Bulletin of the Chemical Society of Japan

Vol. 72, No. 12 (December, 1999)

RETRUN to the front page

Copyright (C) 1999 by The Chemical Society of Japan


CONTENTS


=============================
Accounts
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Positive Feedback Mechanism, Autocatalysis Mechanism, and Dependence on Atomic-Level Surface Structures in Electrochemical Oscillations for H2 O2 Reduction on Pt Electrodes

GO TO the graphical abstract

Yoshiharu Mukouyama, Shuji Nakanishi, and Yoshihiro Nakato*

pages 2573-2590


Carbon-Carbon Bond Cleavage and Selective Transformation of Zirconacycles

GO TO the graphical abstract

Tamotsu Takahashi,* Martin Kotora, Ryuichiro Hara, and Zhenfeng Xi

pages 2591-2602



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Headline Articles
=============================

Pd(II)- and Pt(II)-Linked Tetranuclear Complexes as Assembly Units for Higher Ordered Structures

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Masaru Aoyagi, Kumar Biradha, Makoto Fujita*,,

pages 2603-2606



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Articles
General and Physical
=============================

Numerical Study on the Chaotic Response of the Minimal Chemical Oscillator to a Sinusoidal Perturbation

GO TO the graphical abstract

Yoshihiro Sasaki

pages 2607-2615


Electrochemical Luminescence of ZnGa2 O4 and ZnGa2 O4 : Mn Semiconductor Electrodes. -Emission Mechanism under Cathodic and Anodic Polarization-

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Toshihito Ohtake, Noriyuki Sonoyama, and Tadayoshi Sakata*

pages 2617-2623


Chemically Induced Dynamic Electron Polarization in the Photoreduction of Aromatic Ketones with * -Type Triplet State

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Akio Kawai,* Tetsuya Yamamoto, Tetsuo Okutsu, and Kinichi Obi

pages 2625-2632


Time-Resolved Measurements of the Gas-Phase Reaction of Mo2 (X 1 g+ ) with Some Simple Molecules at Room Temperature

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Yo-ichi Ishikawa,* Yoshitaka Matsumoto, and Tomohiro Wakabayashi

pages 2633-2641


Characterization of CO- and H2 -Adsorbed Au6 Pt-Phosphine Clusters Supported on SiO2 by EXAFS, TPD, and FTIR

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Youzhu Yuan, Kiyotaka Asakura,, Huilin Wan, Khirui Tsai, and Yasuhiro Iwasawa*

pages 2643-2653


89 Y MAS NMR in Red Phosphor, Eu-Doped Y2 O2 S. Assignment of Peaks Shifted by Paramagnetic Eu3+ , Spin Lattice Relaxation Time, and Eu Distribution

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Toshie Harazono,* Ryuji Adachi, Naoto Kijima, and Tokuko Watanabe

pages 2655-2664


Quantum Control of the Photodissociation of Sodium Iodide

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Kunihito Hoki, Yukiyoshi Ohtsuki, Hirohiko Kono, Yuichi Fujimura,* and Shiro Koseki

pages 2665-2671



=============================
Articles
Analitical and Inorganic
=============================

Flow-Type Chemiluminescence Detection Cell Using an Optical Fiber for Capillary Electrophoresis

GO TO the graphical abstract

Masahiko Hashimoto, Takeshi Nakamura, Kazuhiko Tsukagoshi,* Riichiro Nakajima, and Kazuo Kondo

pages 2673-2679


Adduct Polymers and Dimers of Rhodium(II) Pivalate with Pyrazine, 4,4' -Bipyridine, 1,4-Diazabicyclo[2.2.2]octane, Triethylamine, and Pyridine

GO TO the graphical abstract

Makoto Handa,* Mayumi Watanabe, Daisuke Yoshioka, Seiichiro Kawabata, Ryoji Nukada, Masahiro Mikuriya,*, Hiroshi Azuma, and Kuninobu Kasuga

pages 2681-2686


Synthesis and Characterization of Some Cationic 3 -Propargylpalladium Complexes

GO TO the graphical abstract

Ken Tsutsumi,* Tomohiro Kawase, Kiyomi Kakiuchi, Sensuke Ogoshi,*, Yuji Okada, and Hideo Kurosawa*,

pages 2687-2692


Extracted Species of Rare Earth Elements Using Bis(1,1,3,3-tetramethylbutyl)phosphinic Acid as an Extractant and Their Effective Mutual Separation by High-Performance Extraction Chromatography

