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Nobuhiko Iki

Section

Graduate School of Environmental Studies

Job title

Professor

Degree

博士（工学）（東北大学）
工学修士（東北大学）

researchmap

https://researchmap.jp/n_iki

J-GLOBAL ID

200901074715370176

ORCID

https://orcid.org/0000-0003-4698-4992

Researcher ID

H-4448-2011

Profile

Nobuhiko Iki was born in 1966 in Sapporo, Japan and graduated from Tohoku University in 1988. During his postgraduate course (1989-1990), he studied coordination chemistry at Department of Chemistry, Imperial College London, with Prof. D. F. Evans. He received his Ph.D in analytical chemistry from Tohoku University under direction of Prof. T. Yotsuyanagi in 1994. After his postdoctoral work at Ames Laboratory, Iowa State University, with Prof. E. S. Yeung, he joined Prof. S. Miyano's group, Tohoku University, as a research associate to study thiacalixarene chemistry in 1996. He was promoted to an associate professor at Graduate School of Environmental Studies, Tohoku University in 2003, and then to a full professor at the same school in 2014. His research interests focus on multifunctional metal complexes for bioimaging and therapy, capillary electrophoretic reactor for evaluating kinetic stability of metal and biomolecular complexes, and kinetic differentiation mode separation/detection systems for ultratrace metal ions.

Committee Memberships 20

日本素材物性学会　委員

2014/06 - Present
ホスト-ゲスト・超分子化学研究会　幹事

2009/04 - Present
日本分析化学会東北支部　在仙常任幹事

2005/03 - Present
日本化学会東北支部　副支部長

2025/03 - 2026/02
日本化学会東北支部化学教育協議会　議長

2021/03 - 2023/02
日本分析化学会東北支部　支部長

2019/03 - 2021/02
Japan Society for Analytical Chemistry　Senior Associate Editor of Analytical Sciences

2017/03 - 2019/02
日本分析化学会東北支部　副支部長

2017/03 - 2019/02
日本分析化学会　Analytical Sciences編集委員

2015/03 - 2017/02
日本化学会東北支部　幹事

2009/03 - 2010/02
日本分析化学会東北支部　庶務幹事

2007/03 - 2009/02
日本分析化学会　「分析化学」編集委員

2005/03 - 2007/02
日本化学会東北支部　幹事長

2004/03 - 2005/02
日本化学会東北支部　幹事

2003/03 - 2004/02
日本化学会東北支部　幹事

2003/03 - 2004/02
日本分析化学会東北支部　在仙常任幹事

2001/03 - 2004/02
日本分析化学会　Analytical Sciences編集委員

2001/03 - 2003/02
日本分析化学会　Analytical Sciences編集委員

2001/03 - 2003/02
日本化学会東北支部　幹事

2000/03 - 2001/02
日本化学会生体機能関連化学部会　幹事

1999/03 - 2000/02

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Professional Memberships 9

素材物性学会
日本薬学会
Japan Society of Coordination Chemistry
ホスト-ゲスト・超分子化学研究会
日本磁気共鳴医学会
日本分析化学会
Royal Society of Chemistry
American Chemical Society
日本化学会

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Research Interests 2

錯体化学
分析化学

Research Areas 5

Life sciences / Biomedical engineering /
Nanotechnology/Materials / Inorganic and coordination chemistry /
Nanotechnology/Materials / Green/sustainable/environmental chemistry /
Nanotechnology/Materials / Functional solid-state chemistry /
Nanotechnology/Materials / Analytical chemistry /

Awards 12

寺部茂賞

2021/12　日本分析化学会電気泳動分析研究懇談会　ＣＥ分離に基づく金属錯体・分子複合体系の速度・機能・構造解析
科学研究費助成事業審査委員表彰

2017/09　日本学術振興会
Best Poster Award, 40th International Conference on Coordination Chemistry

2012/09/13　40th International Conference on Coordination Chemistry
東北分析化学賞

2011/12/10　日本分析化学会東北支部　錯体を基盤とする分析化学反応系の創造と高次物質機能創成への展開
石田（實）記念財団研究奨励賞

2008/10　石田（實）記念財団　チアカリックスアレーン-ソフト金属-ランタニド三元超分子錯体の設計による高性能発光素子の創製
HGCS Japan Award of Excellence 2008

2008/07/08　ホスト-ゲスト・超分子化学研究会　Non-covalent Strategy for Activating Separation and Detection Functionality by Use of Multifunctional Host Molecule - Thiacalixarene
日本化学会BCSJ賞

2003/12　日本化学会　p-tert-Butylthiacalix[6]arene as a Clustering Ligand. Syntheses and Structures of CoII5, NiII4, and Mixed-metal MIINiII4 (M = Mn, Co, and Cu) Cluster Complexes, and a Novel Metal-induced Cluster Core Rearrangement.
Analytical Sciences Award

2001/08/06　Third International Congress on Analytical Sciences　Poster award for "A New Separation Method for Water-miscible Organic Compounds via Inclusion by Thiacalix[4]arene and Salt-out of the Complexes"
トーキン科学技術振興財団研究奨励賞

2001/03/19　（財）トーキン科学技術振興財団　チアカリックスアレーンの創製と機能開発
日本分析化学会奨励賞

2000/09/27　（社）日本分析化学会　分離計測システムの設計とチアカリックスアレーンの創製
青葉工学振興会研究奨励賞

1999/12/08　（財）青葉工学振興会　新規チアカリックスアレーンの創製と機能開発
ヨシ・エス・クノ奨学賞

1987/06/26　東北大学

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Papers 140

Capillary Electrophoresis as a Versatile Tool for Analysis of Kinetics, Functions, and Structures of Metal and Biomolecular Complexes

Nobuhiko Iki

Talanta　2025/05

DOI： 10.1016/j.talanta.2025.128281 　
Multifunctional metal complex systems emerging from analytical chemistry for theranostic applications

Nobuhiko Iki

Analytical Sciences　2025/03/11

DOI： 10.1007/s44211-025-00740-w 　
Heterotrilanthanide Cluster Complexes Exhibiting Up-conversion Luminescence in Water

Ryunosuke Karashimada, Koki Musha, Nobuhiko Iki

Chemical Communications　2025
Publisher: Royal Society of Chemistry (RSC)
DOI： 10.1039/d4cc06573e 　

ISSN： 1359-7345

eISSN： 1364-548X

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Heterotrinuclear cluster complexes consisting of Er–Yb– and Tb–Yb–thiacalix[4]arene-p-tetrasulfonate exhibited photon up-conversion luminescence in water, in which visible light emission from the Er and Tb center, respectively, was induced by two-photon...
Lanthanide-calixarene complexes and their applications Invited

Naoya Morohashi, Nobuhiko Iki

Handbook on the Physics and Chemistry of Rare Earths　62　1-280　2022/11
Publisher: Elsevier
DOI： 10.1016/bs.hpcre.2022.08.001 　

ISSN： 0168-1273
Selective Photothermal Therapy Using Antioxidant Nanoparticles Encapsulating Novel Near-Infrared-Absorbing Platinum(II) Complexes

Ryota Sawamura, Hiromi Kurokawa, Atsushi Taninaka, Takuto Toriumi, Yukio Nagasaki, Hidemi Shigekawa, Hirofumi Matsui, Nobuhiko Iki

Nanomaterials　2025/05/25

DOI： 10.3390/nano15110796 　
Selective arrangement of three types of calcium–terbium tetranuclear cores by a thiacalixarene ligand using thermodynamic and kinetic strategies Peer-reviewed

Ryunosuke Karashimada, Hironori Matsuoka, Nobuhiko Iki

RSC Advances　15　(5)　3849-3857　2025/02
Publisher: Royal Society of Chemistry (RSC)
DOI： 10.1039/d4ra08259a 　

eISSN： 2046-2069

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Thiacalix[4]arene-p-tetrasulfonate (TCAS) can selectively form three types of heterotetranuclear Ca_xTb_4−xTCAS₂ complexes (x = 1−3) with energy transfer luminescence.
Discrete inorganic molecular upconversion: a dinuclear ytterbium–polyoxometalate complex exhibits cooperative upconversion luminescence

Ryunosuke Karashimada, Motoki Nakahara, Nobuhiko Iki

Dalton Transactions　2025

DOI： 10.1039/D5DT01369K 　
Nanomedicine Based on Metal Complexes for Cancer Treatment Invited Peer-reviewed

Ryota Sawamura, Nobuhiko Iki

Membrane　50　(1)　12-18　2025/01
Publisher: The Membrane Society of Japan
DOI： 10.5360/membrane.50.12 　

ISSN： 0385-1036

eISSN： 1884-6440
Multifunctional Metal Complexes for Cancer Theranostics

Nobuhiko Iki

Nanomedicine and Nanotoxicology　89-105　2024/10/20
Publisher: Springer Nature Singapore
DOI： 10.1007/978-981-97-5288-1_6 　

ISSN： 2194-0452

eISSN： 2194-0460
Study on cellular uptake of a hydrophobic near-infrared-absorbing diradical-platinum(II) complex solubilized by albumin using hyperspectral imaging, spectrophotometry, and spectrofluorimetry Peer-reviewed

Ryota Sawamura, Atsuko Masuya-Suzuki, Nobuhiko Iki

Analytical Sciences　40　1857-1865　2024/06/19
Publisher: Springer Science and Business Media LLC
DOI： 10.1007/s44211-024-00621-8 　

ISSN： 0910-6340

eISSN： 1348-2246

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Abstract Owing to its biopenetrability and minimal invasiveness, near-infrared (NIR) light in the region between 700–1100 nm has attracted attention in cancer diagnosis and therapy. Our group previously reported that the hydrophobic diradical-platinum(II) complex PtL₂ is a promising agent for cancer photothermal therapy (L = 3,5-dibromo-1,2-diiminobenzosemiquinonate radical). Because PtL₂ does not fluoresce, its intercellular uptake of PtL₂ cannot be observed with a fluorescence microscope. In this study, we clarified the uptake and intracellular behavior of PtL₂ solubilized by bovine serum albumin (BSA) using hyperspectral imaging enabling spectrophotometric analysis of the image. The spectral changes in the obtained images indicated that the internalization of PtL₂ was followed by crystallization of the complex during the long incubation period (> 4 h). Additionally, the binding constant K_b = 5.91 × 10⁴ M^–1 could be estimated upon fluorescence quenching analysis of BSA upon binding of PtL₂; K_b is two orders of magnitude smaller than that of albumin–common drugs. Considering the small K_b and low solubility of PtL₂ in water, we ultimately proposed the internalization path and fate of PtL₂ in the cell: release of PtL₂ from BSA near cellular membranes and subsequent cellular uptake via membrane permeation followed by saturation, resulting in crystallization. Graphical abstract
Albumin nanoparticle electrostatically loaded with highly anionic Gd-thiacalixarene complex for MRI-guided neutron capture therapy Peer-reviewed

Kohei Ohama, Miku Komiya, Takumi Yamatoya, Ryota Sawamura, Ryunosuke Karashimada, Shan Gao, Yoshikazu Ozawa, Kensuke Osada, Ichio Aoki, Takeshi Nagasaki, Minoru Suzuki, Nobuhiko Iki

Colloids and Surfaces A: Physicochemical and Engineering Aspects　699　134579-134579　2024/06
Publisher: Elsevier BV
DOI： 10.1016/j.colsurfa.2024.134579 　

ISSN： 0927-7757
Doping a highly charged, water-soluble lanthanide complex into a hydrophobic polymer for the preparation of luminescent films

Narumi Shiraishi, Daisuke Iikura, Ryunosuke Karashimada, Nobuhiko Iki

Journal of Luminescence　269　120521　2024/03
Publisher: Elsevier BV
DOI： 10.1016/j.jlumin.2024.120521 　

ISSN： 0022-2313
MRI Contrasting Agent Based on Mn-MOF-74 Nanoparticles with Coordinatively Unsaturated Sites Peer-reviewed

Nobuhiko Iki, Ryuta Nakane, Atsuko Masuya-Suzuki, Yoshikazu Ozawa, Takako Maruoka, Megumi Iiyama, Akira Sumiyoshi, Ichio Aoki

Molecular Imaging and Biology　25　968-976　2023/01/18
Publisher: Springer Science and Business Media LLC
DOI： 10.1007/s11307-023-01801-0 　

ISSN： 1536-1632

eISSN： 1860-2002
Selective collection of Yb(III) over La(III) and Eu(III) from aqueous solution by bis(tetramethylammonium) salt crystals of p-tert-butylcalix[4]arene-1,3-diphosphonic acid

Naoya Morohashi, Mayu Osawa, Vandana Bhalla, Sahoko Sumida, Yutaka Kato, Ryuki Takahashi, Nobuhiko Iki, Tetsutaro Hattori

CrystEngComm　2023
Publisher: Royal Society of Chemistry (RSC)
DOI： 10.1039/d3ce00525a 　

eISSN： 1466-8033

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Unprecedented, the crystals of bis(tetramethylammonium) salt of p-tert-butylcalix[4]arene-1,3-diphosphonic acid having preorganized hydrophilic guest recognition space sanded by hydrophobic host layers have been prepared for selective collection of Yb(III) from 0.01...
Kinetic aspects of iron(III)-chelation therapy with deferasirox (DFX) revealed by the solvolytic dissociation rate of the Fe(III)–DFX complex estimated with capillary electrophoretic reactor

Ryota Suzuki, Nobuhiko Iki

Journal of Inorganic Biochemistry　112131-112131　2023/01
Publisher: Elsevier BV
DOI： 10.1016/j.jinorgbio.2023.112131 　

ISSN： 0162-0134
Development of a Diradical-platinum(II) Complex Equipped with a Linker Conjugatable to a Targeting-materials for Cancer-selective Imaging and Therapy

Ryota Sawamura, Atsuko Masuya-Suzuki, Nobuhiko Iki

Chemistry Letters　51　(12)　1157-1159　2022/12/08
Publisher: The Chemical Society of Japan
DOI： 10.1246/cl.220443 　

ISSN： 0366-7022

eISSN： 1348-0715
Development of a Selective Synthesis Method and Evaluation of Luminescence Properties of A Heteronuclear Lanthanide-Thiacalixarene Complex Peer-reviewed

Karashimada, R., Musha, K., Iki, N.

