields. In the case of acetonitrile and acetonitrile-water, β-nitrato- and β-hydroxy-α-iodo compounds were obtained, respectively.
The Effect of Substitution of 3-Perylenyl Group, an Aromatic Nucleus with a Very Low Triplet Energy, on Photochemical Isomerization of the Unsaturated Bond. Direct Observation of Triplet State Isomerization of a Styrene Derivative
Authors: Arai Tatsuo , Takahashi Osamu , Asano Tomoyuki , Tokumaru Katsumi
Published: March 2006

3-Styrylperylene undergoes one-way cis → trans photoisomerization in the triplet state through a quantum chain process. The conversion of cis to trans triplet state was directly observed by laser spectroscopy to proceed with an activation energy of 6.6 kcal mol−1. This finding clearly demonstrates that in the series of styrylarenes, ArCH=CHPh, lowering of the triplet excitation energy of Ar group alters the mode of isomerization from two-way to one-way.
Activated Basic Alumina Promotes a Mild, Clean and High-Yield Racemization-Free Synthesis of t-Butyl Esters from Chiral Acid Bromides and t-Butyl Alcohol
Authors: Nagasawa Kazuo , Ohhashi Keiko , Yamashita Asami , Ito Keiichi
Published: March 2006

Esterification of a variety of acid bromides having even steric bulkiness with t-BuOH/activated basic alumina gave the corresponding t-butyl esters in good to excellent yields. In the case of chiral acid bromides, no racemization has been ascertained for the first time.
Construction of Chiral 2-Functionalized Piperidine via Enzymatic Resolution and Palladium-catalyzed N-Alkylation
Authors: Hirai Yoshiro , Nagatsu Mayumi
Published: March 2006

The palladium-catalyzed cyclization of the optically active urethan [(−)-1], which was obtained by enzymatic resolution of the racemic alcohol (1), gave the piperidine 6. This reaction affords highly efficient intramolecular chirality transfer. Compound 6 was converted into (+)-coniine and 2-hydroxymethylpiperidine.
A Novel Chiral Catalyst System, Tin(II) Triflate, a Chiral Diamine, and Tin(II) Oxide, in Asymmetric Aldol Reactions
Authors: Kobayashi Shu , Kawasuji Takashi , Mori Nobuaki
Published: March 2006

In the presence of a novel chiral catalyst system consisting of tin(II) triflate, a chiral diamine, and tin(II) oxide, highly enantioselective aldol reactions of the silyl enol ether of S-ethyl ethanethioate or S-ethyl propanethioate with aldehydes proceeded smoothly to afford the aldol adducts in high yields.
Asymmetric Oxidation of 1,9-Bis(methylthio)dibenzothiophene and First Determination of Optically Active l-Menthoxy Sulfonium Salt by X-Ray Crystallographic Analysis
Authors: Kimura Takeshi , Nakayama Hidetaka , Furukawa Naomichi
Published: March 2006

l-Menthoxy sulfonium salt of 1,9-bis(methylthio)dibenzothiophene was isolated, and the structure was first determined by X-ray crystallographic analysis.
Thermal Stability and Specific Dye Binding of a Hydrogen-Bond-Mediated Bilayer Membrane
Authors: Kimizuka Nobuo , Kawasaki Takayoshi , Kunitake Toyoki
Published: March 2006

A novel aqueous bilayer membrane that is formed from amphiphilic complexes of complementary hydrogen bond pairs provided a specific dye binding site similar to that of the conventional ammonium bilayer. Partial dissociation of the hydrogen bond pairs and the consequent component separation occurred by heating the aqueous bilayer to 80–100 °C.
Highly-selective Li+ Transport through Liquid Membranes with Oligomethylene-bridged Bisphenanthroline Derivatives
Authors: Sugihara Hideki , Collin Jean-Paul , Hiratani Kazuhisa
Published: March 2006