GO TO the graphical abstract

Qiu-quan Wang, Ben-li Huang, Kin-ichi Tsunoda,*, and Hideo Akaiwa

pages 2693-2697


Mixed-Valence Ammonium Trivanadate with a Tunnel Structure Prepared by Pyrolysis of Polyoxovanadate

GO TO the graphical abstract

Haruo Naruke and Toshihiro Yamase*

pages 2699-2702


Solvent Extraction Equilibria and Kinetics of Gallium(III) with 2-Thenoyltrifluoroacetone in the Absence and Presence of Trioctylphosphine Oxide in Toluene

GO TO the graphical abstract

Meri Yamada, Shinya Suganuma, Ichiro Tanaka, Tatsuya Sekine*,

pages 2703-2711


Time-Resolved Near-Infrared Surface-Enhanced Raman Spectroscopy of a Surface-Confined Electrochemical Reaction of 9,10-Phenanthrenequinone

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Toshio Ishioka, Tatsuya Uchida, and Norio Teramae*

pages 2713-2717


Synthesis, Spectroscopy, Electrochemistry, and Mesomorphism of Triple-Decker Porphyrins Consisting of Two Cerium Ions and Three 5,15-Diarylporphyrins

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Hideya Miwa, Nagao Kobayashi,* Kazue Ban, and Kazuchika Ohta,*,

pages 2719-2728



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Articles
Orgainc and Biological
=============================

Formation of Lanthanide Complexes with Bipyridine-Functionalized Amide Compounds and Their Unusually High Amide Reactivity

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Satoshi Kawaguchi, Takeshi Kajikawa, Mariko Kaneko, Takahiro Koshimizu, and Koji Araki*

pages 2729-2736


Regioselective Synthesis of Nitrones by Decarboxylative Oxidation of N -Alkyl- -amino Acids and Application to the Synthesis of 1-Azabicyclic Alkaloids

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Hiroaki Ohtake, Yasushi Imada, and Shun-Ichi Murahashi*

pages 2737-2754


Liquid Crystallinity of 2-Acyl-7-[ p -(alkoxy)benzylideneamino]fluorenes

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Yutaka Takabayashi, Takeshi Yusa, Masahiro Minabe,* Takao Kimura, and Motohiro Tsubota

pages 2755-2760


Solvolysis of 2,2-Dialkylvinyl Iodonium Salt: Alkyl Participation and Possibility of a Primary Vinylic Cation Intermediate

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Tadashi Okuyama,* Hiroshi Yamataka, and Masahito Ochiai

pages 2761-2769


Mechanism of the Benzophenone-Sensitized Photolysis of O -Benzoyl- N -(1-naphthoyl)- N -phenylhydroxylamine in Cationic Micellar Media

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Tsuyoshi Kaneko, Tatsuya Tokue, Kanji Kubo, and Tadamitsu Sakurai*

pages 2771-2780


Different Aggregating Properties of Two Conformationally Frozen Isomers of a Water-Soluble Bridged Calix[6]arene

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Shigehisa Akine, Kei Goto,* Takayuki Kawashima, and Renji Okazaki*,

pages 2781-2783



=============================
Articles
Applied and Materials
=============================

Simple Determination Method of Degree of Substitution for Starch Acetate

GO TO the graphical abstract

Kazuo Ogawa,*, Ikuo Hirai, Choichiro Shimasaki, Toshiaki Yoshimura, Shin Ono,* Seichi Rengakuji, Yuuko Nakamura, and Isao Yamazaki

pages 2785-2790


Reversible Oxygen-Releasing from the Composite of Picketfence-Porphyrinatocobalt and Carbon in Response to a 1.5 V-Application

