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Vol. 80, No. 12 (December, 2007)
[PDF version]
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December 13, 2007
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2247-2261
Theoretical Studies of Chemical Reactions—A Fascinating World of Chemistry from Gas-Phase Elementary Reactions through Nanostructure Formation and Homogeneous Catalysis to Reactions of Metalloenzymes
K. Morokuma
[Full Text PDF(J-STAGE)] Free Access Article
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Author′s recent theoretical/computational studies of chemical reactions have been briefly reviewed, covering gas-phase photochemistry, fullerene and nanotube growth, homogenous catalyses and metalloenzymatic reactions. Theory of chemical reactions provide information not easily obtainable experimentally and is still a fascinating world.
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December 13, 2007
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| 2262-2269
Ionic Liquids Then and Now: From Solvents to Materials to Active Pharmaceutical Ingredients
W. L. Hough and R. D. Rogers*
[Full Text PDF(J-STAGE)] [n=li Information] Free Access Article
Ionic liquids have evolved from their original uses based on their tunable physical properties to unique materials based on their chemical properties and now to active pharmaceutical ingredients based on their biological properties. It seems that the only limit to their applications is one′s imagination.
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December 13, 2007
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| 2270-2284
Studies of Organic Protein Cofactors Using Electron Paramagnetic Resonance
S. Weber and R. Bittl*
[Full Text PDF(J-STAGE)] Free Access Article
Electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) are important tools to elucidate structural and electronic aspects of paramagnetic cofactors in proteins. In this account, emphasis is given to in-depth EPR/ENDOR characterizations of the quinone-type and flavin cofactors in ethanol dehydrogenase and photolyase, and the relative positioning of substrates.
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| The Chemical Society of Japan Award for 2005 |
Web Release Date:
December 13, 2007
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| 2285-2302
Studies on Two- and Three-Dimensional π-Conjugated Systems with Unique Structures and Properties
K. Komatsu
[Full Text PDF(J-STAGE)] Free Access Article
Rigid bicyclic frameworks surrounding two-dimensional π-conjugated systems are effective in stabilizing the corresponding cationic species, which have unique structures and properties. As an unusual three-dimensional conjugated system, endohedral fullerene encapsulating molecular hydrogen was synthesized.
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December 13, 2007
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| 2303-2312
Evidence for Encaging Luminescent Guest Molecules in the Inner Cages of Zeolite Host
T. Kataoka, A. J. Mozer, Y. Tsukahara, T. Yamauchi, and Y. Wada*
[Full Text PDF(J-STAGE)] [n=li Information] Free Access Article
Fluorescence of fluorescein located in the cages of a zeolite was not quenched by a quencher, whereas that of fluorescein adsorbed on the outer surface of the zeolite was effectively quenched, giving clear evidence for the location of fluorescein.
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| Web Release Date:
December 13, 2007
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| 2313-2322
Formation, Structure, and Stability of α- and β-Cyclodextrin Inclusion Complexes of Phenol and Benzoic Acid Derivatives in Vacuo and in Water
L. X. Song,* H. M. Wang, P. Xu, Z. Q. Zhang, and Q. Q. Liu
[Full Text PDF(J-STAGE)]
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The complexation energies (Δ Ecw), deformation energies (Δ Efw), hydration energies (Δ Ehw), and interaction energies (Δ Eiw) of the nineteen inclusion systems were calculated. Sufficiently large negative values of Δ Eiw clearly demonstrated that the formation of the inclusion complexes was energetically favorable.
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December 13, 2007
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| 2323-2328
DFT Analysis of Cubane-Type FeIr3S4 Clusters. Dinitrogen Binding and Activation at the Tetrahedral Fe Site
P. M. Kozlowski,* Y. Shiota, S. Gomita, H. Seino, Y. Mizobe,* and K. Yoshizawa*
[Full Text PDF(J-STAGE)] [n=li Information]
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Cubane-type mixed-metal sulfido clusters with a FeIr3S4 core and possible dinitrogen binding and activation were analyzed by density functional theory (DFT) calculations.
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December 13, 2007
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| 2329-2333
X-ray Diffraction Study on the Structure of Concentrated Aqueous Solutions Involving Alanine Molecules with Different Optical Activities
Y. Kameda,* A. Okuyama, Y. Amo, T. Usuki, and S. Kohara
[Full Text PDF(J-STAGE)]
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X-ray diffraction measurements on aqueous 2.5 mol % DL-, L-, and D-alanine solutions in D2O were carried out at 26 °C in order to obtain information concerning the difference in the hydrogen-bonded structure between aqueous solutions involving amino acid molecules with different optical activities.
