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Nobuhiro Yanai Last modified date:2020.06.27

Associate Professor / Biofunctional Chemistry
Department of Applied Chemistry
Faculty of Engineering

Graduate School
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Academic Degree
Ph. D. (Engineering)
Country of degree conferring institution (Overseas)
Field of Specialization
Functional Chemistry of Triplet State, Photon Upconversion, Hyperpolarization
Total Priod of education and research career in the foreign country
Outline Activities
Development of highly efficient photon upconversion molecular systems, Science of excited triplet state

Lectures of organic chemistry and polymer chemistry
Experimental classes of undergraduate students
Research guidance for Doctor, Master, Undergraduate students in the lab

Award for Encouragement of Research in Polymer Science, the Society of Polymer Science, Japan (2016)
Poster Award, 7th International Conference on Green and Sustainable Chemistry (GSC-7) and 4th JACI/GSC Symposium, 2015, Tokyo
The Award of Encouragement of Research in IUMRS-ICA2014, Fukuoka, Japan
CSJ Presentation Award 2014, Nagoya, Japan
Quadrant Award 2013, Switzerland
Research Interests
  • Development of triplet dynamic nuclear polarization system
    keyword : photo-excited triplet, hyperpolarization, NMR, MRI
  • Development of Photon-Upconversion Molecular Systems
    keyword : Photon Upconversion, Self-Assembly, Energy Migration
  • Construction of highly efficient energy conversion system based on self-assembly
    keyword : self-assembly, energy conversion
Current and Past Project
  • This international collaboration aims to understand a new problem in the field of self-assembly: self-assembly of particles that reconfigure. We envision a tag-team approach between synthetic developments in the Japanese laboratory, and physical exploration of assembly in the U.S. laboratory.
Academic Activities
1. Yuki Kurashige, Nobuhiro Yanai, Yong-Jing Pu, So Kawata, Molecular Technology Volume 1: Energy Innovation , Wiley‐VCH , 155-186, 2018.07.
2. Pengfei Duan, Nobuhiro Yanai, and Nobuo Kimizuka, Functional Organic Liquids, Wiley‐VCH , CHAPTER 7 Organic Liquids in Energy Systems, 2019.03.
1. , [URL].
2. Biplab Joarder, Nobuhiro Yanai,* and Nobuo Kimizuka*, Solid-State Photon Upconversion Materials: Structural Integrity and Triplet/Singlet Dual Energy Migration, J. Phys. Chem. Lett. , 2018, 9, 4613-4624, 2018.07.
3. Pankaj Bharmoria, Nobuhiro Yanai,* and Nobuo Kimizuka*, Recent Progress in Photon Upconverting Gels, Gels, 2019.05.
1. , [URL].
2. , [URL].
3. Biplab Joarder, Arijit Mallick, Yoichi Sasaki, Mika Kinoshita, Rena Haruki, Yusuke Kawashima, Nobuhiro Yanai, Nobuo Kimizuka, Near-Infrared-to-Visible Photon Upconversion by Introducing an S−T Absorption Sensitizer into a Metal-Organic Framework, ChemNanoMat, 10.1002/cnma.202000019, 6, 6, 916-919, 2020.06, Triplet-triplet annihilation-based photon upconversion (TTA-UC) of near-infrared (NIR) light to visible light in the solid-state remains as a great challenge due to the sensitizer aggregation that impedes the efficient triplet energy transfer. Herein, we successfully introduce a molecular sensitizer exhibiting direct singlet-to-triplet (S–T) absorption into a new emitter-based metal-organic framework (MOF) to achieve an efficient triplet sensitization and a NIR-to-visible TTA-UC in the solid-state..
4. Hironori Kouno, Kana Orihashi, Koki Nishimura, Yusuke Kawashima, Kenichiro Tateishi, Tomohiro Uesaka, Nobuo Kimizuka, Nobuhiro Yanai, Triplet dynamic nuclear polarization of crystalline ice using water-soluble polarizing agents, Chemical Communications, 10.1039/d0cc00836b, 56, 26, 3717-3720, 2020.04, Triplet dynamic nuclear polarization (triplet-DNP) allows hyperpolarization at a moderate temperature. While the triplet-DNP of water is strongly desired, water-soluble triplet polarizing agents have not yet been reported. Herein, the first example of triplet-DNP of crystalline ice is demonstrated by molecularly dispersing a novel water-soluble polarizing agent into ice..
5. Shota Hisamitsu, Junji Miyano, Keisuke Okumura, Joseph Ka Ho Hui, Nobuhiro Yanai, Nobuo Kimizuka, Visible-to-UV Photon Upconversion in Nanostructured Chromophoric Ionic Liquids, ChemistryOpen, 10.1002/open.201900304, 9, 1, 14-17, 2020.01, Visible-to-ultraviolet (vis-to-UV) triplet-triplet annihilation based photon upconversion (TTA-UC) is achieved in a non-volatile chromophoric ionic liquid (IL) for the first time. A novel IL is synthesized by combining UV-emitting anion 4-(2-phenyloxazol-5-yl)benzenesulfonate (PPOS) and trihexyltetradecylphosphonium cation (P66614). The nanostructured organization of chromophoric anions is demonstrated by synchrotron X-ray and optical measurements. When the IL is doped with a triplet sensitizer tris(2-phenylpyridinato)iridium(III) (Ir(ppy)3), the visible-to-UV TTA-UC with a relatively low threshold excitation intensity of 61 mW cm−2 is achieved. This is due to a large triplet diffusion coefficient in the IL (1.4×10−7 cm2 s−1) as well as a high absorption coefficient 15 cm−1 and a long PPOS triplet lifetime of 1.55 ms, all implemented in the condensed IL system. This work demonstrates the unique potential of ILs to control chromophore arrangements for desired functions..
