Updated on 2022/10/26

写真a

 
YAGI Akiko
 
Organization
Institute of Transformative Bio-Molecules Designated associate professor
Graduate School
Graduate School of Science
Title
Designated associate professor

Degree 1

  1. 博士(理学) ( 2016.3   名古屋大学 ) 

Research Interests 2

  1. Physical Organic Chemistry

  2. Organic Chemistry

Research Areas 3

  1. Life Science / Bioorganic chemistry

  2. Nanotechnology/Materials / Structural organic chemistry and physical organic chemistry

  3. Nanotechnology/Materials / Structural organic chemistry and physical organic chemistry

Research History 4

  1. JSTさきがけ研究者 「物質探索空間の拡大による未来材料の創製」領域2期生

    2022.10

  2. Nagoya University   Institute of Transformative Bio-Molecules   Designated associate professor

    2021.1

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    Country:Japan

  3. Nagoya University   Graduate School of Science, Department of Chemistry   Assistant Professor

    2017.3 - 2020.12

  4. Japan Society for Promotion of Science

    2016.4 - 2017.2

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    Country:Japan

Education 1

  1. Nagoya University   Graduate School, Division of Natural Science

    2007.4 - 2016.3

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    Country: Japan

Professional Memberships 4

  1. 基礎有機化学会

  2. 日本化学会

  3. THE CHEMICAL SOCIETY OF JAPAN

  4. 基礎有機化学会

 

Papers 16

  1. Synthesis, properties, and material hybridization of bare aromatic polymers enabled by dendrimer support

    Fujiki Shusei, Amaike Kazuma, Yagi Akiko, Itami Kenichiro

    NATURE COMMUNICATIONS   Vol. 13 ( 1 )   2022.9

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  2. N-doped nonalternant aromatic belt via a six-fold annulative double N-arylation

    Sato Hiroki, Suizu Rie, Kato Tomoki, Yagi Akiko, Segawa Yasutomo, Awaga Kunio, Itami Kenichiro

    CHEMICAL SCIENCE   Vol. 13 ( 34 ) page: 9947 - 9951   2022.8

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    Language:Japanese  

    DOI: 10.1039/d2sc02647c

    Web of Science

  3. Perfluorocycloparaphenylenes

    Hiroki Shudo, Motonobu Kuwayama, Masafumi Shimasaki, Taishi Nishihara, Youhei Takeda, Nobuhiko Mitoma, Takuya Kuwabara, Akiko Yagi, Yasutomo Segawa, Kenichiro Itami

    Nature Communications   Vol. 13 ( 1 )   2022.6

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    Language:Japanese   Publishing type:Research paper (scientific journal)   Publisher:Springer Science and Business Media LLC  

    Abstract

    Perfluorinated aromatic compounds, the so-called perfluoroarenes, are widely used in materials science owing to their high electron affinity and characteristic intermolecular interactions. However, methods to synthesize highly strained perfluoroarenes are limited, which greatly limits their structural diversity. Herein, we report the synthesis and isolation of perfluorocycloparaphenylenes (PFCPPs) as a class of ring-shaped perfluoroarenes. Using macrocyclic nickel complexes, we succeeded in synthesizing PF[n]CPPs (n = 10, 12, 14, 16) in one-pot without noble metals. The molecular structures of PF[n]CPPs (n = 10, 12, 14) were determined by X-ray crystallography to confirm their tubular alignment. Photophysical and electrochemical measurements revealed that PF[n]CPPs (n = 10, 12, 14) exhibited wide HOMO–LUMO gaps, high reduction potentials, and strong phosphorescence at low temperature. PFCPPs are not only useful as electron-accepting organic materials but can also be used for accelerating the creation of topologically unique molecular nanocarbon materials.

    DOI: 10.1038/s41467-022-31530-x

    Web of Science

    Other Link: https://www.nature.com/articles/s41467-022-31530-x

  4. Chemical Synthesis of Carbon Nanorings and Nanobelts

    Yuanming Li, Hideya Kono, Takehisa Maekawa, Yasutomo Segawa, Akiko Yagi, Kenichiro Itami

    Accounts of Materials Research   Vol. 2 ( 8 ) page: 681 - 691   2021.8

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    Language:Japanese   Publishing type:Research paper (scientific journal)   Publisher:American Chemical Society ({ACS})  

    The discovery and creation of new forms of carbon have always transformed the scientific landscape. For example, the discoveries of fullerenes, carbon nanotubes (CNTs), and graphenes have opened doors to the science of nanometersized carbon allotropes, otherwise known as nanocarbons. Since then, researchers worldwide have unveiled their outstanding physical and chemical properties, and a number of applications and technologies have arisen in not only materials science but also biological research fields. The synthesis and study of this privileged class of "single-molecule" compounds has become one of the most engaging subjects in chemistry and holds huge promise to establish new fields in molecular science. However, there have been huge gaps between established small-molecule chemistry and nanocarbon science. In the particular case of CNTs, it is still not possible to access structurally uniform CNTs. Although a wide range of synthetic methods have been reported, CNTs are generally accessed as a mixture of various structures. One logical strategy to achieve full synthetic control over CNTs is to build up from a template molecule with structural precision (the so-called "growth-from-template" strategy), where a short CNT segment molecule represents an initial synthetic target. To this end, organic synthesis techniques are our most powerful tools to synthesize short CNT segments such as carbon nanorings and carbon nanobelts. This Account highlights our 16-year campaign in the synthesis and application of carbon nanorings and carbon nanobelts. The first topic is the synthesis of carbon nanorings (cycloparaphenylenes) as substructures of CNTs. The second topic is the synthesis of armchair and zigzag carbon nanobelts, which consist solely of fully fused hexagonal rings and provide a continuous double-stranded cylindrical framework. The third topic is the synthesis of methylene-bridged cycloparaphenylene, an aromatic belt containing nonhexagonal rings, in which the cyclic paraphenylene chain is ladderized by methylene bridges. This nonalternant aromatic belt can be regarded as segments of nonconventional CNTs. During our extensive investigation, we found that the careful design of strainless macrocyclic precursors is crucial to the success of the synthesis of these curved p-conjugated nanorings and nanobelts. In the final section, some of the representative size-dependent properties of these nanorings/belts, including their HOMO-LUMO energies, strain energies, and photophysical properties, are summarized. In addition to basic properties, the utilization of these compounds as supramolecular hosts and organic materials is also briefly introduced. We hope this Account will inspire the development of new forms of nanocarbon molecules that would open doors to new fields and applications.

    DOI: 10.1021/accountsmr.1c00105

    Web of Science

  5. Photo-Induced Arylation of Carbazoles With Aryldiazonium Salts

    Bumpei Maeda, Genki Mori, Yota Sakakibara, Akiko Yagi, Kei Murakami, Kenichiro Itami

    ASIAN JOURNAL OF ORGANIC CHEMISTRY   Vol. 10 ( 6 ) page: 1428 - 1431   2021.6

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    Language:Japanese   Publishing type:Research paper (scientific journal)   Publisher:WILEY-V C H VERLAG GMBH  

    Arylcarbazoles have been widely used in materials science as important organic semiconductor molecules. To investigate the electronic and photophysical properties of arylcarbazole with different substitution patterns, facile and straightforward synthesis of arylcarbazole derivatives is sought after. Herein we report on photo-induced direct arylation reactions of carbazole. Treatment of carbazoles with aryldiazonium salts afforded the arylated carbazole. Although the reaction was not regioselective, C1 and C4-arylated carbazoles were obtained as the major isomers. When N-pyridylcarbazole was employed as the substrate with palladium catalyst, the reaction proceeded selectively at C1 position.

