Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 86 , Issue 7
Showing 1-14 articles out of 14 articles from the selected issue
Award Accounts
The Chemical Society of Japan Award for 2005
  • Hiroshi Masuhara
    2013 Volume 86 Issue 7 Pages 755-783
    Published: July 15, 2013
    Released: July 15, 2013
    JOURNALS FREE ACCESS
    Studies on laser ablation of polymer films, molecular crystals in solution, protein solution, and culture media containing living cells are summarized and considered. Dynamics and mechanism of laser ablation were systematically studied by utilizing time-resolved spectroscopy and imaging; femtosecond–nanosecond transient absorption and emission spectroscopy, nanosecond shadowgraphy, nanosecond–nanometer interferometry, femtosecond surface light scattering imaging. It was confirmed by integrating both data that primary processes of laser ablation can be well understood in the framework of Jablonski diagram. For nanosecond laser ablation of doped polymers, it was demonstrated that cyclic multiphoton absorption is an efficient photothermal conversion process leading to photothermal ablation. For femtosecond laser ablation of dye films, transient pressure mechanism was proposed indicating photomechanical ablation. As applications of laser ablation, nanoparticle preparation, protein crystallization, and manipulation of living cells are presented. Laser ablation of molecular crystals in poor solvent gives small fragments whose size are in a few tens nm. The fabricated nanocolloids are stable without adding detergents and their size was the smallest as nanoparticles produced by the top-down-method. Multiphoton laser ablation of water generates local impulsive force due to bubble formation, shockwave propagation, and local convection flow. The force triggers molecular and protein crystallization in their supersaturated solutions, whose mechanisms are described and considered. The impulsive force is also very useful for manipulating living cells and its high potential was confirmed by examining cell functions such as division, differentiation, death, and migration. Finally summary and future plan are presented.
    Dynamics and mechanism of molecular laser ablation elucidated by time-resolved shadowgraphy, interferometry, surface light scattering imaging, and fluorescence/absorption spectroscopy are summarized and considered. Based on laser ablation in solution, nanoparticle fabrication, protein crystallization, and living cell manipulation are demonstrated. Fullsize Image
     
BCSJ Award Article
  • Naohiro Kirai, Shoichiro Iguchi, Tatsuyoshi Ito, Jun Takaya, Nobuharu ...
    2013 Volume 86 Issue 7 Pages 784-799
    Published: July 15, 2013
    Released: July 15, 2013
    [Advance publication] Released: April 20, 2013
    JOURNALS FREE ACCESS
    Dehydrogenative borylation of alkenes and 1,3-dienes was realized by carrying out the reaction in the presence of bis(pinacolato)diboron (B2pin2) and a catalytic amount of PSiP-pincer palladium complex. This protocol has the following notable features. 1) Monoanionic nature of the PSiP-pincer ligand prevents the formation of boryl(hydrido)- or dihydridopalladium species, enabling synthesis of various vinyl- or dienylboronic esters in good yield from a 1:1 mixture of B2pin2 and alkenes or 1,3-dienes without forming hydroboration or hydrogenation products. 2) Due to the strong trans influence of the silicon atom, PSiP-pincer palladium complex showed high activity toward migratory insertion. 3) Suppression of these side-reactions and the high reactivity of the PSiP-pincer palladium complex enabled an efficient, successive dehydrogenative borylation to give 1,1- or 1,2-diborylated products depending on the kind of substituent on alkenes by using more than 2 equivalents of B2pin2. Mechanistic study revealed that PSiP-pincer borylpalladium complex was generated from hydridopalladium complex and B2pin2, and this complex underwent alkene insertion followed by β-hydride elimination to give alkenylboronic ester with regeneration of the hydridopalladium complex.
    Dehydrogenative borylation of alkenes and 1,3-dienes catalyzed by PSiP-pincer palladium complex was realized. By changing the amount of B2pin2, mono- or diborylated products were obtained selectively without hydroboration or hydrogenation. Fullsize Image
     
 
  • Kenji Nomiya, Kazuaki Ohta, Yoshitaka Sakai, Taka-aki Hosoya, Atsushi ...
