Hidehiro Uekusa

School of Science, Tokyo Institute of Technology
Associate Professor
A01
Research AreasChemical Crystallography
Participating Group (2020-2021)

Structural elucidation of gas-crystal reaction vapochromism in organic crystals

Co-Researcher
Co-Researcher: Akiko Sekine (School of Science, Tokyo Institute of Technology, Assistant Professor)
Co-Researcher: Haruki Sugiyama (The Research and Education Center for Natural Science, Keio University , Assistant Professor)

Research Outline

Vapochromic organic crystals, which react in response to vapor exposure to crystals, reversibly undergo phase transition and change in color. They are typical examples of “soft crystals” and are also important as gas sensor materials. In this research, we aim to create new vapochromic organic crystals and to clarify the principle of vapochromism based on the crystal structures. In particular, the detailed molecular structure and crystal structure changes are important, and it is possible to perform crystal analysis even if the single crystal is disintegrated by crystal transition, utilizing microcrystal analysis or powder crystal analysis method.
As the principle of new organic vapochromism, it is important that the electronic state change induced by the change of the intermolecular interaction due to dehydration. Thus, the target of this research is a molecular system showing molecular structure and property change due to inter- or intra-molecular proton transfer.
The mechanism and design principle of vapochromic organic crystals are expected to be applied to create gas sensor materials for detecting various harmful vapors.

Vapochromic organic crystals
Crystal structure analysis methods of before and after phase transition
Participating Group (2018-2019)

Structure Analysis of Organic Vapochromic crystals by SDPD

Keywords
Vapochromism, Soft Crystal, Organic Crystal, Structure Determination from Powder Diffraction Data, X-ray Crystal Structure Analysis, Vapor Induced Phase Transition, Dehydration Transition, Hydration Transition

Research Outline

Vapochromic organic crystals, which react in response to vapor exposure to crystals, reversibly undergo phase transition and change in color. They are typical examples of “soft crystals” and are also important as gas sensor materials. In this research, we aim to create new vapochromic organic crystals and to clarify the principle of vapochromism based on the crystal structures. In particular, the detailed molecular structure and crystal structure changes are important, and it is possible to perform crystal analysis even if the single crystal is disintegrated by crystal transition, utilizing microcrystal analysis or powder crystal analysis method.
As the principle of new organic vapochromism, it is important that the electronic state change induced by the change of the intermolecular interaction due to dehydration. Thus, the target of this research is a molecular system showing molecular structure and property change due to inter- or intra-molecular proton transfer.
The mechanism and design principle of vapochromic organic crystals are expected to be applied to create gas sensor materials for detecting various harmful vapors.

Vapochromic organic crystals
Crystal structure analysis methods of before and after phase transition