Newly prepared oligomethylene-bridged bisphenanthrolines have been found to transport lithium ion with excellent selectivity among alkali metal ions through chloroform liquid membrane.
Diastereoselective Control of Aggregation of 31-Epimeric Zinc Methyl Bacteriopheophorbides-d in Apolar Solvents
Authors: Tamiaki Hitoshi , Takeuchi Shoichiro , Tanikaga Rikuhei , Balaban Silviu T , Holzwarth Alfred R , Schaffner Kurt
Published: March 2006

Visible absorption spectra of the in-vitro oligomers of the 31-epimeric zinc methyl bacteriopheophorbides-d are different in apolar organic solvents. This indicates structural differences between these oligomers which are controlled by the configuration of the 1-hydroxyethyl group at C-3.
Poly(sulfonium cation) for Synthesis of High Molecular Weight Poly(phenylene sulfide)
Authors: Shouji Eiichi , Nishimura Shinji , Yamamoto Kimihisa , Tsuchida Eishun
Published: March 2006

Solution viscosity of Poly(methyl 4-phenylthiophenylsulfonium trifluoromethanesulfonate) as a novel polycation was measured in aqueous acetonitrile solution and formic acid. In the presence of sodium trifluoromethanesulfonate as supporting electrolyte, K and α values are determined to be K = 7.46 × 10−7 and α = 1.30 of Mark–Houwink equation in formic acid, in which the molecular weight of the poly(sulfonium cation) is estimated from that of poly(phenylene sulfide).
s-cis-(Z,Z) Structure of 1,2-Bis(2-pyridyl)ethylene Dianion in Solution
Authors: Yokoyama Yukihiro , Kikuchi Osamu , Koizumi Terutake , Takahashi Kensuke
Published: March 2006

The 1H, 7Li and 13C NMR spectra have been observed for the dilithium salt of 1,2-bis(2-pyridyl)ethylene in solution. The dianion in solution exists only one species with fixed s-cis-(Z,Z) configuration in contrast to stilbene dianion.
Design and Synthesis of Fibronectin-related Peptides. Ala-analogs of RGDSPASS Containing Cystine Peptide (FR-1)
Authors: Yamamoto Yasuo , Katow Hideki , Sofuku Shosuke
Published: March 2006

The Arg-Gly-Asp (RGD) sequence is an active site in the cell-binding domain of fibronectin. Ala-analogs of RGDSPASS containing cystine peptide (FR-1) were synthesized to investigate the relationship between the functional group and the biological activity of FR-1.
Confirmation of Poly(1,3-dioxolan-2-one) Degrading Microorganisms in Environment
Authors: Nishida Haruo , Tokiwa Yutaka
Published: March 2006

Ecological biodegradability of aliphatic polycarbonates in different environments was estimated by the clear-zone method with an agar medium containing emulsified polycarbonates. It was found that poly(1,3-dioxolan-2-one) can be degraded by microorganisms in certain limited environments.
Improvement in Adsorption Capacity of Nitrogen over X-type Zeolites by n-Hexane Plasma Processing and Heat Treatment
Authors: Sakata Yusaku , Hayashi Shigeya , Funada Ichiro , Kasaoka Shigeaki
Published: March 2006

The X- and Y-type Faujasite zeolites were modified with n-hexane plasma processing followed by thermal treatment at 600 °C to produce the carbon coated zeolites. Amount of carbon coated was up to 2.8 wt% for Ca-X zeolite, depending on the time of plasma processing. Although the pore volume of the zeolites was reduced by the carbon modification, the adsorption uptake of N2 at 30 °C increased preferentially to that of O2 and/or Ar only for the modified X-type zeolites. The increase of the N2 uptake was up to 150% for the Na-X zeolite at carbon coating around 1 wt%. Both H2O–DSC and NH3–TPD measurements supported that carbon cluster from plasma processing was present in the Faujasite cage.
Photoreactions of Palladium Phosphine Complex with Chloroalkane. Production of Ethylene with 1,2-Dichloroethane and Novel Photochromic Behavior
Authors: Tsubomura Taro , Itsuki Atsushi , Homma Masahiko , Sakai Ken
Published: March 2006