    2013 Volume 86 Issue 7 Pages 800-812
    Published: July 15, 2013
    Released: July 15, 2013
    [Advance publication] Released: April 27, 2013
    JOURNALS RESTRICTED ACCESS
    The syntheses, X-ray structures, and homogeneous Lewis acid catalytic activities for the Mukaiyama–aldol reaction of four tetranuclear HfIV and ZrIV cluster cations, which are sandwiched between two 1,2-di-lacunary α-Keggin polyoxometalates (POMs) and between two 1,4-di-lacunary POMs, are described, i.e., [[{M(H2O)}2{M(H2O)2}2(µ-OH)33-OH)2](α-1,2-PW10O37)2]7− (M = Hf 1 and M = Zr 2) and [{M4(H2O)4(µ-OH)23-O)2}(α-1,4-PW10O37)2]8− (M = Hf 3 and M = Zr 4), respectively. Evaluated was homogeneous Lewis acid catalysis of the Mukaiyama–aldol reaction in aqueous/CH3CN mixed media at room temperature under air by water-soluble sodium or lithium salts of sandwich-structured Hf/Zr-containing Keggin and Dawson POMs. In particular, the sodium salts of tetranuclear Hf/Zr cluster cations sandwiched between two di-lacunary α-Keggin POMs, i.e., Na-1Na-4, showed the highest activities, compared with other cluster cations. The present POM-based sandwich-structured compounds gave products with high stereoselectivity, i.e., high anti-selectivity, regardless of high or low activities. The excellent stabilities of Na-1Na-4 as catalysts, i.e., with no reduced activities, were confirmed even after reusing several times.
  • Min Zhang, Md. Mizanur Rahman Badal, Ilmar A. Koppel, Masaaki Mishima
    2013 Volume 86 Issue 7 Pages 813-820
    Published: July 15, 2013
    Released: July 15, 2013
    [Advance publication] Released: April 13, 2013
    JOURNALS OPEN ACCESS
    The gas-phase acidities (GA) of aryl(trifluoromethylsulfonyl)methanes (ArCH2SO2CF3; 1) and arylbis(trifluoromethylsulfonyl)methanes (ArCH(SO2CF3)2; 2) were determined by measuring proton-transfer equilibria. Substituent effects for acidities of a series of ArCH(R1)R2 including 1 and 2 have been analyzed successfully in terms of the Yukawa–Tsuno equation. The resonance demand parameter r value was found to decrease linearly with increasing acidity of the GA values of the unsubstituted parent carbon acids, and the change of the r value was correlated with the acidifying effect of the phenyl group (R = Ph) in the RCH2(R1)R2. In addition, the geometric features and natural charges of the conjugate anions calculated at B3LYP/6-311+G(d,p) were found to be correlated linearly with the r values. Such behavior of the resonance demand parameter in the electron-rich system, ArC(R1)R2, is completely consistent with that observed for the electron-deficient system, ArC+(R1)R2, revealing that the resonance demand is contingent upon the structure of carbanions and carbocations. Furthermore, it was found that the ρ values also decreased with increasing acidity of the GA values of the unsubstituted parent carbon acids. This would be related to the distribution of the charge between the aromatic moiety and the C(R1)R2 moiety.
  • Yuya Oaki, Tatsuya Ikeda, Hiroaki Imai
    2013 Volume 86 Issue 7 Pages 821-828
    Published: July 15, 2013
    Released: July 15, 2013
    [Advance publication] Released: April 13, 2013
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    A microbial-mineralization-inspired approach directed the selective syntheses of copper oxides and related compounds from divalent copper ions in an aqueous solution at room temperature. The systematic syntheses were achieved by three routes; direct, transient-intermediate, and precursor-transformation routes. Inspired by microbial mineralization processes, the oxidation states, crystal phases, and morphologies of copper oxides and related compounds were controlled by the tuning of synthetic conditions. The present approaches facilitated the formation of spherical CuO and Cu2O crystals with hierarchical structures and high specific surface area. The resultant CuO hierarchical spheres showed improved properties as a catalyst for decomposition of an organic molecule in the presence of hydrogen peroxide.