6. Yoichi Sasaki, Mio Oshikawa, Pankaj Bharmoria, Hironori Kouno, Akiko Hayashi-Takagi, Moritoshi Sato, Itsuki Ajioka, Nobuhiro Yanai, Nobuo Kimizuka, Near-Infrared Optogenetic Genome Engineering Based on Photon-Upconversion Hydrogels, Angewandte Chemie - International Edition, 10.1002/anie.201911025, 58, 49, 17827-17833, 2019.12, Photon upconversion (UC) from near-infrared (NIR) light to visible light has enabled optogenetic manipulations in deep tissues. However, materials for NIR optogenetics have been limited to inorganic UC nanoparticles. Herein, NIR-light-triggered optogenetics using biocompatible, organic TTA-UC hydrogels is reported. To achieve triplet sensitization even in highly viscous hydrogel matrices, a NIR-absorbing complex is covalently linked with energy-pooling acceptor chromophores, which significantly elongates the donor triplet lifetime. The donor and acceptor are solubilized in hydrogels formed from biocompatible Pluronic F127 micelles, and heat treatment endows the excited triplets in the hydrogel with remarkable oxygen tolerance. Combined with photoactivatable Cre recombinase technology, NIR-light stimulation successfully performs genome engineering resulting in the formation of dendritic-spine-like structures of hippocampal neurons..
7. Hironori Kouno, Yusuke Kawashima, Kenichiro Tateishi,* Tomohiro Uesaka, Nobuo Kimizuka,* and Nobuhiro Yanai*, Nonpentacene Polarizing Agents with Improved Air Stability for Triplet Dynamic Nuclear Polarization at Room Temperature, JOURNAL OF PHYSICAL CHEMISTRY LETTERS, 10.1021/acs.jpclett.9b00480, 10, 9, 2208-2213, 2019.05, 核磁気共鳴を用いた分光法(NMR)や画像化法(MRI)は非破壊的に分子の構造や運動性を分析できる手法であるが、その感度が非常に低いため、例えばMRIにおいては観測対象が主に生体内に大量に存在する水に限られてきた。感度が低い原因は核スピンの偏極率が低いためであり、その偏極率を向上させる技術として動的核偏極法(DNP)がある。中でも光励起三重項の大きな電子スピン偏極を核スピン偏極へと移行するtriplet-DNPは室温で核スピンの偏極率を高めることが出来る。
8. Hironori Kouno, Yoichi Sasaki, Nobuhiro Yanai,* and Nobuo Kimizuka*, Supramolecular Crowding Can Avoid Oxygen Quenching of Photon Upconversion in Water, Chemistry - A European Journal, 10.1002/chem.201806076, 25, 24, 6124-6130, 2019.04.
9. Rena Haruki, Hironori Kouno, Masanori Hosoyamada, Taku Ogawa, Nobuhiro Yanai,* and Nobuo Kimizuka*, Oligo(ethylene glycol)/alkyl-modified Chromophore Assemblies for Photon Upconversion in Water, Chemistry - An Asian Journal, 10.1002/asia.201801666, 2019.01.
10. Nobuhiro Yanai, Kengo Suzuki, Taku Ogawa, Yoichi Sasaki, Naoyuki Harada, Nobuo Kimizuka, Absolute Method to Certify Quantum Yields of Photon Upconversion via Triplet-Triplet Annihilation, Journal of Physical Chemistry A, 10.1021/acs.jpca.9b08636, 2019.01, For the consistent development of the field of photon upconversion via triplet-triplet annihilation (TTA-UC), it is pivotal to know the true quantum yield of TTA-UC emission. Although TTA-UC quantum yields have been determined by common relative measurements using quantum yield standards, there is still a discrepancy between the reported values even for the benchmark sensitizer-emitter pair of platinum(II) octaethylporphyrin (PtOEP) and 9,10-diphenylanthracene (DPA). Here, to resolve this situation, we show a method to obtain the absolute quantum yield of TTA-UC photoluminescence. The difficulty in obtaining absolute TTA-UC quantum yield by the integrating sphere measurement is to accurately calibrate the contribution of reabsorbed upconverted emission by triplet sensitizers. The reabsorption correction is successfully carried out by comparing sensitizer phosphorescence with and without the integrating sphere. An absolute TTA-UC quantum yield of the PtOEP-DPA pair is obtained as 36%, which shows a good agreement with the relative TTA-UC quantum yield. An absolute TTA-UC quantum yield of another red-to-blue TTA-UC pair, platinum(II) meso-tetraphenyltetrabenzoporphyrin (PtTPBP) and 2,5,8,11-tetra-tert-butylperylene (TTBP), is obtained as 27%. These absolute TTA-UC quantum yields can be used as certified values to check the measurement setup and sample condition for determining relative TTA-UC quantum yields in each laboratory..