Bunseki Kagaku　71　(3)　2022

DOI： 10.2116/bunsekikagaku.71.145 　

ISSN： 0525-1931
Emergence of the super antenna effect in mixed crystals of ytterbium and lutetium complexes showing near-infrared luminescence Peer-reviewed

Atsuko Masuya-Suzuki, Satoshi Goto, Rika Nakamura, Ryunosuke Karashimada, Yasuhiro Kubota, Ryo Tsunashima, Nobuhiko Iki

RSC Advances　12　(47)　30598-30604　2022
Publisher: Royal Society of Chemistry (RSC)
DOI： 10.1039/d2ra06007h 　

eISSN： 2046-2069

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In mixed crystals of Yb and Lu complexes, the Lu complex acts as a light-harvesting antenna for the Yb luminescence.
Selective crystallization of dysprosium complex from neodymium/dysprosium mixture enabled by cooperation of coordination and crystallization

Atsuko Masuya-Suzuki, Koji Hosobori, Ryota Sawamura, Yumika Abe, Ryunosuke Karashimada, Nobuhiko Iki

Chemical Communications　58　(14)　2283-2286　2022
Publisher: Royal Society of Chemistry (RSC)
DOI： 10.1039/d1cc06174g 　

ISSN： 1359-7345

eISSN： 1364-548X

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Cooperation between the coordination and crystallization processes enables a one-step selective crystallization of a Dy³⁺ complex from a Nd³⁺/Dy³⁺ mixture.
Enhanced Tb^III-centered Luminescence due to Elongated Methylene Arms of Tripodal Schiff Base Ligand Peer-reviewed

Ryunosuke Karashimada, Takafumi Kambe, Chikai Igarashi, Atsuko Masuya-Suzuki, Nobuhiko Iki

Chemistry Letters　50　(7)　1382-1384　2021/07/05
Publisher: The Chemical Society of Japan
DOI： 10.1246/cl.210150 　

ISSN： 0366-7022

eISSN： 1348-0715
Short Radiative Lifetime and Non‐Triplet Sensitization in Near‐Infrared‐Luminescent Yb(III) Complex with Tripodal Schiff Base

Atsuko Masuya‐Suzuki, Satoshi Goto, Takafumi Kambe, Ryunosuke Karashimada, Yasuhiro Kubota, Nobuhiko Iki

ChemistryOpen　10　(1)　46-55　2021/01
Publisher: Wiley
DOI： 10.1002/open.202000224 　

ISSN： 2191-1363

eISSN： 2191-1363
Photostable near-infrared-absorbing diradical-platinum(ii) complex solubilized by albumin toward a cancer photothermal therapy agent Peer-reviewed

Ryota Sawamura, Masataka Sato, Atsuko Masuya-Suzuki, Nobuhiko Iki

RSC Advances　10　(11)　6460-6463　2020
Publisher: Royal Society of Chemistry (RSC)
DOI： 10.1039/d0ra00652a 　

eISSN： 2046-2069

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<p>A near-infrared (NIR) absorbing diradical-platinum(<sc>ii</sc>) complex solubilized in PBS by albumin can kill MCF-7 cells by the photothermal effect.</p>
Facile Preparation of Highly Luminescent Materials by Electrostatic Immobilization of Anionic Metal Complex onto Anion-exchanger as Exemplified with Tri-terbium(III) Cluster Complex of Thiacalix[4]arene-p-tetrasulfonate Peer-reviewed

Narumi Shiraishi, Ryunosuke Karashimada, Nobuhiko Iki

Bull. Chem. Soc. Jpn.　92　(11)　2019/08

DOI： 10.1246/bcsj.20190190 　

ISSN： 1348-0634 0009-2673
Capillary electrophoretic reactor for estimation of spontaneous dissociation rate of Trypsin–Aprotinin complex Peer-reviewed

Yumiko Sasaki, Yosuke Sato, Toru Takahashi, Mitsuo Umetsu, Nobuhiko Iki

Anal. Biochem.　585　113406　2019/08

DOI： 10.1016/j.ab.2019.113406 　

ISSN： 1096-0309 0003-2697
Speciation of Chromium

IKI Nobuhiko

Analytical Sciences　35　(1)　1-2　2019/01

DOI： 10.2116/analsci.highlights1901 　

ISSN： 1348-2246 0910-6340
Multi-coloration of Calixarene-coated Silver Nanoparticles for the Visual Discrimination of Metal Elements Peer-reviewed

Norioki Abe, Nobuhiko Iki

ANALYTICAL SCIENCES　33　(10)　1141-1145　2017/10

DOI： 10.2116/analsci.33.1141 　

ISSN： 0910-6340

eISSN： 1348-2246
Capillary electrophoretic separation of cis/trans isomers of bis(o-diiminobenzoquinonato)platinum(II) complexes using beta-cyclodextrins as the selector Peer-reviewed

Atsuko Masuya-Suzuki, Takumi Hayashi, Kosaku Tamura, Nobuhiko Iki

NEW JOURNAL OF CHEMISTRY　41　(15)　7605-7612　2017/08

DOI： 10.1039/c7nj01558e 　

ISSN： 1144-0546

eISSN： 1369-9261
Synthesis, metal binding and spectral properties of novel bis-1,3-diketone calix[4]arenes Peer-reviewed

Sergey N. Podyachev, Svetlana N. Sudakova, Gulnaz Sh. Gimazetdinova, Nataliya A. Shamsutdinova, Victor V. Syakaev, Tatjiana A. Barsukova, Nobuhiko Iki, Dmitry V. Lapaev, Asiya R. Mustafina

NEW JOURNAL OF CHEMISTRY　41　(4)　1526-1537　2017/02

DOI： 10.1039/c6nj03381d 　

ISSN： 1144-0546

eISSN： 1369-9261
Self-Assembly of a Trilanthanide(III) Core Sandwiched between Two Thiacalix[4]arene Ligands Peer-reviewed

Nobuhiko Iki, Teppei Tanaka, Shoichi Hiro-oka, Kozo Shinoda

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY　(31)　5020-5027　2016/11

DOI： 10.1002/ejic.201600762 　

ISSN： 1434-1948

eISSN： 1099-0682
Crystal Structure of the cis-Bis(3-tert-butyl-o-diiminobenzosemiquinonato)platinum(II) Complex Peer-reviewed

Atsuko Masuya-Suzuki, Nobuhiko Iki

X-ray Structure Analysis Online　32　(9)　41-43　2016/09/10

DOI： 10.2116/xraystruct.32.41 　

ISSN： 1883-3578
High kinetic stability of Zn^II coordinated by the tris(histidine) unit of carbonic anhydrase towards solvolytic dissociation studied by affinity capillary electrophoresis Peer-reviewed

Yosuke Sato, Hitoshi Hoshino, Nobuhiko Iki

Journal of Inorganic Biochemistry　161　122-127　2016/08

DOI： 10.1016/j.jinorgbio.2016.05.013 　

ISSN： 0162-0134

eISSN： 1873-3344
Gd₃TCAS₂: An Aquated Gd³⁺-Thiacalix[4]arene Sandwich Cluster with Extremely Slow Ligand Substitution Kinetics Peer-reviewed

Nobuhiko Iki, Eszter Boros, Mami Nakamura, Ryo Baba, Peter Caravan

Inorganic Chemistry　55　(8)　4000-4005　2016/04

DOI： 10.1021/acs.inorgchem.6b00241 　

ISSN： 0020-1669

eISSN： 1520-510X
Topological modulation of the porous structure of a coordination polymer constructed from a flexible building block via framework-guest interaction during self-assembly Peer-reviewed

Atsuko Masuya-Suzuki, Nozomi Matsubara, Ryunosuke Karashimada, Hitoshi Hoshino, Nobuhiko Iki

CRYSTENGCOMM　18　(6)　872-876　2016

DOI： 10.1039/c5ce01804h 　

ISSN： 1466-8033
Thiacalixarene assembled heterotrinuclear lanthanide clusters comprising Tb^III and Yb^III enable f-f communication to enhance Yb^III-centred luminescence Peer-reviewed

Ryunosuke Karashimada, Nobuhiko Iki

Chemical Communications　52　(15)　3139-3142　2016

DOI： 10.1039/c5cc09612j 　

ISSN： 1359-7345

eISSN： 1364-548X
Thermodynamics of binding of a sulfonamide inhibitor to metal-mutated carbonic anhydrase as studied by affinity capillary electrophoresis Peer-reviewed

Yosuke Sato, Hitoshi Hoshino, Nobuhiko Iki

JOURNAL OF INORGANIC BIOCHEMISTRY　150　133-138　2015/09

DOI： 10.1016/j.jinorgbio.2015.06.011 　

ISSN： 0162-0134

eISSN： 1873-3344
Determination Method of Trace Cd(II) in Rice Using a Luminescent Cd(II)-Tb(III)-Thiacalix[4]arene Ternary Complex Peer-reviewed

Norioki Abe, Hitoshi Hoshino, Nobuhiko Iki

BUNSEKI KAGAKU　64　(7)　493-499　2015/07

DOI： 10.2116/bunsekikagaku.64.493 　

ISSN： 0525-1931
One-pot synthesis and structural characterization of a Tb(III) coordination polymer based on a tripodal Schiff base ligand adopting an exo-bridging coordination mode Peer-reviewed

Atsuko Masuya, Chikai Igarashi, Masatoshi Kanesato, Hitoshi Hoshino, Nobuhiko Iki

POLYHEDRON　85　76-82　2015/01

DOI： 10.1016/j.poly.2014.08.033 　

ISSN： 0277-5387
Development of a function of Pt(II)-diradical complex as a near-infrared absorbing probe

Masuya Atsuko, Tamura Kosaku, Hoshino Hitoshi, Iki Nobuhiko

Seibutsu Butsuri　54　(1)　S139　2014
Publisher: The Biophysical Society of Japan General Incorporated Association
DOI： 10.2142/biophys.54.S139_4 　
Regioselective synthesis of 1,2-and 1,3-diaminothiacalix[4]arenes via nucleophilic aromatic substitution and their X-ray structures Peer-reviewed

Hiroshi Katagiri, Shinya Tanaka, Kazuya Ohkubo, Yuki Akahira, Naoya Morohashi, Nobuhiko Iki, Tetsutaro Hattori, Sotaro Miyano

RSC ADVANCES　4　(19)　9608-9616　2014

DOI： 10.1039/c3ra47718e 　

ISSN： 2046-2069
Unique inclusion behaviour of 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetraaminothiacalix[4]arene towards small organic molecules Peer-reviewed

Naoya Morohashi, Hiroshi Katagiri, Takanori Shimazaki, Yuichi Kitamoto, Shinya Tanaka, Chizuko Kabuto, Nobuhiko Iki, Tetsutaro Hattori, Sotaro Miyano

Supramolecular Chemistry　25　(12)　812-818　2013/12/01

DOI： 10.1080/10610278.2013.806808 　

ISSN： 1061-0278 1029-0478
The role of cadmium(II) bridges in the self-assembly with lanthanide(III) and thiacalix[4]arene (TCAS) to selectively form a luminescent ternary Cd^II₂·Tb^III₂·TCAS₂ complex Peer-reviewed

Nobuhiko Iki, Teppei Tanaka, Hitoshi Hoshino

Inorganica Chimica Acta　397　42-47　2013/03/01

DOI： 10.1016/j.ica.2012.11.016 　

ISSN： 0020-1693
Capillary Electrophoretic Reactor and Microchip Capillary Electrophoretic Reactor: Dissociation Kinetic Analysis Method for "Complexes" Using Capillary Electrophoretic Separation Process Peer-reviewed

Toru Takahashi, Nobuhiko Iki

Capillary Electrophoresis and Microchip Capillary Electrophoresis: Principles, Applications, and Limitations　127-143　2013/02/26
Publisher: John Wiley and Sons
DOI： 10.1002/9781118530009.ch7 　
A molecular probe for recognizing the size of hydrophobic cavities based on near-infrared absorbing diradical-Pt-II complexes Peer-reviewed

Kousaku Tamura, Atsuko Masuya, Hitoshi Hoshino, Nobuhiko Iki

CHEMICAL COMMUNICATIONS　49　(42)　4812-4814　2013

DOI： 10.1039/c3cc41468j 　

ISSN： 1359-7345
Dissociation kinetic analysis of Ce(III) complex with quin2 by microchip capillary electrophoretic reactor Peer-reviewed

Kei-ichirou Ohtsukak, Nobuhiko Iki, Hitoshi Hoshino, Toru Takahashi

Analytical Sciences　29　(5)　553-557　2013

DOI： 10.2116/analsci.29.553 　

ISSN： 0910-6340 1348-2246
Kinetically Stable Ln^III Complexes Comprising a Trinuclear Core Sandwiched between Two Thiacalix[4]arene Ligands Self-Assembled in Water (Ln^III = Nd^III, Yb^III) Peer-reviewed

Nobuhiko Iki, Shouichi Hiro-oka, Mami Nakamura, Teppei Tanaka, Hitoshi Hoshino

European Journal of Inorganic Chemistry　2012　(22)　3541-3545　2012/08

DOI： 10.1002/ejic.201200464 　

ISSN： 1434-1948
Highly Efficient Near-Infrared-Emitting Lanthanide(III) Complexes Formed by Heterogeneous Self-Assembly of Ag^I, Ln^III, and Thiacalix[4]arene-p-tetrasulfonate in Aqueous Solution (Ln^III = Nd^III, Yb^III) Peer-reviewed

