Faculty Profiles - TANAKA Kentaro

Significant Effect of the Flexibility of Bridging Alkyl Chains on the Proximity of Stacked Porphyrin and Phthalocyanine Conjugated with a Fourfold Rotaxane Linkage Reviewed

Yasuyuki Yamada, Hayato Iida, Shinya Shibano, Nozomi Mihara, Tatsuhisa Kato, Kentaro Tanaka

Chemistry – A European Journal Vol. 28 ( 37 ) page： e202200819 2022.7

Mesogenic discrete metallofoldamer for columnar liquid crystal Reviewed

Shin-ichiro Kawano, Kazutaka Narita, Yuka Ikemoto, Ako Sasaki, Kentaro Tanaka

Chemical Communications Vol. 58 ( 20 ) page： 3274 - 3277 2022.2

Metalloporphyrins substituted with N-carbazolyl groups quadruply at meso positions Reviewed

Shin-ichiro Kawano, Sae Kawada, Atsuya Matsubuchi, Kentaro Tanaka

Journal of Porphyrins and Phthalocyanines Vol. 26 ( 2 ) page： 140 - 146 2022.2

Direct catalytic benzene hydroxylation under mild reaction conditions by using a monocationic μ-nitrido-bridged iron phthalocyanine dimer with 16 peripheral methyl groups Reviewed International coauthorship

Yasuyuki Yamada, Chee-Ming Teoh, Yuka Toyoda, Kentaro Tanaka

New Journal of Chemistry Vol. 46 ( 3 ) page： 955 - 958 2022.1

Synthesis of a monocationic μ-nitrido-bridged iron porphycene dimer and its methane oxidation activity Invited Reviewed

Yasuyuki Yamada, Yusuke Miwa, Yuka Toyoda, Tomoo Yamaguchi, Shigehisa Akine, Kentaro Tanaka

Dalton Transactions Vol. 50 ( 45 ) page： 16775 - 16781 2021.12

Close-Stacking of Iron-Oxo-Based Double-Decker Complex on Graphite Surface Achieved High Catalytic CH4 Oxidation Activity Comparable to that of Methane Monooxygenases Reviewed

2021.6

Authorship：Last author,　Corresponding author Language：English Publishing type：Research paper (scientific journal) Publisher：American Chemical Society (ACS)

Herein, we report that the close-stacking of a double-decker-type dinuclear iron phthalocyanine complex on a graphite surface is effective for achieving high methane oxidation activity, comparable to those of certain MMOs, in an aqueous solution.

DOI： 10.26434/chemrxiv.14728860.v1

A Light‐Harvesting/Charge‐Separation Model with Energy Gradient Made of Assemblies of meta ‐Pyridyl Zinc Porphyrins Reviewed International coauthorship International journal

Joe Otsuki, Takumi Okumura, Kosuke Sugawa, Shin‐ichiro Kawano, Kentaro Tanaka, Takehiro Hirao, Takeharu Haino, Yu Jin Lee, Seongsoo Kang, Dongho Kim

Chemistry – A European Journal Vol. 27 ( 12 ) page： 4053 - 4063 2021.2

Synthesis of Bis{meso-Tetrakis(4-N-alkylpyridiniumyl)porphyrinato}cerium and Its Redox Switching Behavior Invited Reviewed International journal

Toshio Nishino, Yasuyuki Yamada, Ayumi Yamamoto, Kentaro Tanaka

Molecules Vol. 26 ( 4 ) page： 790 - 790 2021.2

Authorship：Last author,　Corresponding author Language：English Publishing type：Research paper (scientific journal) Publisher：MDPI AG

A novel double-decker porphyrin complex, bis{meso-tetrakis(4-N-alkylpyridiniumyl)porphyrinato}cerium, was prepared. Electrochemical measurements revealed that this complex exhibited reversible redox waves corresponding to a 1e– redox reaction of the cerium center. Treating the complex alternately with an oxidant and a reductant resulted in the reversible redox switching between the oxidized and reduced states in an organic solvent.

DOI： 10.3390/molecules26040790

High catalytic methane oxidation activity of monocationic μ-nitrido-bridged iron phthalocyanine dimer with sixteen methyl groups Reviewed International journal

Yasuyuki Yamada, Jyunichi Kura, Yuka Toyoda, Kentaro Tanaka

Dalton Transactions Vol. 50 ( 19 ) page： 6718 - 6724 2021

Authorship：Last author,　Corresponding author Language：English Publishing type：Research paper (scientific journal) Publisher：Royal Society of Chemistry (RSC)

High catalytic methane oxidation activity of a μ-nitrido-bridged iron phthalocyanine dimer was achieved by introducing 16 electron-donating methyl groups onto the phthalocyanine rings.

DOI： 10.1039/d1dt00941a

Synthesis of a monocationic μ-nitrido-bridged iron porphycene dimer and its methane oxidation activity Reviewed

Yasuyuki Yamada, Yusuke Miwa, Yuka Toyoda, Tomoo Yamaguchi, Shigehisa Akine, Kentaro Tanaka

Dalton Transactions Vol. 50 ( 45 ) page： 16775 - 16781 2021

Authorship：Last author,　Corresponding author Language：English Publishing type：Research paper (scientific journal) Publisher：Royal Society of Chemistry (RSC)

Herein, we synthesized a monocationic μ-nitrido-bridged iron porphycene dimer, a structural analogue of a monocationic μ-nitrido-bridged iron phthalocyanine dimer, which is known as one of the most potent molecule-based catalysts for methane oxidation.

DOI： 10.1039/d1dt02922c

Structure and dynamics of a chiral cubanoid complex composed of lithium and salphen Reviewed International journal

Shin-ichiro Kawano, Kyohei Tomita, Kentaro Tanaka

Inorganica Chimica Acta Vol. 512 page： 119894 - 119894 2020.11

Development of functional molecular assemblies based on programmable construction of face-to-face assemblies of metallo-porphyrinoids Invited Reviewed International journal

Yasuyuki Yamada, Kentaro Tanaka

Journal of Inclusion Phenomena and Macrocyclic Chemistry Vol. 96 ( 3-4 ) page： 197 - 213 2020.4

μ-Nitrido-bridged iron phthalocyanine dimer bearing eight peripheral 12-crown-4 units and its methane oxidation activity Reviewed International journal

Yasuyuki Yamada, Jyunichi Kura, Yuka Toyoda, Kentaro Tanaka

New Journal of Chemistry Vol. 44 ( 44 ) page： 19179 - 19183 2020

Authorship：Last author,　Corresponding author Language：English Publishing type：Research paper (scientific journal) Publisher：Royal Society of Chemistry (RSC)

A novel μ-nitrido-bridged iron phthalocyanine dimer with eight peripheral 12-crown-4 units was synthesized and its methane oxidation activity was investigated.

DOI： 10.1039/d0nj04601a

Liquid-crystalline Metallomacrocycles Composed of Bis(hydroxypyridono)toluene Ligand and Cu2+ Ions. Reviewed International journal

Shin-Ichiro Kawano, Kohei Ideta, Tomohiko Banno, Kentaro Tanaka

Chemistry, an Asian journal Vol. 14 ( 23 ) page： 4415 - 4419 2019.12

Authorship：Last author,　Corresponding author Language：English Publishing type：Research paper (scientific journal)

A series of π-extended chelating scaffolds incorporating two hydroxypyridone moieties were synthesized. X-ray crystallographic analysis revealed that a bis(hydroxypyridono)toluene ligand possessed a unique π-extended structure and exhibited efficient phase segregation from the aliphatic chains attached at the heterocyclic nitrogen. The bis-bidentate ligand formed a metal-coordination-induced macrocycle with Cu2+ ions. During the complexation, a spectral change in the visible region was induced. Furthermore, the successful development of a liquid crystal of the metallomacrocycle with appropriate side chains was achieved. Examples of liquid-crystalline macrocycles formed via metal-mediated self-assembly are still rare. Among them, the macrocycle described in this paper showed an obvious hexagonal columnar phase reflecting the three-fold symmetric planar structure of the mesogenic metal complex.