11. Koki Nishimura, Hironori Kouno, Kenichiro Tateishi, Tomohiro Uesaka, Keiko Ideta, Nobuo Kimizuka, Nobuhiro Yanai, Triplet dynamic nuclear polarization of nanocrystals dispersed in water at room temperature, Physical Chemistry Chemical Physics, 10.1039/c9cp03330k, 21, 30, 16408-16412, 2019.01, While dynamic nuclear polarization using photo-excited triplet electrons (triplet-DNP) can improve the sensitivity of nuclear magnetic resonance at room temperature, it has not been carried out in water. Here, we report the first example of triplet-DNP in water by downsizing the conventional bulk crystals to nanocrystals..
12. Keisuke Okumura, Nobuhiro Yanai, Nobuo Kimizuka, Visible-to-UV photon upconversion sensitized by lead halide perovskite nanocrystals, Chemistry Letters, 10.1246/cl.190473, 48, 11, 1347-1350, 2019.01, Visible-to-UV photon upconversion based on triplet-triplet annihilation (TTA-UC) sensitized by lead halide perovskite nanocrystals is demonstrated for the first time. The surface modification of nanocrystals with energy transmitter ligands plays a key role in the effective triplet sensitization, resulting in high TTA-UC efficiency over 4%. This work proves the promising potential of perovskite nanocrystals as a versatile, next-generation triplet sensitizer..
13. Saiya Fujiwara, Masanori Hosoyamada, Kenichiro Tateishi,* Tomohiro Uesaka, Keiko Ideta, Nobuo Kimizuka,* and Nobuhiro Yanai*, Dynamic Nuclear Polarization of Metal-Organic Frameworks Using Photoexcited Triplet Electrons, Journal of the American Chemical Society, 10.1021/jacs.8b10121, 140, 46, 15606-15610, 2018.11, 原子が持つ微小な磁石である核スピンの振る舞いを電磁波の吸収・放出から観測することで、分子の構造や運動性を非破壊的に分析することができます。この技術は、化学の分野では核磁気共鳴(NMR)分光法、医療の現場では磁気共鳴画像法(MRI)として欠かせないツールとなっています。しかし、これらの感度は他の分析法と比較すると非常に低く、例えばMRIでは主に生体内に膨大に存在する水分子の1H核の画像化に限定されています。
感度が低い原因は核スピンの低い偏極率ですが、その偏極率を向上させる技術が動的核偏極(Dynamic Nuclear Polarization; DNP)法です。中でも、特定の分子(偏極源)を光励起し、三重項電子に出現する大きな偏極を核の偏極へと移行するTriplet-DNP法は、核スピンの偏極率を室温で大幅に向上できるため近年注目を集めています。しかし従来のTriplet-DNP法は、高感度化したい生体分子を取り込むことが難しい有機結晶、もしくは室温で偏極を蓄積することが難しいガラス中でのみ行われており、高感度MRIへの応用は制限されていました。
14. Pankaj Bharmoria, Shota Hisamitsu, Hisanori Nagatomi, Taku Ogawa, Masa-aki Morikawa, Nobuhiro Yanai,* and Nobuo Kimizuka*, Simple and Versatile Platform for Air-Tolerant Photon Upconverting Hydrogels by Biopolymer-Surfactant-Chromophore Co-assembly, Journal of the American Chemical Society, 10.1021/jacs.8b05821, 140, 34, 10848-10855, 2018.08, 生体高分子と界面活性剤の複合体マトリックス中に色素分子を高濃度に分散することで空気中においてアップコンバージョンを示すヒドロゲルを合成することに成功した。複雑な合成を必要とせず、複合体の構造を制御することで容易に空気中で高効率なフォトン・アップコンバージョンを得ることが出来る。.
15. Taku Ogawa, Masanori Hosoyamada, Brett Yurash, Thus-Quyen Nguyen,* Nobuhiro Yanai,* and Nobuo Kimizuka*, Donor-Acceptor-Collector Ternary Crystalline Films for Efficient Solid-State Photon Upconversion, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 10.1021/jacs.8b04542, 140, 28, 8788-8796, 2018.07, 高効率なフォトン・アップコンバージョンを得るうえで、発光体(アクセプター)から増感剤(ドナー)への逆エネルギー移動をいかに阻害するか、ということが重要な課題であった。本研究においてドナー、アクセプターに加えて第三成分として高い蛍光量子収率を示すコレクターを導入することにより、コレクターからドナーへの逆エネルギー移動を抑制し、高効率なフォトン・アップコンバージョン材料を得ることに成功した。.
16. Masanori Hosoyamada, Nobuhiro Yanai, Keisuke Okumura, Takayuki Uchihashi, and Nobuo Kimizuka, Translating MOF chemistry into supramolecular chemistry: soluble coordination nanofibers showing efficient photon upconversion, Chem. Commun., 10.1039/C8CC01594E, 2018.04, [URL].
17. Taku Ogawa, Nobuhiro Yanai, Saiya Fujiwara, Thus-Quyen Thai Nguyen, and Nobuo Kimizuka, Aggregation-free Sensitizer Dispersion in Rigid Ionic Crystals for Efficient Solid-State Photon Upconversion and Demonstration of Defect Effects, J. Mater. Chem. C, 6, 5609-5615, 2018.04, [URL].