Nobuhiko Iki, Shouichi Hiro-oka, Teppei Tanaka, Chizuko Kabuto, Hitoshi Hoshino

Inorganic Chemistry　51　(3)　1648-1656　2012/02

DOI： 10.1021/ic2019583 　

ISSN： 0020-1669
Development of a Near Infrared Fluorescence Labeling Reagent: Synthesis of Indole-Functionalized Indocyanine Green Derivatives Peer-reviewed

Takayuki Doi, Koya Oikawa, Jun Suzuki, Masahito Yoshida, Nobuhiko Iki

SYNLETT　2012　(2)　306-310　2012/01

DOI： 10.1055/s-0031-1290139 　

ISSN： 0936-5214
pH-responsive switching of near-infrared absorption of a diradical complex of Pt-II and 3,4-diaminobenzoate formed in aqueous solutions Peer-reviewed

Kousaku Tamura, Atsuko Masuya, Nobuhiko Iki, Yasunori Ohba, Seigo Yamauchi, Hitoshi Hoshino

INORGANICA CHIMICA ACTA　378　(1)　81-86　2011/11

DOI： 10.1016/j.ica.2011.08.018 　

ISSN： 0020-1693
pH-Responsive Switching of the Near-Infrared Absorption of the Water-Soluble Bis(o-diiminobenzosemiquinonato)platinum(II) Complex Peer-reviewed

Atsuko Masuya, Nobuhiko Iki, Chizuko Kabuto, Yasunori Ohba, Seigo Yamauchi, Hitoshi Hoshino

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY　2010　(22)　3458-3465　2010/08

DOI： 10.1002/ejic.201000343 　

ISSN： 1434-1948
Expanding the scope of CE reactor to ssDNA-binding protein-ssDNA complexes as exemplified for a tool for direct measurement of dissociation kinetics of biomolecular complexes Peer-reviewed

Toru Takahashi, Kei-ichirou Ohtsuka, Yoriyuki Tomiya, Nobuhiko Iki, Hitoshi Hoshino

ELECTROPHORESIS　30　(17)　3079-3085　2009/09

DOI： 10.1002/elps.200900110 　

ISSN： 0173-0835
Detection of cationic guest molecules by quenching of luminescence of a self-assembled host molecule consisting of terbium(III) and calix[4]arene-p-tetrasulfonates Peer-reviewed

Takayuki Horiuchi, Nobuhiko Iki, Hitoshi Hoshino

ANALYTICA CHIMICA ACTA　650　(2)　258-263　2009/09

DOI： 10.1016/j.aca.2009.07.055 　

ISSN： 0003-2670
Ligand-Substitution Mode Capillary Electrophoretic Reactor: Extending Capillary Electrophoretic Reactor toward Measurement of Slow Dissociation Kinetics with a Half-Life of Hours Peer-reviewed

Nobuhiko Iki, Mariko Takahashi, Toru Takahashi, Hitoshi Hoshino

ANALYTICAL CHEMISTRY　81　(18)　7849-7854　2009/09

DOI： 10.1021/ac901296j 　

ISSN： 0003-2700
One-step heterogeneous assembly of terbium(III) and silver(I) with thiacalix[4]arene ligands to form a cage including terbium(III) in an octa-oxygen cube Peer-reviewed

Teppei Tanaka, Nobuhiko Iki, Takashi Kajiwara, Masahiro Yamashita, Hitoshi Hoshino

JOURNAL OF INCLUSION PHENOMENA AND MACROCYCLIC CHEMISTRY　64　(3-4)　379-383　2009/08

DOI： 10.1007/s10847-009-9567-0 　

ISSN： 1388-3127

eISSN： 1573-1111
Non-covalent strategy for activating separation and detection functionality by use of the multifunctional host molecule thiacalixarene Invited Peer-reviewed

Nobuhiko Iki

JOURNAL OF INCLUSION PHENOMENA AND MACROCYCLIC CHEMISTRY　64　(1-2)　1-13　2009/06

DOI： 10.1007/s10847-009-9550-9 　

ISSN： 1388-3127

eISSN： 1573-1111
One-step heterogeneous assembly of terbium(iii) and silver(i) with thiacalix[4]arene ligands to form a cage including terbium(iii) in an octa-oxygen cube Peer-reviewed

Teppei Tanaka, Nobuhiko Iki, Takashi Kajiwara, Masahiro Yamashita, Hitoshi Hoshino

Journal of Inclusion Phenomena and Macrocyclic Chemistry　64　(3-4)　379-383　2009

DOI： 10.1007/s10847-009-9567-0 　

ISSN： 0923-0750
A supramolecular sensing system for Ag-I at nanomolar levels by the formation of a luminescent Ag-I-Tb-III-thiacalix[4]arene ternary complex Peer-reviewed

Nobuhiko Iki, Munehiro Ohta, Teppei Tanaka, Takayuki Horiuchi, Hitoshi Hoshino

NEW JOURNAL OF CHEMISTRY　33　(1)　23-25　2009

DOI： 10.1039/b816596c 　

ISSN： 1144-0546
Highly Luminescent Superparamagnetic Diterbium(III) Complex Based on the Bifunctionality of p-tert-Butylsulfonylcalix[4]arene Peer-reviewed

Takashi Kajiwara, Miki Hasegawa, Ayumi Ishii, Kensuke Katagiri, Munkhtsetseg Baatar, Shinya Takaishi, Nobuhiko Iki, Masahiro Yamashita

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY　2008　(36)　5565-5568　2008/12

DOI： 10.1002/ejic.200800706 　

ISSN： 1434-1948
Hydrophobic and metal coordination interacted architecture based on p-tert-butylthiacalix[4]arene-potassium complex and its vapor absorption capability Peer-reviewed

Manabu Yamada, Yoshihiko Kondo, Nobuhiko Iki, Chizuko Kabuto, Fumio Hamada

TETRAHEDRON LETTERS　49　(24)　3906-3911　2008/06

DOI： 10.1016/j.tetlet.2008.04.057 　

ISSN： 0040-4039
Evaluation of stability against oxidation and acid dissociation properties for tetrahydrocurcumin in aqueous solution Peer-reviewed

Kiyoko Sato, Nobuhiko Iki, Torn Takahshi, Hitoshi Hoshino

BUNSEKI KAGAKU　57　(4)　257-263　2008/04

DOI： 10.2116/bunsekikagaku.57.257 　

ISSN： 0525-1931
Exceptionally long-lived luminescence emitted Ag-I-Tb-III-Thiacalix[4]arene supramolecular from Tb-III ion caged in an complex in water Peer-reviewed

Nobuhiko Iki, Munehiro Ohta, Takayuki Horiuchi, Hitoshi Hoshino

CHEMISTRY-AN ASIAN JOURNAL　3　(5)　849-853　2008

DOI： 10.1002/asia.200700298 　

ISSN： 1861-4728
Voltammetric study of inclusion of p-sulfonated thiacalix[n]arenes (n=4, 6) toward ferrocenyl guests in aqueous solutions Peer-reviewed

Nobuhiko Iki, Satoshi Ogawa, Tomokazu Matsue, Sotaro Miyano

JOURNAL OF ELECTROANALYTICAL CHEMISTRY　610　(1)　90-95　2007/11

DOI： 10.1016/j.jelechem.2007.06.023 　

ISSN： 1572-6657
Estimation of on-capillary dissociation characteristics of Zn(II) complex with 1,5-bis(2-hydroxy-5-sulfophenyl)-3-cyanoformazan by a capillary electrophoretic reactor Peer-reviewed

Kazutaka Ogasawara, Torn Takahashi, Nobuhiko Iki, Hitoshi Hoshino

BUNSEKI KAGAKU　56　(10)　825-831　2007/10

DOI： 10.2116/bunsekikagaku.56.825 　

ISSN： 0525-1931
Conformational Behaviors of tetra-O-methylsulfinylcalix[4]arenes - An approach to control the conformation of thiacalix[4]arenes by oxidizing sulfur bridges Peer-reviewed

Hiroshi Katagiri, Tetsutaro Hattori, Naoya Morohashi, Nobukiho Iki, Sotaro Miyano

JOURNAL OF ORGANIC CHEMISTRY　72　(22)　8327-8331　2007/10

DOI： 10.1021/jo701381h 　

ISSN： 0022-3263
Transition metal and lanthanide cluster complexes constructed with thiacalix[n]arene and its derivatives Invited Peer-reviewed

Takashi Kajiwara, Nobuhiko Iki, Masahiro Yamashita

COORDINATION CHEMISTRY REVIEWS　251　(13-14)　1734-1746　2007/07

DOI： 10.1016/j.ccr.2007.01.001 　

ISSN： 0010-8545
Tetra- and di-nuclear copper(II) complexes with stereoisomers of sulfinylcalix[4]arene arising from the disposition of four S=O groups Peer-reviewed

Nobuhiko Iki, Yusuke Yamane, Naoya Morohashi, Takashi Kajiwara, Tasuku Ito, Sotaro Miyano

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN　80　(6)　1132-1139　2007/06

DOI： 10.1246/bcsj.80.1132 　

ISSN： 0009-2673

eISSN： 1348-0634
Di- and tetracarboxylate ligands for highly luminescent terbium(III) complexes on the basis of sulfonylcalix[4]arene scaffold Peer-reviewed

Takayuki Horiuchi, Nobuhiko Iki, Hitoshi Hoshino, Chizuko Kabuto, Sotaro Miyano

TETRAHEDRON LETTERS　48　(5)　821-825　2007/01

DOI： 10.1016/j.tetlet.2006.11.153 　

ISSN： 0040-4039
Thiacalixarenes Invited Peer-reviewed

Naoya Morohashi, Fumitaka Narumi, Nobuhiko Iki, Tetsutaro Hattori, Sotaro Miyano

CHEMICAL REVIEWS　106　(12)　5291-5316　2006/12

DOI： 10.1021/cr050565j 　

ISSN： 0009-2665

eISSN： 1520-6890
A dodecalanthanide wheel supported by p-tert-butylsulfonylcalix[4]aren Peer-reviewed

Takashi Kajiwara, Kensuke Katagiri, Shinya Takaishi, Masahiro Yamashita, Nobuhiko Iki

CHEMISTRY-AN ASIAN JOURNAL　1　(3)　349-351　2006/09

DOI： 10.1002/asia.200600057 　

ISSN： 1861-4728
Supramolecular assembly based on pi-pi stacking and pi-cation interactions between thiacalix[6]arene and DMF Peer-reviewed

Fumio Hamada, Yutaka Higuchi, Yoshihiko Kondo, Chizuko Kabuto, Nobuhiko Iki

TETRAHEDRON LETTERS　47　(31)　5591-5593　2006/07

DOI： 10.1016/j.tetlet.2006.05.055 　

ISSN： 0040-4039
Conformation-controlled luminescent properties of lanthanide clusters containing p-tert-butylsulfonylcalix[4]arene Peer-reviewed

T Kajiwara, K Katagiri, M Hasegawa, A Ishii, M Ferbinteanu, S Takaishi, T Ito, M Yamashita, N Iki

INORGANIC CHEMISTRY　45　(13)　4880-4882　2006/06

DOI： 10.1021/ic060397t 　

ISSN： 0020-1669
Highly symmetrical tetranuclear cluster complexes supported by p-tert-butylsulfonylcalix[4]arene as a cluster-forming ligand Peer-reviewed

T Kajiwara, T Kobashi, R Shinagawa, T Ito, S Takaishi, M Yamashita, N Iki

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY　2006　(9)　1765-1770　2006/05

DOI： 10.1002/ejic.200501086 　

ISSN： 1434-1948
Topological variation between hexa- and trithiacalix[6]arene-copper(II) complexes: From sphere to wheel by reducing the number of the sulfur bridges Invited Peer-reviewed

Noriyoshi Kon, Nobuhiko Iki, Takashi Kajiwara, Tasuku Ito, Sotaro Miyano

CHEMISTRY LETTERS　35　(4)　430-431　2006/04

DOI： 10.1246/cl.2006.430 　

ISSN： 0366-7022

eISSN： 1348-0715
Sulfinylcalix[4]arene-impregnated Amberlite XAD-7 resin for the separation of niobium(V) from tantalum(V) Peer-reviewed

H Matsumiya, S Yasuno, N Iki, S Miyano

JOURNAL OF CHROMATOGRAPHY A　1090　(1-2)　197-200　2005/10

DOI： 10.1016/j.chroma.2005.06.086 　

ISSN： 0021-9673

eISSN： 1873-3778
Synthesis and crystal structure of p-tert-butylthiacalix[8]arene: A new member of thiacalixarenes Peer-reviewed

Yoshihiko Kondo, Ken Endo, Nobuhiko Iki, Sotaro Miyano, Fumio Hamada

Journal of Inclusion Phenomena　52　(1)　45-49　2005/06

DOI： 10.1007/s10847-004-2384-6 　

ISSN： 0923-0750
Synthesis and crystal structure of p-tert-butylthiacalix[8]arene: A new member of thiacalixarenes Peer-reviewed

Y Kondo, K Endo, N Iki, S Miyano, F Hamada

JOURNAL OF INCLUSION PHENOMENA AND MACROCYCLIC CHEMISTRY　52　(1-2)　45-49　2005/06

DOI： 10.1007/s10847-004-2384-6 　

ISSN： 1388-3127

eISSN： 1573-1111
A microchip capillary electrophoretic reactor: a new methodology for direct measurement of dissociation kinetics of metal complexes Peer-reviewed

T Takahashi, K Ohtsuka, N Iki, H Hoshino

ANALYST　130　(10)　1337-1339　2005

DOI： 10.1039/b509546h 　

ISSN： 0003-2654
A p-tert-butyldithiacalix[4]arene-copper(II) complex having double-cone shape of unique heteroditopic inclusion behavior Peer-reviewed

