Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 85 , Issue 8
Showing 1-12 articles out of 12 articles from the selected issue
Award Accounts
The Chemical Society of Japan Award for Young Chemists for 2010
  • Kosei Ueno, Hiroaki Misawa
    2012 Volume 85 Issue 8 Pages 843-853
    Published: August 15, 2012
    Released: August 15, 2012
    [Advance publication] Released: July 20, 2012
    JOURNALS FREE ACCESS
    We used metallic nanoparticles exhibiting localized surface plasmon resonance and electromagnetic (EM) field enhancement effects induced by plasmon excitation for the photochemical reaction field; this approach makes it possible to increase the probability of an interaction between photons and the materials. EM field enhancement effects induced by gold nanostructures were elucidated using two-photon-induced photoluminescence from nanogap-spaced gold nanoparticles. The photoluminescence was promoted mainly in the surface regions of the gold nanoblocks adjacent to the nanogaps due to the EM field enhancement effect. To elucidate the near-field intensity distribution of the nanogap gold structures, we investigated the photopolymerization of a commercially available negative photoresist assisted by EM field enhancement in the nanogaps separating the gold nanoblocks. Photopolymerization rates were enhanced by several orders of magnitude in the gold nanoblock structures that contained nanogaps narrower than 10 nm. We propose two surface plasmon-assisted nanolithography techniques based on spatially selective photochemical reactions promoted by the EM field enhancement effect. The first method uses ultimate near-field lithography with a local near-field distribution induced in the nanogaps, and the second technique uses the scattering component of multipole plasmon resonance as an exposure mechanism. These lithographic techniques represent a type of application based on plasmon-enhanced chemical reactions.
    Metallic nanoparticles showing localized surface plasmon resonances were used for photochemical reaction field. To elucidate plasmon-enhanced photochemical reaction, we pursued nonlinear photopolymerization of a commercially available negative photoresist assisted by electromagnetic field enhancement, and successfully applied this principle to nanolithography. Fullsize Image
BCSJ Award Article
  • Shinnosuke Kawai, Tamiki Komatsuzaki
    2012 Volume 85 Issue 8 Pages 854-861
    Published: August 15, 2012
    Released: August 15, 2012
    [Advance publication] Released: July 28, 2012
    JOURNALS FREE ACCESS
    The question of what initial conditions or what kinds of laser fields can effectively carry a system to the desired products is one of the most intriguing subjects in chemistry. In this paper, a scheme for designing a laser field to guide a chemical reaction system into the product is presented on the basis of the phase space structure of the reaction with an illustrative simple example. The method exploits recent findings [Kawai et al., J. Chem. Phys. 2011, 134, 024317] that have revealed the existence of a rigorous reactivity boundary separating the reactive and nonreactive trajectories in the phase space (more precisely, the semiclassical phase space representation of the quantum system). Referring to the time propagation of the system, the method designs an electric field that actively shifts this reactivity boundary so that it catches more the system in the reactant and releases the system in the product. The success of this scheme for designing of the field gives a further support to the interpretation for the laser control of chemical reactions.
    Chemical reactions can be controlled by applying a laser pulse designed in such a way that increases the population in the reactive region of the phase space. Fullsize Image
 
  • Hirofumi Nobukuni, Takuya Kamimura, Hidemitsu Uno, Yuichi Shimazaki, Y ...
    2012 Volume 85 Issue 8 Pages 862-868
    Published: August 15, 2012
    Released: August 15, 2012
    [Advance publication] Released: July 28, 2012
    JOURNALS RESTRICTED ACCESS
    Cyclic nickel and free-base porphyrin dimers (Ni2-CPDPy and H4-CPDPy) include [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) both in solution and in the crystals. In the crystal packing of the inclusion complex of Ni2-CPDPy and PCBM, a nanotubular structure is constructed through the self-assembly of the porphyrin moiety. The PCBM molecules are linearly arranged in the inner channel of the nanotube to give a supramolecular peapod. On the other hand, in the crystal of the inclusion complex of H4-CPDPy and PCBM, a dimeric structure of the PCBM molecules is formed through π–π interaction between their phenyl groups.
  • Yasuyuki Takamitsu, Ko Ariga, Satoshi Yoshida, Hiroshi Ogawa, Tsuneji ...