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Hiroyuki Nishide,* Yoko Suzuki, and Eishun Tsuchida*,

pages 2791-2794


Construction of Defect-Diminished Fatty Acid Langmuir-Blodgett Film and Its Optical Waveguide Properties

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Masami Yanagida, Atsushi Takahara, and Tisato Kajiyama*

pages 2795-2802


Pressure-Assisted Cold-Denaturation of Carboxypeptidase Y

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Shigeru Kunugi,* Hiroyuki Yamamoto, Miki Makino, Tomoko Tada, and Yukiko Uehara-Kunugi

pages 2803-2806



Bulletin of the Chemical Society of Japan [Graphical Abstracts]

Bulletin of the Chemical Society of Japan

Vol. 72, No. 12 (December, 1999)

RETRUN to the front page

Copyright (C) 1999 The Chemical Society of Japan


GRAPHICAL ABSTRACTS


=============================
Accounts
=============================


Copyright (C) 1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 72, 2573-2590 (1999) [Vol. 72, No. 12, December, 1999]

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Positive Feedback Mechanism, Autocatalysis Mechanism, and Dependence on Atomic-Level Surface Structures in Electrochemical Oscillations for H2 O2 Reduction on Pt Electrodes

Yoshiharu Mukouyama, Shuji Nakanishi, and Yoshihiro Nakato*


Illustration

Electrochemical reduction of H2 O2 on Pt electrodes shows various oscillations, depending on the electrode potential, the atomic-level flatness of the electrode surface, and the presence of adsorbed metal and halogen atoms. The general behavior, mechanisms, and features are surveyed.

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Copyright (C) 1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 72, 2591-2602 (1999) [Vol. 72, No. 12, December, 1999]

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Carbon-Carbon Bond Cleavage and Selective Transformation of Zirconacycles

Tamotsu Takahashi,* Martin Kotora, Ryuichiro Hara, and Zhenfeng Xi


Illustration

This account describes recent development in carbon-carbon bond cleavage reactions and selective transformation of 5-membered zirconacycles including zirconacyclopentanes, zirconacyclopentenes and zirconacyclopentadienes.

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=============================
Headline Articles
=============================


Copyright (C) 1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 72, 2603-2606 (1999) [Vol. 72, No. 12, December, 1999]

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Pd(II)- and Pt(II)-Linked Tetranuclear Complexes as Assembly Units for Higher Ordered Structures

Masaru Aoyagi, Kumar Biradha, Makoto Fujita*,,


Illustration

The formation of ...Pt(II)...Br-Pt(IV)... mixed-valence complexes was utilized for the assembly of Pt(II) containing macrocyclic complexes: e.g., the reaction of [(en)Pt(4,4' -bpy)]4 (NO3 )8 ( 1 , 4,4' -bpy = 4 ,4' -bipyridine) with [PtBr2 (en)2 ]Br2 gave a stair-like infinite network.

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=============================
Articles
General and Physical
=============================


Copyright (C) 1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 72, 2607-2615 (1999) [Vol. 72, No. 12, December, 1999]

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Numerical Study on the Chaotic Response of the Minimal Chemical Oscillator to a Sinusoidal Perturbation

Yoshihiro Sasaki


Illustration

The choatic response of the minimal chemical oscillator stimulated by a sinusoidal perturbation was studied by computer simulation. There were two types of chaos. The properties of these two types are described in detail and compared with the behaviors of a one-dimensional dynamical system.

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Copyright (C) 1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 72, 2617-2623 (1999) [Vol. 72, No. 12, December, 1999]

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Electrochemical Luminescence of ZnGa2 O4 and ZnGa2 O4 : Mn Semiconductor Electrodes. -Emission Mechanism under Cathodic and Anodic Polarization-

Toshihito Ohtake, Noriyuki Sonoyama, and Tadayoshi Sakata*


Illustration

Under cathodic polarization, emission of ZnGa2 O4 electrode showed a broad peak at 485 nm in Na2 S2 O8 electrolyte, while under strong anodic polarization at +12.5 V (vs. Ag/AgCl), electrochemical luminescence was observed accompanied by avalanche breakdown of the depletion layer of the ZnGa2 O4 electrode based on a impact excitation mechanism.