18. Marleen Haring, Alex Abramov, Keisuke Okumura, Indrajit Ghosh, Burkhard Konig, Nobuhiro Yanai, Nobuo Kimizuka, and David Diaz Diaz, Air-sensitive Photoredox Catalysis Performed under Aerobic Conditions in Gel Networks, J. Org. Chem., 10.1021/acs.joc.8b00797, 2018.04, [URL].
19. Kazuma Mase, Yoichi Sasaki, Yoshimitsu Sagara, Nobuyuki Tamaoki, Christoph Weder, Nobuhiro Yanai, and Nobuo Kimizuka, Stimuli-Responsive Dual-color Photon Upconversion: an S-T Absorption Sensitizer in a Soft Luminescent Cyclophane, Angew. Chem. Int. Ed. , 57, 2806-2810, 2018.02, [URL], 近年、三重項-三重項消滅に基づくフォトン・アップコンバージョン (TTA-UC) の新たな展開として、外部刺激による発光スイッチングが注目されている。しかし、これまでの研究報告例は発光のON/OFFスイッチングに限られており、UC発光色を可逆的に変化させた例は無かった。UC発光色のスイッチングが容易でない理由として、次の二点があげられる。まず、外部刺激によって相互に変換可能な二種類の秩序構造を分子が形成でき、それぞれの秩序構造内で三重項エネルギー拡散が起きる必要がある点、次に秩序構造変化に伴い発光が長波長シフトしても、励起波長とUC発光波長の差 (アンチストークスシフト) が十分に確保できる点である。この二点を満たす系の構築を目指し、室温で二種類の秩序構造を示すシクロファン1を、三重項増感剤として基底一重項から励起三重項への直接S-T吸収が可能なOs錯体と融合させた。
シクロファン 1 は、結晶相 (G-form:緑色発光) と、高温で現れるネマチック相を急冷することで得られる過冷却ネマチック相 (Y-form:黄色発光)をそれぞれ室温で形成し、熱刺激により相互に変換することができる。そこで、項間交差によるエネルギー損失のないS-T吸収を示すOs錯体を用いて1の三重項励起状態を増感することで、G-formだけでなく、より長波長領域に発光を示すY-formにおいてもTTA-UC発光を観測することに成功した。すなわち、UC発光色を熱刺激により可逆的にスイッチングすることに初めて成功した。.
20. Shogo Amemori, Rakesh Kumar Gupta, Marcus Leo Bohm, James Xiao, Uyen Huynh, Tomoki Oyama, Kenji Kaneko, Akshay Rao, Nobuhiro Yanai, and Nobuo Kimizuka, Hybridizing semiconductor nanocrystals with metal-organic frameworks for visible and near-infrared photon upconversion, Dalton Trans., 10.1039/C7DT04794K, 2018.02, [URL].
21. Daisuke Kichise, Kazuma Mase, Shigenori Fujikawa, Nobuhiro Yanai, and Nobuo Kimizuka, Specific Uniaxial Self-assembly of Columnar Perylene Liquid Crystals in Au Nanofin Arrays, Chem. Lett., 47, 354-357, 2018.01, [URL].
22. Hisanori Nagatomi, Nobuhiro Yanai, Teppei Yamada, Kanji Shiraishi, and Nobuo Kimizuka, Synthesis and Electric Properties of a Two-Dimensional Metal-Organic Framework based on Phthalocyanine, Chem.-Eur. J., 24, 1806-1810, 2018.01, [URL].
23. Daisuke Kichise, Kazuma Mase, Shigenori Fujikawa, Nobuhiro Yanai, and Nobuo Kimizuka, Specific Uniaxial Self-assembly of Columnar Perylene Liquid Crystals in Au Nanofin Arrays, Chem. Lett., 47, 354-357, 2018.01, [URL].
24. Angelo Monguzzi, Marco Ballabio, Nobuhiro Yanai, Nobuo Kimizuka, Daniele Fazzi, Marcello Campione, and Francesco Meinardi, Highly Fluorescent Metal-Organic-Framework Nanocomposites for Photonic Applications, Nano Lett., 18, 528-534, 2017.12, [URL].
25. aku Ogawa, Nobuhiro Yanai, Hironori Kouno, and Nobuo Kimizuka, Kinetically controlled crystal growth approach to enhance triplet energy migration-based photon upconversion, J. Photon. Energy, 8, 022003, 2017.11, [URL].
26. Hisanori Nagatomi, Nobuhiro Yanai and Nobuo Kimizuka, Reentrant Gel-Sol-Gel Transition of a Lipophilic Co(II) Coordination Polymer, Chem. Lett., 47, 97-99, 2017.11, [URL].
27. Shota Hisamitsu, Nobuhiro Yanai, Hironori Kouno, Eisuke Magome, Masaya Matsuki, Teppei Yamada, Angelo Monguzzi, and Nobuo Kimizuka, Two-dimensional structural ordering in a chromophoric ionic liquid for triplet energy migration-based photon upconversion, Phys. Chem. Chem. Phys., 20, 3233-3240, 2017.11, [URL].