Photoirradiation on [Pd02(dppm)3] (dppm = bis(diphenylphosphino)methane) in 1,2-dichloroethane solution with visible light yields [PdI2Cl2(dppm)2] (2) and ethylene quantitatively. Irradiation of 2 in various solutions shows interesting photochromic behavior.
N-Salicylidene-2-aminopyridine as a Photochromic Guest for Deoxycholic Acid Crystal Lattice Cavities
Authors: Kawato Toshio , Koyama Hiroyuki , Kanatomi Hajime , Yonetani Kazumi , Matsushita Hideki
Published: March 2006

Deoxycholic acid formed a definite inclusion compound with non-photochromic N-salicylidene-2-aminopyridine.The guest Schiff base exhibited photochromism within the clathrate cavities. First-order rate constants for the thermal bleaching reaction of the photochrome were measured by reflectance spectrophotometry.
Synthesis of [35](1,2,3,4,5)Cyclophane
Authors: Shinmyozu Teruo , Hirakida Mihoko , Kusumoto Shirou , Tomonou Mie , Inazu Takahiko , Rudzinski Jerzy M
Published: March 2006

[35](1,2,3,4,5)Cyclophane 3 was synthesized by an acid-catalyzed eyclization between a pseudogeminally substituted acetyl group and a chloromethyl group of a tetra-bridged compound followed by two-step hydrogenation of the resulting penta-bridged bromo-olefin. 3 shows the strongest transannular π–π interaction among [m.n]- and multibridged benzenophanes synthesized so far. 3 is conformationally mobile at room temperature in CD2Cl2, and two conformers 3a and 3b are observed at −90 °C.
Molecular Ferromagnet, PM[VO(hfac)2]2 (PM = pyrimidine, hfac = 1,1,1,5,5,5-hexafluoropenta-2,4-dionate). Ferromagnetic Assembly of Ground High-Spin Molecules
Authors: Mitsubori Shin-ichi , Ishida Takayuki , Nogami Takashi , Iwamura Hiizu , Takeda Naoya , Ishikawa Masayasu
Published: March 2006

A ferromagnetic transition was observed at about 0.14 K in the molecular crystals of the title complex. The isothermal magnetization measured at 85 mK (below Tc) showed an S-shaped curve characteristic of a ferromagnet with a small hysteresis. The present system realizes the high-spin molecule toward molecular-based ferromagnets.
Effect of Substitution of a 2-Anthryl Group at the N=N and N=C Unsaturated Bonds on Their Photoisomerization in the Triplet State
Authors: Karatsu Takashi , Shiga Tsutomu , Kitamura Akihide , Arai Tatsuo , Sakuragi Hirochika , Tokumaru Katsumi
Published: March 2006

Substitution of a 2-anthryl group at the nitrogen of N=NPh and N=CHPh bonds led to mutual isomerization between Z and E isomers on triplet sensitization giving photostationary mixtures very much rich in E isomers, although the substitution at the carbon of CH=NPh bond resulted in one-way Z → E isomerization in the triplet state likewise to CH=CHPh and C(CH3)=NOCH3 bonds.
Lanthanoid Triflate Catalyzed Conjugate Addition of Amines to α, β-Unsaturated Esters. A Facile Route to Optically Active β-Lactam
Authors: Matsubara Seijiro , Yoshioka Masahito , Utimoto Kiitiro
Published: March 2006

Catalytic amount of lanthanoid(III) triflates promoted the conjugate addition of amines to 2-alkenoic acid esters to give β-amino esters. The reaction of benzylamine with α,β-unsaturated esters containing a stereogenic center at γ-position proceeded diastereoselectivity to yield optically active β-lactam precursors.
Polysilane Synthesis by Catalytic Disproportionation of Alkoxydisilanes
Authors: Kabeta Keiji , Wakamatsu Shigeru , Imai Takafumi
Published: March 2006