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Copyright (C) 1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 72, 2625-2632 (1999) [Vol. 72, No. 12, December, 1999]

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Chemically Induced Dynamic Electron Polarization in the Photoreduction of Aromatic Ketones with * -Type Triplet State

Akio Kawai,* Tetsuya Yamamoto, Tetsuo Okutsu, and Kinichi Obi


Illustration

Time-resolved ESR spectra of ketyl and anion radicals in the photoreduction of aromaticketone/triethylamine systems were measured. Anion radicals with absorption spin polarization were produced in ethanol with KOH, while ketyl radicals with emissive polarization were formed in cyclohexane and benzene. Possible CIDEP mechanisms were discussed for both radicals.

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Copyright (C) 1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 72, 2633-2641 (1999) [Vol. 72, No. 12, December, 1999]

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Time-Resolved Measurements of the Gas-Phase Reaction of Mo2 (X 1 g+ ) with Some Simple Molecules at Room Temperature

Yo-ichi Ishikawa,* Yoshitaka Matsumoto, and Tomohiro Wakabayashi

A multiphoton dissociation of volatile metal carbonyls was applied for pulse production of neutral metal species in the gas-phase kinetic study and its feasibility was discussed in the reaction system of Mo2 with small molecules at room temperature.

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Copyright (C) 1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 72, 2643-2653 (1999) [Vol. 72, No. 12, December, 1999]

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Characterization of CO- and H2 -Adsorbed Au6 Pt-Phosphine Clusters Supported on SiO2 by EXAFS, TPD, and FTIR

Youzhu Yuan, Kiyotaka Asakura,, Huilin Wan, Khirui Tsai, and Yasuhiro Iwasawa*


Illustration

A reversible structure transformation of SiO2 -supported Au6 Pt cluster by the adsorption-desorption of CO without any fragmentation of the Au6 Pt framework was observed by EXAFS as shown in the scheme below. The H2 adsorption at 298 K was weak and showed almost no contribution to the EXAFS.

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Copyright (C) 1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 72, 2655-2664 (1999) [Vol. 72, No. 12, December, 1999]

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89 Y MAS NMR in Red Phosphor, Eu-Doped Y2 O2 S. Assignment of Peaks Shifted by Paramagnetic Eu3+ , Spin Lattice Relaxation Time, and Eu Distribution

Toshie Harazono,* Ryuji Adachi, Naoto Kijima, and Tokuko Watanabe


Illustration

89 Y MAS (Magic angle spinning) NMR was investigated in order to study the local environment of Y sites in a red phosphor, Eu doped-Y2 O2 S (Eu-Y2 O2 S), with varying Eu content. Despite the presence of paramagnetic Eu3+ ions, high resolution spectra were acquired and a number of local environments were detected.

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Copyright (C) 1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 72, 2665-2671 (1999) [Vol. 72, No. 12, December, 1999]

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Quantum Control of the Photodissociation of Sodium Iodide

Kunihito Hoki, Yukiyoshi Ohtsuki, Hirohiko Kono, Yuichi Fujimura,* and Shiro Koseki


Illustration

A quantum control of the photodissocation of NaI NaI* Na + I was theoretically studied by using a locally optimized control method. The control was based on the following pump-and-dump scheme. The optimal dump pulses were shown to be of a linear up-chirp type.

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=============================
Articles
Analitical and Inorganic
=============================


Copyright (C) 1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 72, 2673-2679 (1999) [Vol. 72, No. 12, December, 1999]

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Flow-Type Chemiluminescence Detection Cell Using an Optical Fiber for Capillary Electrophoresis

Masahiko Hashimoto, Takeshi Nakamura, Kazuhiko Tsukagoshi,* Riichiro Nakajima, and Kazuo Kondo


Illustration

A flow-type chemiluminescence detection cell using an optical fiber was designed for capillary electrophoresis. Hydrogen peroxide was delivered through a three-way joint by a syringe pump and mixed with analytes at the capillary outlet. The present flow-type system provided a CL signal with high sensitivity, resolution, and reproducibility.