  • Iman A. Gad El-karim
    2013 Volume 86 Issue 7 Pages 829-838
    Published: July 15, 2013
    Released: July 15, 2013
    [Advance publication] Released: April 27, 2013
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    The influence of nonbonding intramolecular interaction of the nitro group, on the tendency by which its σ- and π-withdrawing characters can affect the puckering of the phenoxathiin nucleus is investigated. The structure of the selected nitrophenoxathiins is predicted with the help of density functional calculations using the B3LYP/6-31+G(d) model. The magnitude of change in the puckering angle of phenoxathiin is found to be dependent on the orientation attained by the nitro groups, which determines the extent by which the π-withdrawing character of the nitro group operates on the phenoxathiin nucleus. The in-plane nitro group in position-2 and -3 and the partially twisted nitro in position-1 induce flattening on the phenoxathiin nucleus while the out-of-plane nitro group in position-4 induces further puckering on the phenoxathiin nucleus. Successive substitution by nitro groups at these positions enhances these effects. 1,8-Dinitrophenoxathiin is predicted to be the least puckered while 4,6-dinitrophenoxathiin is the most puckered in the dinitro-series. Few examples of tetranitrophenoxathiins are investigated and prove to follow the same trends. The encountered changes are analyzed in terms of the changes in the hybridization of the substituted carbon atom. The HOMO and LUMO frontier orbitals of the studied compounds are presented.
  • Ryouichi Yoshida, Takashi Shibahara, Haruo Akashi
    2013 Volume 86 Issue 7 Pages 839-849
    Published: July 15, 2013
    Released: July 15, 2013
    [Advance publication] Released: April 27, 2013
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    The reaction of [Mo3S4(H2O)9]4+ (1) and [Mo3OS3(H2O)9]4+ (2) with hydrotris(pyrazolyl)ethanol (HTpe) ligands produced [Mo3S4(Tpe)3]PF6·3CH2Cl2 ([5]PF6·3CH2Cl2) and [Mo3OS3(Tpe)3]PF6·4CH2Cl2 ([6]PF6·4CH2Cl2), respectively, using solvent extraction. Furthermore, the tungsten analogous compounds, [W3S4(Tpe)3]PF6·4CH2Cl2 ([7]PF6·4CH2Cl2) and [W3OS3(Tpe)3]PF6·2.5CH2Cl2 ([8]PF6·2.5CH2Cl2) have been prepared using a similar procedure to that used in the preparation of 5. The cyclic voltammograms of 5, 6, and 7 show one reversible one-electron oxidation process and one reversible one-electron reduction process (5, E1/2 = −0.96 and 1.10 V; 6, E1/2 = −0.96 and 1.00 V; 7, E1/2 = −1.54 and 0.77 V: all values are given vs. SHE). Complex 8 also shows one reversible (E1/2 = 0.61 V) and one irreversible one-electron oxidation processes (Epc = 1.12 V) and one irreversible one-electron reduction process (Epc = −1.54 V). The reaction of 5 with organometallic compound [Pd2(dba)3] in CH3CN afforded [Mo3PdS4Cl(Tpe)3]·4.5CH2Cl2 ([11]·4.5CH2Cl2). Complex 11 showed a high catalytic activity for the intramolecular cyclization of 4-pentynoic acid to give γ-methylene-γ-butyrolactone in the presence of Et3N. X-ray structure analyses of [5]PF6·3CH2Cl2, [6]PF6·4CH2Cl2, [7]PF6·4CH2Cl2, [8]PF6·2.5CH2Cl2, and [11]·4.5CH2Cl2 revealed that each molybdenum or tungsten atom is bonded to the Tpe ligand.