Network polysilanes with methyl, phenyl, and ethoxy groups (Mw 530–7000) were prepared by a catalytic disproportionation reaction of methylethoxydisilanes in the presence of phenylethoxysilanes. Hexyl or cyclohexyl groups were also incorporated into polysilanes when corresponding alkoxysilanes were employed. Reaction of pentamethylethoxydisilane clarified a mechanism of the reaction.
Photoprotein of Luminous Squid, Symplectoteuthis oualaniensis and Reconstruction of the Luminous System
Authors: Takahashi Hiroyuki , Isobe Minoru
Published: March 2006

The photoprotein in the luminous squid, Symplectoteuthis oualaniensis, was extracted in high salt solutions at low temperatures. It was partially purified to show bioluminescence when warmed to room temperature. To the resulting protein solution after this luminescence, three solutions containing dehydrocoelenterazine, its DTT adduct and GSH adduct were added to observe immediate light, respectively. These recorded the first reconstruction of the luminous system in this squid. Coelenterazine, however, gave only weak light in 2 h after addition.
Selective Electrochemical Formyl Hydrogen-Exchange Fluorination of Aliphatic Aldehydes to Prepare Acyl Fluorides Using HF-Base Solutions
Authors: Yoneda Norihiko , Chen Sheng-Qi , Hatakeyama Tsuyoshi , Hara Syoji , Fukuhara Tsuyoshi
Published: March 2006

The selective displacement of formyl hydrogen (–(C=O)–H) to fluorine in aliphatic aldehydes was successfully carried out electrochemically to give acyl fluorides in base-nHF (base: pyridine or Et3N, n = 3–6) electrolyte solution with or without solvents such as acetonitrile and sulfolane.
Reduction of CO2 with H2O on TiO2(100) and TiO2(110) Single Crystals under UV-irradiation
Authors: Yamashita Hiromi , Kamada Nobuhiro , He Hong , Tanaka Ken-ichi , Ehara Shaw , Anpo Masakazu
Published: March 2006

The reduction of CO2 with H2O was investigated on the single crystals of TiO2(100) and TiO2(110); the former TiO2(100) exhibiting a higher efficiency in the formation of CH4 and CH3OH than TiO2(110). Measurements of the intermediate species formed on the TiO2(100) single crystal were carried out using a high resolution electron energy loss spectroscopy (HREELS).
Nuclear Magnetic Resonance Spectroscopic Study on the Grafting of Ethylene Oxide onto the Interlayer Surface of γ-Zirconium Phosphate
Authors: Nakano Hideyuki , Ohno Takeshi , Yamanaka Shoji
Published: March 2006

The reaction products of γ-zirconium phosphate with ethylene oxide were analyzed by solid-state 31P magic-angle spinning (MAS) NMR, and 31P and 13C solution NMR spectroscopy. γ-Zirconium phosphate can be formulated as Zr(PO4)(H2PO4)·2H2O. Ethylene oxide molecules react with the interlayer H2PO4 groups, forming diester derivatives of ethylene and/or diethylene glycols.
Application of Anodically Oxidized Aluminium Wire to an Electrically Temperature-controlled Catalyst
Authors: Ohji Nobuyuki , Enomoto Nobuhito , Mizushima Takanori , Kakuta Noriyoshi , Nanba Tetsuya , Morioka Yoshio , Ueno Akifumi
Published: March 2006

Nickel metal particles incorporated into pores formed in the anodic alumina films on an aluminium wire was applied to electrically heated catalyst for hydrogenation of 1-butene.
Preparation of CdS Microcrystals Covalently Bound with Viologen Groups and Their Photoelectrochemical Properties
Authors: Torimoto Tsukasa , Maeda Kotaro , Sakata Takao , Mori Hirotaro , Yoneyama Hiroshi
Published: March 2006

CdS microcrystals (Q-CdS) covalently bound with 1-decyl-1′-(3-mercapto)propyl-4,4′-bipyridinium were prepared. The surface viologen groups picked up photo-generated electrons in the conduction band of Q-CdS particles, causing a decrease of their emission. Irradiation of these particles resulted in new absorption peaks which are assigned to viologen radical cation monomers and their dimers. The photo-reduced viologen groups can mediate photo-generated electron transfer from Q-CdS to methylene blue in solution.
Synthesis and Complex Crystal Structure of C60 with Symmetrical Donor of 2,3,6,7,10,11-Hexamethoxytriphenylene (HMT)
Authors: Chiang Long Y , Swirczewski John W , Liang Ken , Millar J
Published: March 2006