DOI： 10.1002/asia.201901323

Catalytic methane oxidation by a supramolecular conjugate based on a mu-nitrido-bridged iron porphyrinoid dimer Reviewed International journal

Yamada, Yasuyuki, Morita, Kentaro, Mihara, Nozomi, Igawa, Kazunobu, Tomooka, Katsuhiko, Tanaka, Kentaro

NEW JOURNAL OF CHEMISTRY Vol. 43 ( 29 ) page： 11477 - 11482 2019.8

Authorship：Last author,　Corresponding author Language：English Publishing type：Research paper (scientific journal) Publisher：ROYAL SOC CHEMISTRY

Catalytic methane oxidation was conducted using a mu-nitrido-bridged dinuclear iron complex of a fourfold rotaxane heterodimer of a porphyrin and a phthalocyanine. Extension of the mu-stacked structure of the four-fold rotaxane-based mu-nitrido-bridged iron porphyrinoid dimer by supramolecular complexation with an additional tetraanionic porphyrin apparently increased the methane conversion ability.

DOI： 10.1039/c9nj02210d

Improved synthesis of monocationic mu-nitrido-bridged iron phthalocyanine dimer with no peripheral substituents Reviewed International journal

Yamada Yasuyuki, Sugiura Takuya, Morita Kentaro, Ariga-Miwa Hiroko, Tanaka Kentaro

INORGANICA CHIMICA ACTA Vol. 489 page： 160 - 163 2019.4

Authorship：Last author,　Corresponding author Language：English Publishing type：Research paper (scientific journal) Publisher：ELSEVIER SCIENCE SA

mu-Nitrido-bridged iron phthalocyanine dimers have attracted considerable attention because of their catalytic ability in alkane oxidation. However, clear and practical synthetic procedures for the simplest mu-nitrido-bridged iron phthalocyanine dimer with no peripheral substituents have not been reported because of its low solubility. In this study, we report improved synthesis and spectroscopic identification of the monocationic species of mu-nitrido-bridged iron phthalocyanine dimers that has no peripheral substituent groups. We observed that the use of iodine as an oxidant for the mu-nitrido-bridged iron phthalocyanine dimer prevents over-oxidation. Pyridine can dissolve its 1e(-)-oxidized monocationic species, which was characterized by H-1 NMR, C-13 NMR, IR, and UV spectroscopy as well as cyclic voltammetry.

DOI： 10.1016/j.ica.2019.02.021

Near-infrared absorption by intramolecular charge-transfer transition in 5,10,15,20-tetra(N-carbazolyl)porphyrin through protonation Reviewed International journal

Kawano Shin-ichiro, Kawada Sae, Kitagawa Yasutaka, Teramoto Rena, Nakano Masayoshi, Tanaka Kentaro

CHEMICAL COMMUNICATIONS Vol. 55 ( 20 ) page： 2992 - 2995 2019.3

Site-Selective Supramolecular Complexation Activates Catalytic Ethane Oxidation by a Nitrido-Bridged Iron Porphyrinoid Dimer Reviewed International journal

Nozomi Mihara, Yasuyuki Yamada, Hikaru Takaya, Yasutaka Kitagawa, Kazunobu Igawa, Katsuhiko Tomooka, Hiroshi Fujii, Kentaro Tanaka

Chemistry - A European Journal Vol. 25 ( 13 ) page： 3369 - 3375 2019.3

Authorship：Last author,　Corresponding author Language：English Publishing type：Research paper (scientific journal)

© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Development of supramolecular methods to further activate a highly reactive intermediate is a fascinating strategy to create novel potent catalysts for activation of inert chemicals. Herein, a supramolecular approach to enhance the oxidizing ability of a high-valent oxo species of a nitrido-bridged iron porphyrinoid dimer that is a known potent molecular catalyst for light alkane oxidation is reported. For this purpose, a nitrido-bridged dinuclear iron complex of porphyrin-phthalocyanine heterodimer 3 5+ , which is connected through a fourfold rotaxane, was prepared. Heterodimer 3 5+ catalyzed ethane oxidation in the presence of H 2 O 2 at a relatively low temperature. The site-selective complexation of 3 5+ with an additional anionic porphyrin (TPPS 4− ) through π–π stacking and electrostatic interactions afforded a stable 1:1 complex. It was demonstrated that the supramolecular post-synthetic modification of 3 5+ enhances its catalytic activity efficiently. Moreover, supramolecular conjugates achieved higher catalytic ethane oxidation activity than nitrido-bridged iron phthalocyanine dimer, which is the most potent iron-oxo-based molecular catalyst for light-alkane oxidation reported so far. Electrochemical measurements proved that the electronic perturbation from TPPS 4− to 3 5+ enhanced the catalytic activity.

DOI： 10.1002/chem.201805580

Intramolecular strong electronic coupling in a discretely H-aggregated phthalocyanine dimer connected with a rigid linker

Specific and Oriented Encapsulation of Fullerene C70 into a Supramolecular Double-Decker Cage Composed of Shape-Persistent Macrocycles Reviewed International journal

Kawano Shin-ichiro, Fukushima Tomoaki, Tanaka Kentaro

ANGEWNDTE CHEMIE-INTERNATIONAL EDITION Vol. 57 ( 45 ) page： 14827 - 14831 2018.11

Liquid-crystalline Phthalocyanine with Short Intercolumnar Distance and Variation of the Liquid Crystallinity Induced by Square-planar Metal Ions Reviewed International journal

Kawano Shin-ichiro, Yamada Yasuyuki, Shu Rongfang, Ishihara Yu, Tanaka Kentaro

CHEMISTRY LETTERS Vol. 47 ( 10 ) page： 1262 - 1264 2018.10

Programmable arrangement of metal ions in a cofacially stacked assembly of porphyrinoids toward molecular tags Reviewed

Mihara Nozomi, Yamada Yasuyuki, Furukawa Ko, Kato Tatsuhisa, Tanaka Kentaro

DALTON TRANSACTIONS Vol. 47 ( 20 ) page： 7044-7049 2018.5

Columnar Liquid-Crystalline Macrocycles Synthesized via Metal Ion-Assisted Self-Assembly Reviewed

Kawano Shin-ichiro, Murai Takafumi, Harada Takahiro, Tanaka Kentaro

INORGANIC CHEMISTRY Vol. 57 ( 7 ) page： 3913-3919 2018.4

Columnar Liquid Crystals from a Giant Macrocycle Mesogen Reviewed

Kawano Shin-ichiro, Kato Masahiro, Soumiya Shinya, Nakaya Masato, Onoe Jun, Tanaka Kentaro

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION Vol. 57 ( 1 ) page： 167-171 2018.1

Yasuyuki Yamada, Yasuyuki Yamada, Yasuyuki Yamada, Katsuhiko Nawate, Tomoaki Maeno, Kentaro Tanaka

Chemical Communications Vol. 54 page： 8226-8228 2018.1

Publishing type：Research paper (scientific journal)

© 2018 The Royal Society of Chemistry. Preparation of an accurate assembly of phthalocyanines is rather difficult because of the high aggregation property of phthalocyanines. In this study, a novel discrete phthalocyanine dimer was prepared in which the relative configuration of each component was tightly and accurately fixed in an H-aggregate form by a rigid U-shaped linker. Electrochemical measurements showed that there were strong intramolecular electronic interactions between the two phthalocyanines.

DOI： 10.1039/c8cc04335c

Programmable Arrangement of Heterometal Ions in a Supramolecular Array of Porphyrin and Phthalocyanine Reviewed

Dynamic Molecular Invasion into a Multiply Interlocked Catenane Reviewed

Yamada Yasuyuki, Itoh Ryohei, Ogino Sayaka, Kato Tatsuhisa, Tanaka Kentaro

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION Vol. 56 ( 45 ) page： 14124-14129 2017.11

Electronic perturbation of supramolecular conjugates of porphyrins and phthalocyanines Reviewed

Mihara Nozomi, Yamada Yasuyuki, Akine Shigehisa, Sugimoto Kunihisa, Tanaka Kentaro

CHEMICAL COMMUNICATIONS Vol. 53 ( 14 ) page： 2230-2232 2017.2

Nozomi Mihara, Yasuyuki Yamada, and Kentaro Tanaka

Bull. Chem. Soc. Jpn. Vol. 90 page： 427-435 2017

Solid-State NMR Study of Dynamic Properties of a Columnar Liquid Crystalline Macrocycle Reviewed

Shin-ichiro Kjawano and Kentaro Tanaka

Bull. Chem. Soc. Jpn. Vol. 90 page： 826–830 2017

Oxygen Reduction to Water by Cofacial Dimer of Fe(III)porphyrin and Fe(III)phthalocyanine Linked via Highly Flexible Four-fold Rotaxane Reviewed

