Direct visualization of the excited state structural dynamics of a synthetic Cu(I)-phenanthroline complex by TR-SFX method

• 研究領域: 高速分子動画法によるタンパク質非平衡状態構造解析と分子制御への応用
• 研究課題/領域番号: 22H04744
• 研究種目: 新学術領域研究(研究領域提案型)
• 配分区分: 補助金
• 審査区分: 複合領域
• 研究機関: 東京工業大学
• 研究代表者: Maity Basudev 東京工業大学, 生命理工学院, 特任助教 (60815421)
• 研究期間 (年度): 2022-04-01 – 2024-03-31
• 研究課題ステータス: 完了 (2023年度)
• 配分額: 11,180千円 (直接経費: 8,600千円、間接経費: 2,580千円); 2023年度: 5,720千円 (直接経費: 4,400千円、間接経費: 1,320千円); 2022年度: 5,460千円 (直接経費: 4,200千円、間接経費: 1,260千円)
• キーワード: TR-SFX / Mn-carbonyl complex / Lysozyme / Serial crystallography / Reaction intermediate / Ferritin cage / Copper complex / ferritin / Metal complex / Light reaction / Ferritin cage crystal / Cu(I) complex / Structural distortion

研究開始時の研究の概要

Excited state structural dynamics of transition metal complexes are important not only for applications but also for rethinking the fundamental concepts. Ultrafast spectroscopy is the common method for such studies. However, real-space determination of the structural changes in the excited state remained challenging due to transient nature of the intermediate(S). In this proposal, we aim to use the TR-SFX method for observing structural dynamics of a tetrahedral Cu(I)-phen complex in ultrafast timescale.

研究実績の概要

We immobilized a light-sensitive Mn-carbonyl complex in the porous lysozyme crystal and characterized by ATR-IR and absorbance spectroscopy. We determined the structure under darkness and compared with metal-free protein. We applied TR-SFX method to determine the changes at the metal reaction center after light irradiation. This gave interesting features such as releasing of CO ligand sequentially and the intermediate in which a water molecule was coordinated. The release of CO ligand was estimated by considering the appearance of negative density features after light irradiation which was were increased with increasing delay time. High laser intensity was found to trigger the CO release reaction. The results were validated by the QM MM calculations.

現在までの達成度 (段落)

令和5年度が最終年度であるため、記入しない。

今後の研究の推進方策

令和5年度が最終年度であるため、記入しない。

研究成果

• [雑誌論文] Real-time observation of a metal complex-driven reaction intermediate using a porous protein crystal and serial femtosecond crystallography (2024)
  • 著者名/発表者名: B. Maity, M. Shoji, F. Luo, T. Nakane, S. Abe, S. Owada, J. Kang, K. Tono, R. Tanaka, T. T. Pham, M. Kojima, Y. Hishikawa, J. Tanaka, J. Tian, M. Nagama, T. Suzuki, H. Noya, Y. Nakasuji, A. Asanuma, X. Yao, S. Iwata, Y. Shigeta, E. Nango, T. Ueno
  • 雑誌名: Nat. Commun 巻: 15 号: 1 ページ: 5518-5518
  • DOI: 10.1038/s41467-024-49814-9
  • 査読あり / オープンアクセス / 国際共著
• [雑誌論文] Atomic-Level Insights into a Unique Semi-Clathrate Hydrate Formed in a Confined Environment of Porous Protein Crystal (2023)
  • 著者名/発表者名: B. Maity, J. Tian, T. Furuta, S. Abe, T. Ueno
  • 雑誌名: Cryst. Growth Des. 巻: 23 号: 10 ページ: 7448-7458
  • DOI: 10.1021/acs.cgd.3c00880
  • 査読あり / オープンアクセス / 国際共著
• [雑誌論文] Fusion of amyloid beta with ferritin yields an isolated oligomeric beta-sheet-rich aggregate inside the ferritin cage (2023)
  • 著者名/発表者名: B. Maity, S. Kameyama, J. Tian, T. T. Pham, S. Abe, E. Chatani, K. Murata, T. Ueno
  • 雑誌名: Biomater. Sci. 巻: 12 号: 9 ページ: 2408-2417
  • DOI: 10.1039/d4bm00173g
  • 査読あり / オープンアクセス / 国際共著