28. Nobuhiro Yanai and Nobuo Kimizuka, New Triplet Sensitization Routes for Photon Upconversion: Thermally Activated Delayed Fluorescence Molecules, Inorganic Nanocrystals, and Singlet-to-Triplet Absorption, Acc. Chem. Res., 50, 2487-2495, 2017.09, [URL].
29. Keisuke Okumura, Masaya Matsuki, Teppei Yamada, Nobuhiro Yanai and Nobuo Kimizuka, Sensitizer-Free Photon Upconversion in Single-Component Brominated Aromatic Crystals, ChemistrySelect, 2, 7597-7601, 2017.08, [URL].
30. Kazuma Mase, Keisuke Okumura, Nobuhiro Yanai and Nobuo Kimizuka, Triplet Sensitization by Perovskite Nanocrystals for Photon Upconversion, Chem. Commun., 10.1039/C7CC03087H, 53, 8261-8264, 2017.06, [URL], フォトン・アップコンバージョンの課題の一つに、三重項増感剤の系間交差によるエネルギーロスが原因でアンチストークスシフトの幅が狭まってしまうという問題があった。そこで鉛ハライドペロブスカイトを三重項増感剤として利用し、太陽光程度の非常に低強度の励起光でフォトン・アップコンバージョンを達成することに成功した。中でも、ペロブスカイトの表面に有機分子を修飾することが三重項エネルギー移動に非常に重要であるという基本的な設計指針を見出すことが出来た。.
31. Yoichi Sasaki, Shogo Amemori, Nobuhiro Yanai, Nobuo Kimizuka, Hironori Kouno, Near infrared-to-blue photon upconversion by exploiting direct S-T absorption of a molecular sensitizer, J. Mater. Chem. C, 10.1039/C7TC00827A, 2017.05, [URL].
32. DUAN PENGFEI, Deepak Asthana, Takuya Nakashima, Tsuyoshi Kawai, Nobuhiro Yanai, Nobuo Kimizuka, All-or-None Switching of Photon Upconversion in Self-Assembled Organogel Systems, Faraday Discussions, 10.1039/C6FD00170J, 196, 305-316, 2016.07, [URL].
33. Shogo Amemori, Yoichi Sasaki, Nobuhiro Yanai, Nobuo Kimizuka, Near Infrared-to-Visible Photon Upconversion Sensitized by a Metal Complex with Spin-Forbidden yet Strong S0-T1 Absorption, J. Am. Chem. Soc., 10.1021/jacs.6b04692, 138, 8702-8705, 2016.06, [URL].
34. Hironori Kouno, Taku Ogawa, Shogo Amemori, Prasenjit Mahato, Nobuhiro Yanai, Nobuo Kimizuka, Triplet energy migration-based photon upconversion by amphiphilic molecular assemblies in aerated water, Chem. Sci., 10.1039/C6SC01047D, 2016.04, [URL].
35. Keisuke Okumura, Kazuma Mase, Nobuhiro Yanai, Nobuo Kimizuka, Employing Core-Shell Quantum Dots as Triplet Sensitizer for Photon Upconversion, Chem.-Eur. J., 10.1002/chem.20160998, 2016.04, [URL].
36. Nobuhiro Yanai, Mariko Kozue, Shogo Amemori, Kabe Ryota, CHIHAYA ADACHI, Nobuo Kimizuka, Increased Vis-to-UV upconversion performance by energy level matching between a TADF donor and high triplet energy acceptors, J. Mater. Chem. C, 10.1039/C6TC01816E, 4, 6447-6451, 2016.04, [URL].
37. Nobuhiro Yanai, Nobuo Kimizuka, Recent emergence of photon upconversion based on triplet energy migration in molecular assemblies, Chem. Commun., 22, 2060-2067, 2016.03, [URL].
38. Nobuhiro Yanai, Nobuo Kimizuka, Masa-aki Morikawa, Photon Upconversion and Molecular Solar Energy Storage by Maximizing the Potential of Molecular Self-Assembly, Langmuir, 10.1021/acs.langmuir.6b03363, 32, 12304-12322, 2016.03, [URL].
39. Masanori Hosoyamada, Nobuhiro Yanai, Nobuo Kimizuka, Molecularly Dispersed Donors in Acceptor Molecular Crystals for Photon Upconversion under Low Excitation Intensity, Chem.-Eur. J., 22, 2060-2067, 2016.01.
40. Shogo Amemori, Nobuhiro Yanai, Nobuo Kimizuka, Metallonaphthalocyanines as triplet sensitizers for near-infrared photon upconversion beyond 850 nm, Physical Chemistry Chemical Physics, 17, 22557-22560, 2015.08, [URL], In triplet–triplet annihilation-based photon upconversion (TTA-UC), the utilization of near-infrared (NIR) light with a wavelength longer than 850 nm remains an outstanding issue. We realized this by employing metallonaphthalocyanines as triplet sensitizers; upon excitation of NIR light (856 nm), upconverted emission was observed in the visible range with remarkable photostability..