Nozomi Mihara, Yasuyuki Yamada, Hikaru Takaya, Yasutaka Kitagawa, Shin Aoyama, Kazunobu Igawa, Katsuhiko Tomooka, and Kentaro Tanaka

Chem. Eur. J. Vol. 23 page： 7508-7514 2017

Electronic Perturbation of Supramolecular Conjugates of Porphyrins and Phthalocyanines Reviewed

Nozomi Mihara, Yasuyuki Yamada, Shigehisa Akine, Kunihisa Sugimoto and Kentaro Tanaka

Vol. 53 page： 2230-2232 2017

Frontispiece: Metal-Ion-Induced Switch of Liquid-Crystalline Orientation of Metallomacrocycles

Shin ichiro Kawano, Takashi Hamazaki, Atsushi Suzuki, Kenshin Kurahashi, Kentaro Tanaka

Chemistry - A European Journal Vol. 22 page： 15674 2016.10

Inside Cover: Assembly of Multi-Phthalocyanines on a Porphyrin Template by Fourfold Rotaxane Formation (Chem. Eur. J. 35/2016)

Yasuyuki Yamada, Yasuyuki Yamada, Tatsuhisa Kato, Kentaro Tanaka

Chemistry - A European Journal Vol. 22 page： 12202 2016.8

Kinetically "Locked" Metallomacrocycle Reviewed

Toshio Nishino, Yasuyuki Yamada, Shigeyuki Akine, Kunihisa Sugimoto and Kentaro Tanaka

Dalton Trans. Vol. 45 page： 3831-3837 2016

Self-Assembled Synthesis and Liquid Crystalline Property of Metallomacrocycle Composed of Naphthalenedihydroxamate and Cu²⁺ Ions Reviewed

Shin-ichiro Kawano, Hiroshi Inada, and Kentaro Tanaka

Chem. Lett. Vol. 45 page： 1105-1107 2016

Metal-Ion-Induced Switch of Liquid Crystalline Orientation of Metallomacrocycles Reviewed

Shin-ichiro Kawano, Takashi Hamazaki, Atsushi Suzuki, Kenshin Kurahashi, and Kentaro Tanaka

Chem. Eur. J. Vol. 22 page： 15674-15683 2016

Assembly of Multi-Phthalocyanines on a Porphyrin Template via Fourfold Rotaxane Formation Reviewed

Yasuyuki Yamada, Tatsuhisa Kato, and Kentaro Tanaka

Chem. Eur. J. Vol. 22 page： 12371-12380 2016

Crystalline Two-dimensional Nanosheet Composed of Tetraanionic Porphyrins and Tetracationic Metallomacrocycles Reviewed

Toshio Nishino, Yasuyuki Yamada, and Kentaro Tanaka

J. Porphyrins and Phthalocyanines Vol. 20 page： 694-699 2016

Stacked Pairing of Anionic Porphyrins on a Tetracationic Macrocyclic Template Reviewed

Toshio Nishino, Yasuyuki Yamada, and Kentaro Tanaka

Chem. Lett. Vol. 45 page： 356-358 2016

Columnar Liquid-Crystalline Metallomacrocycles Reviewed

Sinichito Kawano, Yukari Ishida, Kentaro Tanaka

Journal of American Chemical Society Vol. 137 page： 2295-2302 2015.2

Metal-Induced Dynamic Conformational and Fluorescence Switch of Quinone-Appended Zn-Porphyrin Reviewed

Yasuyuki Yamada, Kosuke Hiraga, Kentaro Tanaka

Journal of Porphyrins and Phthalocyanines Vol. 19 page： 334-351 2015

Crystal Structures of Stacked Ionic Assemblies of Tetracationic and Tetraanionic Porphyrins Reviewed

Yamada Yamada, Satoru Matsumoto, Kazushi Yamada, Toshio Nishino, Nozomi Mihara, Kunihiko Sugimoto, Kentaro Tanaka

Chemistry Letters Vol. 43 page： 1377-1379 2014.8

Coordination Oligomers and Polymers of an Oxazole-Appended Zinc Chlorophyll Derivative Reviewed

Y. Shinozaki, I. Yoshikawa, K. Araki, K. Ohara, K. Yamaguchi, S. Kawano, K. Tanaka, Y. Araki, T. Wada, J. Otsuki

Chemistry Letters Vol. 43 page： 862-864 2014.6

Triply Stacked Heterogeneous Array of Porphyrins and Phthalocyanine through Stepwise Formation of a Fourfold Rotaxane and an Ionic Complex Reviewed

Yasuyuki Yamada, Nozomi Mihara, Shinya Shibano, Kunihiro Sugimoto, Kentaro Tanaka

Journal of American Chemical Society Vol. 135 page： 11505-11508 2013.8

Metal-Induced Structural Switching of a Folded Quinone-Sandwiched Porphyrin Reviewed

Yasuyuki Yamada Kentaro Tanaka

J. Inorg. Organomet. Polym. Vol. 23 page： 180-185 2013.6

Double Helices of a Pyridine-Appended Zinc Chlorophyll Derivative Reviewed

Y. Shinozaki, G. Richards, K. Ogawa, A. Yamano, K. Ohara, K. Yamaguchi, S. Kawano, K. Tanaka, Y. Araki, T. Wada, J. Otsuki

Journal of American Chemical Society Vol. 135 page： 5262–5265 2013.4

Synthesis of a Hetero-Dinuclear Metal Complex in a Porphyrin/Phthalocyanine Four-Fold Rotaxane Reviewed

Yasuyuki Yamada, Nozomi Mihara, Kentaro Tanaka

Dalton Transaction Vol. 42 page： 15873-15876 2013

Repetitive Stepwise Rotaxane Formation toward Programmable Molecular Arraying Reviewed

Yauyuki Yamada, Masaaki Okada, Kentaro Tanaka

Chemical Communications Vol. 49 page： 11053-11055 2013

Synthesis of a hetero-dinuclear metal complex in a porphyrin/phthalocyanine four-fold rotaxane Reviewed

Yamada Yasuyuki, Mihara Nozomi, Tanaka Kentaro

DALTON TRANSACTIONS Vol. 42 ( 45 ) page： 15873-15876 2013

Repetitive stepwise rotaxane formation toward programmable molecular arrays Reviewed

Yamada Yasuyuki, Okada Masa-aki, Tanaka Kentaro

CHEMICAL COMMUNICATIONS Vol. 49 ( 94 ) page： 11053-11055 2013

Harmony of π-π Stacking Interaction and Metal Complexation to Generate Molecular Functional Emergence Invited Reviewed

Yamada Yasuyuki, Tanaka Kentaro

Bull. Jpn. Soc. Coord. Chem. Vol. 62 page： 12 - 22 2013

Authorship：Last author,　Corresponding author Language：English Publishing type：Research paper (scientific journal) Publisher：Japan Society of Coordination Chemistry

In this review, we focus on the integrated assemblies of metal complexes and their functional emergence generated by the synergy effects of π-π stacking interaction and metal complexation. Programmable construction of integrated molecular assemblies is the best measure for bringing out the emergent functions which can be evolved from the intermolecular communications of functional molecular components. Combination of π-π stacking interaction and metal complexation allows not only to reinforce the mutual interactions but also to generate the emergent intermolecular communications. This review introduces the recent studies including the synergy effects on electrical, magnetic, catalytic and molecular recognition functions in soft, crystalline and single molecular materials.