N Kon, N Iki, T Kajiwara, T Ito, S Miyano

CHEMISTRY LETTERS　33　(8)　1046-1047　2004/08

DOI： 10.1246/cl.2004.1046 　

ISSN： 0366-7022

eISSN： 1348-0715
Preconcentration of copper, cadmium, and lead with a thiacalix[4]arenetetrasulfonate-loaded Sephadex A-25 anion-exchanger for graphite-furnace atomic-absorption spectrometry Peer-reviewed

H Matsumiya, N Iki, S Miyano, M Hiraide

ANALYTICAL AND BIOANALYTICAL CHEMISTRY　379　(5-6)　867-871　2004/07

DOI： 10.1007/s00216-004-2655-5 　

ISSN： 1618-2642

eISSN： 1618-2650
Sulfonylcalix[4]arenetetrasulfonate as pre-column chelating reagent for selective determination of aluminum(III), iron(III), and titanium(IV) by ion-pair reversed-phase high-performance liquid chromatography with spectrophotometric detection Peer-reviewed

H Matsumiya, N Iki, S Miyano

TALANTA　62　(2)　337-342　2004/02

DOI： 10.1016/j.talanta.2003.08.001 　

ISSN： 0039-9140

eISSN： 1873-3573
Octalanthanide wheels supported by p-tert-butylsulfonylcalix[4]arene Peer-reviewed

T Kajiwara, HS Wu, T Ito, N Iki, S Miyano

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION　43　(14)　1832-1835　2004

DOI： 10.1022/anie.200353449 　

ISSN： 1433-7851
Facile synthesis of thiacalix[n]arenes (n=4, 6, and 8) consisting of p-tert-butylphenol and methylene/sulfide alternating linkage and metal-binding property of the n=4 homologue Peer-reviewed

N Kon, N Iki, Y Yamane, S Shirasaki, S Miyano

TETRAHEDRON LETTERS　45　(1)　207-211　2004/01

DOI： 10.1016/j.tetlet.2003.10.121 　

ISSN： 0040-4039
Tuning of the cavity of water-soluble thiacalix[4]arene for the control of inclusion ability toward water-miscible organic molecules Peer-reviewed

N Kon, N Iki, Y Sano, S Ogawa, C Kabuto, S Miyano

COLLECTION OF CZECHOSLOVAK CHEMICAL COMMUNICATIONS　69　(5)　1080-1096　2004

DOI： 10.1135/cccc20041080 　

ISSN： 0010-0765
p-tert-Butylthiacalix[6]arene as a clustering ligand. Syntheses and structures of Co-5(II), Ni-4(II), and mixed-metal (MNi4II)-Ni-II (M = Mn, Co, and Cu) cluster complexes, and a novel metal-induced cluster core rearrangement Peer-reviewed

T Kajiwara, R Shinagawa, T Ito, N Kon, N Iki, S Miyano

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN　76　(12)　2267-2275　2003/12

DOI： 10.1246/bcsJ.76.2267 　

ISSN： 0009-2673

eISSN： 1348-0634
Metal-ion extractability of sulfur-bridged oligomers of phenol; distinct effect of the number of sulfur bridges rather than the cyclic/acyclic form Peer-reviewed

N Iki, N Morohashi, Y Yamane, S Miyano

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN　76　(9)　1763-1768　2003/09

DOI： 10.1246/bcsj.76.1763 　

ISSN： 0009-2673

eISSN： 1348-0634
Synthesis of all stereoisomers of sulfinylcalix[4]arenes Peer-reviewed

N Morohashi, H Katagiri, N Iki, Y Yamane, C Kabuto, T Hattori, S Miyano

JOURNAL OF ORGANIC CHEMISTRY　68　(6)　2324-2333　2003/03

DOI： 10.1021/jo026801x 　

ISSN： 0022-3263
Thiacalix[4]arenetetrasulfonate as specific pre-column chelating reagent for nickel(II) ion in kinetic differentiation mode high-performance liquid chromatography Peer-reviewed

H Matsumiya, T Ishida, N Iki, S Miyano

ANALYTICA CHIMICA ACTA　478　(2)　163-170　2003/02

DOI： 10.1016/S0003-2670(02)01516-7 　

ISSN： 0003-2670
Inclusion Behavior of Water-Soluble Thiacalix- and Calix[4]arenes for Substituted Benzenes in Aqueous Solution Peer-reviewed

N. Kon, N. Iki, S. Miyano

Org. Biomol. Chem.　124　(4)　751-755　2003/02

DOI： 10.1039/b210198j 　

ISSN： 1477-0520
Pd(II) complexes with thiacalix[4]-arene and -aniline; subtle, but distinct influences of phenol and aniline units on the 3-D structure

Katagiri, H., Morohashi, N., Iki, N., Kabuto, C., Miyano, S.

Journal of the Chemical Society. Dalton Transactions　(4)　2003

ISSN： 1472-7773
Chelating adsorbent for heavy metal ions prepared by loading anion-exchange resin with thiacalix[4] arenetetrasulfonate Peer-reviewed

H Matsumiya, H Masai, Y Terazono, N Iki, S Miyano

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN　76　(1)　133-136　2003/01

DOI： 10.1246/bcsj.76.133 　

ISSN： 0009-2673

eISSN： 1348-0634
Pd(II) Complexes with thiacalix[4]-arene and -aniline; subtle, but distinct influences of phenol and aniline units on the 3-D structure Peer-reviewed

H Katagiri, N Morohashi, N Iki, C Kabuto, S Miyano

DALTON TRANSACTIONS　2003　(4)　723-726　2003

DOI： 10.1039/b208317e 　

ISSN： 1477-9226
Highly selective luminescence determination of terbium at the sub-ppb level with sulfonylcalix[4]arene-p-tetrasulfonate Peer-reviewed

T Horiuchi, N Iki, H Oka, S Miyano

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN　75　(12)　2615-2619　2002/12

DOI： 10.1246/bcsj.75.2615 　

ISSN： 0009-2673

eISSN： 1348-0634
Synthesis, structure, and ferromagnetic behavior of decacopper(II) cluster complex supported by hexaanionic p-tert-butylthiacalix[6]arene Peer-reviewed

T Kajiwara, N Kon, S Yokozawa, T Ito, N Iki, S Miyano

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY　124　(38)　11274-11275　2002/09

DOI： 10.1021/ja0273391 　

ISSN： 0002-7863
System design of kinetic differentiation mode capillary electrophoresis for separation and determination of ultratrace metal chelates Peer-reviewed

N Iki

BUNSEKI KAGAKU　51　(7)　495-505　2002/07

DOI： 10.2116/bunsekikagaku.51.495 　

ISSN： 0525-1931
Thiacalixarene. A new molecular scaffold for host molecules

N Morohashi, N Iki, S Miyano

JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN　60　(6)　550-562　2002/06

DOI： 10.5059/yukigoseikyokaishi.60.550 　

ISSN： 0037-9980
Complexing ability of p-tert-butylthiacalix[6]arene toward metal ions. Predominant effect of coordination by the bridging sulfur rather than that of the ring-size Peer-reviewed

N Morohashi, N Iki, M Aono, S Miyano

CHEMISTRY LETTERS　(5)　494-495　2002/05

DOI： 10.1246/cl.2002.494 　

ISSN： 0366-7022

eISSN： 1348-0715
Synthesis of p-tert-butylthiacalix[n]arenes (n=4, 6, and 8) from a sulfur-bridged acyclic dimer of p-tert-butylphenol Peer-reviewed

N Kon, N Iki, S Miyano

TETRAHEDRON LETTERS　43　(12)　2231-2234　2002/03

DOI： 10.1016/S0040-4039(02)00214-9 　

ISSN： 0040-4039
Crystal structures of mono-, di-, and tri(p-tert-butyl)-thiacalix[4]arenes: Dimeric self-inclusion behavior Peer-reviewed

C Kabuto, Y Higuchi, T Nimi, F Hamada, N Iki, N Morohashi, S Miyano

JOURNAL OF INCLUSION PHENOMENA AND MACROCYCLIC CHEMISTRY　42　(1-2)　89-98　2002/02

DOI： 10.1023/A:1014558517301 　

ISSN： 1388-3127

eISSN： 1573-1111
Inclusion behavior of thiacalix[4]arenetetrasulfonate toward water-miscible organic molecules studied by salting-out and X-ray crystallography Peer-reviewed

N Iki, T Suzuki, K Koyama, C Kabuto, S Miyano

ORGANIC LETTERS　4　(4)　509-512　2002/02

DOI： 10.1021/ol017053l 　

ISSN： 1523-7060
Acid-base properties of sulfur-bridged calix[4]arenes

Matsumiya, H., Terazono, Y., Iki, N., Miyano, S.

Journal of the Chemical Society, Perkin Transactions 2　(6)　2002

DOI： 10.1002/chin.200235067 　

ISSN： 1470-1820
Crystal structures of mono-, di-, and tri(p-tert-butyl)-thiacalix[4]arenes: Dimeric self-inclusion behavior Peer-reviewed

Chizuko Kabuto, Yutaka Higuchi, Tomohiro Niimi, Fumio Hamada, Nobuhiko Iki, Naoya Morohashi, Sotaro Miyano

Journal of Inclusion Phenomena　42　(1-2)　89-98　2002

DOI： 10.1023/A:1014558517301 　

ISSN： 0923-0750
Acid-base properties of sulfur-bridged calix[4]arenes Peer-reviewed

H Matsumiya, Y Terazono, N Iki, S Miyano

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2　(6)　1166-1172　2002

DOI： 10.1039/b200228k 　

ISSN： 1472-779X
Proximal O,O '-capped calix[4]arenes with a disiloxane bridge as highly efficient synthetic intermediates for 1,2-dialkylation at the lower rim Peer-reviewed

F Narumi, N Morohashi, N Matsumura, N Iki, H Kameyama, S Miyano

TETRAHEDRON LETTERS　43　(4)　621-625　2002/01

DOI： 10.1016/S0040-4039(01)02202-X 　

ISSN： 0040-4039
Zinc(III) slides on a ligand surface: The X-ray crystal structure and dynamic behavior in solution of [Zn(H2L)(tacn)] Peer-reviewed

T Kajiwara, S Yokozawa, T Ito, N Iki, N Morohashi, S Miyano

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION　41　(12)　2076-2078　2002

DOI： 10.1002/1521-3773(20020617)41:12<2076::AID-ANIE2076>3.0.CO;2-2 　

ISSN： 1433-7851
'Thiacalix[4]aniline' as a highly specific extractant for Au(III) and Pd(II) ions Peer-reviewed

H Katagiri, N Iki, Y Matsunaga, C Kabuto, S Miyano

CHEMICAL COMMUNICATIONS　2002　(18)　2080-2081　2002

DOI： 10.1039/b205303a 　

ISSN： 1359-7345
Can thiacalixarene surpass calixarene? Peer-reviewed

Nobuhiko Iki, Sotaro Miyano

Journal of Inclusion Phenomena　41　(1-4)　99-105　2001/12

DOI： 10.1023/A:1014406709512 　

ISSN： 0923-0750
Can thiacalixarene surpass calixarene? Peer-reviewed

N Iki, S Miyano

JOURNAL OF INCLUSION PHENOMENA AND MACROCYCLIC CHEMISTRY　41　(1-4)　99-105　2001/12

DOI： 10.1023/A:1014406709512 　

ISSN： 1388-3127

eISSN： 1573-1111
Energy transfer luminescence of Tb3+ ion complexed with calix[4]arenetetrasulfonate and the thia and sulfonyl analogue. The effect of bridging groups Peer-reviewed

N Iki, T Horiuchi, H Oka, K Koyama, N Morohashi, C Kabuto, S Miyano

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2　(11)　2219-2225　2001/11

DOI： 10.1039/b009151k 　

ISSN： 1472-779X
Thiacalixarenes. Novel host compounds with high versatility Peer-reviewed

N Iki, S Miyano

NIPPON KAGAKU KAISHI　2001　(11)　609-622　2001/11

DOI： 10.1246/nikkashi.2001.609 　

ISSN： 0369-4577
Selective oxidation of thiacalix[4]arenes to the sulfinyl and sulfonyl counterparts and their complexation abilities toward metal ions as studied by solvent extraction Peer-reviewed

N Morohashi, N Iki, A Sugawara, S Miyano

TETRAHEDRON　57　(26)　5557-5563　2001/06

DOI： 10.1016/S0040-4020(01)00482-3 　

ISSN： 0040-4020
チアカリックスアレーン．分離・センシング機能試薬の新規プラットホームの創製

壹岐伸彦

化学と工業　54　(2)　124-127　2001/02
Publisher:
ISSN： 0022-7684
Energy transfer luminescence of Tb³⁺ ion complexed with calix[4]arenetetrasulfonate and the thia and sulfonyl analogue. The effect of bridging groups

Iki, N., Horiuchi, T., Oka, H., Koyama, K., Morohashi, N., Kabuto, C., Miyano, S.