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Copyright (C) 1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 72, 2681-2686 (1999) [Vol. 72, No. 12, December, 1999]

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Adduct Polymers and Dimers of Rhodium(II) Pivalate with Pyrazine, 4,4' -Bipyridine, 1,4-Diazabicyclo[2.2.2]octane, Triethylamine, and Pyridine

Makoto Handa,* Mayumi Watanabe, Daisuke Yoshioka, Seiichiro Kawabata, Ryoji Nukada, Masahiro Mikuriya,*, Hiroshi Azuma, and Kuninobu Kasuga


Illustration

Adduct polymers and dimers of rhodium(II) pivalate ([Rh2 (O2 CCMe3 )4 ]) with pyrazine (pyz), 4,4' -bipyridine (4,4' -bpy), 1,4-diazabicyclo[2.2.2]octane (dabco), triethylamine (tea), and pyridine (py)) have been prepared. The tea adduct has a considerably long Rh-Rh bond (2.395(1) ).

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Copyright (C) 1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 72, 2687-2692 (1999) [Vol. 72, No. 12, December, 1999]

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Synthesis and Characterization of Some Cationic 3 -Propargylpalladium Complexes

Ken Tsutsumi,* Tomohiro Kawase, Kiyomi Kakiuchi, Sensuke Ogoshi,*, Yuji Okada, and Hideo Kurosawa*,


Illustration

The reactions of 1 -allenyl- and 1 -chloro(propargyl)palladium complexes with Ag+ afford cationic 3 -propargylpalladium complexes. The cationic 3 -propargylpalladium complex could be also observed as an equilibrium mixture with the 1 -allenyl(chloro)palladium one. The factors favoring 3 -coordination of the propargyl ligand are discussed.

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Copyright (C) 1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 72, 2693-2697 (1999) [Vol. 72, No. 12, December, 1999]

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Extracted Species of Rare Earth Elements Using Bis(1,1,3,3-tetramethylbutyl)phosphinic Acid as an Extractant and Their Effective Mutual Separation by High-Performance Extraction Chromatography

Qiu-quan Wang, Ben-li Huang, Kin-ichi Tsunoda,*, and Hideo Akaiwa


Illustration

The extracted species of rare earth elements (REEs) in bis(1,1,3,3-tetramethylbutyl)phosphinic acid (Hmbp)-HNO3 system was identified by the saturated extraction method, elemental analysis, IR, and 1 H NMR as being [M(mbp)3 (Hmbp)3 ] (M = REE ). The quantitative mutual separation of REEs was achieved on a Hmbp modified C18 column by high-performance extraction chromatography utilizing the characteristics of high selectivity and low acidity of Hmbp for REEs extraction, and pH gradient elution.

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Copyright (C) 1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 72, 2699-2702 (1999) [Vol. 72, No. 12, December, 1999]

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Mixed-Valence Ammonium Trivanadate with a Tunnel Structure Prepared by Pyrolysis of Polyoxovanadate

Haruo Naruke and Toshihiro Yamase*


Illustration

The pyrolysis of a polyoxovanadate solid, (NH4 )12 [V18 O42 (H2 O)].n H2 O (n 11 ), at 300 °C in an Ar+NH3 atmosphere gave a mixed-valence vanadium oxide, (NH4 )x V3 O7 (x 0.6 ), with a tunnel-structure. (NH4 )x V3 O7 comprises edge- and corner-sharing VIV/V O5 square-pyramids with an approximate ratio of VIV : VV 0.49 : 0.51 , to form a columnar cavity which accommodates ammonium N atoms.

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Copyright (C) 1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 72, 2703-2711 (1999) [Vol. 72, No. 12, December, 1999]

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Solvent Extraction Equilibria and Kinetics of Gallium(III) with 2-Thenoyltrifluoroacetone in the Absence and Presence of Trioctylphosphine Oxide in Toluene

Meri Yamada, Shinya Suganuma, Ichiro Tanaka, Tatsuya Sekine*,


Illustration

The solvent extraction of gallium(III) with Htta in toluene was enhanced by an addition of TOPO. TOPO also enhances the rate of extraction. The association of Htta and TOPO in toluene is very marked; the effects on the degree of and rate of extraction appear smaller than when no association is assumed. Extraction with Htta (), with Htta+TOPO (, , , ).