  • Ramesh Chitrakar, Yoji Makita, Kenta Ooi, Akinari Sonoda
    2013 Volume 86 Issue 7 Pages 850-855
    Published: July 15, 2013
    Released: July 15, 2013
    [Advance publication] Released: April 06, 2013
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    Magnesium-doped lithium manganese oxides LimMgxMnIIIyMnIVzO4 (0 < x ≤ 0.5) with cubic spinel structure were synthesized by a coprecipitation method followed by calcination at 450 °C in air. Protonated samples were obtained after treatment with HCl solution. Chemical stability is very important for lithium uptake in industry. We used 0.5 M HCl for desorption of lithium, then dissolution of Mn decreased from 5.8 wt % for a sample without Mg to 1.0 wt % for a Mg-doped sample (Mg/Mn = 0.33). Raw brine was collected from the Salars de Uyuni, Bolivia. The effects of magnesium-doping on lithium adsorptive properties of the protonated samples in NaHCO3 containing brine were studied by a batch method. The results showed that lithium adsorptive capacity and chemical stability of the protonated samples increased with increase in Mg/Mn ratio. The regeneration of the sample with Mg/Mn = 0.33 up to 10 cycles showed good performance with lithium adsorptive capacity of 23–25 mg g−1 at pH 6.6, and the dissolution of manganese ca. 0.25 wt % Mn.
  • Md. Mizanur Rahman Badal, Min Zhang, Shinjiro Kobayashi, Masaaki Mishi ...
    2013 Volume 86 Issue 7 Pages 856-863
    Published: July 15, 2013
    Released: July 15, 2013
    [Advance publication] Released: April 13, 2013
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    The asymmetric stretching frequencies of the ketene group of the m,p-substituted phenylketenes were found to be correlated with σ. The substituent effects for the second-order rate constants of phenylketenes with various amines were not correlated linearly with any single substituent constants. The curved σ°-correlations with a plateau at a high reactivity region were observed for meta-substituents and p-chloro. The substituent effects including para-π-acceptors were described in terms of the Yukawa–Tsuno equation modified by a quadratic term as an approximation. The resultant ρ value decreases significantly from 2.92 for 2,2,2-trifluoroethylamine to 0.83 for benzylamine while an r value increases from 0.50 to 1.10. The opposite change of ρ and r with amines was interpreted by the dual electronic interactions between substituents and positive/negative charges at the zwitterionic transition structure. According to this interpretation, benzylamine with small ρ value and large r value attributes to early transition state and larger ρ value with smaller r value for 2,2,2-trifluoroethylamine attributes to late transition state.
  • Ning Wang, Kento Imai, Cui-Qing Pang, Ming-qi Wang, Mizuho Yonezawa, Y ...
    2013 Volume 86 Issue 7 Pages 864-869
    Published: July 15, 2013
    Released: July 15, 2013
    [Advance publication] Released: April 27, 2013
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    The treatment of 6-chloroindolo[3,2-c]quinoline 6 with NaH–MeI led to methylation at N-11, forming 8, while the reaction of 6 with MeI with heating gave the corresponding 5-methylated quinolinium salt whose SNAr with water smoothly proceeded to form 5-methylindolo[3,2-c]quinolin-6-one 3b. The amination reactivity at the C-6 was assigned in the order of 6 > 11-methylated 8.
  • Md. Imran Hossain, Elkhabiry Shaban, Taku Ikemi, Wei Peng, Hiroyuki Ka ...