Journal of the Chemical Society, Perkin Transactions 2　(11)　2001

ISSN： 1470-1820
Calix[4]arenes comprised of aniline units Peer-reviewed

H Katagiri, N Iki, T Hattori, C Kabuto, S Miyano

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY　123　(4)　779-780　2001/01

DOI： 10.1021/ja005573q 　

ISSN： 0002-7863
Synthesis and structural characterization of a Pd2+ complex with p-tert-butylsulfinylcalix[4]arene Peer-reviewed

N Morohashi, N Iki, S Miyano, T Kajiwara, T Ito

CHEMISTRY LETTERS　(1)　66-67　2001/01

DOI： 10.1246/cl.2001.66 　

ISSN： 0366-7022

eISSN： 1348-0715
Sulfonylcalix[4]arene as a bis-tridentate facial ligand: Syntheses and structures of dinuclear complexes, [M-2(L)(H2O)(2)(dmf)(4)] (M = Co(II), Ni(II); H4L = p-tert-butylsulfonylcalix[4]arene) Peer-reviewed

T Kajiwara, S Yokozawa, T Ito, N Iki, N Morohashi, S Miyano

CHEMISTRY LETTERS　(1)　6-7　2001/01

DOI： 10.1246/cl.2001.6 　

ISSN： 0366-7022

eISSN： 1348-0715
Syntheses of inherently chiral monosulfinyltrithiacalix[4]arenes by the oxidation of one of the bridging sulfurs of a tetrathiacalix[4]arene fixed in the 1,3-alternate conformation Peer-reviewed

N Morohashi, R Naito, N Iki, S Miyano

ISRAEL JOURNAL OF CHEMISTRY　41　(4)　303-307　2001

ISSN： 0021-2148
A capillary electrophoretic reactor with an electroosmosis control method for measurement of dissociation kinetics of metal complexes Peer-reviewed

N Iki, H Hoshino, T Yotsuyanagi

ANALYTICAL CHEMISTRY　72　(20)　4812-4820　2000/10

DOI： 10.1021/ac000312k 　

ISSN： 0003-2700
Fluorescent chemo-sensor for metal cations based on thiacalix[4]arenes modified with dansyl moieties at the lower rim Peer-reviewed

Y Higuchi, M Narita, T Niimi, N Ogawa, F Hamada, H Kumagai, N Iki, S Miyano, C Kabuto

TETRAHEDRON　56　(27)　4659-4666　2000/06

DOI： 10.1016/S0040-4020(00)00377-X 　

ISSN： 0040-4020
Novel molecular chirality in the calixarene family: formation of chiral disulfinyldithiacalix[4]arenes via partial oxidation of two adjacent sulfides of tetrathiacalix[4]arene Peer-reviewed

N Morohashi, N Iki, T Onodera, C Kabuto, S Miyano

TETRAHEDRON LETTERS　41　(26)　5093-5097　2000/06

DOI： 10.1016/S0040-4039(00)00780-2 　

ISSN： 0040-4039
Crystal structure and inclusion property of p-tert- butylthiacalix[6]arene Peer-reviewed

Nobuhiko Iki, Naoya Morohashi, Tomohiro Suzuki, Satoshi Ogawa, Mitsuru Aono, Chizuko Kabuto, Hitoshi Kumagai, Haruhiko Takeya, Setsuko Miyanari, Sotaro Miyano

Tetrahedron Letters　41　(15)　2587-2590　2000/04/08

DOI： 10.1016/S0040-4039(00)00211-2 　

ISSN： 0040-4039
Stereocontrolled oxidation of a thiacalix[4]arene to the sulfinyl counterpart of a defined S = O configuration Peer-reviewed

N Morohashi, N Iki, C Kabuto, S Miyano

TETRAHEDRON LETTERS　41　(16)　2933-2937　2000/04

DOI： 10.1016/S0040-4039(00)00313-0 　

ISSN： 0040-4039
Synthesis of p-tert-butylthiacalix[4]arene and its inclusion property Peer-reviewed

N Iki, C Kabuto, T Fukushima, H Kumagai, H Takeya, S Miyanari, T Miyashi, S Miyano

TETRAHEDRON　56　(11)　1437-1443　2000/03

DOI： 10.1016/S0040-4020(00)00030-2 　

ISSN： 0040-4020
Syntheses of chirally modified thiacalix[4]arenes with enantiomeric amines and their application to chiral stationary phases for gas chromatography Peer-reviewed

F Narumi, N Iki, T Suzuki, T Onodera, S Miyano

ENANTIOMER　5　(1)　83-93　2000

ISSN： 1024-2430
Thiacalixarene

Nobuhiko Iki, Hitoshi Kumagai

Catalysis　41　(8)　612-615　1999/12
Publisher:
ISSN： 0559-8958
Novel molecular receptors based on a thiacalix[4]arene platform. Preparations of the di- and tetracarboxylic acid derivatives and their binding properties towards transition metal ions Peer-reviewed

N Iki, N Morohashi, F Narumi, T Fujimoto, T Suzuki, S Miyano

TETRAHEDRON LETTERS　40　(41)　7337-7341　1999/10

DOI： 10.1016/S0040-4039(99)01503-8 　

ISSN： 0040-4039
Almost complete removal of trace amount of halogenated organic compounds in water: An approach by use of a combination of water-soluble thiacalixarene and ion-exchange resins Peer-reviewed

N Iki, T Fujimoto, T Shindo, K Koyama, S Miyano

CHEMISTRY LETTERS　(8)　777-778　1999/08

DOI： 10.1246/cl.1999.777 　

ISSN： 0366-7022

eISSN： 1348-0715
Coordination of epithio groups of p-tert-butylthiacalix[4]arene in a Zn2+ complex studied by X-ray crystallography Peer-reviewed

N Iki, N Morohashi, C Kabuto, S Miyano

CHEMISTRY LETTERS　(3)　219-220　1999/03

DOI： 10.1246/cl.1999.219 　

ISSN： 0366-7022

eISSN： 1348-0715
Selective synthesis of three conformational isomers of tetrakis[(ethoxycarbonyl)methoxy]thiacalix[4]arene and their complexation properties towards alkali metal ions Peer-reviewed

N Iki, F Narumi, T Fujimoto, N Morohashi, S Miyano

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2　(12)　2745-2750　1998/12

ISSN： 0300-9580
Selective oxidation of thiacalix[4]arenes to the sulfinyl- and sulfonylcalix[4]arenes and their coordination ability to metal ions Peer-reviewed

N Iki, H Kumagai, N Morohashi, K Ejima, M Hasegawa, S Miyanari, S Miyano

TETRAHEDRON LETTERS　39　(41)　7559-7562　1998/10

DOI： 10.1016/S0040-4039(98)01645-1 　

ISSN： 0040-4039
A new chiral stationary phase for gas chromatography by use of a chiral thiacalix[4]arene derivative Peer-reviewed

N Iki, F Narumi, T Suzuki, A Sugawara, S Miyano

CHEMISTRY LETTERS　(10)　1065-1066　1998/10

DOI： 10.1246/cl.1998.1065 　

ISSN： 0366-7022

eISSN： 1348-0715
A new water-soluble host molecule derived from thiacalixarene Peer-reviewed

N Iki, T Fujimoto, S Miyano

CHEMISTRY LETTERS　(7)　625-626　1998/07

DOI： 10.1246/cl.1998.625 　

ISSN： 0366-7022

eISSN： 1348-0715
High complexation ability of thiacalixarene with transition metal ions. The effects of replacing methylene bridges of tetra(p-t-butyl)calix[4]arenetetrol by epithio groups Peer-reviewed

N Iki, N Morohashi, F Narumi, S Miyano

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN　71　(7)　1597-1603　1998/07

DOI： 10.1246/bcsj.71.1597 　

ISSN： 0009-2673

eISSN： 1348-0634
High-performance liquid chromatographic methods for the specific monitoring of nickel and vanadium in municipal air at the nanogram per cubic meter levels Peer-reviewed

N Iki, K Irie, H Hoshino, T Yotsuyanagi

ENVIRONMENTAL SCIENCE & TECHNOLOGY　31　(1)　12-16　1997/01

DOI： 10.1021/es950713v 　

ISSN： 0013-936X
Electrostatic and hydrodynamic separation of DNA fragments in capillary tubes Peer-reviewed

N Iki, Y Kim, ES Yeung

ANALYTICAL CHEMISTRY　68　(24)　4321-4325　1996/12

DOI： 10.1021/ac9605814 　

ISSN： 0003-2700
Non-bonded poly(ethylene oxide) polymer-coated column for protein separation by capillary electrophoresis Peer-reviewed

N Iki, ES Yeung

JOURNAL OF CHROMATOGRAPHY A　731　(1-2)　273-282　1996/04

DOI： 10.1016/0021-9673(95)01158-7 　

ISSN： 0021-9673
2-PYRIDYLALDEHYDEBENZOYLHYDRAZONE DERIVATIVES AS HIGHLY SELECTIVE PRECOLUMN CHELATING REAGENTS FOR NICKEL(II) ION IN KINETIC DIFFERENTIATION MODE HIGH-PERFORMANCE LIQUID-CHROMATOGRAPHY Peer-reviewed

N IKI, H HOSHINO, T YOTSUYANAGI

MIKROCHIMICA ACTA　113　(3-6)　137-152　1994

DOI： 10.1007/BF01243607 　

ISSN： 0026-3672
ION-ASSOCIATION CAPILLARY ELECTROPHORESIS - NEW SEPARATION MODE FOR EQUALLY AND HIGHLY-CHARGED METAL-CHELATES Peer-reviewed

N IKI, H HOSHINO, T YOTSUYANAGI

JOURNAL OF CHROMATOGRAPHY A　652　(2)　539-546　1993/10

DOI： 10.1016/0021-9673(93)83276-X 　

ISSN： 0021-9673
HIGH-PERFORMANCE SEPARATION AND DETERMINATION OF CO(III) AND NI(II) CHELATES OF 4-(2-PYRIDYLAZO)RESORCINOL AT FEMTOMOLE LEVELS BY CAPILLARY ELECTROPHORESIS Peer-reviewed

N IKI, H HOSHINO, T YOTSUYANAGI

CHEMISTRY LETTERS　(4)　701-704　1993/04

DOI： 10.1246/cl.1993.701 　

ISSN： 0366-7022

eISSN： 1348-0715
金属錯体の高性能キャピラリー電気泳動

壹岐伸彦, 四ツ柳隆夫

化学　48　(6)　434-435　1993
Publisher:
ISSN： 0451-1964
Nuclear magnetic resonance studies of complexes of aluminium(III), gallium(III), and indium(III) with disulphonated 2,2′-dihydroxyazobenzene ligands in aqueous solution Peer-reviewed

DF EVANS, N IKI

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS　(12)　3773-3779　1990/12

DOI： 10.1039/DT9900003773 　

ISSN： 0300-9246
金属イオンの吸光検出高速液体クロマトグラフィーに適合する有機試薬の設計

壹岐伸彦, 星野仁

Dojin News　48　3-8　1989

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Misc. 13

化学の感動を共有する喜び Invited

壹岐伸彦

化学と工業　72　(9)　791　2019/09
Central Scienceとしての分析化学 Invited

壹岐伸彦

ぶんせき　2019　(5)　185　2019/05
Pt(II)-diradical Complex toward Theranostics of Cancer

Ryota Sawamura, Atsuko Masuya-Suzuki, Nobuhiko Iki

IEICE Technical Report　OME2019　(3)　9-12　2019/04
Silver Nanoparticles Invited

Nobuhiko Iki

Analytical Sciences　34　(11)　1223-1224　2018/11

DOI： 10.2116/analsci.highlights1811 　

ISSN： 1348-2246
医療への展開を志向した多機能性金属錯体の創製 Invited

壹岐伸彦

翠巒　31　37-40　2017/02
CEの解き明かす溶液内分子複合体の熱力学的・速度論的描像

壹岐伸彦

電子情報通信学会技術研究報告　116　(437)　27-28　2017/01/28
アフィニティーキャピラリー電気泳動の解き明かす酵素活性中心の配位化学

壹岐伸彦, 佐藤陽介

IEICE Technical Report　115　(18)　11-14　2015/04/29
Publisher: 電子情報通信学会
ISSN： 0913-5685

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SDM2015-3
セラノスティクスを志向した多機能性金属錯体の創製

田村昂作, 升谷敦子, 星野仁, 壹岐伸彦

IEICE Technical Report　114　(341)　17-20　2014/11/21
Publisher: The Institute of Electronics, Information and Communication Engineers
ISSN： 0913-5685

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OME2014-62
Designing strategies for supramolecular luminescent complex of lanthanide-heterometal assembly

Nobuhiko Iki

SUPRAMOLECULAR CHEMISTRY　23　(1-2)　160-168　2011

DOI： 10.1080/10610278.2010.514915 　

ISSN： 1061-0278
チアカリックスアレーンの高次機能

壹岐伸彦

日本化学会生体機能関連化学部会ニュースレター　21　(4)　20-24　2007/02/28
Publisher: 日本化学会
「生命科学と分析化学」特集号の刊行にあたって

壹岐伸彦

分析化学 = Japan analyst　55　(12)　889-889　2006/12/05

ISSN： 0525-1931
'Thiacalix[4]aniline' as a highly specific extractant for Au(III) and Pd(II) ions (pg 2080, 2002)

H Katagiri, N Iki, Y Matsunaga, C Kabuto, S Miyano

CHEMICAL COMMUNICATIONS　(21)　2592-2592　2002

ISSN： 1359-7345
ION-ASSOCIATION CAPILLARY ELECTROPHORESIS - NEW SEPARATION MODE FOR EQUALLY AND HIGHLY-CHARGED METAL-CHELATES (VOL 652, PG 539, 1993)

N IKI, H HOSHINO, T YOTSUYANAGI

JOURNAL OF CHROMATOGRAPHY A　669　(1-2)　278-278　1994/05

ISSN： 0021-9673

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Books and Other Publications 6

キャピラリー電気泳動法・イオンクロマトグラフィーの分析テクニック

壹岐伸彦

(株)技術情報協会　2023/12/27
クリスチャン分析化学原書7版，I. 基礎編

今任稔彦, 角田欣一, 壹岐伸彦

丸善出版　2016/12/30

ISBN: 9784621301098

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http://pub.maruzen.co.jp/book_magazine/book_data/search/9784621301098.html
Calixarenes and Beyond

Nobuhiko Iki

Springer International Publishing　2016/08/13

DOI： 10.1007/978-3-319-31867-7_13 　

ISBN: 9783319318653
Capillary Electrophoresis and Microchip Capillary Electrophoresis: Principles, Applications, and Limitations

