| 研究課題/領域番号 |
20F20329
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| 研究種目 |
特別研究員奨励費
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| 配分区分 | 補助金 |
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| 応募区分 | 外国 |
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| 審査区分 |
小区分33020:有機合成化学関連
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| 研究機関 | 名古屋大学 |
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研究代表者 |
CRUDDEN Cathleen 名古屋大学, トランスフォーマティブ生命分子研究所, 客員教授 (10721029)
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| 研究分担者 |
YI HONG 名古屋大学, トランスフォーマティブ生命分子研究所, 外国人特別研究員
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| 研究期間 (年度) |
2020-11-13 – 2023-03-31
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| 研究課題ステータス |
交付 (2021年度)
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| 配分額 *注記 |
2,200千円 (直接経費: 2,200千円)
2021年度: 1,100千円 (直接経費: 1,100千円)
2020年度: 600千円 (直接経費: 600千円)
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| キーワード | Nano Materials / Nanocluster / N-Heterocyclic Carbene / Gold / Photocatalysis / ナノクラスター / 金 / N-ヘテロサイクリックカルベン / 光触媒 |
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| 研究開始時の研究の概要 |
NHC-金ナノクラスターの一般的合成法の開発を行う。まずNHC-金錯体を様々な還元剤を作用させることでNHC-金ナノクラスターの合成を試みる。その後、合成したNHC-金ナノクラスターの光触媒としての機能開拓を行う。また開発した触媒反応を不斉反応への展開を試みる。
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| 研究実績の概要 |
N-heterocyclic carbenes (NHCs) have recently emerged as valuable alternatives to thiols or phosphines for the stabilization of metal surfaces, nanoparticles, and clusters. The neutral, electron-rich NHCs form a strong covalent bond with the metal, which is important in providing stability to metal nanoclusters.
Thus far we have been able to synthesize a series of chiral Au13 nanoclusters via the direct reduction of achiral dinuclear Au(I) halide complexes ligated by ortho-xylyl-linked bis-N-heterocyclic carbene (bisNHC) ligands. A broad range of functional groups are tolerated as wingtip substituents, allowing for the synthesis of a variety of functionalized chiral Au13 nanoclusters. We have used single-crystal X-ray crystallography to confirm the molecular formula to be [Au13(bisNHC)5Cl2]Cl3, with a chiral helical arrangement of the five bidentate NHC ligands around the icosahedral Au13 core. This Au13 nanocluster is highly luminescent, with a quantum yield of 23%. The two enantiomers of the Au13 clusters can be separated by chiral HPLC, and the isolated enantiomers characterized by circular dichroism spectroscopy. The clusters synthesized by us show remarkable stability, including configurational stability, opening the door to further investigation of the effect of chirality on these clusters. Our preliminary results showed that this bisNHC Au13 nanocluster is friendly to cells and can be used for the cell imaging.
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| 現在までの達成度 (区分) |
現在までの達成度 (区分)
2: おおむね順調に進展している
理由
The research is proceeding according to the research plan.
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| 今後の研究の推進方策 |
In the next FY, we will use the above Au13 nanoclusters protected by bisNHC carbine to test their catalytic activity in the direct C-H functionalization of alkylamines under visible light conditions. Both TON and TOF will be used to compare the catalytic reactivity of synthesized Au clusters. Under the photocatalytic system, highly reactive oxygen species may be formed by the interaction between NHC modified Au nanoclusters and O2, which can be also used for the oxidative radical coupling of Csp3C-H compounds in the photocatalytic system. