Copyright (C) 2003 The Chemical Society of Japan

Web Release Date: December 15, 2003

2233-2252 From How to Why. Graph-Theoretical Verification of Quantum-Mechanical Aspects of π-Electron Behaviors in Conjugated Systems  H. Hosoya [Full Text PDF(J-STAGE)]

Novel relations among the three bond orders, Coulson, Pauling, and topological, work as the key role in the graph-theoretical molecular orbital theory for explaining the topological dependency of the π-electronic structure of conjugated systems.

Web Release Date: December 15, 2003

2253-2266 Recent Progress in the Chemistry of Rare Earth Metal Alkyl and Hydrido Complexes Bearing Mono(cyclopentadienyl) Ligands  Z. Hou [Full Text PDF(J-STAGE)]

Rare earth metal alkyl and hydrido complexes bearing mono(cyclopentadienyl) ancillary ligands can show unique characteristics both in structure and in reactivity.

Web Release Date: December 15, 2003

2267-2275 p-tert-Butylthiacalix[6]arene as a Clustering Ligand. Syntheses and Structures of CoII5, NiII4, and Mixed-Metal MIINiII4 (M = Mn, Co, and Cu) Cluster Complexes, and a Novel Metal-Induced Cluster Core Rearrangement  T. Kajiwara,* R. Shinagawa, T. Ito,* N. Kon, N. Iki, and S. Miyano* [Full Text PDF(J-STAGE)]

When p-tert-butylthiacalix[6]arene (H6L) was used as a clustering ligand, homonuclear CoII5 and NiII4 and heteronuclear MIINiII4 (M = Co, Mn, and Cu) complexes were synthesized. The latter were derived from a novel metal-induced core rearrangement reaction of NiII4.

Web Release Date: December 15, 2003

2277-2283 Merocyanine Dye-Sensitization of Polythiophene in a Conjugated Polymer/TiO2 p–n Hetero-Junction Solar Cell  K. Imoto, K. Takahashi,* T. Yamaguchi, T. Komura, J. Nakamura, and K. Murata [Full Text PDF(J-STAGE)]

The enhanced photovoltaic properties in MC + PTh/TiO2 p–n hetero-junction solar cells are attributable to the dye-sensitization of the conjugated polymer. The solar cells are different from so-called Grätzel cell.

Web Release Date: December 15, 2003

2285-2292 Molecular Modeling of the Solvent Structuring of Chloroform around Cellulose Triacetate  I. Yu, K. Iwata, K. Ueda,* and H. Nakayama [Full Text PDF(J-STAGE)]

A molecular dynamics simulation was performed to investigate the solvation and dynamics behavior of chloroform around CTA. Chloroform is attracted to the carbonyl oxygen of CTA, but the interaction is weak. It causes a large fluctuation on the conformation of CTA.

Web Release Date: December 15, 2003

2293-2299 Hydration Structure around the Methylene Group of Glycine Molecule  M. Sasaki, Y. Kameda,* M. Yaegashi, and T. Usuki [Full Text PDF(J-STAGE)]

Neutron diffraction measurements have been carried out on H/D isotopically substituted aqueous 4 mol% glycine solutions. Information concerning the hydration structure around the methylene-hydrogen atoms of the glycine molecule is obtained from observed partial structure factors.

Web Release Date: December 15, 2003

2301-2305 Dynamics of n-Alkylammonium Ions Intercalated in Saponite  M. Yamauchi,* S. Ishimaru, and R. Ikeda [Full Text PDF(J-STAGE)]

Two-dimensional motional states of alkylammonium ions in the interlayer space of saponite were investigated by solid NMR. The intercalated organic cations exhibit unique motions characterized by distributed motional correlation times.

Web Release Date: December 15, 2003

2307-2313 Assemblies Possessing Rich Hydrogen Bonds Derived from trans-Oxamidato-Bridged Dicopper(II) Complexes and Carboxyl Auxiliary Ligands  H.-X. Zhang,* B.-S. Kang,* Z.-N. Chen, C.-Y. Su, and K.-B. Yu [Full Text PDF(J-STAGE)]

Assembly of trans-oxamidato-bridged unit [Cu2(trans-oxamidato)]2+ with the auxiliary ligand 4-hydroxybenzoic acid (Hhyba) or nicotinic acid (Hnic) provided three complexes [Cu2(trans-oxap)(nic)(H2O)2]n(ClO4)n·0.5nH2O 1, [Cu2(trans-oxen)(nic)2(H2O)2]·2H2O 2, [Cu2(trans-oxen)(hyba)2(H2O)2] 3. Their structures were determined by X-ray crystallography and the magnetic properties of 3 were studied.