41. Shota Hisamitsu, Nobuhiro Yanai, Nobuo Kimizuka, Photon-Upconverting Ionic Liquids: Effective Triplet Energy Migration in Contiguous Ionic Chromophore Arrays, Angew. Chem., Int. Ed., 54, 11550-11554, 2015.08, 低エネルギーの光を高エネルギーの光に変換する技術であるフォトン・アップコンバージョンの実用化に不可欠な、太陽光程度の弱い光で効率を最大化する有機―無機複合材料を世界で初めて開発しました。我々は既に分子組織化を利用し溶液中で高効率なアップコンバージョンに成功していましたが、そこで困難であった溶媒を含まない固体中での高効率化に今回成功しました。フォトン・アップコンバージョンは、太陽電池や人工光合成の効率を飛躍的に向上するなどの再生可能エネルギー技術への応用が期待されており、学術的のみならず産業的にも大きな波及効果をもたらす成果です。.
42. Taku Ogawa, Nobuhiro Yanai, Angelo Monguzzi, Nobuo Kimizuka, Highly Efficient Photon Upconversion in Self-Assembled Light-Harvesting Molecular Systems, Scientific Reports, 5, 10882, 2015.06, [URL], エネルギーの光を高エネルギーの光に変換する技術のフォトン・アップコンバージョンの実用化に必要な、高効率で、太陽光などの弱い光でも機能し、空気中で安定である条件を満たす分子組織体を世界で初めて開発しました。
43. Shota Hisamitsu, Nobuhiro Yanai, Shigenri Fujikawa, Nobuo Kimizuka, Photoinduced Crystallization in Ionic Liquids: Photodimerization-induced Equilibrium Shift and Crystal Patterning, Chemistry Letters, 7, 908-910, 2015.05, [URL], An ionic liquid (IL) composed of 9–anthracene carboxylate anion and ammonium cation possessing three diethylene glycol chains shows photo–triggered dimerization of anthracence chromophores. It causes segregation and crystallization of protonated 9–anthracene carboxylic acid dimer, which is associated with the concurrent liberation of the free amine in the IL. This work provides a new molecular design for photoresponsive ILs, whose first application for site–selective photo–patterning is demonstrated..
44. DUAN PENGFEI, Nobuhiro Yanai, Yuki Kurashige, Nobuo Kimizuka, Aggregation-Induced Photon Upconversion through Control of theTriplet Energy Landscapes of the Solution and Solid States, Angew. Chem. Int. Ed., 54, 7554-7549, 2015.05, [URL], Aggregation-induced photon upconversion (iPUC) based on control of the triplet energy landscape is demonstrated for the first time. When a triplet state of a cyano-substituted 1,4-distyrylbenzene derivative is sensitized in solution, no upconverted emission based on triplet–triplet annihilation (TTA) was observed. In stark contrast, crystalline solids obtained by drying the solution revealed clear upconverted emission. Theoretical studies unveiled an underlying switching mechanism: the excited triplets in solution immediately decay back to the ground state through conformational twisting around a C[DOUBLE BOND]C bond and photoisomerization, whereas this deactivation path is effectively inhibited in the solid state. The finding of iPUC phenomena highlights the importance of controlling excited energy landscapes in condensed molecular systems..
45. DUAN PENGFEI, Nobuhiro Yanai, Hisanori Nagatomi, Nobuo Kimizuka, Photon Upconversion in Supramolecular Gel Matrixes: Spontaneous Accumulation of Light-Harvesting Donor-Acceptor Arrays in Nanofibers and Acquired Air Stability, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 10.1021/ja511061h, 137, 5, 1887-1894, 2015.02, [URL], 三重項―三重項消滅を利用したフォトン・アップコンバージョン(TTA-UC)はエネルギーからバイオまで幅広い分野での応用が期待されているが、励起三重項が空気中の酸素によって消光されてしまう致命的な問題を有する。今回我々は、超分子ゲルファイバー中に色素分子を高密度に自己組織化させれば、大気下においてもTTA-UCを発現できることを見いだしたので報告する(Figure 1)。超分子ゲルを形成する際にドナー、アクセプターを加えておくだけで空気中においてTTA-UCを観測できた。また、色素の種類を変えることで近赤外光から可視光、赤色光から緑色光、緑色光から青色光、可視光から紫外光への波長変換を達成した。.
46. DUAN PENGFEI, Nobuhiro Yanai, Nobuo Kimizuka, A Bis-Cyclometalated Iridium Complex as a Benchmark Sensitizer for Efficient Visible-to-UV Photon Upconversion, Chem. Commun., 10.1039/c4cc05718j, 50, 13111-13113, 2014.10, [URL], 可視光から紫外光領域への三重項-三重項消滅機構によるフォトンアップコンバージョン(TTA-UC)は、光触媒の高効率化をはじめ多くの応用が期待されるが、効率の低さが問題となっている。この原因として、ドナーならびにアクセプター分子の三重項エネルギー準位を制御する方法論が確立されていないことや、低いアクセプターの発光量子収率が挙げられる。本研究ではこの領域におけるUC効率の向上を目指し、新規アクセプター分子の設計・合成を行った。
紫外域に発光を持ち、高い発光量子収率を示すアクセプターとしてスチルベン誘導体を合成し、UCを検討した。445 nmの波長で励起したところ355 nm に明確なUC発光が観測され、その効率は1.4%とこれまでで最も高い値であった。.
47. Takashi Uemura, Gosuke Washino, Yanai Nobuhiro, Susumu Kitagawa, Controlled Encapsulation of Photo-Responsive Macromolecules in Porous Coodination Polymer, Chem. Lett., 42, 222-223, Editor's Choice, 2013.02.