DOI： 10.4019/bjscc.62.12

Other Link： https://jlc.jst.go.jp/DN/JALC/10031164206?from=CiNii

Room-Temperature Single Molecular Memory Reviewed

S. Kano, Y. Yamada, K. Tanaka, Y. Majima

App. Phys. Lett. Vol. 100 page： 053101(1-3) 2012.1

Switchable Intermolecular Communication in a Four-Fold Rotaxane Reviewed

Yasuyuki Yamada, Mitsuyoshi Okamoto, Ko Furukawa, Tatsuhisa Kato, Kentaro Tanaka

Angewandte Chimie International Edition Vol. 51 page： 709–713 2012

Direct Conductance Measurement of Individual Metallo-DNA Duplexes within Single-Molecule Break Junctions Reviewed

S. Liu, G. H. Clever, Y. Takezawa, M. Kaneko, K. Tanaka, X. Guo, M. Shionoya

Angewandte Chemie International Edition Vol. 50 page： 9048-9052 2011

Discrete Self-Assembly of Iron(III) Ions inside Triple-Stranded Artificial DNA Reviewed

Y. Takezawa, W. Maeda, K. Tanaka, and M. Shionoya

Angew. Chem. Int. Ed. Vol. 48 page： 1081-1084 2009

Discrete Self-Assembly of Iron(III) Ions inside Triple-Stranded Artificial DNA Reviewed

Takezawa Yusuke, Maeda Wakana, Tanaka Kentaro, Shionoya Mitsuhiko

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION Vol. 48 ( 6 ) page： 1081-1084 2009

Soft metal-mediated base pairing with novel synthetic nucleosides possessing an O,S-donor ligand Reviewed

Takezawa Yusuke, Tanaka Kentaro, Yori Maiko, Tashiro Shohei, Shiro Motoo, Shionoya Mitsuhiko

JOURNAL OF ORGANIC CHEMISTRY Vol. 73 ( 16 ) page： 6092-6098 2008.8

Ni(II)-Mediated self-assembly of artificial beta-dipeptides forming a macrocyclic tetranuclear complex with interior spaces for in-line molecular arrangement Reviewed

Miyake Ryosuke, Tashiro Shohei, Shiro Motoo, Tanaka Kentaro, Shionoya Mitsuhiko

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Vol. 130 ( 17 ) page： 5646-+ 2008.4

A close-packed, highly insulating organic thin monolayer on Si(111) Reviewed

Tanaka Kentaro, Tanaka Taishi, Hasegawa Takeshi, Shionoya Mitsuhiko

CHEMISTRY LETTERS Vol. 37 ( 4 ) page： 440-441 2008.4

A Closed-packed, Highly-insulating Organic Thin Monolayer on Si(111) Reviewed

K. Tanaka, T. Tanaka, T. Hasegawa, and M. Shionoya

Chem. Lett. Vol. 37 page： 440-441 2008

バイオインスパイアードなテンプレートを用いた精密分子組織の構築 Invited

田中健太郎

液晶 Vol. 13 page： 33-41 2008

Soft Metal-Mediated Base Pairing with Novel Synthetic Nucleosides Possessing an O,S-Donor Ligand Reviewed

Y. Takezawa, K. Tanaka, M. Yori, S. Tashiro, M. Shiro, and M. Shionoya

J. Org. Chem. Vol. 73 page： 6092-6098 2008

Ni(II)-Mediated Self-Assembly of Artificial β-Dipeptides Forming a Macrocyclic Tetranuclear Complex with Interior Spaces for In-Line Molecular Arrangement Reviewed

R. Miyake, S. Tashiro, M. Shiro, K. Tanaka, and M. Shionoya

J. Am. Chem. Soc. Vol. 130 page： 5646-5647 2008

Synthesis of a macrocyclic tetranuclear Ni(II) complex possessing functional holes from artificial beta-dipeptides Reviewed

Miyake Ryosuke, Tashiro Shohei, Shiro Motoo, Tanaka Kentaro, Shionoya Mitsuhiko

YAKUGAKU ZASSHI-JOURNAL OF THE PHARMACEUTICAL SOCIETY OF JAPAN Vol. 128 page： 74 2008

Synthesis of a metal-salen base pair for the assembly of programmed metal arrays inside DNA Reviewed

Clever Guido H., Tanaka Kentaro, Takezawa Yusuke, Kaul Corinna, Carell Thomas, Shionoya Mitsuhiko

YAKUGAKU ZASSHI-JOURNAL OF THE PHARMACEUTICAL SOCIETY OF JAPAN Vol. 128 page： 67 2008

Discrete self-assembly of iron (III) ions inside triple-stranded artificial DNA Reviewed

Takezawa Yusuke, Kaneko Motoo, Maeda Wakana, Clever Guido H., Tanaka Kentaro, Shionoya Mitsuhiko

YAKUGAKU ZASSHI-JOURNAL OF THE PHARMACEUTICAL SOCIETY OF JAPAN Vol. 128 page： 78 2008

A template-directed synthetic approach to halogen-bridged mixed-valence platinum complexes on artificial peptides in solution Reviewed

Tanaka Kentaro, Kaneko Kenji, Watanabe Yusuke, Shionoya Mitsuhiko

DALTON TRANSACTIONS ( 46 ) page： 5369-5371 2007.12

Programmable metal assembly on bio-inspired templates Reviewed

Tanaka Kentaro, Shionoya Mitsuhiko

COORDINATION CHEMISTRY REVIEWS Vol. 251 ( 21-24 ) page： 2732-2742 2007.11

Programmable self-assembly of metal ions inside artificial DNA duplexes (vol 1, pg 190, 2006) Reviewed

Tanaka Kentaro, Clever Guido H., Takezawa Yusuke, Yamada Yasuyuki, Kaul Corinna, Shionoya Mitsuhiko, Carell Thomas

NATURE NANOTECHNOLOGY Vol. 2 ( 1 ) page： 63 2007.1

A template-directed synthetic approach to halogen-bridged mixed-valence platinum complexes on artificial peptides in solution Reviewed

Kentaro Tanaka, Kenji Kaneko, Yusuke Watanabe and Mitsuhiko Shionoya

Dalton Transactions Vol. 2007 page： 5369-5371 2007

Authorship：Lead author Language：English Publishing type：Research paper (scientific journal)

A template-directed synthetic approach to halogen-bridged mixed-valence platinum complexes has been performed in organic media using, for instance, a synthetic peptide bearing two bis(ethylenediamine)-based Pt(IV) complexes with two axial bromide anionic ligands,5 [1a(Pt(IV)Br2 (en))2 ](RSO3 )4 , and a [Pt(II)(en)2 ](RSO3 )2 complex (R = (C12 H25 OCH2 )2 CHO(CH2 )3 -).

生体高分子に学ぶ“ものづくり”－金属イオンの精密配列化 Invited

田中健太郎

超分子研究会アニュアルレビュー Vol. 28 page： 2-3 2007

Programmable metal assembly on bio-inspired templates Invited Reviewed

Kentaro Tanaka and Mitsuhiko Shionoya

Coordination Chemistry Reviews Vol. 251 page： 1731-2742 2007

Programmed metal arrays by means of designable biological macromolecules

Kentaro Tanaka, Kentaro Tanaka, Tokomo Okada, Mitsuhiko Shionoya

Redox Systems Under Nano-Space Control page： 155-165 2006.12

Publishing type：Research paper (scientific journal)

9.4 Conclusion: In this study, we demonstrate that biopolymers such as DNA and peptides can be precisely redesigned and reconstructed as templates for homogeneous or even heterogeneous assembly of metal ions in a programmable manner by chemically modiyfing their building blocks. This bottom-up strategy based on biorelated molecules would generate not only a new structuralmotif formetal clusters in the biomolecules but also a metal-triggered information-transfer system. © 2006 Springer-Verlag Berlin Heidelberg.

DOI： 10.1007/3-540-29580-1_9

Molecular orientation of organic monolayers on Si(111)

Programmable self-assembly of metal ions inside artificial DNA duplexes Reviewed

Tanaka Kentaro, Clever Guido H., Takezawa Yusuke, Yamada Yasuyuki, Kaul Corinna, Shionoya Mitsuhiko, Carell Thomas

NATURE NANOTECHNOLOGY Vol. 1 ( 3 ) page： 190-U5 2006.12

Bio-inspired programmable self-assembly on DNA templates Reviewed

Tanaka Kentaro, Shionoya Mitsuhiko

CHEMISTRY LETTERS Vol. 35 ( 7 ) page： 694-699 2006.7

Toward a protecting-group-free halogen-metal exchange reaction: Practical, chemoselective metalation of functionalized aromatic halides using dianion-type zincate, (Bu4ZnLi2)-Bu-t Reviewed

Uchiyama Masanobu, Furuyama Taniyuki, Kobayashi Minoru, Matsumoto Yotaro, Tanaka Kentaro

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Vol. 128 ( 26 ) page： 8404-8405 2006.7

Bio-Inspired Programmable Self-Assembly on DNA Templates Invited

K. Tanaka and M. Shionoya

Chem. Lett. Vol. 35 page： 694-699 2006

Authorship：Lead author Language：English Publishing type：Research paper (scientific journal)

Besides the biological importance of DNA as storage of genetic information, DNA is a smart molecule to assemble functional units since it is possible to use sequences of nucleobases to encode molecular assembled systems in a predetermined fashion over a wide range in size. This review highlights recent advance in precise control of molecular assembly on DNA templates directed towards functionalized materials.