Toru Takahashi, Nobuhiko Iki

Wiley　2013/03

ISBN: 9780470572177
計測工学ハンドブック

2001
分析化学反応の基礎-演習と実験改訂版

1994/10

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Presentations 4

Luminescent Supramolecular Complexes of Ag(I)-Tb(III)-Thiacalix[4]arene Formed in Aqueous Solutions: Structure, Photophysical Properties, and Applications International-presentation

10th International Conference on Calixarenes (CALIX 2009)　2009/07/13
Thiacalixarene: A versatile reagent for separation of metal ions and organic pollutants International-presentation

2005 International Chemical Congress of Pacific Basin Societies (PACIFICHEM 2005)　2005/12/15
Thiacalixarene -A Versatile Functional Material for Separation and Sensing International-presentation

The Fifth International Conference on Material Engineering for Resources　2005/10/20
Supramolecular Sensing Systems Based on Thiacalixarene-Terbium(III) Complex International-presentation

8th International Conference on Calixarenes (CALIX 2005)　2005/07/25

Industrial Property Rights 1

環状フェノール硫化物のスルホン酸化合物及びその製造方法

宮野壮太郎, 壹岐伸彦, 藤本豊久, 濱田文男, 加藤真吾, 平石佳之, 熊谷仁志, 長谷川実治, 宮成節子, 栖川能裕, 石塚昌宏

4180238

Property Type: Patent

Research Projects 30

多機能性金属錯体の創製と分析化学的応用 Competitive

2009/04 - Present
Development of Novel Functionality of Thiacalixarene Competitive

1996/04 - Present
Kinetic Differentiation Mode High-Performance Separation and Determination Method Competitive

1987/04 - Present
配位不飽和サイトを持つ多孔性配位高分子による革新的MRI造影剤の創製

壹岐伸彦, 唐島田龍之介, 澤村瞭太, 松井裕史

Offer Organization: 日本学術振興会

System: 科学研究費助成事業

Category: 基盤研究(B)

Institution: 東北大学

2025/04/01 - 2028/03/31
二核ランタニド-ポリオキソメタレート錯体を基盤としたセラノスティクス試薬

唐島田龍之介, 壹岐伸彦

Offer Organization: 日本学術振興会

System: 科学研究費助成事業

Category: 基盤研究(C)

Institution: 東北大学

2023/04/01 - 2026/03/31
ジラジカル錯体をがん認識光熱変換プローブとするがんの未来型セラノスティクス

壹岐伸彦, 西條芳文, 高橋透, 唐島田龍之介, 権田幸祐

Offer Organization: 日本学術振興会

System: 科学研究費助成事業

Category: 基盤研究(B)

Institution: 東北大学

2022/04/01 - 2025/03/31
分離化学的アプローチによる新規なバイサルファイトフリーDNAメチル化検出法の開発

高橋透, 壹岐伸彦

Offer Organization: 日本学術振興会

System: 科学研究費助成事業

Category: 基盤研究(C)

Institution: 福井大学

2020/04/01 - 2023/03/31

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がんの早期診断に有用な分子マーカーとして5-メチルシトシン(5-mC)が非常に注目されており，国内外を問わず5-mCをターゲットとするDNAメチル化検出の新規技術開発が行われている．既往のほぼすべてのDNAメチル化検出法ではバイサルファイト（BS）処理の利用が前提となっているが，本研究課題では，その開発が強く望まれている，BS処理を必要としない新規なBSフリーDNAメチル化検出法の開発を目指す．特に，5-mCとシトシン(C)の直識別を達成するための手段として，申請者が独自に開発した等鎖長配列異性一本鎖DNAのキャピラリー電気泳動（CE）分離法を利用し，これをベースに，酸塩基平衡，水素結合をはじめとする種々の相互作用を駆使する新たなDNAの精密分離法を開発し，BSフリーDNAメチル化検出法を構築することを着想した．今年度は，昨年度に引き続き，BSフリーDNAメチル化検出法を構築するための基盤技術として，98塩基長の遺伝子断片およびこれにメチル化処理を施した模擬メチル化試料のCE分離条件の検討を行うとともに，CE系の検出感度の向上を目的として，蛍光検出を行うための検討を行った．また，従前使用してきたCE分離装置が故障，修理不能となったため，その代替手段の検討を行った．
配位子の構造柔軟性がもたらす多様な平衡を利用するfブロック金属の高選択的結晶化

鈴木敦子, 唐島田龍之介, 壹岐伸彦, 原賀智子

Offer Organization: 日本学術振興会

System: 科学研究費助成事業

Category: 基盤研究(B)

Institution: 東北大学

2019/04/01 - 2022/03/31

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高レベル放射性廃液は長寿命の放射性核種アクチノイド(An)を含み，処分方法に関する社会的合意を形成することが難しい廃棄物である．この高レベル放射性廃液処理において，Anと同じfブロック金属であるランタノイド(Ln)を分離する技術が近年必要とされている．本研究では，三脚型シッフ塩基配位子錯体を生成し結晶化させることを利用し，An/Ln分離法を開発することを目指している．本年度は，昨年度に続いて放射性がなく取り扱いが容易なLnを用いて分離条件の最適化及び分離機構の検討を行った．分離対象としては，ネオジム磁石スクラップからネオジム (Nd) とディスプロシウム (Dy) を分離回収する技術へ展開する可能性を考え，NdとDyを選択して実験を行なった．以下に本年度得た成果の概要を示す． (1) 核磁気共鳴分光法によりNd錯体とDy錯体の溶液内構造を検討した．その結果，ジメチルスルホキシドと2-プロパノールの混合溶媒中でどちらの錯体も7配位構造をとる可能性が示唆された． (2) 分離を行う際のジメチルスルホキシドと2-プロパノールの混合比を最適化するため，各混合比で錯体の溶解度を決定した．その結果，ジメチルスルホキシド : 2-プロパノール = 1 : 3の体積比の混合溶媒に対するNd錯体とDy錯体の溶解度の差が大きく，Dy錯体の溶解度が低くなり，分離に適していることが分かった． (3) 配位子，金属イオン，塩基であるジイソプロピルエチルアミン (DIEA)の混合比を変え，生成する結晶中に含まれるDyの純度を調べた．その結果，Dy : Nd : 配位子 : DIEA = 1 : 1 : 2 : 3の条件でDyの純度が高くなり99.4(1)%となることが分かった．以上，錯体生成過程と結晶化過程の協働に基づき，一段階で高純度のDy錯体を結晶化できる条件を決定することに成功した．
Exploration of Science for Designing High Performance MRI Contrast Agents - A New Approach Using Coordinatively Unsaturated Coordination Polymers as a Substrate

Iki Nobuhiko

Offer Organization: Japan Society for the Promotion of Science

System: Grants-in-Aid for Scientific Research

Category: Grant-in-Aid for Challenging Research (Exploratory)

Institution: Tohoku University

2018/06/29 - 2022/03/31

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Having high resolution, magnetic resonance imaging (MRI) is one of the most powerful imaging-based diagnostic modalities. To circumvent the low sensitivity, Gd(III)-based contrasting agents (CAs) are used. Recently, because of the safety concern of Gd(III) on human body, safer CAs are required. Seeking new motives of contrast agents, we notice porous coordination polymer (PCP) having coordinatively unsaturated site (CUS) can be a promising candidate for CAs. By using Mn(II) and dihidroxyterephthalic acid, we clarified the conditions to synthesize nano-sized CUS-PCP and to modify the surface with PEG to gain high-water solubility and bio-compatibility. The relaxivity of the PEG-modified CUS-PCP was higher than that of a conventional Gd(III)-based CA. In vivo T1-weighted MRI of tumor-bearing mouse clearly showed the tumor region by selective delivery of the PCP. Thus, this study clarified that CA design by using CUS-PCP is a very promising approach.
Development of high-accuracy and low-cost DNA methylation detection method for supporting epigenetics research

TAKAHASHI Toru

Offer Organization: Japan Society for the Promotion of Science

System: Grants-in-Aid for Scientific Research

Category: Grant-in-Aid for Scientific Research (C)

Institution: University of Fukui

2017/04/01 - 2020/03/31

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In recent years, the importance of epigenetics has attracted attention in many research fields related to life science. The basis of epigenetics research is to detect DNA modification, i.e. DNA methylation. In study, we aimed to provide a novel DNA methylation detection method as an important research tool to support epigenetics research. We have developed a new method for detecting DNA methylation with high accuracy and low cost based on the capillary electrophoretic separation method for sequence isomers of single-stranded DNA with same chain length, which utilizes the difference in the proton dissociation properties of nucleobases.
Cancer theranostics using near-infrared absorbing metal complex as a photothermal probe

Iki Nobuhiko

Offer Organization: Japan Society for the Promotion of Science

System: Grants-in-Aid for Scientific Research

Category: Grant-in-Aid for Scientific Research (B)

Institution: Tohoku University

2017/04/01 - 2020/03/31

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We studied functions of a series of Pt(II)-diradical complexes aimed at application to a probe for theranostics of cancer to provide accurate but affordable diagnostics and therapeutic method. The prerequisites of the probe are functions such as near-infrared (NIR) absorption, its switching, photothermal effect, delivery to cancer cells or tumor, stability in cancer cells. We modeled four Pt(II) complexes that can partially fulfill those prerequisites and successfully obtained guidelines for molecular design of a probe for theranostics. This study is a milestone to provide a clear path to obtain the ultimate probe that can meet the requirement of theranostics and to proceed to animal experiment.
Photon conversion materials prepared with Ln-cluster complex: An approach from coordination chemistry

IKI Nobuhiko, KARASHIMADA Ryunosuke

Offer Organization: Japan Society for the Promotion of Science

System: Grants-in-Aid for Scientific Research

Category: Grant-in-Aid for Challenging Exploratory Research

Institution: Tohoku University

2015/04/01 - 2018/03/31

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Ultimate goal of this study was preparation of a photonic material to convert photon energy by use of heteronuclear lanthanide cluster complex. For this purpose, we used thiacalix[4]arene (TCAS) which form the complex Tb3-xYbxTCAS2 (x = 1,2) with Tb and Yb. In the complex, the Tb to Yb energy transfer efficiency was high. Also, they were separated by electrophoresis and prepared by stepwise manner. Luminescent material was prepared by doping phosphonium salt of Tb3TCAS2 in a polymer, PMMA, showing that de-activation was suppressed. These outcomes are basic but essential to prepare photonic material by doping Tb3-xYbxTCAS2 (x = 1 or 2) into PMMA.
Development of extended capillary electrophoretic reactor as novel methodology for kinetic analysis of chemical reactions in solution

TAKAKAHSI Toru

Offer Organization: Japan Society for the Promotion of Science

System: Grants-in-Aid for Scientific Research

Category: Grant-in-Aid for Scientific Research (C)

Institution: University of Fukui

2014/04/01 - 2017/03/31

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There are urgent and strong demands for the development of useful kinetic analysis method in a variety of research fields. The aim of this research program is the construction of “extended” capillary electrophoretic reactor (CER), which is based on the basic concept using capillary electrophoretic separation process as “reactor” for the reaction of complexes. Zone-passing mode CER (ZP-CER) was developed as a novel methodology for the kinetic analysis of the formation reaction of a metal complex. The scope of the application of ZP-CER was extended to the kinetic analysis of the formation reaction of a nonmetal complex, and hydrolysis of a dye. A temperature variable type ZP-CER was also developed, and was successfully applied to the acquisition of the activation parameters of the formation reaction of a nonmetal complex.
MRI contrast agents for high relaxivity, kinetic stability, and targeting

Iki Nobuhiko, CARAVAN Peter

Offer Organization: Japan Society for the Promotion of Science

System: Grants-in-Aid for Scientific Research

Category: Grant-in-Aid for Scientific Research (B)

Institution: Tohoku University

2013/04/01 - 2017/03/31

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In about 30% of magnetic resonance imaging (MRI), contrast agents (CAs) are used aiming at enhancing the sensitivity and contrast. Currently, Gd complexes of poly(aminocarboxylate) are commonly used, which however have limitation of sensitivity and side effects known as nephrogenic systemic fibrosis. Here we propose a new molecular motif of CA, Gd3TCAS2, on the basis of a complex of tri-Gd cluster sandwiched between two thiacalixarene (TCAS) ligands. In this study, we elucidated the formation behavior of the trinuclear complex, solution structure, relaxivity of Gd3TCAS2 to lead to design of new CA.
Development of the novel high precision low labor load gene-diagnosis system towards realization of tailor-made medical care

TAKAHASHI Toru, IKI Nobuhiko

Offer Organization: Japan Society for the Promotion of Science

System: Grants-in-Aid for Scientific Research

Category: Grant-in-Aid for Scientific Research (C)

Institution: University of Fukui

2011 - 2013

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A multiple detection method for single nucleotide polymorphism (SNP) based on the CE separation technique for single base substituted sequence isomers of single stranded DNA was proposed. In the CE separation method where an acidic aqueous urea solution was employed as an electrophoretic buffer solution, the separation of single base substituted sequence isomers of single stranded DNA was achieved according to the difference of the proton dissociation properties of each DNA bases at acidic condition. A clear criterion for determining of existence or nonexistence of SNP by the peak pattern of the electropherogram allows high reliability of the proposed method. The proposed method can be applied to all substitution patterns with identical condition. The proposed method was successfully applied to the SNP detection and genotyping for extracted human gene fragment sample including ALDH2 gene region.
Design of Dual Imaging Probes for Magnetic Resonance and Luminescence via Self-assembly of Lanthanide and Thiacalixarene

IKI Nobuhiko, HOSHINO Hitoshi, TAKAHASHI Toru

Offer Organization: Japan Society for the Promotion of Science

System: Grants-in-Aid for Scientific Research

Category: Grant-in-Aid for Challenging Exploratory Research

Institution: Tohoku University

2011 - 2012

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The study is aimed at a developing dual imaging probe (DIP) for magnetic resonance imaging (MRI) and luminescence imaging to enhance the sensitivity and resolution of the current imaging techniques. Here we used thiacalixarene as a clustering ligand for multi-lanthanide core enabling both magnetic relaxation and luminescence. We have successfully elucidated that the multi-nuclear complex fulfill prerequisites for DIP such as (1) formation of single species, (2) high kinetic stability, (3) relaxivity, and(4) luminescence functions.
Integrated Analytical System for Biomolecular Interactions on the Basis of Capillary Electrophoretic Reactor