Publications

Academic papers/reviewed

A01-15

  1. “Dehydration and Rehydration Mechanisms of Pharmaceutical Crystals: Classification of Hydrates by Activation Energy” M. Takahashi and H. Uekusa*, J. Pharm. Sci., 111, 618-627 (2022).
    DOI: 10.1016/j.xphs.2021.10.033
  2. "van der Waals solid solution crystals for highly efficient in-air photon upconversion under subsolar irradiance"　R. Enomoto, M. Hoshi, H. Oyama, H. Agata, S. Kurokawa, H. Kuma, H. Uekusa, Y. Murakami*, Mater. Horiz., 8, 3449-3456 (2021).
    DOI: 10.1039/D1MH01542G
  3. "Pillar[6]quinone: facile synthesis, crystal structures and electrochemical properties"　T. Hirohata, N. Shida, H. Uekusa, N. Yasuda, H. Nishihara, T. Ogoshi, I. Tomita, S. Inagi*, Chem. Commun., 57, 6360-6363 (2021).
    DOI: 10.1039/D1CC02413B
  4. "Solid-state dehydration mechanism of diclofenac sodium salt hydrates" H. Oyama, T. Miyamoto, A. Sekine, I. Nugrahani, H. Uekusa*, Crystals, 11, 412 (2021).
    DOI: 10.3390/cryst11040412
  5. "Crystal structures of antiarrhythmic drug disopyramide and its salt with phthalic acid” M. Tamboli, Y. Okamoto, Y. Utsumi, T. Furuishi, S. Wang, D. Umeda, O. Putra, K. Fukuzawa, H. Uekusa, E. Yonemochi*, Crystals, 11, 379 (2021).
    DOI: 10.2116/xraystruct.36.31
  6. "New Sodium Mefenamate - Nicotinamide Multicomponent Crystal Development to Modulate Solubility and Dissolution: Preparation, Structural, and Performance Study" I. Nugrahani*, F. Fisandra, A. Horikawa, H. Uekusa, J. Pharm. Sci., 110, 3246-3260 (2021).
    DOI: 10.1016/j.xphs.2021.05.022
  7. "Enantioselective Synthesis of Polycyclic Aromatic Hydrocarbon (PAH)-Based Planar Chiral Bent Cyclophanes by Rhodium-Catalyzed [2+2+2] Cycloaddition" Y. Aida, J. Nogami, H. Sugiyama, H. Uekusa, K. *Tanaka, Chem. - Eur. J., 26, 12579-12588 (2020).
    DOI: 10.1002/chem.202001450
  8. "Salt Cocrystal of Diclofenac Sodium-L-Proline: Structural, Pseudopolymorphism, and Pharmaceutics Performance Study" *I. Nugrahani, R. A. Kumalasari, N. A. Winni, A. Horikawa, H. Uekusa, Pharmaceutics, 12, 690 (2020).
    DOI: 10.3390/pharmaceutics12070690
  9. "Two-step crystal-crystal phase transformation of N-salicylidene-p-aminobenzoic acid by gas-solid reaction with aqua-ammonia vapor" H. Sugiyama, *H. Uekusa, Acta Crystallogr., Sect. C: Struct. Chem., 77, 56-60 (2021).
    DOI: 10.1107/S2053229620016411
  10. "Relationship between Crystal Structure, Crystal Morphology, and Mechanochromic Luminescence of Triphenylimidazolylbenzothiadiazole Derivatives" *S. Ito, S. Nagai, T. Ubukata, T. Ueno, H. Uekusa, Cryst. Growth Des., 20, 4443-4453 (2020). (領域内共同研究 A02公募 伊藤傑)
    DOI: 10.1021/acs.cgd.0c00253
  11. "Synthesis of Belt- and Möbius-Shaped Cycloparaphenylenes by Rhodium-Catalyzed Alkyne Cyclotrimerization", S. Nishigaki, Y. Shibata, A. Nakajima, H. Okajima, Y. Masumoto, T. Osawa, A. Muranaka, H. Sugiyama, A. Horikawa, H. Uekusa, H. Koshino, M. Uchiyama, A. Sakamoto, *K. Tanaka, J. Am. Chem. Soc., 141, 14955-14960 (2019).
    DOI: 10.1021/jacs.9b06197
  12. "In-Situ Photochromism Switching with Crystal Jumping through the Deammoniation of N-Salicylideneaniline Ammonium Salt", H. Sugiyama, K. Johmoto, A. Sekine, *H. Uekusa, Cryst. Growth Des., 19, 4324-4331 (2019).
    DOI: 10.1021/acs.cgd.9b00039
  13. "Elucidation of the crystal structures and dehydration behaviors of ondansetron salts", R. Mizoguchi, *H. Uekusa, Crystals, 9, 180/1-180/16 (2019).
    DOI: 10.3390/cryst9030180
  14. "Development of Visible-Light Driven Cu(I) Complex Photosensitizers for Photocatalytic CO2 Reduction", H. Takeda, Y. Monma, H. Sugiyama, H. Uekusa, *O. Ishitani, Front. Chem., 7, 418/1-418/12 (2019).
    DOI: 10.3389/fchem.2019.00418
  15. "Ambipolar transistors based on chloro-substituted tetraphenylpentacene" R. Sato, S. Eda, H. Sugiyama, H. Uekusa, T. Hamura, *T. Mori, J. Mater. Chem. C, 7, 3294-3299 (2019).
    DOI: 10.1039/C8TC06603E
  16. "Multicomponent Crystal of Mefenamic Acid and N-Methyl-D-Glucamine: Crystal Structures and Dissolution Study. " E. Zaini, L. Fitriani, R. Sari, H. Rosaini, A. Horikawa, H. Uekusa, J. Pharm. Sci., 108, 2341-2348 (2019).
    DOI: 10.1016/j.xphs.2019.02.003
  17. “Triplon band splitting and topologically protected edge states in the dimerized antiferromagnet” *K. Nawa, K. Tanaka, N. Kurita, T. J. Sato, H. Sugiyama, H. Uekusa, S. Ohira-Kawamura, K. Nakajima, *H. Tanaka, Nature Commun., 10, 2096 (2019).
    DOI: 10.1038/s41467-019-10091-6
  18. “Reversible on/off switching of photochromic properties in N-salicylideneaniline co-crystals by heating and humidification” H. Sugiyama, K. Johmoto, A. Sekine, *H. Uekusa, CrystEngComm, 21, 3170–3175 (2019). (
    DOI: 10.1039/C9CE00442D
  19. "Capturing a new hydrate polymorph of amodiaquine dihydrochloride dihydrate via heterogeneous crystallisation" P. O. Dwichandra, A. Pettersen, S. O.N. Lill, D. Umeda, E. Yonemochi, Y. P. Nugraha, *H. Uekusa, CrystEngComm, 21, 2053-2057 (2019).
    DOI: 10.1039/C8CE01720D

International conferences

A01-15

  1. "Ab-initio powder structure analysis for polymorphism and phase transformation studies with pharmaceutical applications" H. Uekusa, IUCr2021 (Prague, Czech, Aug. 14-22, 2021)
  2. "Vapor-Responsive Metal Complexes Exhibiting Chromic Phenomena" H Uekusa (Plenary), International Conferenceon Contemporary Science and Clinical Pharmacy 2021, (Padang, Indonesia, Sep.9-19, 2021)"
  3. “Pharmaceutical Co-crystals: Crystal Structure and Property relationship”, Pacifichem 2021 (Honolulu, USA, Dec. 16-22, 2021)
  4. ”Pharmaceutical Co-crystals: Crystal Structure and Property Relationship” H. Uekusa (Plenary), The 1st International Conference on Pharmaceutical Sciences and Pharmacy (Bandung, Indonesia, Oct. 7-8, 2020)
Related Website(s)
Contact
uekusa[at]chem.titech.ac.jp