    2012 Volume 85 Issue 8 Pages 869-876
    Published: August 15, 2012
    Released: August 15, 2012
    [Advance publication] Released: July 28, 2012
    JOURNALS RESTRICTED ACCESS
    Alkali metal ion-exchanged ZSM-5 and β-zeolites were tested as hydrocarbon traps for reducing cold-start emissions. The hydrocarbon trap performances were investigated by temperature-programmed desorption employing toluene as a probe molecule both in the presence and absence of water. Toluene adsorption was significantly inhibited in the presence of water. The extent of this inhibitory effect was strongly dependent on the nature of the alkali metal cation. The Cs cation was the most effective in suppressing the inhibition. The suppression of the inhibition is likely due to an enhancement of the interaction between the toluene molecules and zeolite-framework oxygens bearing high negative charge. Having investigated hydrocarbon trap performances of alkali metal ion-exchanged Y and mordenite zeolites as well as ZSM-5 and β, it was concluded that both the type of alkali metal cation employed and the Si/Al ratio of zeolite were the major factors that affected the hydrocarbon trap performance rather than the nature of framework structure of zeolite. On the other hand, the durability was influenced by the type of framework structure used. The stability decreased in the order: Cs/ZSM-5 > Cs/β > Cs/Y ≈ Cs/mordenite. The adsorption capacity of Cs/ZSM-5 was preserved even after thermal treatment at 900 °C.
  • Tomonori Kawashima, Sushma Manda, Yoshihiro Uto, Kei Ohkubo, Hitoshi H ...
    2012 Volume 85 Issue 8 Pages 877-883
    Published: August 15, 2012
    Released: August 15, 2012
    [Advance publication] Released: August 03, 2012
    JOURNALS OPEN ACCESS
    The kinetics for the reaction of the 2,2-diphenyl-1-picrylhydrazyl radical (DPPH) with artepillin C, a prenylated phenylpropanoid found specifically in Brazilian propolis, and its analogues was examined in deaerated acetonitrile (MeCN) to shed light on the mechanism for the radical-scavenging reaction of phenolic antioxidants as well as on the structure–activity relationship. Among the examined analogues, a compound having a catechol moiety is found to have the largest second-order rate constant (k) for the DPPH-scavenging reaction. The deuterium kinetic isotope effect of 1.6 was observed for the DPPH-scavenging reaction of artepillin C in the presence of 0.13 M CD3OD or CH3OH in deaerated MeCN at 298 K. The log k values were found to be linearly correlated with calculated energy difference values (DHT, HT: hydrogen transfer) between the artepillin C analogues and the corresponding phenoxyl radicals, while such a linear correlation cannot be observed between the log k values and calculated ionization potentials (IP), DHT − IP, or experimental one-electron-oxidation potentials of the artepillin C analogues. These results together with a calculated structure of the transition state for the reaction between the artepillin C analogue and DPPH suggest that the DPPH-scavenging reaction of the artepillin C analogues in deaerated MeCN proceeds via a one-step hydrogen-atom transfer from the phenolic OH group to DPPH rather than an electron transfer followed by proton transfer.
  • Joaquín Cortés, Eliana Valencia, Carlos González, ...
    2012 Volume 85 Issue 8 Pages 884-891
    Published: August 15, 2012
    Released: August 15, 2012
    [Advance publication] Released: August 08, 2012
    JOURNALS RESTRICTED ACCESS
    Kinetics experiments for the CO–NO reaction over copper oxide supported on zirconia are interpreted adequately by theoretical activity decay models. A redox-type reaction mechanism is proposed for the process. A kinetic Monte Carlo simulation algorithm is developed for the case of a redox mechanism. Its results give a reasonable interpretation of the order of the experimental reaction.
  • Kayako Hori, Hanako Ouchi
    2012 Volume 85 Issue 8 Pages 892-894
    Published: August 15, 2012
    Released: August 15, 2012
    [Advance publication] Released: August 03, 2012
    JOURNALS RESTRICTED ACCESS
    The title compound has two crystal forms I and II mediated by CH–π interactions at room temperature. Molecular long axes are parallel in I while crossed in II. On cooling, II transforms to three metastable forms with similar structures to II.
  • Yuji Miyazato, Eiji Asato, Masaaki Ohba, Tohru Wada
    2012 Volume 85 Issue 8 Pages 895-901
    Published: August 15, 2012
    Released: August 15, 2012
    [Advance publication] Released: August 03, 2012
    JOURNALS RESTRICTED ACCESS
    A tetranucleating macrocyclic ligand bearing four acetate pendants, L6−, was newly yielded by a stepwise synthesis from [Zn4(L′)(AcO)2(OH)2](ClO4)2·H2O (1), which was prepared from [2 + 2] Schiff-base condensation of 2,6-diformyl-4-methylphenol and 1,2-bis(2-aminoethoxy)ethane in the presence of Zn(ClO4)2·6H2O, sodium acetate, and triethylamine. A µ4-oxo tetracopper(II) complex [Cu4(L)(µ4-O)]·H2O (2) was obtained from the reaction of Cu(ClO4)2·6H2O and Na2H4L in methanol under basic conditions, and characterized by X-ray crystallography. Two adjacent copper centers were bridged by the phenoxo oxygen of L6− to form [Cu2(µ-OPh)] unit, two pairs of which were further linked by an oxo anion with a distorted tetrahedral geometry, finally creating a tetracopper core [{Cu2(µ-OPh)}24-O)]. Cryomagnetic measurements of 2 in the range of 2–300 K exhibited antiferromagentic behavior. Magnetic analysis of 2 was carried out by the four spin-exchange interactions model based on the bridging mode and the Cu–(µ4-O)–Cu angles, JA: Cu1/Cu4, JB: Cu2/Cu3, JC: Cu1/Cu2 and Cu3/Cu4, and JD: Cu1/Cu3 and Cu2/Cu4 pairs. The estimated four magnetic exchange interactions (JA, JB, JC, and JD) were −17, −161, −108, and −109 cm−1, respectively.