    DOI: 10.1002/ajoc.202100191

    Web of Science

  6. Development of potent inhibitors for strigolactone receptor DWARF 14

    Masahiko Yoshimura, Sojung F. Kim, Ryosuke Takise, Shuhei Kusano, Sakuya Nakamura, Masanori Izumi, Akiko Yagi, Kenichiro Itami, Shinya Hagihara

    CHEMICAL COMMUNICATIONS   Vol. 56 ( 94 ) page: 14917 - 14919   2020.12

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    Language:Japanese   Publishing type:Research paper (scientific journal)   Publisher:ROYAL SOC CHEMISTRY  

    Strigolactones (SLs) are plant hormones that suppress shoot branching through perception by their receptor protein DWARF 14 (D14). The artificial regulation of SL signaling has been considered a potent agricultural technique because plant architecture is strongly related to crop yield. In this communication, we describe the development of a small-molecule D14 inhibitor that functions at sub-micromolar levels. This potent inhibitor may be a lead compound for a first-in-class plant growth regulator.

    DOI: 10.1039/d0cc01989e

    Web of Science

  7. Programmable synthesis of multiply arylated cubanes through C–H metalation and arylation

    Ryo Okude, Genki Mori, Akiko Yagi, Kenichiro Itami

    Chemical Science   Vol. 11 ( 29 ) page: 7672 - 7675   2020.8

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    Language:Japanese   Publishing type:Research paper (scientific journal)   Publisher:Royal Society of Chemistry ({RSC})  

    Cubane (C8H8), a cubic alkane, has long attracted attention owing to its unique 3D structure. In order to utilize the cubane scaffold widely in science and technology, a powerful method for synthesizing diverse cubane derivatives is required. Herein, we report the synthesis of mono-, di-, tri-, and tetra-arylated cubanes. Directedortho-metalation with lithium base/alkyl zinc and subsequent palladium-catalyzed arylation enabled C-H metalation and arylation of cubane. This reaction allows the late-stage and regioselective installation of a wide range of aryl groups, realizing the first programmable synthesis of diverse multiply arylated cubanes.

    DOI: 10.1039/d0sc01909g

    Web of Science

  8. A Nonalternant Aromatic Belt: Methylene-Bridged [6]Cycloparaphenylene Synthesized from Pillar[6]arene

    Yuanming Li, Yasutomo Segawa, Akiko Yagi, Kenichiro Itami

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   Vol. 142 ( 29 ) page: 12850 - 12856   2020.7

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

    The synthesis, structure, and properties of methylene-bridged [6]cycloparaphenylene ([6]CPP), a nonalternant aromatic belt, are described. This belt-shaped methylene-bridged [6]CPP, in which each phenylene unit is tethered to its neighbors by methylene bridges, was constructed through 6-fold intramolecular nickel-mediated aryl-aryl coupling of triflate-functionalized pillar[6]arene in 18% isolated yield. As compared to the analogous [6]CPP, the methylene bridges coplanarize neighboring paraphenylene units and enhance the degree of pi-conjugation, which results in a significant decrease in energy gap. Moreover, the incorporation of small molecules in the defined pocket of methylene-bridged [6]CPP makes it an attractive supramolecular architecture. Methylene-bridged [6]CPP is characterized by high internal strain energy reaching 110.2 kcal mol(-1), attributed to its restricted structure. This work not only exhibits an efficient strategy to construct a new family of aromatic belt, but also showcases their properties, which combine the merits of CPPs and pillararenes.