We have successfully synthesized the complex of C60 fullerene with a three-fold symmetrical donor of 2,3,6,7,10,11-hexamethoxytriphenylene (HMT). All spectroscopic data and analyses support the chemical composition of this complex as C60(HMT)2. Individually, each C60 fullerene sphere was found to be surrounded by four HMT molecules in distinctive tetrahedral arrangement. The closest distance from one C60 centroid to the next C60 centroid in the adjacent chain is 13.099 Å.
Preparation of Long Alkyl-substituted Oligothiophenes
Authors: Sato Masa-aki , Hiroi Masao
Published: March 2006

New hexyl-substituted oligothiophenes (sexi-, novi-, duodeci-, and quindeci-thiophenes) were prepared by a Ni(O)-catalyzed coupling reaction of a 5,5″-dibromo-3,3″-dihexyl-2,2′:5′,2″-terthiophene. The structures were determined by 1H NMR spectra, GPC data, and elemental analyses. Their π–π* transitions were compared with those of poly(alkylthiophenes).
Calix[4]arene-Capped Tetraphenylporphyrin. Synthetic Approach to a Chiral Capped Porphyrin with Regular C4 Symmetry
Authors: Nagasaki Takeshi , Fujishima Hiroyuki , Shinkai Seiji
Published: March 2006

A tetraphenylporphyrin capped with a calix[4]arene through four chiral pillars has been synthesized. This molecule retains C4 symmetry characteristic of porphyrins. The preliminary experiments indicated that the cavity shows unique guest-binding properties.
Synthesis of Cubic Pm3n Mesostructured Titanium Oxophosphate
Authors: Zhang Yifeng , Li Yongsheng , Sakamoto Yasuhiro , Terasaki Osamu , Che Shunai
Published: March 2006

A mesostructured titanium oxophosphate (designated as TOP) possessing a periodic three dimensional (3D) cubic symmetry has been synthesized for the first time, via using divalent cationic surfactants in a post-synthesis strategy. And it was further found that 3D cubic mesostructured TOP was more thermally stable than 2D hexagonal P6mm mesostructured counterpart.
Blue Electrophosphorescent Light-emitting Device Using a Novel Nonconjugated Polymer as Host Materials
Authors: Shao Ke-Feng , Xu Xin-Jun , Yu Gui , Liu Yun-Qi , Yang Lian-Ming
Published: March 2006

Blue electrophosphorescent organic light-emitting devices (PHOLEDs) were fabricated by doping a phosphorescent iridium complex, bis[(4,6-difluorophenyl)pyridinato-N,C2](picolinato)iridium(III) (Firpic) into a novel nonconjugated polymer, poly[(9,9-diethylfluoren-2,7-ylene)diphenylsilylene] (PF-Si). A device with the same configuration using the widely applied poly(9-vinylcarbazole) (PVK) as the host material was also prepared under the identical conditions for comparison. The luminance and current efficiency of the PF-Si:Firpic device were over four times higher than those of the PVK–Firpic device at a current density of 200 mA/cm2 (1260 cd/m2 vs 275 cd/m2, 0.61 cd/A vs 0.13 cd/A).
Size-controlled Gold-catalyzed Growth of Prussian Blue Nanopillars
Authors: Sunkari Sailaja , Nagashima Sayoko , Murata Masaki , Nishihara Hiroshi , Matsui Yoshitaka , Nishio Kazuyuki , Masuda Hideki
Published: March 2006

Size-dependent nanopillars of Prussian blue were obtained by chemical deposition technique and porous alumina membranes coated with a bottom gold layer.
Three-step α-Acylation of (E)-Cinnamate Esters with Inversion of Stereochemistry through Formation and Cleavage of Carbon–Pentamethylcyclopentadienyl Bonds
Authors: Uemura Minoru , Yorimitsu Hideki , Oshima Koichiro
Published: March 2006

