Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 86 , Issue 11
Showing 1-15 articles out of 15 articles from the selected issue
Award Accounts
The Chemical Society of Japan Award for Young Chemists for 2012
  • Takuya Hashimoto, Keiji Maruoka
    2013 Volume 86 Issue 11 Pages 1217-1230
    Published: November 15, 2013
    Released: November 15, 2013
    JOURNALS FREE ACCESS
    Diazocarbonyl compounds have long been utilized in the field of transition-metal catalysis, wherein the formation of a metal–carbene complex is involved as a key step. On the other hand, diazocarbonyl compounds can be utilized in acid catalysis owing to their intrinsic property to act as a nucleophile to an acid-activated electrophile. However, in sharp contrast to the metal–carbene chemistry, this research field has not been well developed to date as a means to synthesize complex molecular architectures. In the last several years, we have been interested in the exploration of this untapped research area to provide novel ways to synthesize a variety of complex molecules stereoselectively.
    Based on the nucleophilicity of the α-carbon of diazocarbonyl compounds, acid-catalyzed reactions of diazocarbonyl compounds with electrophiles such as aldehydes and aldimines, have been developed as a facile way to provide a diverse array of optically enriched molecules. Fullsize Image
     
  • Kazuo Tanaka, Yoshiki Chujo
    2013 Volume 86 Issue 11 Pages 1231-1239
    Published: November 15, 2013
    Released: November 15, 2013
    [Advance publication] Released: September 07, 2013
    JOURNALS FREE ACCESS
    The concept of “chemicals-inspired biomaterials” and several examples are demonstrated in this review. The idea and background for the design of chemicals-inspired biomaterials which are constructed based on the chemistry and characteristics in material science are explained. As an example, we show several chemicals-inspired materials utilizing polyhedral oligomeric silsesquioxane (POSS) as a building block to apply the material functions of the POSS chemicals for fabricating a series of biomaterials having superior properties. Initially, the filler effects of POSS are explained. Because of the robust silica cube, POSS derivatives can show significant effect as a filler reinforcing the thermal and mechanical properties of conventional plastics simply by mixing. Based on these results, we designed rigid chelators for the complexation with gadolinium ions as an MRI contrast agent. It is demonstrated that the enhancement of the rigidity is a valid strategy for the improvement of the sensitivity. Next, we assembled the functional molecules into the POSS-core dendrimer. We observed from the dendrimer complexes that photon upconversion can be accomplished via an optical process which should be suppressed in electroluminescence devices. The last topic concerns the selective encapsulation by the POSS-core dendrimer for biomolecules. From the study of POSS-based ionic liquids, it was found that the strength of the hydrogen bonds with the ion pair moiety was significantly increased by tethering to POSS. Based on this enhancement, we accomplished selective encapsulation with the POSS-core dendrimer. The results and the prominent properties of the chemicals-inspired biomaterials are shown in this review.
    By using natural materials or mimicking mechanisms in the nature, functionalized materials, called bioinspired materials, can be obtained, yet the reverse is very rare. Recently, based on the chemistry in these artificial products unrelated to biology, various unique biomaterials can be obtained. In this review, the concept and several examples of such “chemicals”-inspired biomaterials are demonstrated. Fullsize Image
     
BCSJ Award Article
  • Jin Matsumoto, Tomoya Kubo, Tomohiko Shinbara, Naomi Matsuda, Tsutomu ...
