Mitsuhiko Shionoya

The University of Tokyo, 白山, Tōkyō, Japan

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Publications (192)1174.42 Total impact

  • Teruki Kobayashi · Yusuke Takezawa · Akira Sakamoto · Mitsuhiko Shionoya
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    ABSTRACT: We have developed a novel method to synthesise artificial ligand-bearing DNAs utilising a template-independent DNA polymerase. Hydroxypyridone ligand-bearing nucleotides (H) were successively appended to DNA primers by the enzyme. The resulting strands, tailed with H nucleotides, formed CuII-mediated metallo-DNA duplexes through the formation of metal-mediated artificial base pairs (H–CuII–H).
    No preview · Article · Jan 2016 · Chemical Communications
  • Ryou Kubota · Shohei Tashiro · Mitsuhiko Shionoya
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    ABSTRACT: Porous molecular solids composed of discrete macrocycles/cages have great potential for catalysis, separation and sensing techniques. Dynamic structural transformation of the host building blocks, especially a helicity inversion responsive to chemical triggers, is central to upgrading the spatial functions. Here we have achieved the syntheses of homochiral porous molecular solids composed of helical metal macrocycles through supramolecular chirality induction to both enantiomorphic forms with the aid of two different enantiopure sugar-derived lactones in the crystallization process. Moreover, we found that the helicity of the macrocyclic skeletons can be inverted in the crystalline state only by changing the type of solvent. This finding would lead to dynamic control of space chirality in connection with optical resolution, chiral amplification and asymmetric reactions.
    No preview · Article · Jan 2016 · Chemical Science
  • Kenichiro Omoto · Shohei Tashiro · Mitsuhiko Shionoya
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    ABSTRACT: Host-guest complexation driven by metal-to-metal dative bonding was studied using a mono-nuclear AgI complex of 2,9-bis(9-anthracenyl)-1,10-phenanthroline as a simple metallo-host. This host molecule can capture a ruthenocene with a Ru–Ag dative bond in solution as revealed by NMR spectroscopy and ESI-TOF MS spectrometry. Single-crystal XRD analysis of the host-guest complex revealed a Ru–Ag type dative bond with a significant change in the coordination arrangement of the central Ru atom of ruthenocene. The binding constant for the host-guest complexation was estimated to be over 104M–1 in CD2Cl2 at 300 K.
    No preview · Article · Oct 2015 · Zeitschrift für anorganische Chemie
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    ABSTRACT: A novel bifacial ligand-bearing nucleobase, 5-hydroxyuracil (U(OH) ), which forms both a hydrogen-bonded base pair (U(OH) -A) and a metal-mediated base pair (U(OH) -M-U(OH) ) has been developed. The U(OH) -M-U(OH) base pairs were quantitatively formed in the presence of lanthanide ions such as Gd(III) when U(OH) -U(OH) pairs were consecutively incorporated into DNA duplexes. This result established metal-assisted duplex stabilization as well as DNA-templated assembly of lanthanide ions. Notably, a duplex possessing U(OH) -A base pairs was destabilized by addition of Gd(III) ions. This observation suggests that the hybridization behaviors of the U(OH) -containing DNA strands are altered by metal complexation. Thus, the U(OH) nucleobase with a bifacial base-pairing property holds great promise as a component for metal-responsive DNA materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    No preview · Article · Aug 2015 · Chemistry - A European Journal
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    ABSTRACT: This chapter highlights the recent developments in the use of DNA-programmed self-assembly to guide the construction of discrete photonic nanostructures. It discusses the advantages and disadvantages of using DNA-programmed self-assembly to construct arrays of organic fluorophores and proteins. The chapter reviews efforts focusing on different modes of DNA-programmed self-assembly to fabricate optoelectronic circuits and light-harvesting complexes. It presents a review by Albinsson, Hannestad and Börjesson to explain specific applications of DNA-directed assembly for the construction of supramolecular photosynthetic mimics. Su et al. developed a highly efficient DNA-programmed photonic wire where the energy transfer efficiency is enhanced by the use of DNA-binding polyamides. Su et al. extended this work to programme the uni-directional transfer of excitation energy along a DNA three-way junction. Although minor-groove recognition is still an emergent concept in DNA nanotechnology, examples of the assembly of minor-groove binders in the presence of the double stranded DNA-templates have been reported. π-Conjugated molecules constitute a very interesting class of compounds with versatile optoelectronic properties. The rise of π-Conjugated compounds is, to a large extent, the result of concomitant developments in molecular electronics, organic synthesis and computational property prediction. For π-Conjugated DNA binders that have tunable structures and accessible properties, the desired properties for various applications need to be established. These properties strongly depend on the particular application, although there is considerable cross-over between the properties that are required for different applications. The chapter explores these for π-Conjugated DNA binders for molecular diagnostics, therapeutics and optoelectronics. The most sensitive sensor designs that rely on spectroscopic detection involve fluorescence. The development of π-Conjugated DNA binders for use in biosensors may present the challenge of requiring specific structural and optoelectronic properties, but application in therapy provides a different set of challenges. This chapter focuses on metal-ion complexes and π–π interacting perylene diimides (PDIs), which