Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 89 , Issue 4
Showing 1-12 articles out of 12 articles from the selected issue
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The Chemical Society of Japan Award for Creative Work for 2013
  • Yasuhiro Kajihara
    2016 Volume 89 Issue 4 Pages 409-423
    Published: April 15, 2016
    Released: April 15, 2016
    [Advance publication] Released: November 05, 2015
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    Our research group demonstrated the semi-synthesis of complex-type biantennary sialyloligosaccharide-library by means of branch-specific glycosidase and several sialyltransferase reactions toward complex-type H2N-Asn-(biantennary compex-type sialyloligosaccharide)-COOH isolated from egg yolk at over a gram scale. This methodology yielded 35 kinds of homogeneous complex-type oligosaccharides. Using this oligosaccharide library, an efficient Boc solid phase peptide synthesis (SPPS) of acid labile sialylglycopeptide-α-thioester was demonstrated. Our research group showed that the sialoside in which the carboxylic acid is protected with a phenacyl group is stable under strong acidic conditions, and this critical finding enabled us to demonstrate the first Boc-SPPS for the synthesis of a sialylglycopeptide-α-thioester. Using both a synthetic method of sialylglycopeptide-α-thioester and native chemical ligation (NCL), our research group synthesized several glycoproteins such as chemokine MCP-3, three kinds of erythropoietin analogues, and interferon-ß. Our research group also demonstrated a unique synthesis that was an intentional synthesis of homogeneous misfolded glycoproteins bearing M9-high-mannose-type oligosaccharide. This unique synthetic misfolded-glycoprotein is useful for the purpose of uncovering the mechanism of molecular recognition in glycoprotein quality control (GQC) in the endoplasmic reticulum (ER). This account discusses the function of the oligosaccharides of glycoproteins based on our research findings.
    This account describes synthetic approaches for the synthesis of glycoproteins bearing homogeneous complex-type biantennary sialyloligosaccharides as well as high-mannose-type oligosaccharides. Fullsize Image
     
 
  • Tsubasa Konishi, Kazuo Yamaguchi
    2016 Volume 89 Issue 4 Pages 424-429
    Published: April 15, 2016
    Released: April 15, 2016
    [Advance publication] Released: January 05, 2016
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    A highly hydrophobic self-assembled monolayer (SAM) with high photosensitivity to soft UV (λ = 365 nm) was formed on thermally surface-oxidized silicon wafers by a silane coupling agent bearing a 2-nitrobenzyl carbamate moiety. Very smooth SAM was obtained by the use of 1,3-bis(trifluoromethyl)benzene as a solvent. Photopatterning of the SAM was carried out by irradiation with soft UV at 2 J cm−2 (80 s) in acetone under a photomask. Selective deposition of Ag nanoparticulate ink by spin coating on the resulting patterned surface afforded a well-defined 10 µm line and space pattern. Subsequent photodeprotection to generate amino groups enabled the space regions to be selectively modified with fluorescent dye bearing a succinimidyl ester moiety.
  • Yuji Miyazato, Eiji Asato, Masaaki Ohba, Tohru Wada
    2016 Volume 89 Issue 4 Pages 430-436
    Published: April 15, 2016
    Released: April 15, 2016
    [Advance publication] Released: January 15, 2016
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    A tetracopper(II) complex containing two oxalate anions in the metal-based host cavity, [Cu4(Lpy)(µ-ox)2](PF6)2·2(2-PrOH), where ox2−: oxalato (C2O42−), was prepared by reacting H2Lpy, a phenol-based tetranucleating macrocyclic ligand with four pyridylmethyl pendant arms, Cu(ClO4)2·6H2O, and sodium oxalate (1:4:2 stoichiometry, respectively) in methanol, followed by exchange of the counteranion with excess of NH4PF6. Single-crystal X-ray diffraction of 1 revealed that two {Cu(II)Cu(II)} units, bridged by a phenolato group of Lpy2−, were connected by two oxalato anions, to construct a rectangular “{CuCu}(µ-ox)2{CuCu}” tetranuclear framework. This rectangular framework was maintained in DMF solution. The magnetic measurement of 1 in the 2–300 K range revealed antiferromagnetic behavior. The antiferromagnetic interaction in this complex occurs between the Cu(II) centers bridged by an oxalate (J = −140 cm−1).
  • Hitoshi Shirai, Tomoyuki Tajima, Kentaro Kubo, Takuya Nishihama, Hidea ...
    2016 Volume 89 Issue 4 Pages 437-443
    Published: April 15, 2016
    Released: April 15, 2016
    [Advance publication] Released: January 26, 2016
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    We succeeded in the first isolation of a single pure regioisomer of a C70–acene monoadduct. 1,9-Diels–Alder monoadducts of C70 with pentacene derivatives were obtained by not only the Diels–Alder reaction but also a one-pot reaction using stable dihydropentacene derivatives, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), and C70. The X-ray crystallographic study of a single pure regioisomer 2b confirmed positions of the linkage between C70 and acenes for the first time, and revealed unique columnar stacks.