    2013 Volume 86 Issue 11 Pages 1240-1247
    Published: November 15, 2013
    Released: November 15, 2013
    [Advance publication] Released: September 07, 2013
    JOURNALS FREE ACCESS
    Much attention has been paid to water-soluble porphyrins and metalloporphyrins as potential sensitizers for photodynamic therapy (PDT). Thus, water-soluble tricationic phosphorus porphyrin complexes were prepared via the introduction of an N-alkylpyridinio group on the axial ligands of phosphorus porphyrins. The resulting tricationic phosphorus porphyrins readily dissolve in aqueous solutions without the formation of aggregates, even at high concentration. Moreover, the affinity of the porphyrins to human serum albumin (HSA) is a key factor in their application to PDT since HSA plays an important role in the transport of drug molecules to a target cell. Interactions between the tricationic phosphorus porphyrins and HSA were examined on the basis of changes in the Soret bands of the absorption and fluorescence spectra of phosphorus porphyrin solutions in the presence of HSA and the fluorescence quenching of HSA by the tricationic phosphorus porphyrins. Tricationic phosphorus porphyrins with moderately long alkyl chains on the pyridinio group were strongly adsorbed on the HSA at a position near the tryptophan residue of HSA. This result suggests that tricationic phosphorus porphyrins containing alkyl groups are good candidates as PDT reagents because of their high water solubility and high affinity for HSA.
    Phosphorus porphyrins bearing alkylpyridinio groups as axial ligands were newly synthesized. The porphyrins achieved high water solubility and high affinity to human serum albumin based on the interaction between the alkyl group and the hydrophobic pocket of the albumin. Fullsize Image
     
 
  • Xuan Liu, Haruhiko Ito, Eiko Torikai
    2013 Volume 86 Issue 11 Pages 1248-1255
    Published: November 15, 2013
    Released: November 15, 2013
    [Advance publication] Released: August 10, 2013
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    We select a couple of density functional formalisms suitable for the computation of the highest spin clusters composed of a small number of heavy alkali-metal atoms such as Rb and Cs. Using B3P86 and PW91PW91 density functional methods with Lanl2dz basis set, we analyze the geometry, the binding energy, and the bond length of Rbn and Csn with n = 2–14 in the highest spin state. The exchange energy of the highest spin clusters increases the binding energy with the number of the constituent atoms.
  • Aki Hayashi, Keisuke Yoshida, Hirokazu Nakayama
    2013 Volume 86 Issue 11 Pages 1256-1260
    Published: November 15, 2013
    Released: November 15, 2013
    [Advance publication] Released: August 31, 2013
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    Etodolac (2-[(1RS)-1,8-diethyl-1,3,4,9-tetrahydropyrano[3,4-b]indol-1-yl]acetic acid) is a nonsteroidal anti-inflammatory drug (NSAID) with a bitter taste. It is slightly soluble in water. Hydrotalcite is a carbonate-type MgAl-layered double hydroxide (CO3-LDH) that is used as an antacid. A complex of etodolac with hydrotalcite was synthesized in methanol via an ion-exchange reaction. The carboxy groups of etodolac were exchanged with carbonate ions in the interlayer region of CO3-LDH. Ion exchange was confirmed by IR and 13C CP/MAS NMR spectra. The complex of nitrate-type LDH (NO3-LDH) was obtained in a mixed solvent composed of equal volumes of methanol or ethanol, and water. The complex had an interlayer distance of 2.20 nm, and a bilayer structure of etodolac in the interlayer region of the complex was observed. The uptake amount increased to 3.0 mmol per gram of CO3-LDH depending on the concentration of etodolac, reaction temperature, and reaction time. The etodolac in the interlayer region of the complex was completely released after 120 min in phosphate buffer. The release of etodolac occurred through exchange with phosphate ions. Thus, the bitterness of etodolac can be suppressed by coating it with LDH.