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December 13, 2007
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| 2334-2341
NMR Study on Solubilization of Sterols and Aromatic Compounds in Sodium Taurodeoxycholate Micelles
K. Matsuoka,* S. Ishii, C. Honda, K. Endo, A. Saito, Y. Moroi, and O. Shibata
[Full Text PDF(J-STAGE)]
Image of the estimated pyrene solubilization site in the sodium taurodeoxycholate micelle. The bile salt containing methyl protons at 19 positions is directly influenced by the solubilized pyrene.
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| Web Release Date:
December 13, 2007
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| 2342-2349
Ferromagnetic Interactions in Non-Kekulé Polymers
M. Hatanaka* and R. Shiba
[Full Text PDF(J-STAGE)]
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Ferromagnetic interactions in non-Kekulé polymers were analyzed in relation to anti-parallel-spin instabilities in the product of the ν-th and (ν + 1)-th Wannier functions (PNBCOν,ν+1). The instabilities consisted of on-site and through-space amplitude product of PNBCOν,ν+1.
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December 13, 2007
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| 2350-2356
Cyano-Bridged Gadolinium–Tungstate Bimetallic One-Dimensional Chains with a Dimethylacetamide Ligand
W. Kosaka, K. Hashimoto, and S. Ohkoshi*
[Full Text PDF(J-STAGE)] [n=li Information]
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Reaction of GdIII(NO)3·6H2O and (Bu3NH)3[WV(CN)8] (Bu3N = tributylamine) in N,N-dimethylacetamide (DMA) yielded two types of Gd–W bimetallic one-dimensional chains with pyroelectric crystal structures: GdIII(DMA)n[WV(CN)8] (n = 6, 1; n = 5, 2).
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| Web Release Date:
December 13, 2007
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| 2357-2364
Synergistic Extraction and Solution Structures of Ternary Complexes of Lanthanoids with 2-Thenoyltrifluoroacetone and Linear Poly(oxyethylene) in 1,2-Dichloroethane
G. F. Gagabe, Y. Satoh, K. Satoh, and K. Sawada*
[Full Text PDF(J-STAGE)]
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Synergistic extraction of lanthanoid–tta complexes with linear poly(oxyethylene) (POE) is significantly enhanced by the formation of the 1:1 adduct in the organic phase. The structures of the POE adduct complexes, [Ln(tta)3·(POE)], in solution are proposed.
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December 13, 2007
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| 2365-2374
Syntheses, Structures, and Properties of a Series of Metal Ion-Containing Dialkylimidazolium Ionic Liquids
C. Zhong, T. Sasaki,* A. Jimbo-Kobayashi, E. Fujiwara, A. Kobayashi, M. Tada, and Y. Iwasawa
[Full Text PDF(J-STAGE)] [n=li Information]
A series of metal ion-containing ionic liquids [Bmim]2[MCl4] (M = Sn, Cu, Ni, Mn, Fe, Co, Zn, and Pt; [Bmim] = 1-butyl-3-methylimidazolium) and [Bmim]2[ZrCl6] were synthesized, and their structures were determined by X-ray crystallographic analysis. It was found unambiguously that these salts behave as ionic liquids.
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| Web Release Date:
December 13, 2007
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| 2375-2377
Spin-Crossover Behavior of Isomorphous Bi- and Mononuclear Iron(III) Complexes
S. Imatomi, T. Sato, T. Hamamatsu, R. Kitashima, and N. Matsumoto*
[Full Text PDF(J-STAGE)]
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Isomorphous bi- and mononuclear iron(III) complexes showed two-step spin-crossover (SCO) behavior with T1/2 = 60 and 90 K and a one-step SCO behavior at T1/2 = 215 K, respectively. The different SCO behavior was ascribed to one-dimensional structure constructed by π–π stacking and the binuclear structure.
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| Web Release Date:
December 13, 2007
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| 2378-2383
The β-Silicon Effect. III. Substituent Effects of the β-Si-Aryl Moiety in the Solvolysis of 1-Aryl-2-(aryldimethylsilyl)ethyl 3,5-Dinitrobenzoates
M. Fujio,* M. A. Alam, Y. Umezaki, K. Kikukawa, R. Fujiyama, and Y. Tsuno
[Full Text PDF(J-STAGE)]
The aryl substituent effect on the Si atom in the solvolysis of 1-aryl-2-(aryldimethylsilyl)ethyl system gave a remarkably small ρ value of ca. −1.0 with r = 0.1 in terms of the Yukawa–Tsuno Eq.