  • Perumal Rajakumar, Kathiresan Visalakshi, Shanmugam Ganesan, Pichai Ma ...
    2012 Volume 85 Issue 8 Pages 902-911
    Published: August 15, 2012
    Released: August 15, 2012
    [Advance publication] Released: August 08, 2012
    JOURNALS RESTRICTED ACCESS
    Synthesis of dendrimers with pyrene at the surface and benzenetricarboxylic acid and phloroglucinol at the core and with ester functionality as branching points has been described. When such dendrimers are used as an additive in DSSC, power conversion efficiency of 6.78% is observed.
  • Jun Nakazawa, Jun Hagiwara, Yuichi Shimazaki, Fumito Tani, Yoshinori N ...
    2012 Volume 85 Issue 8 Pages 912-919
    Published: August 15, 2012
    Released: August 15, 2012
    [Advance publication] Released: August 03, 2012
    JOURNALS RESTRICTED ACCESS
    New host molecules “Dicavitand-Porphyrins” [H2C2P(syn,syn) (3), H2C2P(syn,anti) (4)] with small cavities on one or both sides of the porphyrin plane were synthesized from 5,10-bis(2,6-dihydroxyphenyl)-15,20-diphenylporphyrin and bis(chloromethyl)cavitand in 15 and 34% yield, respectively. Similarity of guest size selectivity of the host 4 in comparison with the reported “Cavitand-porphyrin” [H2CP(syn) (1)] suggests that these hosts have the same cavity size. The 1:1 and 1:2 association constants (K11 and K12) of the guest encapsulations into 3 were also obtained by 1H NMR titration and nonlinear least square fittings. The guest size dependences of K11 and K12 values of 3 show that the initial cavity prefers larger guests such as ethane, while the second one does not. The induced-fit type very small structural changes (estimated within 1 Å) upon first guest encapsulation of the host 3 affects the guest encapsulation of the other cavity through the covalent linkages.
  • Shin-Pin Chen, Bo-Wei Chen, Chang-Feng Dai, Ping-Jyun Sung, Yang-Chang ...
    2012 Volume 85 Issue 8 Pages 920-922
    Published: August 15, 2012
    Released: August 15, 2012
    [Advance publication] Released: August 03, 2012
    JOURNALS RESTRICTED ACCESS
    Two new dihydrofuranocembranoids 1 and 2 with three known sarcophytonin A (3), sarcophytonin C (4), and sarcophytoxide (5) have been isolated from a Dongsha Atoll soft coral Sarcophyton sp. The structures of metabolites were elucidated on the basis of extensive spectroscopic analysis and cytotoxic activity of 15 against the proliferation of a limited panel of cancer cell lines was measured.
  • Hidekatsu Maeda, Yasushi Soneda, Aya Higuchi, Miki Iizuka, Hidetoshi N ...
    2012 Volume 85 Issue 8 Pages 923-929
    Published: August 15, 2012
    Released: August 15, 2012
    [Advance publication] Released: August 03, 2012
    JOURNALS RESTRICTED ACCESS
    Current generation from Na2SO3 aqueous solution was found to occur by using PAN-based carbon fibers with heat treatment at 700 °C. Sixty mL of 0.1 M Na2SO3 and 80 mL of 0.5 M H2SO4 were added into the anode cell and cathode cell, respectively, and current generation was performed for 10 h. As a result, the current value increased from background current of 0.04 to 22.3 mA after 5 min. Afterward, the current was almost constant, and decreased a little in the final stage, accompanied by decrease of the amount of Na2SO3. The current efficiency was calculated to be 91%. The mechanism of the current generation is assumed to be described by the equation: SO32− + 2OH → SO42− + H2O + 2e. In the current generation using a 30 Ω resistor, the current was 11.3 mA, so that the voltage is calculated to be 0.339 V. The maximum electric power of this cell is calculated to be 3.83 mW. Next, 60 mL of 0.02 M H2SO3 was added to the anode cell, and current generation was performed for 4 h as well as in the case of Na2SO3. As a result, the current was 8.25 mA after 6 min. Afterward, the value linearly decreased, and the value was 3.80 mA after 3 h. The current generation almost finished after 4 h. In this case, the current efficiency was 28%. Furthermore, chemical groups on the surface of carbon fibers with heat treatment were measured by X-ray photoelectron spectroscopy. The element analysis on the surface resulted in: C, 82 atom %; N, 7.2 atom %; and O, 10.9 atom %; the existence of COO, C=O, C–O, C–C, C=C, C–N, and C=N groups was thus suggested.
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