  • Heidar Raissi, Azadeh Khanmohammadi, Fariba Mollania
    2013 Volume 86 Issue 11 Pages 1261-1271
    Published: November 15, 2013
    Released: November 15, 2013
    [Advance publication] Released: August 31, 2013
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    The effect of substitution (F, Cl, SH, NO2, CH2F, CH2Cl, CH2COOH, CH2OCH3, and SCOCH3) on the hydrogen-bond strengths, vibrational frequencies, and physical properties such as dipole moment, chemical potential, and chemical hardness of substituted (Z)-N-(thionitrosomethylene)thiohydroxylamine compound has been systematically explored. All the studied derivatives have been optimized at the B3LYP/6-311++G** level of theory in gas phase, water and carbon tetrachloride solutions. The aromaticity of the formed ring is measured through the structurally based harmonic oscillator model of aromaticity (HOMA), and the magnetic based nucleus independent chemical shift (NICS) measurements. The topological properties of the electron density distributions for S–H···S intramolecular bridges have been analyzed in terms of the Bader theory of atoms in molecules (AIM). Natural population analysis data, the electron density and Laplacian properties, as well as ν(S–H) have been used to evaluate the hydrogen-bonding interactions. Furthermore, calculated 1H NMR chemical shifts (δH) correlate well with the hydrogen-bond distance and ν(S–H) as well as electron density at the bond critical points in the molecular electron density topography.
  • Muhammad Imran Abdullah, Muhammad Ramzan Saeed Ashraf Janjua, Muhammad ...
    2013 Volume 86 Issue 11 Pages 1272-1281
    Published: November 15, 2013
    Released: November 15, 2013
    [Advance publication] Released: August 31, 2013
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    In the present study, ten metal-free dyes for dye-sensitized solar cells (DSSCs) have been designed. These dyes have designed by structural modification of TC4. Density functional theory was used for structure optimization and determination of photophysical properties. These dyes contain triphenylamine as electron donor and cyanoacrylic acid as electron acceptor. Five π-spacers are used to connect the donor and acceptor. Two auxiliary donors are also used to assist the donor. Results of this study indicate that stronger electron-donating auxiliary groups and longer π-conjugation enhance, while electron-withdrawing fluorine at a π-spacer decreases the performance of dyes in DSSC. As compared to auxiliary electron donors, π-spacers have a strong impact on the performance of the dyes in the DSSCs. Major absorption peaks of all dyes were in the visible region. These absorption peaks are associated with the π–π* transitions of the entire molecule. From calculations it is clear that all dyes will be good photosensitizers in DSSC. The present calculations will provide new ways for experimentalists to synthesize high-performance dyes.
  • Hedayat Haddadi, Mohammad Rezaee, Abolfazl Semnani, Hossein Ali Mashay ...
    2013 Volume 86 Issue 11 Pages 1282-1286
    Published: November 15, 2013
    Released: November 15, 2013
    JOURNALS RESTRICTED ACCESS
    In this article, a new method using homogeneous liquid–liquid microextraction via flotation assistance (HLLME-FA) combined with gas chromatography-flame ionization detection (GC-FID) for the determination of butachlor in water samples was developed. In this research, a special extraction cell was designed to facilitate collection of the low-density solvent extraction. No centrifugation was required in this procedure. The water sample solution was added into the extraction cell which contained an appropriate mixture of extraction and homogeneous solvents. By using air flotation, the organic solvent was collected at the conical part of the designed cell. The effect of different parameters on the efficiency of the extraction such as kind and the volume of extraction and homogeneous solvents, ionic strength, and extraction time were studied and optimized. Under the optimum conditions, the calibration graph was linear in the range of 1.0–200 µg L−1 with the detection limit of 0.2 µg L−1. The results show that HLLME-FA is a simple, rapid, sensitive, and efficient analytical method for the determination of butachlor in water samples, and satisfactory results were obtained.
  • Biny Balan, Damodaran Bahulayan
    2013 Volume 86 Issue 11 Pages 1287-1294
    Published: November 15, 2013
    Released: November 15, 2013
    [Advance publication] Released: August 31, 2013
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    A convenient synthetic pathway to triazole-functionalized oxazolone peptidomimetics by click fragment assembly is described. The target molecules were obtained by the ligation of oxazolone-based peptides with azidopeptides via Cu(I)-catalyzed Huisgen cycloaddition reaction (“Click Chemistry”).
  • Shiho Hirohara, Kohei Sharyo, Yuji Kawasaki, Masayasu Totani, Ayumi To ...