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| Web Release Date:
December 13, 2007
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| 2384-2388
Synthesis and Photocleavage of 7-[{Bis(carboxymethyl)amino}coumarin-4-yl]methyl-Caged Neurotransmitters
N. Senda, A. Momotake, and T. Arai*
[Full Text PDF(J-STAGE)]
7-[[Bis(carboxymethyl)amino]coumarin-4-yl]-caged neurotransmitters were synthesized, showed sufficient stability in the dark, were water-soluble at pH 7.2 without using organic solvents, and exhibited relatively high quantum yield for photolysis on irradiation with 390 nm light.
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December 13, 2007
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| 2389-2394
Optical Resolution of Selenonium Imides Stabilized by an 8-Dimethylamino-1-naphthyl Group
T. Soma, N. Kamigata,* K. Hirabayashi, and T. Shimizu*
[Full Text PDF(J-STAGE)]
Optically active selenonium imides, stabilized by intramolecular coordination of amino group of 8-(dimethylamino)-1-naphthyl group, were isolated by chromatographic resolution using optically active columns. Stereochemistry of the optically active selenonium imides was also examined.
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December 13, 2007
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| 2395-2399
Rumphellatins B and C, Two New Caryophyllane-Type Hemiketal Norsesquiterpenoids from the Formosan Gorgonian Coral Rumphella antipathies
P.-J. Sung,* L.-F. Chuang, and W.-P. Hu
[Full Text PDF(J-STAGE)]
Two new caryophyllane-type hemiketal norsesquiterpenoid alcohols, rumphellatins B (1) and C (2), were obtained from the gorgonian coral Rumphella antipathies. Structures of natural products 1 and 2 were established by analyzing the spectral data. Rumphellatin B (1) showed antibacterial activity toward the bacterium Staphylococcus aureus.
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December 13, 2007
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| 2400-2405
Synthesis of β,γ-Unsaturated Ketones from Acid Chlorides through Carbon–Pentamethylcyclopentadienyl Bond Formation and Cleavage
M. Uemura, M. Iwasaki, E. Morita, H. Yorimitsu,* and K. Oshima*
[Full Text PDF(J-STAGE)]
A new route to β,γ-unsaturated ketones is reported. Allylation of pentamethylcyclopentadienyl ketones, followed by removal of pentamethylcyclopentadiene, afforded β,γ-unsaturated ketones in good yields.
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December 13, 2007
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| 2406-2412
Enantioselective Trifluoromethylation of Ketones with (Trifluoromethyl)trimethylsilane Catalyzed by Chiral Quaternary Ammonium Phenoxides
H. Nagao, Y. Kawano, and T. Mukaiyama*
[Full Text PDF(J-STAGE)]
Trifluoromethylation of various ketones with (trifluoromethyl)trimethylsilane catalyzed by cinchonidine-derived quaternary ammonium phenoxides proceeded smoothly to afford optically active trifluoromethylated compounds in high yields with moderate to high enantioselectivities.
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December 13, 2007
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| 2413-2417
Nucleophilic Substitution Accompanying Carbon–Carbon Bond Cleavage Assisted by a Nitro Group
Y. Nakaike, N. Taba, S. Itoh, Y. Tobe, N. Nishiwaki,* and M. Ariga*
[Full Text PDF(J-STAGE)] [n=li Information]
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A 2-nitrated 3-oxoester reacted with amines to afford malonic acid amide esters due to the formation of an intimate pair, followed by pseudo intramolecular nucleophilic substitution.
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December 13, 2007
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| 2418-2424
Diastereoselective Allylation of 3,4-Dihydro-4-phenylisoquinoline. Convenient Methods for the Preparation of cis- and trans-1-Allyl-4-phenyl-1,2,3,4-tetrahydroisoquinoline
A. Taketoshi, N. Hosoda, Y. Yamaguchi, and M. Asami*
[Full Text PDF(J-STAGE)] [n=li Information]
Diastereoselective allylation reaction of 3,4-dihydro-4-phenylisoquinoline (1) was examined. Either cis- or trans-1-allyl-4-phenyl-1,2,3,4-tetrahydroisoquinoline was obtained predominantly by choosing the appropriate allylating reagent. The cis-isomer was transformed to (6S*,10bR*)-hexahydro-6-phenylpyrrolo[2,1-a]isoquinoline in five steps.
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| Web Release Date:
December 13, 2007
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| 2425-2435
Chalcogenation Reactions of Overcrowded Doubly Bonded Systems between Heavier Group 15 Elements
T. Sasamori, E. Mieda, and N. Tokitoh*
[Full Text PDF(J-STAGE)]
Novel heterocyclic compounds containing chalcogen (S, Se, and Te) and pnictogen (P, Sb, and Bi) atoms were obtained by the chalcogenation reactions of the doubly bonded systems between heavier group 15 elements (dipnictenes) kinetically stabilized by 2,6-bis[bis(trimethylsilyl)methyl]-4-[tris(trimethylsilyl)methyl]phenyl (Bbt) groups.