  • Wei Wang, Yoshinori Hirano, Takanori Uzawa, Makoto Taiji, Yoshihiro It ...
    2016 Volume 89 Issue 4 Pages 444-446
    Published: April 15, 2016
    Released: April 15, 2016
    [Advance publication] Released: January 27, 2016
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    Conjugation of small molecular inhibitor with a site recognition peptide would generate highly potent peptide–drug conjugate inhibitors of protein kinases. A peptide selected by ribosome display with a tRNA carrying an inhibitor-conjugated amino acid exhibited up to 10- to 100-fold higher inhibitory effects towards different kinases than solely the inhibitor.
  • Radhika Narayanan, Archana Velloth, Takuya Kurahashi, Hiroshi Fujii, M ...
    2016 Volume 89 Issue 4 Pages 447-454
    Published: April 15, 2016
    Released: April 15, 2016
    [Advance publication] Released: January 20, 2016
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    Di-µ-oxo dimetal cores can form dinuclear complexes with definite stereochemistries. Recent studies describing the synthesis and evaluation of titanium(IV) and manganese(IV) di-µ-oxo dimetal chiral salen complexes prompted us to explore the corresponding vanadium(IV) and chromium(IV) complexes. We therefore modeled a series of di-µ-oxo dimetal complexes of titanium(IV), vanadium(IV), chromium(IV), and manganese(IV) with tetradentate salen ligands bearing different degrees of steric bulk. Quantum mechanical calculations were conducted to compare the stabilities and molecular structures of these complexes. The results of natural population analysis gave an insight into the charge distribution characteristics of the di-µ-oxo dimetal cores of these complexes. Our calculations showed that the di-µ-oxo dimetal complexes bearing the least sterically encumbered model ligand 1 preferred the M-helical form over the P-helical one. In the titanium(IV) and chromium(IV) complexes containing a practical chiral salen ligand 2, the P-helical form was found to be more stable than the corresponding M-form. In contrast, the corresponding vanadium(IV) and manganese(IV) complexes preferred to exist in the M-helical form. The degree of distortion of the di-µ-oxo dimetal core and the inter ligand interactions were key factors for determining the stability of these complexes.
  • Takasuke Mukaiyama, Tadafumi Uchimaru, Yujiro Hayashi
    2016 Volume 89 Issue 4 Pages 455-459
    Published: April 15, 2016
    Released: April 15, 2016
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    The stability of E/Z-alkoxyenamines from α-alkoxyaldehyde with pyrrolidine was discussed by conducting density functional theory (DFT) calculations with natural bond orbital (NBO) analysis.
BCSJ Award Article
  • Daijiro Hayashi, Tomoyuki Narisawa, Yoichi Masui, Makoto Onaka
    2016 Volume 89 Issue 4 Pages 460-471
    Published: April 15, 2016
    Released: April 15, 2016
    [Advance publication] Released: January 08, 2016
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    The 1,4-addition of benzene derivatives to acrolein is a straightforward way to synthesize 3-arylpropanals. A survey of acid catalysts for the 1,4-addition of methoxy-substituted benzenes to acrolein revealed that H-Beta and H-Y were the most suitable catalysts. We hypothesized three side-reactions: (1) the double 1,4-addition of acrolein to the starting benzene derivatives, (2) the Friedel–Crafts-type alkylation to the desired product, and (3) the self-polymerization of acrolein. The type (3) side-reaction was inhibited by two different methods which kept the concentration of acrolein low in the reaction mixture or in the zeolite pores. First, acrolein monomers were in situ generated through the gradual monomerization of an acrolein cyclic trimer. Second, using a reaction solvent lowered the acrolein concentration in the zeolite pores due to the competitive adsorption. We discovered that the content of monomeric acrolein in a solvent was closely related to the polarity of the solvent. Actually, both methods improved the yields for the 1,4-additions of 1,3-dimethoxybenzene to acrolein. Other electron-rich benzene derivatives, such as phenol and N,N-dimethylaniline, were also applicable to the 1,4-addition reactions.
    1,4-Addition of benzene derivatives to acrolein catalyzed by H-type zeolite in the liquid phase is studied. Two methods, the slow generation of acrolein from its cyclic trimer and the competitive adsorption of a solvent are effective to suppress the self-polymerization of acrolein. Fullsize Image
     
 
  • Yasutaka Kuwahara, Shigetaka Tamagawa, Tadahiro Fujitani, Hiromi Yamas ...