*Programmable Self-Asembly of Metal Ions Inside Artificial DNA Duplexes Reviewed

K. Tanaka, G. Clever, Y. Takezawa, Y. Yamada, C. Kaul, M. Shionoya, and T. Carell

Nature Nanotech. Vol. 1 page： 190-194 2006

Toward a Protecting-Group-Free Halogen-Metal Exchange Reaction:Practical, Chemoselective Metalation of Functionalized Aromatic HalidesUsing Dianion-type Zincate, tBu4ZnLi2 Reviewed

Masanobu Uchiyama, Taniyuki Furuyama, Minoru Kobayashi, Yotaro Matsumoto, and Kentaro Tanaka

J. Am. Chem. Soc. Vol. 128 page： 8404-8405 2006

Language：English Publishing type：Research paper (scientific journal)

A versatile preparation method for aromatic zincate compounds through a halogen-zinc exchange reaction using dilithium tetra-tert-butylzincate (tBu4ZnLi2) has been developed. This reagent permits efficient preparation of highly functionalized aromatic zincates, particularly, those with electrophilic functional groups, such as ester, amide, alcohol, and phenol. Halogen-zinc exchange reactions followed by electrophilic trapping (with allyl bromide or benzaldehyde) proved to be a powerful tool for C-C bond formation on functionalized aromatic rings. The functionalized aromatic zincate intermediate was also found to undergo copper- and palladium-catalyzed C-C bond-forming reactions with good yields and high chemoselectivity.

Taishi Tanaka, Kentaro Tanaka, Kentaro Tanaka, Hiroyuki Kakuda, Takeshi Hasegawa, Takeshi Hasegawa, Mitsuhiko Shionoya

Polymer Preprints, Japan Vol. 54 page： 3329-3330 2005.12

Publishing type：Research paper (scientific journal)

Alkenes form self-assembled monolayers on a hydrogen-terminated Si(111) surface via hydrosilylation of defines. Since the monolayers are attached onto the substrate covalently through direct Si-C bonding, the molecular orientation of the monolayer is strongly influenced by compatibility between the crystal structure of Si(111) surface and the molecular structure of the olefin. In this study, we examined the formation of various monolayers and their molecular orientations on Si(111).

Heterogeneous metal arrays into artificial metallo-DNAs as templates International journal

Kentaro Tanaka, Kentaro Tanaka, Yusuke Takezawa, Takuya Agata, Atsushi Katagiri, Tatsuhisa Kato, Mitsuhiko Shionoya

Polymer Preprints, Japan Vol. 54 page： 5126 - 5127 2005.12

Language：English Publishing type：Research paper (scientific journal)

Besides the biological importance of DNA as storage of genetic information, the fundamental and canonical structure of duplex DNA can be regarded as a template for the bio-inspired molecular architectures to develop new functions. DNA has an attractive system to assemble functional building blocks, because automated synthesizers can routinely make oligomers with desired lengths and sequences. Replacement of hydrogen-bonded base pairing of DNA by metal-mediated base pairing could lead to "metallo-DNA" in which metal ions are aligned along the helix axis in a controllable fashion (Chart 1). We report here the de novo designed heterogeneous metal array in artificial metallo-DNA. To heterogeneously array metal ions in double helices, d(5′-GHPHC-3′)2, d(5′-GHHPHHC-3′)2, and d(5′-GHVHC- 3′)2were synthesized, where H is a hydroxypyridone-bearing nucleotide forming a square planar complex with a Cu2+ion, P is a pyridine-bearing nucleotide forming a linear complex with an Ag+or an Hg2+ion, and V is an abasic site. Stepwise photometric titration experiments of Cu2+and subsequent Hg2+to the duplexes and electrospray ionization mass spectroscopy clearly demonstrated the quantitative and site-selective formation of Cu2+-Hg2+-Cu2+, Cu2+-Cu2+-Hg2+-Cu2+-Cu2+and Cu2+- Cu2+arrays in the centers of the duplexes, respectively (Fig. 2).

Analysis of hydrogen-terminated Si(1 1 1) surface by infrared multiple-angle incidence resolution spectroscopy

Hiroyuki Kakuda, Takeshi Hasegawa, Takeshi Hasegawa, Taishi Tanaka, Kentaro Tanaka, Kentaro Tanaka, Mitsuhiko Shionoya

Chemical Physics Letters Vol. 415 page： 172-175 2005.10

Publishing type：Research paper (scientific journal)

The infrared multiple-angle incidence resolution spectroscopy (MAIRS) has been employed to analyze the hydrogen-terminated Si(1 1 1) 1 × 1-H surface. The new technique of infrared MAIRS provides two absorption spectra simultaneously on an identical sample, which separately reveal the surface-parallel and surface-normal vibration spectra. It has been exhibited in the present study that the infrared MAIRS technique is powerful to discuss some infrared key bands in terms of molecular orientation concerned with Si-H vibrational modes on the Si(1 1 1) 1 × 1-H surface with the use of the two spectra. © 2005 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.cplett.2005.09.017

Artificial metallo-DNA: Structural control of DNA and nano-assembly of metal complexes

Heterogeneous assembly of silver(I) and calcium(II) ions accompanying a dimer formation of cyclo(L-Ala-L-Met)3. Reviewed

Okada T, Tanaka K, Shiro M, Shionoya M

Chemical communications (Cambridge, England) ( 11 ) page： 1484-1486 2005.3

Analysis of Hydrogen-Terminated Si(111) Surface by Infrared Multiple-Angle Incidence Resolution Spectroscopy Reviewed

Hiroyuki Kakuda, Takeshi Hasegawa, Taishi Tanaka, Kentaro Tanaka, and Mitsuhiko Shionoya

Chem. Phys. Lett. Vol. 415 page： 172-175 2005

Heterogeneous Assembly of Silver(I) and Calcium(II) Ions Accompanying a Dimer Formation of cyclo(L-Ala- L -Met)3 Reviewed

T. Okada, K. Tanaka, M. Shiro, and M. Shionoya

Chem. Commun. Vol. 2005 page： 1484/1486 2005

Artificial metallo-DNA: a bio-inspired approach to metal array programming. Reviewed

Shionoya M, Tanaka K

Current opinion in chemical biology Vol. 8 ( 6 ) page： 592-597 2004.12

[Artificial metallo-DNA: arraying metal ions using DNA]. Reviewed

Shionoya M, Tanaka K

Tanpakushitsu kakusan koso. Protein, nucleic acid, enzyme Vol. 49 ( 10 ) page： 1438-1443 2004.8

Interaction of plastocyanin with oligopeptides: effect of lysine distribution within the peptide. Reviewed

Hirota S, Okumura H, Arie S, Tanaka K, Shionoya M, Takabe T, Funasaki N, Watanabe Y

Journal of inorganic biochemistry Vol. 98 ( 5 ) page： 849-855 2004.5

Kentaro Tanaka, Mitsuhiko Shionoya

Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry Vol. 62 page： 508-513 2004.1

Publishing type：Research paper (scientific journal)

DNA has a structural basis for the "bottom-up" fabrication of functionalized molecular building blocks. In particular, the replacement of hydrogen-bonded DNA base pairing for alternative one would lead to a novel tool for re-engineering DNA. Recently, we have synthesized a series of artificial nucleosides bearing metal ligands instead of natural nucleobases and demonstrated that metal complexation between the nucleosides effectively drives base pairing. This review describes our recent approaches to metal-based strategy directed towards self-assembled metal arrays within DNA as well as towards structural control of DNA. This strategy provides a new method for self-assembled metal arrays in a predesigned fashioji, leading possibly to metal-based molecular devices such as molecular magnets and wires.