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Copyright (C) 1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 72, 2713-2717 (1999) [Vol. 72, No. 12, December, 1999]

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Time-Resolved Near-Infrared Surface-Enhanced Raman Spectroscopy of a Surface-Confined Electrochemical Reaction of 9,10-Phenanthrenequinone

Toshio Ishioka, Tatsuya Uchida, and Norio Teramae*


Illustration

A time-resolved surface-enhanced Raman measurement system was developed by combining step-scan and a near-infrared FT-Raman spectrometer. A redox reaction of 9,10-phenanethrenequinone on a gold electrode could be monitored in situ dynamically within 1 ms time resolution.

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Copyright (C) 1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 72, 2719-2728 (1999) [Vol. 72, No. 12, December, 1999]

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Synthesis, Spectroscopy, Electrochemistry, and Mesomorphism of Triple-Decker Porphyrins Consisting of Two Cerium Ions and Three 5,15-Diarylporphyrins

Hideya Miwa, Nagao Kobayashi,* Kazue Ban, and Kazuchika Ohta,*,


Illustration

Triple-decker sandwich complexes, which consist of two cerium ions and three strip-like diarylporphyrins substituted by long alkoxyl chains, have been synthesized. Their spectroscopic and electrochemical properties and mesomorphism are reported and compared with those of the corresponding double deckers and the parent monomers.

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Articles
Orgainc and Biological
=============================


Copyright (C) 1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 72, 2729-2736 (1999) [Vol. 72, No. 12, December, 1999]

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Formation of Lanthanide Complexes with Bipyridine-Functionalized Amide Compounds and Their Unusually High Amide Reactivity

Satoshi Kawaguchi, Takeshi Kajikawa, Mariko Kaneko, Takahiro Koshimizu, and Koji Araki*


Illustration

The amide bond of 1a -lanthanide complex was efficiently cleaved to give 2a and ester almost quantitatively at 30 °C.

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Copyright (C) 1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 72, 2737-2754 (1999) [Vol. 72, No. 12, December, 1999]

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Regioselective Synthesis of Nitrones by Decarboxylative Oxidation of N -Alkyl- -amino Acids and Application to the Synthesis of 1-Azabicyclic Alkaloids

Hiroaki Ohtake, Yasushi Imada, and Shun-Ichi Murahashi*


Illustration

Tungstate-catalyzed oxidation of N -alkyl- -amino acids with hydrogen peroxide under phase-transfer conditions gives regiochemically defined nitrones in satisfactory yields. Chiral cyclic nitrones, readily prepared from 4-(t -butyldimethylsilyloxy)- L -proline and 3-(t -butyldimethylsilyloxy)pyrrolidine, are successfully applied to the asymmetric synthesis of the Geissman-Waiss lactone, a monohydroxylated pyrrolizidine, and a monohydroxylated indolizidine.

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Copyright (C) 1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 72, 2755-2760 (1999) [Vol. 72, No. 12, December, 1999]

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Liquid Crystallinity of 2-Acyl-7-[ p -(alkoxy)benzylideneamino]fluorenes

Yutaka Takabayashi, Takeshi Yusa, Masahiro Minabe,* Takao Kimura, and Motohiro Tsubota


Illustration

The title compounds show only a smectic phase over a wide range of temperatures. The propionyl group is effective for the thermal stability of the mesophase compared to the acetyl group as an acyl substituent of the title substances. The Schiff base derived from 1- or 3-fluoreneamine scarcely shows liquid crystallinity.

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Copyright (C) 1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 72, 2761-2769 (1999) [Vol. 72, No. 12, December, 1999]

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Solvolysis of 2,2-Dialkylvinyl Iodonium Salt: Alkyl Participation and Possibility of a Primary Vinylic Cation Intermediate

Tadashi Okuyama,* Hiroshi Yamataka, and Masahito Ochiai


Illustration

Solvolysis of both E and Z isomers of the iodonium ( 1 ) tetrafluoroborate was carried out in various solvents at 60 °C. Extensive rearrangements mainly due to -alkyl participation followed by hydride shift were observed.