are two important types of modifications able to introduce not only additional structural motifs to the purely hydrogen-bonded base pairing in DNA architectures, but also have the potential to improve the electron transfer abilities of DNA. Nucleosides bearing a metal-binding ligand are referred to as “ligandosides” in the literature. In principle, there are three categories for preparing these DNA–metal conjugates. The first is the substitution of a natural base pair by a metal-mediated base pair. The second is achieved by modifying the nucleoside with a ligand. In the third category, a metal binding ligand is tethered terminally to DNA, which forms a metal complex upon metal addition. Molecular beacons (MBs) are single stranded nucleic acids possessing a stem-and-loop structure, which are used for the specific detection of DNA targets. The canonical DNA duplex has two major stabilising parameters, namely, hydrogen bonds between complementary bases and p-stacking interactions between neighbouring bases. Complementary nucleobases may also pair via coordinate bonds to a metal ion located in the centre of the duplex if ligand-based nucleosides are present. The replacement of natural nucleosides by suitable ligands hence leads to the formation of metal-mediated base pairs. The first metal-mediated base pairs were proposed in the 1960s, when the interaction of Hg(II) with polynucleotides was studied. The natural nucleobases can be modified in a way that increases their affinity towards transition metal ions. Accordingly, various derivatives of purine and pyrimidine nucleosides have been reported with pendant ligands. Upon attaching two pyridyl moieties or one bipyridyl entity to a purine or pyrimidine, tridentate artificial nucleobases can be generated. Doubly metalated base pairs are applied in the sole example of duplexes comprising metal-mediated base pairs only. This chapter focuses on the metal-aided construction of unusual DNA structural motifs, as promising components for DNA-based nanoarchitectures and molecular machines. Since metal coordination bonds are generally stronger than hydrogen bonds, incorporation of metal-mediated base pairs leads to significant stabilization of the DNA duplex. Various types of metallo-DNA triplexes, quadruplexes and also junction structures were constructed using the same design strategy. The advantages of using metallo-DNA motifs include: the stability of DNA structures is enhanced by the additional metal coordination bonding; the hybridization or self-assembly of DNA strands can be modulated based on the metal coordination; and the conversion of DNA structural motifs can be induced by addition and removal of metal ions. The metallo-DNA structural motifs presented here will be applied to the development of metal-driven or stimuli-responsive DNA molecular machines and devices, which should be among the next and most challenging targets in supramolecular chemistry and nanotechnology.
    No preview · Article · Jul 2015
  • Shohei Tashiro · Mihoko Yamada · Mitsuhiko Shionoya
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    ABSTRACT: The cleavage of CC bonds in π-conjugated systems is an important method for controlling their shape and coplanarity. An efficient way for the cleavage of an aromatic CC bond in a typical buckybowl corannulene skeleton is reported. The reaction of 2-pyridylcorannulene with a catalytic amount of IrCl3 ⋅n H2 O in ethylene glycol at 250 °C resulted in a structural transformation from the curved corannulene skeleton to a strain-free flat benzo[ghi]fluoranthene skeleton through a site-selective CC cleavage reaction. This cleavage reaction was found to be driven by both the coordination of the 2-pyridyl substituent to iridium and the relief of strain in the curved corannulene skeleton. This finding should facilitate the design of carbon nanomaterials based on CC bond cleavage reactions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
    No preview · Article · Mar 2015 · Angewandte Chemie International Edition in English
  • Shohei Tashiro · Mihoko Yamada · Mitsuhiko Shionoya
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    ABSTRACT: The cleavage of CC bonds in π-conjugated systems is an important method for controlling their shape and coplanarity. An efficient way for the cleavage of an aromatic CC bond in a typical buckybowl corannulene skeleton is reported. The reaction of 2-pyridylcorannulene with a catalytic amount of IrCl3⋅n H2O in ethylene glycol at 250 °C resulted in a structural transformation from the curved corannulene skeleton to a strain-free flat benzo[ghi]fluoranthene skeleton through a site-selective CC cleavage reaction. This cleavage reaction was found to be driven by both the coordination of the 2-pyridyl substituent to iridium and the relief of strain in the curved corannulene skeleton. This finding should facilitate the design of carbon nanomaterials based on CC bond cleavage reactions.
    No preview · Article · Mar 2015 · Angewandte Chemie
  • Kenichiro Omoto · Shohei Tashiro · Masumi Kuritani · Mitsuhiko Shionoya
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    ABSTRACT: A macrocyclic host molecule possessing a nano-cavity with two AgI centers for guest binding and four anthracene walls has been developed. This dimetal-macrocycle forms stable inclusion complexes with ditopic aromatic guest molecules, [2.2]paracyclophane and ferrocene, in solution and/or in the solid state through Ag-π interactions within the nano-cavity. The binding constants for the inclusion complexes were found to range roughly from 104 to 109 M-1. Electrochemical measurement revealed that the oxidized form of the included cationic ferrocene was less stabilized due to the direct binding to the cationic two AgI centers.
    No preview · Article · Dec 2014 · Journal of the American Chemical Society
  • Ryou Kubota · Shohei Tashiro · Motoo Shiro · Mitsuhiko Shionoya