DOI： 10.5059/yukigoseikyokaishi.62.508

Syntheses of nucleic acid mimics designed for metal-induced strand formation on DNA

金属錯体型人工ＤＮＡ Invited

塩谷光彦, 田中健太郎

蛋白質核酸酵素 Vol. 49 page： 1438-1443 2004

金属錯体型人工ＤＮＡ：ＤＮＡ構造制御と金属錯体ナノ集積化 Invited

田中健太郎, 塩谷光彦

有機合成化学協会誌 Vol. 8 page： 592-579 2004

Interaction of plastocyanin with oligopeptides: effect of lysine distribution within the peptide Reviewed

Shun Hirota, Hisano Okumura, Sachiko Arie, Kentaro Tanaka, Mitsuhiko Shionoya, Teruhiro Takabe, Noriaki Funasaki, amd Yoshihito Watanabe

Journal of Inorganic Biochemistry Vol. 98 page： 849-855 2004

Authorship：Lead author Language：English Publishing type：Research paper (scientific journal)

We synthesized and purified four oligopeptides containing four lysines (KKKK, GKKGGKK, KKGGGKK, and KGKGKGK) as models for the plastocyanin (PC) interacting site of cytochrome f. These peptides competitively inhibited electron transfer between cytochrome c and PC. The inhibitory effect increased as the peptide concentrations were increased. The association constants between PC and the peptides did not differ significantly (3500-5100 M

Artificial Metallo-DNA: A Bio-Inspired Approach to Metal Array Programming Invited Reviewed

M. Shionoya and K. Tanaka

Curr. Opin. Chem. Biol. Vol. 8 page： 592-579 2004

Authorship：Lead author Language：English Publishing type：Research paper (scientific journal)

The structure of DNA is such that the multi-array of functionalized units with desired numbers and sequences within the DNA is possible. In particular, to replace DNA bases, which are biologically important elements for gene expression, by alternative bases would provide powerful tools for programming molecular arrays in a pre-designed manner. This review focuses on recent chemical approaches to
self-assembled metal arrays within DNA with metal-mediated base pairing.

Role of a non-natural beta-C-nucleotide unit in DNA as a template for DNA and RNA syntheses and as a substrate for nucleolytic digestion. Reviewed

Aketani S, Tanaka K, Yamamoto K, Ishihama A, Cao H, Tengeiji A, Shionoya M

European journal of pharmaceutical sciences : official journal of the European Federation for Pharmaceutical Sciences Vol. 20 ( 1 ) page： 43-51 2003.9

A discrete self-assembled metal array in artificial DNA. Reviewed

Tanaka K, Tengeiji A, Kato T, Toyama N, Shionoya M

Science (New York, N.Y.) Vol. 299 ( 5610 ) page： 1212-1213 2003.2

Artificial nucleosides possessing metal binding sites at the 3'- and 5'-positions of the deoxyribose moieties. Reviewed

Chiba JY, Tanaka K, Ohshiro Y, Miyake R, Hiraoka S, Shiro M, Shionoya M

The Journal of organic chemistry Vol. 68 ( 2 ) page： 331-338 2003.1

Artificial Nucleosides Possessing Metal Binding Sites at the 3'- and 5'-Positions of the Deoxyribose Moieties Reviewed

J. Chiba, K. Tanaka, Y. Ohshiro, R. Miyake, M. Shiro, and M. Shionoya

J. Org. Chem. Vol. 68 page： 331-338 2003

Role of a Non-natural β-C-Nucleotide Unit in DNA as a Template for DNA and RNA Syntheses and as a Substrate for Nucleolytic Digestion Reviewed

S. Aketani, K. Tanaka, K. Yamamoto, A. Ishihama, H. Cao, A. Tengeiji, and M. Shionoya

Eur. J. Pharm. Sci. Vol. 20 page： 43-51 2003

Artificial Metallo-DNA: Structural Control and Discrete Metal Assembly Reviewed

K. Tanaka, Y. Yamada, A. Tengeiji, T. Kato, N. Toyama, Y. Takezawa, M. Yori, M. Shiro, and M. Shionoya

Nucleic Acids Research Supplement Vol. 3 page： 121-122 2003

Artificial metallo-DNA: structural control and discrete metal assembly. Reviewed

Tanaka K, Yamada Y, Tengeiji A, Kato T, Toyama N, Takezawa Y, Yori M, Shiro M, Shionoya M

Nucleic acids research. Supplement (2001) ( 3 ) page： 121-122 2003

Syntheses and structure-activity relationships of nonnatural beta-C-nucleoside 5'-triphosphates bearing an aromatic nucleobase with phenolic hydroxy groups: inhibitory activities against DNA polymerases. Reviewed

Aketani S, Tanaka K, Yamamoto K, Ishihama A, Cao H, Tengeiji A, Hiraoka S, Shiro M, Shionoya M

Journal of medicinal chemistry Vol. 45 ( 25 ) page： 5594-5603 2002.12

Efficient incorporation of a copper hydroxypyridone base pair in DNA. Reviewed

Tanaka K, Tengeiji A, Kato T, Toyama N, Shiro M, Shionoya M

Journal of the American Chemical Society Vol. 124 ( 42 ) page： 12494-12498 2002.10

Formation of silver(I)-mediated DNA duplex and triplex through an alternative base pair of pyridine nucleobases. Reviewed

Tanaka K, Yamada Y, Shionoya M

Journal of the American Chemical Society Vol. 124 ( 30 ) page： 8802-8803 2002.7

Akihiko Hatano, Kentaro Tanaka, Motoo Shiro, Mitsuhiko Shionoya

Tetrahedron Vol. 58 page： 2965-2972 2002.4

Publishing type：Research paper (scientific journal)

This paper describes design and syntheses of a new class of chelator-type nucleic acid mimics. Four nucleic acid mimics 7, 11, 15, 17 possess a nucleobase and two ethylenediamine moieties for intermolecular metal coordination. We expected that chelator-type nucleic acid mimics formed a strand in the presence of metal ion and then interacted with a single-stranded DNA. Efficient synthetic routes leading to the four nucleic acid analogues have been achieved via the key intermediate compound 5 which was derived from 3,5-dimethylphenol in five steps. Compound 7 was treated with zinc nitrate and Zn complex 8 was isolated as crystals.1H NMR study of Zn complex 8 in D2O showed the single-strand formation. Job plots showed that mixture of (dT)70with Zn complex 8 at 5°C reached a minimum absorbance at a mole ratio of 2:1, and the hypochromic effect showed the π-π stacking interaction between the nucleobases. Thermal denaturation study at 2:1 mole ratio of complexes between (dT)70and Zn complex 8 showed melting point at 27°C. © 2002 Elsevier Science Ltd. All rights reserved.

DOI： 10.1016/S0040-4020(02)00203-X

Toward nano-assembly of metals through engineered DNAs

Kentaro Tanaka, Motoyuki Tasaka, Honghua Cao, Mitsuhiko Shionoya

Supramolecular Chemistry Vol. 14 page： 255-261 2002.1

Towards Nano-Assembly of Metals with Engineered DNAs Reviewed

K. Tanaka, M. Tasaka, H. Cao, and M. Shionoya

Supramol. Chem. Vol. 14 page： 255-261 2002

Syntheses of Nucleic Acid Mimics Designed for Metal-Induced Strand Formation on DNA Reviewed

A. Hatano, K. Tanaka, M. Shiro and M. Shionoya

Tetrahedron Vol. 58 page： 2965-2972 2002

Synthesis and Structure-Activity Relationships of Nonnatural β-C-Nucleoside Triphosphates Bearing an Aromatic Nucleobase with Phenolic Hydroxyl Groups: Inhibitory Activities against DNA Polymerases Reviewed

S. Aketani, K. Tanaka, K. Yamamoto, A. Ishihama, H. Cao, A. Tengeiji, S. Hiraoka, M. Shiro, and M. Shionoya

J. Med. Chem. Vol. 25 page： 5594-5603 2002

Formation of Silver(I)-Mediated DNA Duplex and Triplex through an Alternative Base Pair of Pyridine Nucleobases Reviewed

K. Tanaka, Y. Yamada, and M. Shionoya

J. Am. Chem. Soc. Vol. 124 page： 8802-8803 2002

Spontaneously resolved chiral interpenetrating 3-D nets with two different zinc coordination polymers [7]

M. Sasa, K. Tanaka, X. H. Bu, M. Shiro, M. Shionoya

Journal of the American Chemical Society Vol. 123 page： 10750-10751 2001.10

Nickel-mediated alcoholysis reaction of carbon-nitrogen triple bond: Structural characterization of an unprecedented moisture stable imido ester with an E-configuration

Xian He Bu, Miao Du, Kentaro Tanaka, Mitsuhiko Shionoya, Motoo Shiro

Inorganic Chemistry Communications Vol. 4 page： 150-152 2001.4

Novel organic crystals as candidates for frequency up-converted materials: Syntheses and crystal structures of two Tröger's bases