Web Release Date: December 15, 2003

2315-2319 Adsorption of Phenols by Alkylamine-Intercalated α-Zirconium Phosphate  A. Hayashi, H. Nakayama, and M. Tsuhako* [Full Text PDF(J-STAGE)]

Alkylamine-intercalated α-ZrP could adsorb harmful pollutants such as phenol, chlorophenol, and 2,4-dichlorophenol. The adsorption amounts of phenols strongly depended on the content of alkylamine in the intercalation compound and on the hydrophobicity of phenols.

Web Release Date: December 15, 2003

Selected Paper 2321-2328 Structure and Electronic Properties of Biferrocene–TCNQ Charge-Transfer Complexes: Effects of Acceptors and Crystal Environment on the Mixed-Valence States  T. Mochida,* S. Yamazaki, S. Suzuki, S. Shimizu, and H. Mori [Full Text PDF(J-STAGE)]

The stable averaged valence states in TCNQ complexes of biferrocenes were found to be ascribable to the symmetrical crystal environment and the shielding of interactions by TCNQ columns, while valence localization in F4TCNQ salts can be rationalized by electrostatic interactions.

Web Release Date: December 15, 2003

2329-2333 N2O Removal by Catalytic Decomposition and Reduction with CH4 over Fe/Al2O3  M. Haneda,* M. Shinriki, Y. Nagao, Y. Kintaichi, and H. Hamada [Full Text PDF(J-STAGE)]

The catalytic removal of N2O over Fe/Al2O3 is effectively promoted by the addition of CH4. Catalyst characterizations revealed the presence of Fe2O3 and FeAlO3. The former acts as a catalytically active species for N2O decomposition, while the latter acts as that for N2O reduction.

Web Release Date: December 15, 2003

2335-2339 Kinetics and Mechanism of the Oxidation of Some α-Hydroxy Acids by Benzyltrimethylammonium Dichloroiodate  A. Goyal and S. Kothari* [Full Text PDF(J-STAGE)]

The oxidation of lactic, mandelic, and ten monosubstituted mandelic acids by benzyltrimethylammonium dichloroiodate in glacial acetic acid in the presence of zinc chloride involves a carbocationic transition state leading to the formation of the corresponding oxo acid.

Web Release Date: December 15, 2003

Selected Paper 2341-2352 Synthesis of Tetrahydropyran-2-carboxylic Acid Derivatives of Lipid A Containing an Olefin in Their Chains and Their LPS-Antagonistic Activities  Y. Watanabe, M. Shiozaki,* D. Tanaka, T. Shimozato, S. Kanai, and S. Kurakata [Full Text PDF(J-STAGE)]

These synthetic compounds showed LPS-antagonistic activities toward human monoblastic U937 cells, human whole blood cells and mouse peritoneal resident macrophages.

Web Release Date: December 15, 2003

2353-2360 On the Mechanism of the Oxidation of Toluenes in Artificial P450 Model Systems: Formation of Benzyl Alcohols, Benzaldehydes, and Phenols  T. Nakano,* S. Kawabata, T. Sugihara, N. Agatsuma, H. Kakuda, and Y. Mori [Full Text PDF(J-STAGE)]

The oxidation products in the systems (left) were mainly the corresponding benzyl alcohols and benzaldehydes. Curiously, the ratios (ald/alc) increased with the electronegativities of the substituents on the phenyl rings. We suggest that during the reactions benzyl radicals are attacked by a second oxidant.

Web Release Date: December 15, 2003

2361-2387 Fundamental Studies on the Structures and Spectroscopic Properties of Imidazo[1,2-a]pyrazin-3(7H)-one Derivatives  S. Nakai, M. Yasui, M. Nakazato, F. Iwasaki, S. Maki, H. Niwa, M. Ohashi, and T. Hirano* [Full Text PDF(J-STAGE)]

The fundamental physical properties of the π-system of 2-methyl and 2-phenylimidazopyrazinone and their N- and O-alkylated derivatives were investigated by X-ray crystallography, absorption spectroscopy, NMR, and MO calculation for explaining the chemi- and bioluminescence mechanism of imidazopyrazinone derivatives.