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    ABSTRACT: Molecular adsorption is a fundamental phenomenon in porous materials and is usually characterized by the efficiency and selectivity of molecular separations and reactions. However, for functional porous materials, analysis of the dynamic behaviour of molecular adsorbents is a major challenge. Here, we use in situ single-crystal X-ray diffraction to analyse multi-step molecular adsorption in a crystalline nanochannel of a metal-macrocycle framework. The pore surface of the metal-macrocycle framework crystal contains five different enantiomerically paired binding pockets, to which the adsorption of a (1R)-1-(3-chlorophenyl)ethanol solution was monitored with time. The resulting X-ray snapshot analyses suggest that the guest adsorption process takes a two-step pathway before equilibrium, in which the guest molecule is temporarily trapped by a neighbouring binding site. This demonstrates the potential for using X-ray analyses to visualize a transient state during a non-covalent self-assembly process.
    No preview · Article · Oct 2014 · Nature Chemistry
  • Shohei Tashiro · Mitsuhiko Shionoya
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    ABSTRACT: Porous crystals such as metal-organic framework (MOF), porous coordination polymer (PCP), and porous organic crystals have shown promise as solid materials in terms of their great potentials for catalysis, separation and refinement techniques, environmental protection, nanoengineering, and pharmaceutical applications. Here we discuss cavity-assembled porous solids (CAPSs) formed as the result of self-assembly of macrocycles or cage compounds possessing well-defined binding cavities for guest molecules. In addition to conventional macrocycles such as cyclodextrin, crown ether, cucurbituril, calixarene, cyclotriveratrylene, pillararene, and organic cages, we have recently reported a novel crystalline nanochannel (metal-macrocycle framework: MMF) composed of macrocyclic trinuclear Pd-II complexes with tris(o-phenylenediamine)cyclophane. This account focuses on how cavities with guest-binding capability assemble to form porous structures taking recent examples.
    No preview · Article · Sep 2014 · ChemInform
  • Mihoko Yamada · Kei Ohkubo · Mitsuhiko Shionoya · Shunichi Fukuzumi
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    ABSTRACT: A charge-transfer (CT) complex was formed between corannulene (C20H10) and lithium ion-encapsulated [60]fullerene (Li+@C60) with the binding constant KG = 1.9 × 10 M-1 by concave-convex π-π CT interactions in benzonitrile at 298 K, exhibiting a broad CT absorption extended to the NIR region. Femotosecond laser excitation of the C20H10/Li+@C60 CT complex resulted in the singlet charge-separated (CS) state, 1(C20H10•+/Li+@C60•-), which decayed with the lifetime of 1.4 ns. Nanosecond laser excitation of Li+@C60 resulted in intermolecular electron transfer (ET) from C20H10 to the triplet excited state of Li+@C60 [3(Li+@C60)*] to produce the triplet CS state 3(C20H10•+/Li+@C60•-). The distance between two electron spins in the triplet CS state was estimated to be 10 Å from the zero-field splitting pattern observed by EPR measurements at 4 K. The triplet CS state decayed to the ground state via intramolecular back electron transfer (BET) in the CS state. The CS lifetime was determined to be 240 μs in benzonitrile at 298 K. The temperature dependence of the rate constant of BET afforded the reorganization energy (λ = 1.04 eV) and the electronic coupling term (V = 0.0080 cm-1). The long lifetime of CS state results from the spin-forbidden BET process and a small V value.
    No preview · Article · Aug 2014 · Journal of the American Chemical Society
  • Shohei Tashiro · Tsutomu Umeki · Ryou Kubota · Mitsuhiko Shionoya
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    ABSTRACT: Porous crystals are excellent materials with potential spatial functions through molecular encapsulation within the pores. Co-encapsulation of multiple different molecules further expands their usability and designability. Herein we report the simultaneous arrangement of up to three different guest molecules, TTF (tetrathiafulvalene), ferrocene, and fluorene, on the pore surfaces of a porous crystalline metal–macrocycle framework (MMF). The position and orientation of adsorbed molecules arranged in the pore were determined by single-crystal X-ray diffraction analysis. The anchoring effect of hydrogen bonds between the hydroxy groups of the guest molecules and inter-guest cooperation and competition are significant factors in the adsorption behaviors of the guest molecules. This finding would serve as a design basis of multicomponent functionalized nanospaces for elaborate reactions that are realized in enzymes.
    No preview · Article · Aug 2014 · Angewandte Chemie
  • Shohei Tashiro · Tsutomu Umeki · Ryou Kubota · Mitsuhiko Shionoya
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    ABSTRACT: Porous crystals are excellent materials with potential spatial functions through molecular encapsulation within the pores. Co-encapsulation of multiple different molecules further expands their usability and designability. Herein we report the simultaneous arrangement of up to three different guest molecules, TTF (tetrathiafulvalene), ferrocene, and fluorene, on the pore surfaces of a porous crystalline metal-macrocycle framework (MMF). The position and orientation of adsorbed molecules arranged in the pore were determined by single-crystal X-ray diffraction analysis. The anchoring effect of hydrogen bonds between the hydroxy groups of the guest molecules and inter-guest cooperation and competition are significant factors in the adsorption behaviors of the guest molecules. This finding would serve as a design basis of multicomponent functionalized nanospaces for elaborate reactions that are realized in enzymes.
    No preview · Article · Aug 2014 · Angewandte Chemie International Edition in English
  • Shohei Tashiro · Mitsuhiko Shionoya