    DOI: 10.1021/jacs.0c06007

    Web of Science

  9. Six-fold C-H borylation of hexa-peri-hexabenzocoronene

    Mai Nagase, Kenta Kato, Akiko Yagi, Yasutomo Segawa, Kenichiro Itami

    BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY   Vol. 16   page: 391 - 397   2020.3

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    Language:Japanese   Publishing type:Research paper (scientific journal)   Publisher:BEILSTEIN-INSTITUT  

    Hexa-peri-hexabenzocoronene (HBC) is known to be a poorly soluble polycyclic aromatic hydrocarbon for which direct functionalization methods have been very limited. Herein, the synthesis of hexaborylated HBC from unsubstituted HBC is described. Iridium-catalyzed six-fold C-H borylation of HBC was successfully achieved by screening solvents. The crystal structure of hexaborylated HBC was confirmed via X-ray crystallography. Optoelectronic properties of the thus-obtained hexaborylated HBC were analyzed with the support of density functional theory calculations. The spectra revealed a bathochromic shift of absorption bands compared with unsubstituted HBC under the effect of the sigma-donation of boryl groups.

    DOI: 10.3762/bjoc.16.37

    Web of Science

  10. Synthesis of Highly Twisted, Nonplanar Aromatic Macrocycles Enabled by an Axially Chiral 4,5-Diphenylphenanthrene Building Block

    Li, Yuanming, Yagi, Akiko, Itami, Kenichiro

    Journal of the American Chemical Society   Vol. 142 ( 6 ) page: 3246 - 3253   2020.2

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

    The synthesis, structures, and properties of highly twisted, nonpianar aromatic macrocycles are described. These macrocycles with an approximately 90 degrees twist angle were synthesized by an effective synthetic approach through a quadruple Suzuki-Miyaura coupling of 4,5-bisarylphenanthrene, a novel axially chiral nonplanar building block. By varying the cross-coupling partner as the spacer, a family of twisted macrocycles was synthesized, allowing for a systematic study of the effect of the spacer on macrocycle shape and photophysical properties. For example, a unique macrocyclic aggregation-induced emission (AIE) emitter with double tetraphenylethylene units as the spacers was readily synthesized. Furthermore, attributed to its conformationally restricted twisted structure, a 3,6-disubstituted-1,8-naphthalimide-incorporated macrocycle showed remarkable solvatofluorochromism with high fluorescence quantum yields. The excellent conformational stability of these macrocycles further enabled complete enantiomeric resolution and characterization. The racemization barrier of macrocycle was determined experimentally and supported by DFT calculations.

    DOI: 10.1021/jacs.9b13549

    Web of Science

  11. Ni-Catalyzed alpha-Selective C-H Borylations of Naphthalene-Based Aromatic Compounds

    Kamei, Toshiyuki, Nishino, Soshi, Yagi, Akiko, Segawa, Yasutomo, Shimada, Toyoshi

    The Journal of Organic Chemistry   Vol. 84 ( 21 ) page: 14354 - 14359   2019.11

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

    DOI: 10.1021/acs.joc.9b02333

    Web of Science

  12. Synthesis of sterically hindered 4,5-diarylphenanthrenes via acid-catalyzed bisannulation of benzenediacetaldehydes with alkynes

    Li, Yuanming, Yagi, Akiko, Itami, Kenichiro

    Chemical Science   Vol. 10 ( 21 ) page: 5470 - 5475   2019.6

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    Language:Japanese   Publishing type:Research paper (scientific journal)   Publisher:ROYAL SOC CHEMISTRY  

    The synthesis of sterically hindered phenanthrenes via acid-catalyzed bisannulation reaction is described. Treatment of 1,4-benzenediacetaldehyde with terminal aryl alkynes in the presence of B(C6F5)(3) provides 4,5-diarylphenanthrenes in good yields with excellent regioselectivity. The use of internal alkyne substrates enabled the synthesis of sterically hindered 3,4,5,6-tetrasubstituted phenanthrenes displaying augmented backbone helicity. Furthermore, 1,5-disubstituted, 1,8-disubstituted, 1,2,5,6-tetrasubstituted, and 1,2,7,8-tetrasubstituted phenanthrenes can be obtained through the reaction of alkynes with 1,3-benzenediacetaldehyde or 1,2-benzenediacetaldehyde disilyl acetal.