The reaction of cinnamate esters with lithium pentamethylcyclopentadienide in the presence of chlorodiethylaluminum provides the corresponding 1,4-adducts in high yield. The adducts undergo α-acylation reaction upon treatment with lithium diisopropylamide and acid chlorides. Removal of the pentamethylcyclopentadienyl group by the action of base affords α-acylcinnamate esters, in which the aryl and alkoxycarbonyl groups are in cis relationship.
Photocatalytic Reduction in Microreactors
Authors: Matsushita Yoshihisa , Kumada Shinji , Wakabayashi Kazuhito , Sakeda Kosaku , Ichimura Teijiro
Published: March 2006

Photocatalytic reduction of benzaldehyde and nitrotoluene in microspace was investigated by using a microreactor with immobilized titanium dioxide. Advantages of a photocatalytic microreaction system which has a remarkably large surface-to-volume ratio have been examined.
Validation of Micelle Formation of Proteins and Determination of Their Critical Micelle Concentrations by Measuring Synchronous Light Scattering Signals Using a Common Spectrofluorometer
Authors: Zhao Hua Wen , Huang Cheng Zhi , Li Yuan Fang
Published: March 2006

Micellization of proteins was validated and a method was developed to determine their critical micelle concentration (CMC) values by measuring synchronous light scattering (SYLS) signals using a common spectrofluorometer.
Excellent Promoting Effect of Ba Addition on the Catalytic Activity of Ir/WO3–SiO2 for the Selective Reduction of NO with CO
Authors: Takahashi Atsushi , Fujitani Tadahiro , Nakamura Isao , Katsuta Yasuhiro , Haneda Masaaki , Hamada Hideaki
Published: March 2006

The catalytic performance of Ba-doped Ir/WO3–SiO2 for the selective reduction of NO with CO in an oxidizing atmosphere was investigated. The NO reduction activity and durability of the Ir/WO3–SiO2 catalyst were drastically improved by the addition of Ba. Ba played an important role to stabilize the catalytically active Ir–WOx (x < 3) sites of Ir/WO3–SiO2 during the reaction.
Structure and Electrochemical Property of Novel 1,4-Diselenins
Authors: Yamamoto Tatsuya , Ogawa Satoshi , Sato Ryu
Published: March 2006

Novel isomeric 1,4-diselenins constituted of five rings showed well-defined intermolecular interactions, π–π and Ch–Ch contacts, in crystals. Investigation of electrochemical properties for 1,4-diselenins revealed unusual redox properties by CV measurements.
Prevalence of naturally occurring viral infections, Mycoplasma pulmonis and Clostridium piliforme in laboratory rodents in Western Europe screened from 2000 to 2003
Authors: Schoondermark-van de Ven E M E , Philipse-Bergmann I M A , van der Logt J T M
Published: March 2006

In this report prevalence rates of rodent viruses in laboratory animals are presented based on routine serological screening of mouse and rat colonies from European institutes. The prevalences found during the period 2000–2003 are compared with those reported for 1981–1984 and 1990–1993. It is shown that some infections were eliminated from laboratory animal colonies (e.g. K-virus and polyomavirus) by taking preventative measures whereas other infections such as mouse hepatitis virus and parvoviruses remained at a high rate. Further decreases in prevalence rates in the last 10 years were found for infections such as pneumonia virus of mice, reovirus type 3, Sendai virus, sialodacryoadenitis/rat coronavirus and Mycoplasma pulmonis. The introduction of new detection methods showed that mouse parvovirus and rat parvovirus, both members of the Parvoviridae family, remain a major threat to laboratory mice and rats. Guineapig cytomegalovirus and parainfluenzavirus appeared to be the most prevalent agents among laboratory guineapigs. The importance of a standardized, up-to-date screening programme is discussed.
Facial atrophy in HIV-related fat redistribution syndrome: a plastic surgical perspective on treatment options and a look to the future
Authors: Abood Ahid , Ong Juling , Withey Simon , Johnson Margaret , Butler Peter
Published: March 2006