HOSHINO Hitoshi, IKI Nobuhiko, TAKAHASHI Toru

Offer Organization: Japan Society for the Promotion of Science

System: Grants-in-Aid for Scientific Research

Category: Grant-in-Aid for Scientific Research (C)

Institution: Tohoku University

2008 - 2010

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In this research project, in the broadest sense, and other complex biological molecules, complex with the goal of their research to create a new methodology for quantitative evaluation of the overall binding ability. Developing a reactor with a reaction field representation capillary electrophoresis of metal complexes in homogeneous solution, which enables the direct analysis of the rate constant for dissociation of the complex biological molecules. Demonstrate the ability to track the behavior of complex formation reaction by adding a ligand to the reaction field, demonstrating that the system can obtain a comprehensive quantitative analysis.
Development of Facile and Rapid Method for Determination of Ultra trace Amount of Heavy Metal Ions in Soil Aiming at Secure Society

IKI Nobuhiko, HOSHINO Hitoshi, TAKAHASHI Toru

Offer Organization: Japan Society for the Promotion of Science

System: Grants-in-Aid for Scientific Research

Category: Grant-in-Aid for Scientific Research (B)

Institution: Tohoku University

2008 - 2010

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This study was aimed at developing a facile and rapid method to determine exchangeable heavy metal ions such as Cd and Pb in soil. In the first step, thiacalix[4] arene was utilized as the extractant to accelerate the leaching processes from 6 h to only 10 min, owing to the complexation ability toward Cd and Pb. This step was followed by quantitative ligand replacement with the thiosemicarbazone ligand, the resulting complex of which was then subjected to kinetic differentiation mode HPLC to enable highly selective and sensitive detection of exchangeable Cd and Pb at the ppb levels without interference from soil matrices.
水溶液を反応場とする近距離金属相乗効果系化合物の自律的形成と発光機能制御

壹岐伸彦, 諸橋直弥

Offer Organization: 日本学術振興会

System: 科学研究費助成事業

Category: 特定領域研究

Institution: 東北大学

2007 - 2007

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チアカリックスアレーン(TCAS)を配位子として用い,水溶液系での元素相乗系化合物を創製し,光物理特性を明ちかにした.Ag^I-Tb^<III>-TCAS三元系について水-DMF系から錯体Ag^I4-Tb^<III>-TCAS_2(Na_9[Ag^I_4Tb^<III>[tcas^<8->)_2]・dmf_8(H_20)_6の単結晶を得た.結晶構造解析の結果,本錯体は二つのTCASが4重のS-Ag-S架橋により結ばれたdouble-cone形状をとることを明らかにした.錯体はTb^<III>に対称心を持つが,大まかにはTCASの中心を軸とするC_4対称をとる.TCAS骨格はわずかに歪んだconeコンホメーションを取っており,その疎水空孔にDMF(4)を包接する.Tb^<III>は計8個のフェノール酸素で構成される8配位立方体構造を持つ.特筆すべきはTb^<III>は配位水分子を持たないことである.これは励起Tb^<III>からOH振動子へのエネルギー移動による緩和を防止する上で重要な配位環境である.合成的にこのような配位環境を作り出すことは難しく,TCASとAg^Iとの混合により各構成要素が相乗的に作用し,超分子構造を組み上げるアプローチが奏功したといえる.なおAg^I_4・Tb^<III>コアにおいてAg^I-Tb^<III>距離はそれぞれ3.3233,3.2383Åであり,直接的な相互作用は認められなかった.単離した単結晶錯体の発光量子収率は20%程度であったが,結晶サイズが小さくなるにつれ減少した(21〜17%).また^5D_4→^7F_5遷移帯の形状の変化が観測され,Tb中心の対象性の差異が示唆された.発光寿命は2msであった.
超分子Gd(III)錯体の自発的形成を用いる高緩和性MRIコントラスト剤の創製

壹岐伸彦, 星野仁, 高橋透

Offer Organization: 日本学術振興会

System: 科学研究費助成事業

Category: 萌芽研究

Institution: 東北大学

2006 - 2007

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高緩和性MRIコントラスト剤創製に向け,前年度に引き続き1.超分子Gd(III)錯体の構造解析,および新たに2.速度論的安定性の評価を行った. 1.モデルとなるAg-Tb-TCAS系について種々のpH,溶媒組成を検討し,DMFの蒸気拡散法により三元錯体の単結晶を得ることに成功した.結晶構造解析したところ,錯体の組成はNa_9[Ag^I_4Tb^<III>(tcas^<8->)_2]・dmf_<8>・(H_2O)_6であった(Ag^I_4・Tb^<III>・TCAS_2と略記).本錯体は二つのTCASが4重のS-Ag-S架橋により結ばれたdouble-cone形状をとる.一方Tb^<III>イオンは錯体の中心部に位置し,上下のTCASから計8個のフェノール酸素の配位を受けている.一方NMR緩和過程で重要となる配位水分子は見られず,Ag^I_4・Gd^<III>・TCAS_2錯体はMRI造影剤としては適合しないといえる.しかし本Ag^I_4・Tb^<III>・TCAS_2錯体は,前年度明らかにしたAg^I_2・Tb^<III>_2・TCAS_2錯体のdouble-cone構造を間接的に支持する重要な結果である. 2.超分子錯体の速度論的安定性は,MRI造影剤への応用の前提となる.前年度その存在を明らかにしたAg^I_2・Tb^<III>・TCAS_2錯体について,キャピラリー電気泳動反応器により加溶媒分解反応速度定数k_dを3.1×10^<-3>s^<-1>と決定した.これは半減期t_<1/2>=3.8分に相当し速度論的安定性の向上が必要であった.そこでAgリンカーを用いないランタニド-TCAS二元系について種々検討した結果,Tb^<III>過剰の条件でTb^<III>_3・TCAS_2錯体を得た.k_dを決定したところ5.5×10^<-4>s^<-1>(t_<1/2>=21分)となり,安定性の向上に成功した.また配位水分子数は2.2となり,Gd^<III>_3・TCAS_2錯体の高緩和性が示唆された.
Design of NIR-Luminescent Probes with Long-life Emission on the Basis of Thiacalixarene-Lanthanide-Silver Supramolecular Complexes

IKI Nobuhiko, HOSHINO Hitoshi, TAKAHASHI Toru

Offer Organization: Japan Society for the Promotion of Science

System: Grants-in-Aid for Scientific Research

Category: Grant-in-Aid for Scientific Research (B)

Institution: Tohoku University

2004 - 2006

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Probes with long-lived luminescence in near-infrared region were obtained with supramolecular formation in lanthanide(III)-silver(I)-thiacalix[4]arene-p-tetrasulfonate (TCAS) ternary systems via following studies. 1.Structural characterization of Tb(III)-Ag(I)-TCAS supramolecular complex with ES-MS : It was clarified that supramolecular complex Ag_2・Tb_2・TCAS (1) was formed at pH 6.5, whereas Ag_2・Tb・TCAS (2) was formed at pH 10.0. Complexes 1 and 2 adopted double-cone structures, in which two Ag(I) ions bridges two cone-shaped TCAS by Ag(I)-S-Ag(I) bridges. In complex 1, TCAS coordinate to Tb(III) with two sets of O,S,O-coordination, whereas in complex 2 each TCAS coordinate to Tb(III) center with two sets of O,O,O,O-coordination. 2.Determination of photophysical properties : For complex 1, determined parameters are as follows: luminescence quantum yield Φ = 0.16, luminescence lifetime τ= 1.09 ms, and number of coordinating water to Tb(III) q = 2.4. For complex 2, Φ (=0.11) was smaller than that of 1, but τ (= 4.61 ms) was as large as intrinsic luminescence lifetime of Tb(III) ion (4.7 ms). This owes to the fact that number of coordinating water was almost zero (q = 0.1). Removal of coordinating water from lanthanide center is a key to realize NIR luminescence in aqueous solutions, because coordinating water strongly quenches NIR luminescence via high-energy vibrational modes. Therefore, we selected supramolecular complex 2 as a candidate for NIR probe. 3.Characterization of NIR probes : Yb(III) ion formed supramolecule 2 at pH 9.9, which emitted MIR light at 983 nm with Φ = 2.5x10^<-3>. On the other hand, Nd(III) formed Ag_3 Td TCAS (3) under the same conditions, which exhibited luminescence at 1050 nm (0=2.9x 10^<-4>). 4.Elucidation of kinetic stability : Solvolytic dissociation rate constant for Ag_2 Tb TCAS.( was determined to be 3.1x10^<-3> s^<-1> with a capillary electrophoretic reactor. This corresponds to half-life of 3.8 min, which is rather small from a view point of biological application. It was concluded that improvement of kinetic stability is next challenge for practical application of supramolecular NIR-luminescence probes.
Development of the Methodology for Dissociation Kinetic Analysis of Biomolecular Complexes with Capillary Electrophotetic Reactor

TAKAHASHI Toru, IKI Nobuhiko, SAITOH Shingo

Offer Organization: Japan Society for the Promotion of Science

System: Grants-in-Aid for Scientific Research

Category: Grant-in-Aid for Scientific Research (B)

Institution: Tohoku University

2003 - 2004

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A microchip capillary electrophoretic reactor (MCER), a practical and powerful tool for dissociation kinetic analysis of metal complexes, has been proposed. In the dissociation kinetic analysis of metal complexes using conventional batch reaction techniques, owing to the difficulty in dividing between reactant (metal complex) and products (metal ion and free ligand), the direct measurement of the dissociation kinetics had not been achieved. On the contrary, MCER revolutionized the measurement of the dissociation rate constant of metal complexes since its accomplishment of the direct measurement. The basic idea of a MCER was provoked by the concentration jump character of the sharp band profiles in microchip capillary electrophoresis (MCE) ; i.e. metal complexes during the MCE separation processes, in which there had been no ligand in the electrophoretic buffer solution, were exposed to overwhelming force to dissociation caused by a steep concentration jump of the ligand. The time depending dissociation reaction profile of metal complex of Ce^<3+> with a polyaminocarboxylic ligand, 8-amino-2-[(2-amino-5-methylphenoxyl)methyl]-6-methoxyquinoline-N,N,N',N',-tetraacetic acid ([CeL]^-) was described using both internal and external standard. The solvolytic dissociation rate constant of [CeL]^-have been determined directly as 6.2 X 10^<-3> s^<-1> at 303 K with MCER. Capillary electrophoretic reactor (CER) was applied to the determination of dissociation reaction rate constant of bio-molecular complexes. Both an immunocomplex of anti digoxin IgG with digoxin and a complex double stranded DNA with ethidium bromide were chosen as analytical model compounds. Unfortunately, determination of dissociation reaction rate constants could not be achieved with CER in both systems, since their properties of small electrophoretic mobility and lower kinetically inertness.
分子認識と相分離を利用する易水容性分子の水溶液からの高効率分離回収法

壹岐伸彦, 宮野壮太郎, 服部徹太郎, 壹岐伸彦

Offer Organization: 日本学術振興会

System: 科学研究費助成事業

Category: 萌芽研究

Institution: 東北大学

2002 - 2003

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当研究の目的は新規ホスト分子チアカリックスアレーン(TCA)の易水溶性分子に対する包接能を活用し,その高効率分離回収法の可能性を検討するところにある.前年度までに1.ゲスト分子の適用限界の調査,2.包接機構の解明を行った.本年度は3.TCAの分子修飾による包接能の高度化を検討した. 3.TCAの分子修飾による包接能の高度化 TCAは溶液中でコンホメーション変換運動をしており,これは易水溶性分子の包接能を弱めていると予想できる.そこで分子修飾を施し,コンホメーションの動的な揺らぎを制限することを企図した.まず,分子修飾としてTCAのフェノール性OHの一つをアルキル化し,OCH_2COOHとした.アルコールやケトン,ニトリルなど水溶性ゲストに対する包接能を調べた.TCAの場合より大きなゲスト分子に対して高い包接能を示したが,TCAモノカルボン酸はより小さなゲストに対し,高い包接能を示した.特にメタノールに対し10^2M^<-1>を越える大きな包接能を示した。これはモノアルキル化の結果,空孔の形状が制御され,あるいは空孔サイズが制限され,小分子の包接に適合したと考えた.一方大きなゲスト分子は生成したホストゲスト錯体において疎水的アルキル部位を空孔の外に露出するため,不安定となると考えた. 一方,TCAの最大の特徴である,金属イオンとの錯形成能を利用し,TCAのフェノール部位を固定した.Cu(II),Cd(II)イオンのTCA錯体について易水溶性分子の包接能を評価した.その結果TCAに比べ,錯体は一桁程度の包接能の向上を示すことがわかった.これは統計的な効果を上回る包接能の向上であり,コンホメーション固定の効果と考えられる. 以上から易水溶性分子のホスト設計の指針が得られ,これを塩析などの相転移と組み合わせれば,易水溶性分子の分離回収技術の開発につながると考えられる.
硫黄架橋したフェノールの新規環状オリゴマーの創製と機能開発