    2013 Volume 86 Issue 11 Pages 1295-1308
    Published: November 15, 2013
    Released: November 15, 2013
    [Advance publication] Released: August 24, 2013
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    To examine the versatility of the trans-bisglycoconjugation architecture for 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (TFPP) derivative-based photodynamic therapy (PDT), 25 porphyrin derivatives bearing D-glucopyranose moieties were prepared, and their in vitro photocytotoxicities were examined. trans-Bisglycoconjugated TFPP derivatives exerted the best photocytotoxicity among TFPP derivatives in the same category, regardless of the central metal ion and the type of glycoconjugation. trans-Bisglycoconjugated free-base TFPP bearing β-D-glucopyranosylthio groups (trans-H22SGlc) was found to be the most potent photosensitizer, not only in HeLa cells (EC50 < 5 nM), but also in highly metastatic cancer cell lines such as B16-BL6 melanoma cells (EC50 < 10 nM). UV–vis and dynamic light-scattering measurements suggested that trans-bisglycoconjugated TFPP derivatives formed relatively large J-aggregates in an aqueous solution. trans-Bisglycoconjugated TFPP derivatives exhibited greater uptake by HeLa cells than those with different glycoconjugation patterns, with the exception of Zn(II) complexes. trans-Bisglycoconjugated TFPP derivatives efficiently generated hydrogen peroxide and hydroxyl radical by a type I photoreaction, while no significant differences were found in the efficiency of singlet oxygen generation by a type II photoreaction. These unique characteristics of trans-bisglycoconjugated TFPP derivatives support the conclusion that trans-bisglycoconjugation is a highly efficient and robust architecture for TFPP-based PDT development.
  • Shinji Toyota, Takuya Tsuya, Tetsuo Iwanaga
    2013 Volume 86 Issue 11 Pages 1309-1316
    Published: November 15, 2013
    Released: November 15, 2013
    [Advance publication] Released: August 14, 2013
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    Anthracene–diacetylene cyclic dimers having two alkoxy groups (OMe, OEt, or OPr groups) at the intraannular positions were synthesized by dimerization of 1,8-diethynylanthracene precursors. For the OEt and OPr compounds, anti- and syn-stereoisomers that differed in the direction of the alkyl groups were separated by chromatography. Kinetic measurements showed that the barriers to isomerization from syn-isomer to anti-isomer were 124 and >146 kJ mol−1 for the OEt and OPr compounds, respectively. The molecular structures of these compounds were examined by X-ray analysis and DFT calculations. The preference for anti-isomers is attributable to the intramolecular C–H···O hydrogen bonds. The effects of substituents on the molecular structures and the barriers to isomerization are discussed.
  • Toru Matsumoto, Naoaki Sata, Kiyoshi Kobayashi, Yoko Yamabe-Mitarai
    2013 Volume 86 Issue 11 Pages 1317-1322
    Published: November 15, 2013
    Released: November 15, 2013
    JOURNALS RESTRICTED ACCESS
    The electrochemical activities of binary metals in a Pd–Nb system were investigated as a function of their compositions, crystal structures, using a hydrogen peroxide and ascorbic acid redox reaction. High activities for the redox reaction of hydrogen peroxide were observed when an alloy of composition 75 atom % Pd–25 atom % Nb (Pd–25Nb) with Pd3Nb phase was used. Tests on six electrodes showed that at a constant potential of 0.7 V, the Pd–25Nb electrode had the best hydrogen peroxide detection capability (Pd–25Nb: 3.2 µA mm−2; Pd: 2.4 µA mm−2; Pt: 2.2 µA mm−2; Pd–10Nb: 1.8 µA mm−2; Pd–30.8Nb: 2.4 µA mm−2; Pd–54.4Nb: 0.6 µA mm−2 for 2 mM hydrogen peroxide). And then, Pd–25Nb gave the best performance in terms of preferential hydrogen peroxide oxidation against ascorbic acid. Subsequently, the Pd–25Nb electrode which had excellent hydrogen peroxide detection capability, Pd and Pt were used for the fabrication of amperometric glucose sensors. To fabricate the glucose sensors, we coated the three electrodes first with γ-aminopropyltriethoxysilane, and then with crosslinked bovine serum albumin and glutaraldehyde containing glucose oxidase. Tests on the Pd–25Nb, Pd, and Pt electrode glucose sensors showed that the Pd–25Nb glucose sensor had a better glucose detection capability than the Pd and Pt glucose sensors: 0.468 µA mm−2 mM−1 for the Pd–25Nb sensor, 0.307 µA mm−2 mM−1 for the Pd sensor, and 0.276 µA mm−2 mM−1 for the Pt sensor with 1.67 mM glucose. We discuss the relation between electrode responses to both hydrogen peroxide and ascorbic acid and electrode surface structures.