X. H. Bu, M. Du, L. J. Zhao, K. Tanaka, M. Shionoya, M. Shiro

Journal of Chemical Research - Part S page： 243-245 2001.1

Spontaneously Resolved Chiral Interpenetrating 3-D Nets with Two Different Zinc Coordination Polymers Reviewed

M. Sasa, K. Tanaka, M. Shiro, X.-H. Bu, and M. Shionoya

J. Am. Chem. Soc. Vol. 123 page： 10750-10751 2001

A Palladium-Mediated DNA Base Pair of a beta-C-Nucleoside Possessing a 2-Aminophenol as the Nucleobase Reviewed

M. Tasaka, K. Tanaka, M. Shiro, and M. Shionoya

Supramol. Chem. Vol. 13 page： 671-675 2001

An approach to metal-assisted DNA base pairing: Novel β-C-nucleosides with a 2-aminophenol or a catechol as the nucleobase International journal

Kentaro Tanaka, Motoyuki Tasaka, Honghua Cao, Mitsuhiko Shionoya

European Journal of Pharmaceutical Sciences Vol. 13 ( 1 ) page： 77 - 83 2001

Language：English Publishing type：Research paper (scientific journal)

The metal-chelating β-C-nucleoside having a phenylenediamine moiety as the nucleobase was previously found to form a stable 2:1 complex with a Pd2+ ion in aqueous media, where hydrogen bonding is replaced by metal coordination in the base pairing, thereby creating a novel hybridization motif in duplex DNA. In this regard, we have further designed two types of artificial β-C-nucleosides possessing a metal-chelating site (a 2-aminophenol or a catechol) as the nucleobase moiety. These artificial nucleosides are directed toward controlling the net charges of the metal-assisted base pairs. This paper describes convenient syntheses of the artificial nucleosides bearing a 2-aminophenol or a catechol moiety. Each nucleoside was directly synthesized through 2′-deoxy derivative via a Friedel-Crafts coupling reaction as the key step between the aromatic ring and ribose moiety, whereas the nucleoside having a phenylenediamine moiety was prepared in rather longer steps through an RNA type intermediate followed by the removal of 2′-hydroxyl group. © 2001 Elsevier Science B.V.

DOI： 10.1016/S0928-0987(00)00210-4

A novel polymeric Ag(I) complex consisting of two three-dimensional networks which are enantiometric and interpenetrating

X. H. Bu, K. Biradha, T. Yamaguchi, M. Nishimura, T. Ito, K. Tanaka, M. Shionoya

Chemical Communications page： 1953-1954 2000.10

Synthetic incorporation of metal complexes into nucleic acids and peptides directed toward functionalized molecules

M. Shionoya, K. Tanaka

Bulletin of the Chemical Society of Japan Vol. 73 page： 1945-1954 2000.9

Publishing type：Research paper (scientific journal)

Novel synthetic approaches for incorporation of metal complexes into nucleic acids and peptides are described. First, novel artificial β-C-nucleosides bearing a chelator nucleobase (2-aminophenol, catechol, or o-phenylenediamine) have been synthesized. These artificial nucleobases were introduced for alternative base pairing through metal coordination instead of the hydrogen bonding in natural DNA.1HNMR and mass spectral studies clearly showed that o-phenylenediamine-type nucleoside forms a stable 2: 1 square-planar complex with a Pd(II) ion, providing an alternative DNA base pairing through metal complexation. Secondly, an efficient strategy for the liquid-phase synthesis of cyclic metallopeptides having a repeating Gly-L-Cys(terpyPt(II)) sequence, cyclo[-Gly-L-Cys(terpyPt(II))-](n)Cl(n) (n = 3, 4), has been developed. These cyclic metallopeptides were obtained by cyclization of the corresponding linear peptides, H2[-Gly-L-Cys(terpyPt(II))-](n)OH-(CF3CO2)(n+1) (n = 3, 4), in moderate yields. The former cyclic hexapeptide was found to act as a positively charged anion receptor. This synthetic approach would provide a powerful tool for arraying metal centers on cyclopeptide frameworks.

DOI： 10.1246/bcsj.73.1945

A spontaneously resolved chiral molecular box: A cyclic tetranuclear Zn(II) complex with DPTZ (DPTZ = 3,6-di-2-pyridyl-1,2,4,5-tetrazine)

Xian He Bu, Xian He Bu, Xian He Bu, Hiromasa Morishita, Kentaro Tanaka, Kumar Biradha, Sanae Furusho, Mitsuhiko Shionoya

Chemical Communications page： 971-972 2000.6

An alternative base-pairing of catechol-bearing nucleosides by borate formation

Honghua Cao, Kentaro Tanaka, Mitsuhiko Shionoya

Chemical and Pharmaceutical Bulletin Vol. 48 page： 1745-1748 2000.1

Publishing type：Research paper (scientific journal)

A chelator-type β-C-nucteoside having a catechol ligand as the nucleobase was found to form a stable 2 : 1 complex with trimethyl borate, which was characterized by1H-NMR and etectrospray ionization time-of-flight (ESI-TOF) mass speetroseopies. Both phosphoramidite and phosphotriester derivatives of this nueleoside were also prepared as synthetic precursors for DNA oligomer syntheses.

DOI： 10.1248/cpb.48.1745

Self-assembly of chelator-type nucleic acid mimics into a single-stranded Zn^IIcoordination polymer

Akihiko Hatano, Kentaro Tanaka, Motoo Shiro, Mitsuhiko Shionoya

Chemistry Letters page： 822-823 2000.1

Publishing type：Research paper (scientific journal)

The synthesis of a "chelator-type" adenine mimic, which has two metal binding sites, and its ZnII-assisted self-assembly into a single-stranded coordination polymer are described. The UV absorption changes of a 1 : 1 mixture of the ZnIIcomplex and a single-stranded DNA oligomer (dT)70showed the temperature-dependent hyperchromic effect in an analogous manner as thermal denaturation processes of natural DNA duplexes.

DOI： 10.1246/cl.2000.822

Cyclic metallopeptides, cyclo[Gly-L-Cys(terpyPt(II))](n)Cl(n)

Kentaro Tanaka, Kentaro Tanaka, Kazuki Shigemori, Mitsuhiko Shionoya, Mitsuhiko Shionoya

Chemical Communications page： 2475-2476 1999.12

Synthesis of a novel nucleoside for alternative DNA base pairing through metal complexation

Kentaro Tanaka, Mitsuhiko Shionoya, Mitsuhiko Shionoya

Journal of Organic Chemistry Vol. 64 page： 5002-5003 1999.7

Artificial DNAs with metal-assisted base pairs.

K. Tanaka, H. Cao, M. Tasaka, M. Shionoya

Nucleic acids symposium series page： 111-112 1999.1

Anisotropic electric conductivity in an aligned DNA cast film

Y. Okahata, T. Kobayashi, K. Tanaka, M. Shimomura

Journal of the American Chemical Society Vol. 120 page： 6165-6166 1998.1

DNA-aligned cast film and its anisotropic electron conductivity International journal

Y. Okahata, T. Kobayashi, H. Nakayama, K. Tanaka

Supramolecular Science Vol. 5 ( 3-4 ) page： 317 - 320 1998

Language：English Publishing type：Research paper (scientific journal) Publisher：Elsevier Sci Ltd

A DNA-lipid cast film was prepared, in which counter cations of DNA phosphates were replaced by cationic amphiphiles. The film is transparent, physically strong, and water-insoluble. DNA strands could be aligned in one direction by stretching the film. The aligned-DNA film showed a large anisotropic and ohmic electric current (10-5 S cm-1, A⊥/A = 104) along DNA strands in the film.

DOI： 10.1016/S0968-5677(98)00025-X

Oriented thin films of a DNA-lipid complex

Yoshio Okahata, Kentaro Tanaka

Thin Solid Films Vol. 284-285 page： 6-8 1996.9

Publishing type：Research paper (scientific journal)

Organic thin films in which DNA double strands aligned in one direction were prepared by two methods: 1) polyion complexes of DNA anions and cationic amphiphiles was prepared and the organic solution of the DNA-lipid complex was cast and the obtained transparent film was stretched in one direction, and 2) DNA anions were solubilized in subphase with intercalated dyes and were transferred with cationic lipid monolayers by vertical dipping method. DNA strands could be aligned along stretching direction in the cast film and along dipping direction in the LB film. The orientation of DNA strands in the thin films were confirmed by X-ray diffraction and polarized absorption spectra.