48. DUAN PENGFEI, Nobuhiro Yanai, Nobuo Kimizuka, Photon Upconverting Liquids : Matrix-Free Molecular Upconversion Systems Functioning in Air, J. Am. Chem. Soc., 2013, 135, 19056-19059, 10.1021/ja411316s, 135, 19056-19059, 2013.12, [URL], 低エネルギーの光を高エネルギーの光に変換する機能を有する“フォトン・アップコンバージョン”液体システムを世界で初めて開発した.従来のアップコンバージョン技術が抱えていた①空気中(酸素の存在下)で機能しない,②揮発性の有機溶媒を用いる,③短い励起寿命の間に2つの励起分子が拡散衝突する必要がある などの問題を一挙に解決するものであり,学術的にも応用的にも大きなインパクトを与える画期的な成果である..
49. Melinda Sindoro, Nobuhiro Yanai, Ah-Young Jee, Steve Granick, Collidal-sized Metal-Organic Frameworks: Synthesis and Applications, Acc. Chem. Res., 10.1021/ar400151n, 47, 459-469, 2013.12, Colloidal metalorganic frameworks (CMOFs), nanoporous colloidal-sized crystals that are uniform in both size and polyhedral shape, are crystals composed of metal ions and organic bridging ligands, which can be used as building blocks for self-assembly in organic and aqueous liquids. They stand in contrast to conventional metalorganic frameworks (MOFs), which scientists normally study in the form of bulk crystalline powders. However, powder MOFs generally have random crystal size and shape and therefore do not possess either a definite mutual arrangement with adjacent particles or uniformity. CMOFs do have this quality, which can be important in vital uptake and release kinetics. In this Account, we present the diverse methods of synthesis, pore chemistry control, surface modification, and assembly techniques of CMOFs. In addition, we survey recent achievements and future applications in this emerging field. There is potential for a paradigm shift, away from using just bulk crystalline powders, towards using particles whose size and shape are regulated. The concept of colloidal MOFs takes into account that nanoporous MOFs, conventionally prepared in the form of bulk crystalline powders with random crystal size, shape, and orientation, may also form colloidal-sized objects with uniform size and morphology. Furthermore, the traditional MOF functions that depend on porosity present additional control over those MOF functions that depend on pore interactions. They also can enable controlled spatial arrangements between neighboring particles. To begin, we discuss progress regarding synthesis of MOF nano- and microcrystals whose crystal size and shape are well
regulated. Next, we review the methods to modify the surfaces with dye molecules and polymers. Dyes are useful when seeking to observe nonluminescent CMOFs in situ by optical microscopy, while polymers are useful to tune their interparticle interactions. Third, we discuss criteria to assess the stability of CMOFs for various applications. In another section of this Account, we give examples of supracrystal assembly in liquid, on substrates, at interfaces, and under external electric fields. We end this Account with discussion of possible future developments, both conceptual and technological..
50. Hirotaka Ejima, Nobuhiro Yanai, James P. Best, Melinda Sindoro, Steve Granick, Frank Caruso, Near-Incompressible Faceted Polymer Microcapsules from Metal-Organic Framework Templates, Advanced Materials, 10.1002/adma.201302442, 25, 5767-5771, 2013.08, Faceted polymer microcapsules are prepared from metal-organic framework (MOF) templates. The MOF templates are removable under mild aqueous conditions. The obtained microcapsules are stiffer than their spherical counterparts, reflecting the near-incompressibility of the facet edges, and indicating that the faceting might be a useful strategy for controlling the mechanical properties of polymer microcapsules..
51. Yanai Nobuhiro, Melinda Sindoro, Jing Yan, Steve Granick, Electric Field-Induced Assembly of Monodisperse Polyhedral Metal-Organic Framework Crystals, J. Am. Chem. Soc., 135, 34-37, 2013.01, 多孔性金属錯体のマイクロ結晶を電場をかけることにより配向を制御して集積化し、超結晶構造を形成することに成功した。大面積で結晶の配向を制御する簡易かつ効果的な方法論となりうる。また電場下での多面体粒子の集合を初めて明らかにしたため、コロイド自己集合の分野に新たな領域をもたらした。.
52. Yanai Nobuhiro, Takashi Uemura, Susumu Kitagawa, Behavior of Binary Guests in a Porous Coordination Polymer, Chem. Mater., 24, 4744-4749, 2012.12.
1. 楊井 伸浩, Materials Chemistry of triplet-DNP, Weekly ssNMR/DNP Zoominar, 2020.07, [URL].
2. 楊井 伸浩, Functional chemistry of triplet state, the SPIRITS international symposium – Shaping self-assembled mesoscale (bio)materials with microengineering, 2020.02.
3. 楊井 伸浩, Near infrared-to-blue photon upconversion for optogenetics, ISIPS2019, 2019.11.
4. 楊井 伸浩, Materials chemistry of photo-excited triplet state for dynamic nuclear polarization, 第57回日本生物物理学会年会, 2019.09.
5. 楊井 伸浩, Functional chemistry of triplet state, 化学と生命のかけはし 2019, 2019.07.
6. 楊井 伸浩, Near Infrared-to-Visible Photon Upconversion, China-Japan-Singapore Joint Symposium on Supramolecular Systems and Optoelectronic Functions, 2019.06.