  • Hidetoshi Miyazaki, Hiroaki Ichioka, Hisao Suzuki, Toshitaka Ota
    2013 Volume 86 Issue 11 Pages 1323-1326
    Published: November 15, 2013
    Released: November 15, 2013
    [Advance publication] Released: August 27, 2013
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    Molybdenum-based photochromic composite films were fabricated using peroxoisopolymolybdic acid (Mo-IPA) solution and transparent urethane resin. Colors of the prepared films using the α-, β-, or γ-Mo-IPA solution were transparent, slight blue, and azure, respectively. All the composite films turned brown when exposed to UV–vis light irradiation for ten minutes. The colored films bleached to the initial colors after 120 h.
  • Kenji Tanimoto, Hirokazu Kato, Shoya Takeshita, Miyuki Hidaka, Satoshi ...
    2013 Volume 86 Issue 11 Pages 1327-1332
    Published: November 15, 2013
    Released: November 15, 2013
    [Advance publication] Released: August 24, 2013
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    A stable colloidal sol consisting of CeO2–ZrO2 solid solution (CZ) was studied as an efficient modifier for supported Rh catalysts. After coating CZ sol onto Al2O3 by simple impregnation, the catalytic activity for CO–NO–C3H6–O2 reaction increased to a different extent depending on an air-to-fuel weight ratio (A/F). A significant effect on the activity arises largely from water-gas shift reaction and C3H6 steam-reforming in a rich region (A/F < 14.6), and promoted C3H6–O2 reaction in a lean region (A/F > 14.6). Moreover, CZ coating yielded an oxygen storage capacity (OSC), the effect of which could be highlighted in the catalytic reaction under a dynamic lean–rich perturbation.
  • Naoki Yamanaka, Masaya Itakura, Yoshimichi Kiyozumi, Masahiro Sadakane ...
    2013 Volume 86 Issue 11 Pages 1333-1340
    Published: November 15, 2013
    Released: November 15, 2013
    [Advance publication] Released: September 07, 2013
    JOURNALS RESTRICTED ACCESS
    FAU–CHA interzeolite conversions were investigated in the presence of benzyltrimethylammonium hydroxide (BTMAOH) and 1-adamantyltrimethylammonium hydroxide (AdaTMOH) as organic structure-directing agents (OSDAs). AdaTMOH was well able to both decompose/dissolve the starting FAU-type zeolites into locally ordered aluminosilicate species (nanoparts) and transform them into CHA-type zeolites. In contrast, although BTMAOH did not show such high performance in the decomposition and transformation as compared to AdaTMOH, the obtained CHA-type zeolites exhibited higher acid stability. Next, the application of the highly acid-resistant CHA-type zeolites to membranes was investigated. The CHA zeolite membrane prepared on the outer surface of a porous α-alumina tube by FAU–CHA interzeolite conversion demonstrated excellent pervaporation performance in the dehydration of acetic acid aqueous solution. A high permeate flux of ca. 8 kg m−2 h−1 with a high separation factor of ca. 2500 was maintained during long-term (1700 h) testing.
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