服部徹太郎, 宮野壮太郎, 壹岐伸彦, 服部徹太郎

Offer Organization: 日本学術振興会

System: 科学研究費助成事業

Category: 特定領域研究

Institution: 東北大学

2002 - 2003

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当年度は,S-CH_2交互架橋型カリックス[4]アレーンの金属錯体の調製および硫黄架橋基酸化誘導体の合成,カリックス[4]アレーンおよびチアカリックス[4]アレーンの隣接水酸基の立体選択的ジアルキル化と分子不斉カリックスアレーンの合成について検討し,以下の成果を得た。 1.S-CH_2交互架橋型ジチアカリックス[4]アレーン(H_4L)を酢酸銅(II)または四塩化チタンと処理して錯体を調製し,対応する既知のチアカリックス[4]アレーン(H_4L')の錯体と構造を比較した。H_4LはH_4L'と同様に錯形成能が高く,H_4L'が向かい合った二つの架橋硫黄で配位して錯体を形成するチタン錯体Ti_2L'では同じ構造の錯体が得られ,四つの架橋基が配位する銅錯体Cu_4L'_2では,異なった構造Cu_3(HL)(H_2L)(OAc)の錯体が得られることがわかった。 2.ジチアカリックス[4]アレーンの架橋硫黄を酸化し,syn-およびtrans-ジスルフィニルカリックス[4]アレーン,ジスルホニルカリックネ[4]アレーンを合成する経路を確立した。 3.カリックス[4]アレーンおよびチアカリックス[4]アレーンの二つの隣接する水酸基をテトライソプロピルジシロキサン-1,3-ジイル(TIPDS)基で保護し,塩基存在下,ハロゲン化アルキルと反応させることで,二つの隣接する水酸基をsyn-,anti-選択的にジアルキル化する方法を確立し,その選択性の発現機構を解明した。また,分子不斉anti-1,2-O-ジブチル誘導体の絶対配置をX線結晶構造解析により決定した。
Application of use "unclassical nucleophilic aromatic substitution" protocol to thiacalixarene derivatives for developing novel functional materials

IKI Nobuhiko, HATTORI Tesutaro

Offer Organization: Japan Society for the Promotion of Science

System: Grants-in-Aid for Scientific Research

Category: Grant-in-Aid for Scientific Research (B)

Institution: Tohoku University

2001 - 2003

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Aminothiacalixarenes, new members of the thiacalixa[4]arene (TCA) family having amino functions at the lower rim, were prepared from sulfur-oxygenated derivatives of TCA by applying the chelation-assisted nucleophilic aromatic substitution (S_NAr) reaction to estimate their intrinsic abilities for developing novel functional materials. 1.Selective syntheses of tetraamino, 1,2-and 1,3-diamino, and monoamino TCAa were achieved by using the S_NAr reaction on tetra-O-methylsulfonyl-and sulfinylcalix[4]arenes by lithium amides as the key step. Conformational analysis of the substrates indicated that the methoxy groups in a cis relationship with at least one adjacent sulflinyl group selectively underwent the S_NAr reaction. 2.Inclusion behavior of tetraamino TCA was investigated by crystallizing the host molecule from a series of solvents. It was found that the compound selectively formed 1:1 complexes with acetonitrile and dichloromethane. The acetonitrile complex adopted a cone conformation, while the host molecule crystallized out in a 1,3-alternate information from methanol without forming any inclusion complex, indicating that the complexation was accompanied by the conformational change of the host molecule (induced fit to the guest molecule). 3.Complexation ability of tetraamino TCA was investigated by solvent extraction experiments. It was found that tetraamino TCA served as a highly specific extractant for Au(III) and Pd(II) ions. The X-ray crystallographic analysis of a Pd(II) complex indicated that tetraamino TCA ligated is the metal ion with the bridging sulfur atoms and deprotonated amino functions. On the other hand, 1,2-diamino TCA was found to flexibly ligate to soft and hard metal ions by changing the ligation site (NH_2,OH). 4.Derivatization of the amino TCAs gave tetra(N-ethoxycarbonylmethyl) and bis(salicylideneamino) derivatives. The amino groups of amino TCAs were displaced with iodine atoms via the diazonium salts.
Development of Capillary Electriphoretic Reactor and Its Application to Kinetically High-Peformance Metal Complexes

HOSHINO Hitoshi, IKI Nobuhiko

Offer Organization: Japan Society for the Promotion of Science

System: Grants-in-Aid for Scientific Research

Category: Grant-in-Aid for Scientific Research (C)

Institution: TOHOKU UNIVERSITY

2001 - 2002

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The capillary electrophoretic reactor (CER) has been developed. The basic idea of CER is to consider the separation process of CE as a chemical reactor for metal complexes. CER method was applied to investigate the dissociation kinetics of lanthanide (III) polyaminocarboxylate complexes and tetradentate cyanoformazane complexes with Zn(II) and Mn(II). In general, complexes of metal ions, such as lanthanide ions, Zn(II) and Mn(II), had been thought to be labile because of large substitution rate constants of coordinated water molecules at the metal ions. On the contrary, it was found that these camplexes had been inert to be amenable to the detection in pre-capillary derivatization CE system with no addition of the ligand in a carrier buffer solution. Inquires into new kinetically high-peformance metal complexes has been made. Thiacalix[4]arenetetrasulfonate (TCAS) and 2-(2'-Hydroxyphenyl)-10-hydroxybenzo[h]quinoline (HPHBQ) were examined as a pre-column chelating reagent for the determination of ultra trace Ni(II) and Be(II) by KD-HPLC of the pre-column derivatization HPLC system with no addition of the ligand in an eluent, respectively. The practical applicability of KD-HPLC methods with TCAS and HPHBQ was also demonstrated.
チアカリックスアレーンの超分子錯体形成を利用する水中の微量有機分子のセンシング

壹岐伸彦

Offer Organization: 日本学術振興会

System: 科学研究費助成事業

Category: 奨励研究(A)

Institution: 東北大学

2000 - 2001

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本研究は新しいホスト分子、水溶性チアカリックスアレーン(TCAS)とその架橋硫黄酸化体(SO_2CAS)の希土類金属錯体を発光レセプターとして利用し、その超分子形成による水溶性有機分子のセンシングを目的としている。前年度までに、(i)TCAS、SO_2CASおよび従来のカリックスアレーンCASを用い、発光レセプター([Tb^<III>(tcas)]、[Tb^<III>(so_2cas)]および[Tb^<III>(cas)_2])を生成させ、(ii)これらの良好なエネルギー移動発光特性を。明らかにしている。これらをもとに、本年度は下記(III)を検討した。 (III)カチオン性ゲストとの超分子錯体形成における発光挙動変化の評価・テトラアルキルアンモニウムイオン:ゲストの添加に対して各レセプターの励起スペクトル変化は小さく、感度は高くなかった。これはレセプターゲストの会合定数が小さいためと考えられる。・エチルビリジニウム(EtP^+イオン:[Tb^<III>(tcas)]および[Tb^<III>(cas)_2]の発光を感度良く消光した。これは各レセプターからEtP^+への電子移動によるためと考えられる。Stern-Volmerプロットから、EtP^+の検出限界(S/N=3)はそれぞれ5.6、5.9×10^<-8>Mであった。・エチルキノリニウム(EtQ^+)イオン:[Tb^<III>(tcas)]を高感度に消光し、検出限界(S/N=3)は6.7×10^<-10> Mであった。発光強度および寿命に対するStern-Volmerプロットは一致し、Tb(III)の励起状態からの失活を示唆している。また、消光速度定数は1.0×10^<10>M^<-1>s^<-1>であり、消光は拡散律速であることが分かった。以上、架橋硫黄型カリックスアレーンの錯形成能とゲスト分子認識能を超分子的に利用し、微量有機分子をセンシングできることを明らかにした。
Molecular System Designing for Capillary Electrophoresis

YOTSUYANAGI Takao, IKI Nobuhiko, HOSHINO Hitoshi

Offer Organization: Japan Society for the Promotion of Science

System: Grants-in-Aid for Scientific Research

Category: Grant-in-Aid for Scientific Research (B).

Institution: TOHOKU UNIVERSITY

1998 - 1999

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The aim of this research project is the exploitation of a 'chemical system' approach to novel CE separation modes for metal complexes via a better understanding of the underlying solution chemistry of the CE separation. (1) Ionic mobilities are controlled by ion-ion interactions in electrophoretic buffer solutions ; an addition of polymer electrolyte such as poly(diallyldimethyl ammonium chloride) was found to be very effective for the fine separation of anionic metal chelates of polyaminocarboxylates, EDTA, Quin 2, and HBED complexes. (2) Polyaminocarboxylate ligands possessing phenolate moieties were sought ; the CE selectivity of HBED towards trivalent metal ion was demonstrated and a dibromo derivative, BrィイD22ィエD2HBED was prepared and the reaction with Fe(III) ion was examined. (3) The unique selectivity of phenylenediamine-N,N,N',N'-tetraacetate towards Ca(II) ion was found. (4) A novel class of metal-ligating functions, thiacalix[4]arenes are exploited for the metal CE analysis ; The selective oxidation methods for the sulfur atoms which is linking four phenol moieties were first reported. This doubtless expands the metal selectivity control of the thiacalix[4]arenes via the production of the sulfone and sulfoxide derivatives.
新規チオカリックスアレーンの創製とその機能開発

壹岐伸彦

Offer Organization: 日本学術振興会

System: 科学研究費助成事業

Category: 奨励研究(A)

Institution: 東北大学

1997 - 1998

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本年度はチオカリックス[4]アレーン(1)を修飾して次の3項目の機能開発を行い,当研究課題の目標を達成した. 1. 金属イオンの高性能認識機能:1の架橋硫黄をSO及びSO_2に選択的に酸化し,それぞれスルフィニルカリックス[4]アレーン(2)及びスルホニルカリックス[4]アレーン(3)を合成した.1〜3の金属イオンの認識機能を溶媒抽出法で比較検討した.40種類もの広範な金属イオンの中から3はハードな金属イオンを,1はソフトな金属イオンを,2は両方を認識した.この様に架橋Sの酸化状態により金属イオンの認識選択性を制御できた.また架橋部位に配位原子を持たない通常のカリックス[4]アレーン(4)は同条件下で錯形成しないことを確認した.一方1のフェノール性水酸基をアルキル化し,テトラキス((エトキシカルボニル)メトキシ)チオカリックス[4]アレーン(5)を合成した.5のcone,partial cone,及びl,3-alternateの立体配座は塩基触媒によって制御できた.また5の立体配座によりアルカリ金属イオンの認識選択性が制御できた.以上は合成化学や錯体化学的に興味深いだけでなく,将来,金属錯体触媒や,金属イオンのセンシング法,高効率的分離回収法に応用を拓く,重要な発見である. 2. 新規不斉識別機能素子:5に不斉アミンを導入した誘導体6を合成し,ガスクロマトグラフィー用の不斉固定相として用い光学異性体の分離に成功した.4から同様に得られた不斉固定相は不斉識別せず,本系でも架橋基の重要性が示された. 3. 環境浄化機能材料:1を直接スルホン化し,水溶性ホスト化合物チオカリックス[4]アレーンテトラスルホン酸(7)を合成した.7は有機ハロゲン化合物等の環境中の有害物質を高効率で捕捉した.7とイオン交換材料を複合化し,水中のppmレベルの有機ハロゲン化合物の除去機能材料を創製した.
Development of a Highly Stereoselective Remote Asymmetric Induction Method by Means of the Binaphthalene-Template Conformation Control

MIYANO Sotaro, IKI Nobuhiko, OI Shuichi, HATTORI Tetsutaro, TAMAI Yasufumi, INOUE Yoshio

Offer Organization: Japan Society for the Promotion of Science

System: Grants-in-Aid for Scientific Research

Category: Grant-in-Aid for Scientific Research (A)

Institution: Tohoku University

1996 - 1998

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We have developed diastereoselective asymmetric reactions using the 2,2'-positions of 1, l'-binaphthyl compounds as a chiral field. Synthesis of novel binaphthyls and thiacalixarenes and exploration of the functions of the latter compounds are the other targets of this research. The summary of the results is itemized as follows : 1. Treatment of gamma-keto esters of l , 1'-binaphthyl-2-ol bearing an appropriate oligoether tether at the 2'-position with DIBAL-H in the presence of magnesium bromide gave, after LAH reduction of the resulting diastereomeric hydroxy esters, I , 4-diols with high enantiomeric excesses. On the other hand, Grignard reaction of the relevant gamma-keto esters gave gamma-lactones having a chiral quaternary carbon center with up to 99% ee. 2. The remote asymmetric inductive Grignard reaction was found to be applicable to delta- and epsilon-keto esters and was advantageously utilized for the synthesis of a marine antibiotic, malyngolide. 3. The corresponding Grignard reaction of zeta- to theta-keto esters was realized by using BINOL as the chiral auxiliary. Thus, the Grignard reaction of the mono omega-keto esters of BINOL in the presence of magnesium bromide proceeded with more than 80% de. 4. Several binaphthyl compounds were effectively prepared in an atropisomeric or racemic form via the nucleophilic aromatic substitution on 1-alkoxynaphthalenes bearing an ester, sulfonyl, or nitro group at the 2-position as the activating group by 1-naphthyl Grignard reagents. 5. A novel calixarene, p-tert-butylthiacalix[4]arene, which is expected to be a potential substitute for BINOL framework, was effectively prepared from p-tert-butylphenol and powdered sulfur. The derivatives were found to function as a host molecule to bind specific metal ions and toxic halogenated organic compounds and as a chirality-recognizing element for a stationary phase for gas chromatography.

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Social Activities 3

みやぎ県民大学

2004/08 - 2004/10

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環境科学に関する市民向け公開講座
出前授業「化学分析と環境の理解」山形県立寒河江高校

2008/09/17 -

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山形県立寒河江高校において出前授業を行った．
出前授業「色で計るイオンの濃度」仙台市立八軒中学校

2006/11/08 -

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金属錯体の呈色と発光現象をもとに金属イオンの濃度を測る手法を演示実験を交え分かりやすく解説した．

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簡易・迅速・低コストな土壌の重金属汚染判定キットの開発

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本研究では土壌汚染対策法の趣旨である土壌汚染リスク評価に資するため，土地所有者や建設業者が現場で簡易に使用できる交換態重金属汚染の簡易判定キットを開発する．