    No preview · Article · Jul 2014 · ChemInform
  • Ryosuke Miyake · Mitsuhiko Shionoya
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    ABSTRACT: To understand reversible structural switching in crystalline materials, we studied the mechanism of reversible crystal-to-crystal transformation of a tetranuclear Ni(II) macrocycle consisting of artificial β-dipeptides. On the basis of detailed structural analyses and thermodynamic measurements made in a comparison of pseudo-isostructural crystals (NO3 and BF4 salts), we herein discuss how ligand-exchange reactions take place in the crystal due to changes in water content and temperature. Observations of the structural transformation of NO3 salt indicated that a pseudo crystalline phase transformation takes place through concerted ligand-exchange reactions at the four Ni(II) centers of the macrocycle with hydrogen bond switching. A mechanism for this ligand exchange was supported by IR spectroscopy. Thermodynamic measurements suggested that the favorable compensation relationship of the enthalpy changes due to water uptake and structural changes are keys to the reversible structural transformation. On the basis of a comparison with the pseudo-isostructural crystals, it is apparent that the crystal packing structure and the types of counter anions are important factors for facilitating reversible ligand exchange with single crystallinity.
    No preview · Article · Jun 2014 · Inorganic Chemistry
  • Yusuke Takezawa · Mitsuhiko Shionoya