DOI： 10.1016/S0040-6090(96)08830-X

Orientation of DNA double strands in a Langmuir-Blodgett film

Yoshio Okahata, Takuya Kobayashi, Kentaro Tanaka

Langmuir Vol. 12 page： 1326-1330 1996.3

Publishing type：Research paper (scientific journal)

A cationic amphiphile monolayer was spread on a subphase containing DNA double strands and intercalating dyes, and the polyion complex DNA/dye/cationic monolayer was transferred to a substrate by the vertical dipping method. It was confirmed by X-ray diffraction patterns and polarized absorption spectra that the dye-intercalated DNA strands were aligned along the dipping direction in the LB film. DNA strands are not aligned in the LB film without intercalating dye molecules. When the DNA-lipid monolayers were deposited by a horizontal lifting method instead of a vertical dipping method, DNA strands were randomly oriented in the film. The orientation of DNAs was decreased when the monolayer packing was decreased by using a low surface pressure or an expanded monolayer. Thus, the rigid, dye-intercalated DNA strands could be oriented during the vertical dipping process.

A DNA-lipid complex in organic media and formation of an aligned cast film

K. Tanaka, Y. Okahata

Journal of the American Chemical Society Vol. 118 page： 10679-10683 1996.1

Publishing type：Research paper (scientific journal)

A novel DNA-lipid complex is prepared by replacing sodium counter cations by cationic amphiphilic lipids (1). The DNA-lipid complex is insoluble in aqueous solutions, but is soluble in most orgamc media such as benzene, ethanol, and chloroform. The DNA-lipid complex was confirmed to form double helical strands even in organic media, and the internal conformation of DNA strands could be reversibly changed from B-form to C-form in the organic solution (CHCl3/EtOH = 4:1) by changing the water content. A self-standing, water-insoluble DNA-lipid (1) film was prepared by casting from the organic solution and could be stretched to produce oriented DNA strands with their axes aligned along the stretching direction. The film can be impregnated with the drug ethidium bromide in the aqueous solution. The linear dichroism characteristics of the drug-DNA film show that the DNA strands are well oriented and the ethidium molecules are intercalated, as they are in normal aqueous solutions.

DOI： 10.1021/ja9617855

Evaluation of a Transfer Process for Langmuir-Blodgett Films by Means of a Quartz-Crystal Microbalance

Yoshio Okahata, Katsuhiko Ariga, Kentaro Tanaka

Thin Films Vol. 20 page： 317-329 1995.1

Quartz Crystal Microbalance and UV-Vis Absorption Study of Q-State CdS Particle Formation in Cadmium Arachidate Langmuir-Blodgett Films

Robert S. Urquhart, D. Neil Furlong, Herman Mansur, Herman Mansur, Franz Grieser, Franz Grieser, Kentaro Tanaka, Kentaro Tanaka, Yoshio Okahata, Yoshio Okahata

Langmuir Vol. 10 page： 899-904 1994.3

Publishing type：Research paper (scientific journal)

The formation of Q-state CdS particles in cadmium arachidate (CdAr) Langmuir-Blodgett films has been monitored using the quartz crystal microbalance (QCM) and UV-vis absorption measurements. QCM studies showed that the mass uptake of different thickness CdAr films on exposure to hydrogen sulfide was consistent with that expected for the quantitative conversion of Cd2+ ions in the films to CdS and the corresponding conversion of CdAr to arachidic acid. UV-vis absorbance measurements showed an optical blue shift typical of particles between 2 and 3 nm in diameter. Complimentary electron microscopic studies showed a polydisperse size distribution of CdS particles. The most common particle size observed in the electron micrographs was found to be close to the particle size determined from the optical properties of the semiconductor particles. There was a linear relationship between the mass uptake of a film on H2S exposure and changes in its absorption properties due to Q-state particle formation. The linear relationship was used to calculate the optical extinction coefficient of the Q-state particles in the film. Mass uptake measurements on CdAr films extensively exposed to H2S gas showed that the arachidic acid molecules left after Q-state particle formation could be quantitatively converted to CdAr by immersing the film in a stirred aqueous solution containing cadmium chloride. Subsequent reexposure of the film to H2S increased the mole fraction of CdS in the film. © 1994, American Chemical Society. All rights reserved.

DOI： 10.1021/la00015a047

Size-quantised cadmium sulfide particles in Langmuir-Blodgett films: Film thermal stability

D. Neil Furlong, Robert Urquhart, Franz Grieser, Franz Grieser, Kentaro Tanaka, Kentaro Tanaka, Yoshio Okahata, Yoshio Okahata

Journal of the Chemical Society, Faraday Transactions Vol. 89 page： 2031-2035 1993.12

Publishing type：Research paper (scientific journal)

The fabrication of particles in Langmuir-Blodgett films of cadmium icosanoate and nonacosa-10,12-diynoate is followed using a quartz crystal microbalance. The mass changes accompanying the exposure of the film to hydrogen sulfide are consistent with a chemical reaction in the film which also produces the acid form of the surfactant. Film thermal stability is greatly reduced after the particles are formed, a result also consistent with formation of the more volatile acid form. The extent of film removal by heating/outgassing suggests that particles are capped by adsorbed icosano or diynoic acid. It is likely that this capping plays a role in particle growth control.

DOI： 10.1039/FT9938902031

GROWTH OF CDS PARTICLES IN CADMIUM ARACHIDATE FILMS - MONITORING BY SURFACE-PLASMON RESONANCE, UV-VISIBLE ABSORPTION-SPECTROSCOPY, AND QUARTZ-CRYSTAL MICROGRAVIMETRY International journal

NJ GEDDES, RS URQUHART, DN FURLONG, CR LAWRENCE, K TANAKA, Y OKAHATA

JOURNAL OF PHYSICAL CHEMISTRY Vol. 97 ( 51 ) page： 13767 - 13772 1993.12

Language：English Publishing type：Research paper (scientific journal) Publisher：AMER CHEMICAL SOC

The growth of Q-state CdS particles during exposure of Langmuir-Blodgett films of cadmium arachidate to hydrogen sulfide has been monitored by surface plasmon resonance (SPR), UV-visible absorption, and quartz crystal microbalance (QCM) measurements. The growth kinetic profile, expressed in terms of increasing refractive index (SPR), absorption or mass increase (QCM), was the same when films were gassed under similar conditions. Microgravimetry showed the quantitative conversion of Cd2+ to CdS in such systems; UV-visible absorption exhibited the blue shift typical of Q-state particles of 2-3-nm diameter. SPR reflectance curves obtained after H2S treatment were initially fitted assuming that either the film thickness or the real component of the relative permittivity (epsilon(r)) was constant during Q-state particle formation. Film thickness changes (assuming epsilon(r) was constant) were similar to those previously reported. Relative permittivity changes, determined assuming the film thickness was constant, indicated that for thinner films (i.e., fewer than about 10 layers) effects such as film breakup during particle;formation and HS exposure to the gold surface of the SPR crystal were important. The change in epsilon(r) for a 20-layer cadmium arachidate film after-extensive gassing was calculated using Maxwell-Garnett theory. Use of this value in the fitting routine indicated that the film thickness change during particle formation was 0.13 nm/layer or 4.9%.

DOI： 10.1021/j100153a054

Evaluation of a horizontal lifting method of Langmuir-Blodgett films using a quartz-crystal microbalance

Y. Okahata, K. Ariga, K. Tanaka

Thin Solid Films Vol. 210-211 page： 702-706 1992.4

Publishing type：Research paper (scientific journal)

A quartz-crystal microbalance (QCM) was employed as a substrate for a horizontal lifting method of various LB films, in which the QCM plate was touched to monolayers on a subphase and lifted horizontally. The transferred mass of monolayers on the QCM could be measured directly at a nanogram level from a frequency decrease of the QCM plate: two monolayers were deposited each cycle (Y-type, transfer ratio 2). The QCM method gave more precise transfer information than the conventional method using the moving area of the barrier on the trough. It was found by the QCM method that Y-type horizontal lifting methods could be widely applied for most monolayers to form well-layered LB films, compared with the conventional vertical dipping method. © 1992.

DOI： 10.1016/0040-6090(92)90379-P