    DOI: 10.1039/c9sc00334g

    Web of Science

  13. Armchair and Chiral Carbon Nanobelts: Scholl Reaction in Strained Nanorings

    Yagi, Akiko, Segawa, Yasutomo, Itami, Kenichiro

    Chem   Vol. 5 ( 4 ) page: 746 - 748   2019.4

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

    DOI: 10.1016/j.chempr.2019.03.013

    Web of Science

  14. Catalytic Activation of Carbon-Carbon Bond in CycloPentanone Derivatives Reviewed

    Akiko Yagi

    JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN   Vol. 75 ( 8 ) page: 864 - 865   2017.8

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    Language:Japanese   Publishing type:Research paper (scientific journal)   Publisher:SOC SYNTHETIC ORGANIC CHEM JPN  

    Catalytic cleavage and reconnection of carbon-carbon bond is a powerful tool for organic synthesis. Recently, activation of inert carbon-carbon bonds has been rapidly developed. This review summarizes the progress of catalytic activation of carbon-carbon bonds in cyclopentanone derivatives.

    DOI: 10.5059/yukigoseikyokaishi.75.864

    Web of Science

  15. Synthesis and properties of [8]-, [10]-, [12]-, and [16] cyclo-1,4-naphthylenes Reviewed

    Keishu Okada, Akiko Yagi, Yasutomo Segawa, Kenichiro Itami

    CHEMICAL SCIENCE   Vol. 8 ( 1 ) page: 661 - 667   2017.1

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    Language:Japanese   Publishing type:Research paper (scientific journal)   Publisher:ROYAL SOC CHEMISTRY  

    The synthesis and properties of various [n]cyclo-1,4-naphthylenes ([n]CNs, n = 8, 10, 12, and 16) are described. Initially, extended L-shaped units, which could be converted into quater- or quinquenaphthylenes were prepared. Nickel-or palladium-mediated couplings of these extended L-shaped units, followed by reductive aromatization of the coupling products afforded [8]-, [10]-, [12]-, and [16]CNs. The size-dependent photophysical properties of these CNs were confirmed by measuring their UV-vis absorption and fluorescence spectra. The theoretical studies supported substantial effects of the number of naphthalene rings on the structural and photophysical properties of these CNs. A kinetic study on the thermal conversion of the C-5-symmetric conformer of [10]CN into its most stable D-5d-symmetric conformer indicated that ring strain affects the rotation barrier of the naphthalene rings in [10]CN.

    DOI: 10.1039/c6sc04048a

    Web of Science

  16. Chemical Synthesis of Cycloparaphenylenes Reviewed

    Segawa Yasutomo, Yagi Akiko, Itami Kenichiro

    PHYSICAL SCIENCES REVIEWS   Vol. 2 ( 1 )   2017.1

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:WALTER DE GRUYTER GMBH  

    Cycloparaphenylenes and analogues thereof are substances having excellent structural and electronic properties due to radial pi-conjugation modes and porous structures. Since they are partial structures of carbon nanotubes, they have also attracted attention as a template for carbon nanotube synthesis. In this chapter, we introduce a series of research on the synthesis of cycloparaphenylenes and their analogues.

    DOI: 10.1515/psr-2016-0102

    Web of Science

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MISC 1

  1. 研究物語 世界初,カーボンナノベルト合成までの軌跡 : 12年の歴史とドラマ

    伊丹 健一郎, 瀬川 泰知, 大町 遼, 八木 亜樹子

    化学 = Chemistry   Vol. 72 ( 8 ) page: 29 - 37   2017.8

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    Language:Japanese   Publisher:化学同人  

    CiNii Books

KAKENHI (Grants-in-Aid for Scientific Research) 2

  1. Synthesis and Material Hybridization of Pooly Soluble Functional Molecules

    Grant number:22K14677  2022.4 - 2024.3

    Grants-in-Aid for Scientific Research  Grant-in-Aid for Early-Career Scientists

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    Authorship:Principal investigator 