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Copyright (C) 1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 72, 2771-2780 (1999) [Vol. 72, No. 12, December, 1999]

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Mechanism of the Benzophenone-Sensitized Photolysis of O -Benzoyl- N -(1-naphthoyl)- N -phenylhydroxylamine in Cationic Micellar Media

Tsuyoshi Kaneko, Tatsuya Tokue, Kanji Kubo, and Tadamitsu Sakurai*


Illustration

The quantum yields for the sensitized photolysis of 1 in cationic micelles showed that 2 and 3 are derived from the radical pair existing at the micellar surface, whereas the radical pair that is penetrated deeply into the micellar interior is responsible for the appearance of 4 and 5 .

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Copyright (C) 1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 72, 2781-2783 (1999) [Vol. 72, No. 12, December, 1999]

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Different Aggregating Properties of Two Conformationally Frozen Isomers of a Water-Soluble Bridged Calix[6]arene

Shigehisa Akine, Kei Goto,* Takayuki Kawashima, and Renji Okazaki*,


Illustration

Two conformationally frozen isomers (cone and 1,2,3-alternate) of a water-soluble calix[6]arene were synthesized and found to show the critical micelle concentrations quite different from each other, which was explained in terms of their monomer structures with different arrangements of the charged groups.

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Articles
Applied and Materials
=============================


Copyright (C) 1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 72, 2785-2790 (1999) [Vol. 72, No. 12, December, 1999]

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Simple Determination Method of Degree of Substitution for Starch Acetate

Kazuo Ogawa,*, Ikuo Hirai, Choichiro Shimasaki, Toshiaki Yoshimura, Shin Ono,* Seichi Rengakuji, Yuuko Nakamura, and Isao Yamazaki


Illustration

Two peaks assigned to the COO- symmetric and asymmetric vibrations were observed for the difference spectra between the saponified starch acetate and the native starch. The peak areas linearly increased with increasing the degree of substitution (dS), suggesting that the dS values can be evaluated from the correlation.

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Copyright (C) 1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 72, 2791-2794 (1999) [Vol. 72, No. 12, December, 1999]

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Reversible Oxygen-Releasing from the Composite of Picketfence-Porphyrinatocobalt and Carbon in Response to a 1.5 V-Application

Hiroyuki Nishide,* Yoko Suzuki, and Eishun Tsuchida*,


Illustration

A disk was prepared with the powders of the oxygen-absorbing, but electrically insulating, 5,10,15,20-tetrakis( -o -pivalamidophenyl)porphyrinatocobalt(II)-N -tritylimidazole complex and of electrically conductive carbon. A 1.5 V-application induced a temperature elevation in the disk, which momentarily released the absorbed oxygen. The oxygen-releasing and -absorbing cycle could be repeated quickly.

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Copyright (C) 1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 72, 2795-2802 (1999) [Vol. 72, No. 12, December, 1999]

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Construction of Defect-Diminished Fatty Acid Langmuir-Blodgett Film and Its Optical Waveguide Properties

Masami Yanagida, Atsushi Takahara, and Tisato Kajiyama*


Illustration

A novel monolayer preparation method which was referred to as cooling multi-step creep method was described. The cooling multi-step creep method could provide the defect-diminished crystalline monolayer by control of both the thermal molecular motion in the monolayer and the structural relaxation induced by the area-creep.

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Copyright (C) 1999 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 72, 2803-2806 (1999) [Vol. 72, No. 12, December, 1999]

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Pressure-Assisted Cold-Denaturation of Carboxypeptidase Y

Shigeru Kunugi,* Hiroyuki Yamamoto, Miki Makino, Tomoko Tada, and Yukiko Uehara-Kunugi

The pressure and temperature dependence of the catalysis and fluorescence of carboxypeptidase Y was studied in the range of 5-40 °C and 0.1-400 MPa. In the high-pressure, lower-temperature region, disactivation and a fluorescence decrease were observed and explained by the so-called pressure-assisted cold-denaturation of the protein.

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