    2016 Volume 89 Issue 4 Pages 472-480
    Published: April 15, 2016
    Released: April 15, 2016
    [Advance publication] Released: January 14, 2016
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    A layered double hydroxide (LDH) type adsorbent for phosphate removal from aqueous solution was prepared from blast furnace slag (BFS) which is vastly discharged by the iron manufacturing industry. The phosphate adsorption performances of the prepared adsorbent and its calcined derivatives were examined using simulated wastewater solutions containing 124 P-mg L−1 which is close to the effluent produced by the sewage sludge dewatering process, and factors such as pH, nature, and amount of adsorbent were studied to establish the optimum adsorption conditions. The adsorbent exhibited a great ability to efficiently remove phosphate in a variety of environments, especially even from 15 ppm phosphorus aqueous solutions, owing to a strong affinity of Ca(OH)x species and an ion-exchange ability of Cl anions accommodated in the layers. The maximum phosphorus adsorption uptake reached 91.9 P-mg g−1 after 24 h of adsorption at an initial pH of 7.0 and at 25 °C, which was 126-fold higher than that of raw BFS (0.73 P-mg g−1). The adsorption process followed a pseudo-second-order kinetic model and Freundlich adsorption isotherms. The results suggest that the slag-made LDH is a promising low-cost adsorbent for efficient phosphate removal from wastewater streams and phosphorus recovery processes.
  • Shota Yamamoto, Hidemi Tochigi, Shuya Yamazaki, Seiichi Nakahama, Kazu ...
    2016 Volume 89 Issue 4 Pages 481-489
    Published: April 15, 2016
    Released: April 15, 2016
    [Advance publication] Released: January 15, 2016
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    Two photodegradable heterobifunctional linkers (PHBL) connected by a N-(2-nitrobenzyl)imide structure have been developed as tools to obtain photodegradable diblock copolymers with precisely controlled molecular weight. They can undergo two different click reactions, i.e., Huisgen cycloaddition and Michael addition. One linker has an alkyne moiety and maleimide protected as adduct with furan. Reaction of azido-terminated polystyrene (PS), poly(ε-caprolactone) (PCL) or poly(ethylene glycol) (PEG) with this PHBL followed by deprotection affords the corresponding maleimide-terminated polymer, which was coupled with thiol-terminated PEG or poly(N-isopropylacrylamide) (PNIPAM) to synthesize PS-b-PHBL-b-PEG, PCL-b-PHBL-b-PEG, and PEG-b-PHBL-b-PNIPAM. The other linker has maleimide and an alkyne protected by a trimethylsilyl group. This affords diblock copolymers by the reverse route, i.e., maleimide reacts with thiol-terminated PS to obtain a product by Michael addition, and then after deprotection, Huisgen cycloaddition of the generated alkyne- and azido-terminated PEG affords PEG-b-PHBL-b-PS. The resulting photosensitive diblock copolymers were characterized by UV spectroscopy in solution before and after photoirradiation. The energy needed for photolysis of the diblock copolymers in solution ranged from 12 to 17 J cm−2, and was independent of polymer type and molecular weight.
  • Pavitra V. Kumar, Beena G. Singh, Amit Kunwar, Michio Iwaoka, K. Indir ...
    2016 Volume 89 Issue 4 Pages 490-497
    Published: April 15, 2016
    Released: April 15, 2016
    [Advance publication] Released: February 02, 2016
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    Two cyclic organoselenium compounds, DHS (trans-3,4-dihydroxy-1-selenolane) and MAS (3-amino-1-selenolane) were examined for their reaction with peroxynitrite. Both DHS and MAS scavenge peroxynitrite with rate constants of the order of 103 M−1 s−1. Additionally the two compounds efficiently react with carbonate (CO3•−) radical (formed by reaction of peroxynitrite with carbon dioxide) by one-electron oxidation and their selenoxides convert the nitrite formed by peroxynitrite reduction to nitrate. Even though the reactivity of DHS/MAS was fairly the same with peroxynitrite and its derived radicals, they differ in their ability to protect plasmid pBR322 DNA and CHO cells from peroxynitrite induced toxicity. To understand this, analysis of crucial products formed during peroxynitrite reaction was carried out. On reaction with peroxynitrite, both the compounds were converted to their corresponding selenoxide, identified and estimated by NMR and HPLC. Comparing the relative yields of the selenoxides, it has been confirmed that DHS produced significantly higher amount of selenoxide than MAS. The selenoxide can be regenerated back to the parent compound, either by thiols or by nitrite. Based on these results it is concluded that formation of stable and recyclable selenoxide makes selenolanes, a novel class of selenium compounds as antioxidants for peroxynitrite degradation.
  • Beatriz Lozano-Torres, Sameh El Sayed, Ana M. Costero, Salvador Gil, M ...
    2016 Volume 89 Issue 4 Pages 498-500
    Published: April 15, 2016
    Released: April 15, 2016
    [Advance publication] Released: January 22, 2016
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    An azopyridine derivative for the selective and sensitive chromogenic detection of trivalent metal cations in water is described.
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