    2013 Volume 86 Issue 7 Pages 870-879
    Published: July 15, 2013
    Released: July 15, 2013
    [Advance publication] Released: April 20, 2013
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    2H-Pyrans are constructed on a 1-oxa- or 1-azacyclohexane-2,4-dione core via Knoevenagel condensation with enals followed by 6π-electrocyclization, which are readily catalyzed with ethylenediammonium diacetate. This formal [3 + 3] strategy constitutes C–O and C–C bond making and the diastereomer formation is circumvented using 6,6-disubstitution with the same aryl group in the 1-oxacyclohexane-2,4-diones. This facile methodology significantly advances the access to polysubstituted bicyclic 2H-pyrans with a versatile substrate choice and improved stability of the product.
  • Yuta Igarashi, Koichi Kajihara, Kiyoshi Kanamura
    2013 Volume 86 Issue 7 Pages 880-883
    Published: July 15, 2013
    Released: July 15, 2013
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    Cosolvent-free hydrolytic polycondensation of trimethoxy(3-sulfanylpropyl)silane under acidic conditions was found to yield thiol-containing polysilsesquioxane (PSQ) liquid. The resultant PSQ liquid is stable at room temperature and serves as a precursor of sulfur-containing transparent organic–inorganic hybrid monoliths prepared via ultraviolet (UV) photoinduced thiol–ene reaction. The factors that determine the UV transparency of the hybrids were investigated. Sulfur-containing organic–inorganic hybrids showing good transparency in the UV spectral region are obtained using a vinyl compound, which is transparent around the UV absorption edge of thiol groups.
  • Shuo Zhai, Shin-ichi Yusa, Kenichi Nakashima
    2013 Volume 86 Issue 7 Pages 884-890
    Published: July 15, 2013
    Released: July 15, 2013
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    Spherical hollow zinc oxide (ZnO) nanoparticles have been successfully synthesized by templating micelles of poly(styrene-b-acrylic acid-b-ethylene oxide) (PS-b-PAA-b-PEO). This polymer forms a micelle with a PS core, a PAA shell, and a PEO corona in aqueous solutions. Zinc chloride (ZnCl2) and sodium hydrogen carbonate (NaHCO3) were used as precursors of ZnO. In the synthesis, the PS core acts as a template for cavities of the hollow particles, the PAA shell is beneficial for arresting zinc ions for further mineralizing, and the PEG corona stabilizes the zinc hydrogen carbonate (Zn(HCO3)2)/polymer nanocomposite to prevent secondary aggregate formation. Hollow ZnO nanoparticles were obtained after the calcination of the separated (Zn(HCO3)2)/polymer nanocomposite at 500 °C for 4 h. The hollow ZnO nanoparticles were characterized by various techniques including transmission electron microscopy and X-ray diffraction analysis. The hollow ZnO particles have a spherical shape, a narrowly distributed size of 24.7 ± 1.3 nm, and a shell thickness of 6.9 ± 0.7 nm. Compared with other methods, the present method gives hollow ZnO nanoparticles with smaller size (ca. 25 nm), narrow size distribution, controlled shape, and robust shell. This result strongly demonstrates the advantages of the present synthesis route.
  • Atsushi Okumura, Kou Yamada, Kenji Todori, Shigeru Machida
    2013 Volume 86 Issue 7 Pages 891-895
    Published: July 15, 2013
    Released: July 15, 2013
    [Advance publication] Released: May 09, 2013
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    In order to apply gold nanoparticles to the materials for electronic and optical devices, they are required to be tolerant of heat applied in the fabrication processes. In our previous study, novel gold nanoparticles with excellent thermal stability were developed by introducing an amide bond and a condensed ring into the ligand molecules. On the other hand, particle size is a key factor in determining device performance, gaining control over the size is highly advantageous. In this study, a size-increase reaction of the pyrene-containing gold nanoparticle was carried out. The particle size was successfully increased from 2 to ca. 10 nm, without lowering the thermal stability. Furthermore, their interligand interactions could be probed using fluorescence measurements based on the characteristic excimer emission of pyrene. It is suggested that strong π–π stacking occurred around the particles, even after the size-increase reaction, contributing to maintaining the thermal stability.
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