Approximately 50% of patients on highly active antiretroviral therapy (HAART) develop lipodystrophy with central and visceral fat accumulation and/or facial and limb atrophy. Although the exact mechanisms of this are not fully understood, the facial atrophy encountered is secondary to atrophy of the subcutaneous fat, and not the deeper fat pads, as has been suggested. More recently, the above features in combination with hyperlipidaemia and insulin resistance have been described and are referred to as HIV-related fat redistribution syndrome. This review looks at treatment options available for this stigmatizing condition.
Rectal gonorrhoea in men – is microscopy still a useful tool?
Authors: Grover D , Prime K P , Prince M V , Ridgway G , Gilson R J C
Published: March 2006

Rectal gonorrhoea (GC) in men may cause anal discharge or proctitis, but these symptoms have been shown to correlate poorly with rectal infection. Culture of Neisseria gonorrhoeae from an exposed site offers a readily available, sensitive and cheap diagnostic test, and is currently the gold standard for diagnosis; however, these results can take a few days and therefore do not offer an instant diagnosis. Gram staining of rectal smears for N. gonorrhoeae has a low sensitivity but a high specificity when performed by experienced personnel. We audited whether rectal microscopy increased the number of patients diagnosed and treated for rectal GC at initial presentation at one inner London genitourinary clinic over a 12-month period. One hundred and thirty-six episodes of rectal GC were identified in 132 men. In all, 134/136 had rectal microscopy of whom, 47/134 (35%) were smear-positive for GC. Of the 136 cases, 90 received antibiotics for GC at their first presentation. Twenty-four of 90 (27%) would not have been treated until culture results were available, if rectal microscopy had not been performed. These results suggest that rectal microscopy remains an important tool and increases the proportion of men treated for GC at their first attendance.
Population-based enrolment of adolescents in a long-term follow-up trial of human papillomavirus vaccine efficacy
Authors: Lehtinen M , Idänpään-Heikkilä I , Lunnas T , Palmroth J , Barr E , Cacciatore R , Isaksson R , Kekki M , Koskela P , Kosunen E , Kuortti M , Lahti L , Liljamo T , Luostarinen T , Apter D , Pukkala E , Paavonen J
Published: March 2006

We evaluated a study setting for assessment of the long-term vaccine efficacy (VE) of human papillomavirus (HPV) virus-like-particle (VLP) vaccine against cervical carcinoma. A total of 22,412 16- to 17-year old adolescent women from seven cities in Finland were invited by letter to participate in a phase III study of a quadrivalent HPV (types 6, 11, 16, 18) VLP vaccine, between September 2002 and March 2003. A total of 30,947 18-year old women were invited to participate as unvaccinated controls. These women were asked about their willingness to participate in an HPV vaccination trial and to fill a health questionnaire. These three population-based cohorts of adolescent women, including women vaccinated with HPV vaccine or placebo vaccine and unvaccinated control women, are systematically followed over time. The study cohort database will be linked with the Finnish Cancer Registry using cervical carcinoma in situ (CIS) and invasive cervical carcinoma (ICC) as endpoints. Assuming that the cumulative incidence of CIS and ICC over 15 years is 0.45%, and that there is no loss to follow-up, and power of 80%, the determination of 70% total VE will require 3357 HPV vaccine recipients, 3357 placebo vaccine recipients, and 6714 unvaccinated controls. At the baseline, 2632 (12%) of the invited adolescents volunteered to the phase III vaccination trial, and 6790 (22%) responded to the questionnaire study. During a recruitment period of 10 months, 874 HPV vaccine recipients, 875 placebo recipients and 1919 unvaccinated controls were enrolled. Population-based enrolment of large cohorts of vaccinated and unvaccinated adolescents for passive registry-based follow-up with cervical carcinoma as the end-point is feasible and currently going on in Finland.