7. 楊井 伸浩, Functional Chemistry of Photo-excited Triplet State: from Photon Upconversion to Dynamic Nuclear Polarization, 15th International Symposium on Applied Bioinorganic Chemistry (ISABC15), 2019.06.
8. 楊井 伸浩, Near Infrared-to-Visible Photon Upconversion, China-Japan-Singapore Joint Symposium on Supramolecular Systems and Optoelectronic Functions, 2019.06.
9. 楊井 伸浩, NIR-to-Visible Photon Upconversion for Energy Applications, International Conference on Photocatalysis and Photoenergy 2019 (ICoPP 2019), 2019.05.
10. 楊井 伸浩, Making Triplet Dynamic Nuclear Polarization More Accessible and Feasible, 60th Experimental Nuclear Magnetic Resonance Conference (ENC 2019), 2019.04, 核磁気共鳴分光法(NMR)は、分子の構造や運動性を非破壊的に分析できる有力な手法の一つであり、磁気共鳴画像法(MRI)としても応用されている。しかし室温における核スピンの偏極率が低いため、NMRやMRIの感度は非常に低い。この問題を解決する方法として、より大きな電子スピンの偏極を核スピンへと移行する動的核偏極法(DNP)がある。中でも励起三重項電子を偏極源として用いるtriplet-DNPは、室温でNMRやMRIを高感度化できるとして注目を集めている。
11. 楊井 伸浩, Photon Upconverting Molecular Systems, Pusan National University, 2018.12.
12. 楊井 伸浩, Photon Upconversion in Molecular Assemblies, 10th Asian Photochemistry Conference (APC) 2018, 2018.12.
13. 楊井 伸浩, Molecular Materials for Photon Upconversion, ICPAC Langkawi 2018, 2018.10.
14. 楊井 伸浩, Photon Upconversion in Self-Assembled Molecular Materials, SPIE Optics + Photonics 2018, 2018.08.
15. 楊井 伸浩, Photon Upconversion in Self-Assembled Molecular Systems, Spring Meeting of the Polymer Society of Korea, 2018.04.
16. 楊井 伸浩, Photon Upconversion in Self-Assembled Molecular Systems, Department of Chemistry, University of Liverpool, 2018.04.
17. 楊井 伸浩, Photon Upconversion based on Triplet Energy Migration, RSC Inorganic Chemistry Symposium, 2016.10.
18. 楊井 伸浩, Photon Upconversion in Chromophore Arrays Preorganized by Coordination Chemistry, 第66回錯体化学討論会, 2016.09.
19. 楊井 伸浩, Photon upconverting molecular assemblies, Japan-Taiwan Joint Seminar on Energy and Environment for Young Chemists, 2016.06.
20. 楊井 伸浩, Photon Upconversion by Triplet Energy Migration in Molecular Assemblies, Seminar at Center for Plastic Electronics, 2015.10.
21. 楊井 伸浩, Photon Upconversion in Organic Nanomaterials, MNC2015, 2015.10.
22. 楊井 伸浩, Photon Upconversion by Triplet Energy Migration in Molecular Assemblies, Seminar at Cavendish laboratory, 2015.10.
23. 楊井 伸浩, Supramolecular Systems for photon conversion technologies, China-Japan Joint Symposium on Functional Supramolecular Architectures, 2014.12.
24. 楊井 伸浩, 君塚 信夫, Photon Upconversion Meets Supramolecular Self-Assembly, IPC2014, 2014.12.
25. 楊井 伸浩, Prasenjit Mahato, 君塚 信夫, Photon Upconversion in MOFs, MOF2014, 2014.09.
26. 楊井 伸浩, Prasenjit Mahato, Angelo Monguzzi, 君塚 信夫, Photon Upconversion in Self-Assembled Molecular Systems, IUMRS-ICA2014, 2014.08.
27. 楊井 伸浩, DUAN PENGFEI, Prasenjit Mahato, Angelo Monguzzi, 君塚 信夫, Triplet Exciton Migration and Photon Upconversion in Self-Assembled Molecular Systems, Gordon research conference on Electronic Processes in Organic Materials, 2014.05.
Membership in Academic Society
  • The Royal Society of Chemistry
  • The Japanese Photochemistry Association
  • American Chemical Society
  • Japan Society of Coordination Chemistry
  • Development of Molecular Assemblies Having Photon Upconversion Functions
  • Quadrant Award 2013, "Controlling Polymer Properties in Coordination Nanospaces"
Educational Activities
Guidance of experimental class (Undergraduate, 3rd year)
Research guidance in the lab (Undergraduate, 4th year)
Research guidance in the lab (Master, Doctor course)
Other Educational Activities
  • 2016.03.
  • 2014.04, I mentored master and undergraduate students to accomplish the outstanding scientific findings. The results of this research guidance was highly evaluated, as evidenced by the awards of master students in the national conference of coordination chemistry and workshop of polymer society in Kyushu. I organized Kyushu University-UIUC Kickoff Meeting of ICC Program for Synthesis and Assembly of Reconfigurable Nanocrystals, and brought 5 master students to there. This gave great chances for the students to give presentations in English, discuss in English, and communicate with foreign young researchers, which helped them to construct international research network among young researchers..
  • 2013.03.