    Grant amount:\4550000 ( Direct Cost: \3500000 、 Indirect Cost:\1050000 )

  2. 固相合成法を用いた難溶性ナノカーボンの精密合成

    Grant number:19K15537  2019.4 - 2022.3

    科学研究費助成事業  若手研究

    八木 亜樹子

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    Authorship:Principal investigator 

    Grant amount:\4160000 ( Direct Cost: \3200000 、 Indirect Cost:\960000 )

    グラフェンやカーボンナノチューブなどのナノカーボン類は特異な機械的・電子的性質をもち、広く研究、応用されている物質群である。ナノカーボン類は溶媒中で凝集しやすいという性質をもち、精密に合成するには凝集を防ぐための嵩高い修飾が必要であった。しかし修飾基にはナノカーボンの性質を変えてしまうという問題がある。そこで本研究では、修飾基をもたないナノカーボン類を、固相合成法を用いることで精密に合成する。自在に様々な構造のナノカーボンを合成し、広く科学の進展に寄与する。
    本年度は、固相合成法を用いた難溶性ナノカーボンの精密合成を実現するため、以下の事項に注力して取り組んだ。
    まず、難溶性の無修飾オリゴパラフェニレンの精密合成を目指し、固相担体やカップリング反応条件の最適化を行った。結果、逐次的なカップリング反応を用いることで、現在のところ9つのベンゼン環からなる無修飾オリゴパラフェニレンの固相合成に成功している。オリゴパラフェニレンはベンゼン環が6つ以上連結されると難溶性となり精密合成が困難となるため、本研究で開発した手法を用いることで難溶性オリゴパラフェニレンの精密合成が実現することを示すことができた。無修飾オリゴパラフェニレン合成で得た知見を活かし、新たに独自の担体を設計・合成することで、長鎖無修飾オリゴチオフェンの合成も行った。開発した担体は溶解性が高いことから、担体に担持した状態での性質評価が可能である。現在、合成した無修飾ナノカーボンの性質評価を行なっている他、その担体を活用することでグラフェンナノリボンやカーボンナノチューブなど、さらに難易度の高い無修飾ナノカーボン合成に取り組んでいる。
    また、ポリエチレングリコール担体上での2次元ナノグラフェン合成を目指し、その第一段階となるヘキサベンゾコロネン合成を行った。ヘキサフェニルベンゼン誘導体を別途合成し、担体上に担持させ、縮環反応を行うことでヘキサベンゾコロネン合成に成功した。現在、そのパイ拡張反応を行っている。
    本研究は前例のない「無修飾ナノカーボンの精密合成」に取り組んでおり、基盤となる固相担体の選定・設計・合成に多くの時間を割くと予想していた。実際に、固相担体の取り扱いはシンプルな有機溶媒中での反応に比べ困難であり、予想外の実験結果にも多く直面した。しかし、それらを糧として現在、無修飾ナノカーボン合成に適した担体の設計・合成に成功しつつあり、研究としておおむね順調に進展していると考えている。また、本研究で合成した無修飾ナノカーボン類の性質に関しても興味深いことがわかってきており、今後のユニークな研究展開にも期待がもてると考えている。
    今後は、引き続き固相合成法を用いた難溶性ナノカーボンの精密合成を推進する。具体的には、これまでに独自で設計・合成した担体を用いて、グラフェンナノリボンやカーボンナノチューブなどを無修飾状態で合成する。グラフェンナノリボンについては、当研究室で開発したAPEX反応を駆使することで精密に合成することができると考えている。カーボンナノチューブについても、当研究室で合成したカーボンナノベルトに対し伸長反応を施すことにより合成することができる。また、合成した無修飾ナノカーボンの性質を詳細に調査し、機能開拓へと展開する。