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December 13, 2007
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| 2436-2442
Molecular Properties of 2-Pyrone-4,6-dicarboxylic Acid (PDC) as a Stable Metabolic Intermediate of Lignin Isolated by Fractional Precipitation with Na+ Ion
T. Michinobu, M. Bito, Y. Yamada, Y. Katayama, K. Noguchi, E. Masai, M. Nakamura, S. Ohara, and K. Shigehara*
[Full Text PDF(J-STAGE)] [n=li Information]
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Lignin-derived stable metabolic intermediate, 2-pyrone-4,6-dicarboxylic acid (PDC), was isolated. PDC has many attractive properties, such as easy sublimation, characteristic fluorescence, and strong acidity, which lead to the exceptionally short intermolecular contacts in the crystal structures.
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December 13, 2007
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| 2443-2445
Novel Photoinduced Reduction of Conjugate Dienes by the Combination of Benzenethiol and Diphenyl Diselenide
T. Mitamura, Y. Imanishi, A. Nomoto, M. Sonoda, and A. Ogawa*
[Full Text PDF(J-STAGE)]
By using a binary system that consisted of benzenethiol and diphenyl diselenide under photoirradiation through a Pyrex vessel with a xenon lamp (λ>300nm), a variety of conjugate dienes could be reduced to the corresponding internal alkenes under mild conditions.
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December 13, 2007
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| 2446-2450
Low Driving Voltage of Twisted Nematic Liquid Crystal Displays Doped with CdS Nanoparticles
Y. Du and N. Toshima*
[Full Text PDF(J-STAGE)]
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Doped with 0.2 wt % CdS, the lowest driving voltage of TN-LCD devices decreased from 1.8 V (pure 5CB) to 1.2 V, at which the on–off transformation of the doped cell occurred well, whereas there was a weak response for the cell of pure 5CB.
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December 13, 2007
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| 2451-2456
Colloidal State of Exfoliated Oxide Nanosheets of Layered Niobate Characterized with a Molecular-Level Spectroscopic Technique and Macroscopic Observations
T. Nakato* and J. Sugawara
[Full Text PDF(J-STAGE)]
Spectroscopic behavior of a cationic porphyrin, 5,10,15,20-tetrakis(N-methylpyridinium-4-yl)-21H,23H-porphine (H2TMPyP) added to a colloidal dispersion of exfoliated nanosheets of layered hexaniobate K4Nb6O17 was utilized to detect the irreversible alteration of the colloidal properties at the microscopic level induced by concentrating the suspension.
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| Web Release Date:
December 13, 2007
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| 2457-2464
Role of Iron Ion Electron Mediator on Photocatalytic Overall Water Splitting under Visible Light Irradiation Using Z-Scheme Systems
H. Kato, Y. Sasaki, A. Iwase, and A. Kudo*
[Full Text PDF(J-STAGE)] [n=li Information]
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Water formation from H2 and O2 and reduction of Fe3+, which usually occur on Pt, were suppressed in the presence of Fe3+ ion species. It is a key role of the iron ions in water splitting using Z-scheme systems with an Fe3+/Fe2+ electron mediator.
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December 13, 2007
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| 2465-2472
Photoinduced Charge Separation of the Covalently Linked Fullerene–Triphenylamine–Fullerene Triad. Effect of Dual Fullerenes on Lifetimes of Charge-Separated States
M. E. El-Khouly,* J. H. Kim, M. Kwak, C. S. Choi, O. Ito, and K.-Y. Kay*
[Full Text PDF(J-STAGE)] [n=li Information]
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For C60–triphenylamine–C60 triad, photoinduced charge-separation takes place generating a stabilized ion radical pair, in which cation radical is localized on the triphenylamine moiety and radical anion on the interacting two C60 moieties.
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December 13, 2007
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| 2473-2475
Dye-Sensitized Solar Cells Based on Quaternary Phosphonium Ionic Liquids as Electrolytes
Y. Kunugi,* H. Hayakawa, K. Tsunashima, and M. Sugiya
[Full Text PDF(J-STAGE)]
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Dye-sensitized solar cells using quaternary phosphonium ionic liquids as their electrolytes have been successfully fabricated, and the energy conversion efficiencies for the quaternary phosphonium ionic liquid electrolytes are higher than those for the corresponding quaternary ammonium ionic liquids.
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Errata
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December 13, 2007
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| 2476
Through-Space Interactions in Non-Kekulé Biradicals
M. Hatanaka* and R. Shiba
[Full Text PDF(J-STAGE)]
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