    No preview · Chapter · May 2014
  • Elizabeth M Nolan · Mitsuhiko Shionoya

    No preview · Article · Apr 2014 · Current opinion in chemical biology
  • Takashi Nakamura · Hitoshi Ube · Ryosuke Miyake · Mitsuhiko Shionoya
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    ABSTRACT: Coordination-driven self-assembly utilizing labile capping ligands has been exploited as a novel strategy for metallo-cage containers. Herein, we report a tetrameric porphyrin barrel complex [C60⊂Zn814(H2O)4(OTs)12](OTs)4 (2) (OTs = p-CH3C4H6SO3) formed from a tetrakis(bipyridyl)porphyrin ligand 1, Zn(OTs)2, and a template guest, C60 fullerene. The tetrameric-barrel 2 contains two kinds of bis(bpy) ZnII centers coordinated by TsO- anions which serve as labile capping ligands in the formation of the finite structure of 2.
    No preview · Article · Dec 2013 · Journal of the American Chemical Society
  • Takashi Nakamura · Hitoshi Ube · Mitsuhiko Shionoya
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    ABSTRACT: Guests welcome: Complex formation between Ag(I) ions and a Zn-porphyrin ligand (L) possessing four 2,2'-bipyridyl groups produced a dimeric complex [Ag4 L2 ](4+) , wherein the interplane distance between the Zn-porphyrin groups was ideal for intercalation of aromatic molecules through π-π interactions. The cofacial dimer [Ag4 L2 ](4+) serves as an excellent receptor for π-electron-deficient guests.
    No preview · Article · Nov 2013 · Angewandte Chemie International Edition
  • Source
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    ABSTRACT: The syntheses and properties of corannulenes carrying electron-withdrawing groups (F, CF3, C6F5 ) are reported. Direct fluorination of corannulene (C20H10) was carried out with xenon difluoride, and the crystal structure of the product was confirmed by the X-ray analysis. Novel trifluoromethylated corannulenes, including the versatile 4,9-dibromo-1,2-bis(trifluoromethyl)corannulene, were obtained by various established ring-closing reactions. Besides the use of hexafluorobutyne for the construction of fluoranthenes by Diels-Alder reaction as precursor molecules to form 1,2-disubstituted corannulenes, bis(pentafluorophenyl)acetylene was employed as dienophile. The molecular structure and crystal packing of a trifluoromethylated corannulene was determined by single-crystal X-ray analysis and compared with those known brominated and trifluoromethylated corannulenes. The general electron-acceptor properties of corannulenes bearing substituents introduced in particular positions by liquid-phase synthesis are discussed together with published computational results.
    Full-text · Article · Sep 2013 · Chemistry - A European Journal

Publication Stats

5k Citations
1,174.42 Total Impact Points

Institutions

  • 1999-2016
    • The University of Tokyo
      • Department of Chemistry
      白山, Tōkyō, Japan
    • Kumamoto University
      • Department of Applied Chemistry and Biochemistry
      Kumamoto, Kumamoto, Japan
  • 2014
    • Massachusetts Institute of Technology
      Cambridge, Massachusetts, United States
  • 2012
    • Georg-August-Universität Göttingen
      • Institute of Inorganic Chemistry
      Göttingen, Lower Saxony, Germany
  • 2001-2010
    • Nankai University
      • Department of Chemistry
      T’ien-ching-shih, Tianjin Shi, China
  • 1998
    • Institute for Molecular Science
      Okazaki, Aichi, Japan
  • 1987-1995
    • Hiroshima University
      • • Department of Dental and Medical Biochemistry
      • • School of Medicine
      Hirosima, Hiroshima, Japan
  • 1991
    • Shionogi & Co., Ltd.
      Ōsaka, Ōsaka, Japan