Web Release Date: December 15, 2003

Selected Paper 2389-2394 Syntheses and Structural Characterizations of a Novel Bowl-Type Germanol and Its Derivatives  K. Goto,* I. Shimo, and T. Kawashima* [Full Text PDF(J-STAGE)]

A novel bowl-type triarylgermyl group (denoted as TRMG) was designed, and a germanol and its derivatives bearing this framework were synthesized. The structures of TRMG–OH and TRMG–SH were established by X-ray crystallographic analysis.

Web Release Date: December 15, 2003

2395-2397 Enzymatic Synthesis of (R)-Flurbiprofen  Y. Terao, Y. Ijima, H. Kakidani, and H. Ohta* [Full Text PDF(J-STAGE)]

(R)-Flurbiprofen, which exhibits anti-cancer activity, was prepared via an enzymatic asymmetric decarboxylation of the corresponding malonate.

Web Release Date: December 15, 2003

Selected Paper 2399-2403 Copper-Catalyzed Oxidation of Amines with Molecular Oxygen  Y. Maeda, T. Nishimura, and S. Uemura* [Full Text PDF(J-STAGE)]

An improved system for selective aerobic oxidation of amines to nitriles is presented. It involves commercially available and inexpensive copper(I) or (II) chloride as catalyst, toluene as solvent, and MS3A as dehydrating agent.

Web Release Date: December 15, 2003

2405-2411 Factors Affecting the Conformational Preference and Magnetic Shielding of Isobutenylene Chains in Macrocyclic Salicylideneaniline Derivatives  H. Houjou,* S. Tsuzuki, Y. Nagawa, M. Kanesato, and K. Hiratani [Full Text PDF(J-STAGE)]

The relationship between the conformation and 1H NMR chemical shift of the isobutenylene chains was examined in detail. The relationship can be generalized, if the changes in the conformational preference and magnetic shielding are correctly taken into account.

Web Release Date: December 15, 2003

2413-2414 Charge-Transfer Quenching of Excited Ketones by Selenides  Y. Yamazaki, T. Nakamura, and T. Hasegawa* [Full Text PDF(J-STAGE)]

Diphenyl selenide and selenoxide quenched the Type II reaction of butyrophenone through a charge-transfer process more efficiently than the corresponding sulfide and sulfoxide. The irradiation of 2-(benzylseleno)ethyl benzoylacetate gave bis[2-(benzoylacetoxy)ethyl] diselenide and 1,2-diphenylethane.

Web Release Date: December 15, 2003

2415-2418 Pore Size Distribution and Porosities of Nano-TiO2 Films Made by Using Cellulosic Thickener and Their Influence on Performance of Dye-Sensitized Solar Cells  K.-J. Jiang, T. Kitamura, Y. Wada, and S. Yanagida* [Full Text PDF(J-STAGE)]

Morphology of mesoporous TiO2 film was controlled by addition of cellulosic thickener into the paste for doctor-blading. The dye-sensitized solar cell based on the TiO2 film showed conversion efficiency up to 6.4%.

Web Release Date: December 15, 2003

2419-2422 Immobilization of Aqueous Heavy Metal Cations with Phosphates and Sulfates  S. Sugiyama,* M. Fujisawa, T. Koizumi, S. Tanimoto, K. Kawashiro, T. Tomida, and H. Hayashi [Full Text PDF(J-STAGE)]

The immobilization of aqueous Pb2+, Cd2+, Co2+ and Cu2+ favorably proceeded with Na2HPO4, K2HPO4, MgHPO4 and CaHPO4 based on the dissolution–precipitation mechanism. The removal of Pb2+ with MgSO4 and CaSO4 was also possible.

Web Release Date: December 15, 2003

2423-2429 Preparation and Photochromic Properties of Powder and Films of DNA–Dodecyltrimethylammonium Ion Complex Containing Spiropyran Derivatives  M. Saito, K. Musha, Y. Yokoyama, and Y. Yokoyama* [Full Text PDF(J-STAGE)]

DNA–dodecyltrimethylammonium ion complex powder and films doped with spiropyrans showed thermally reversible photochromism.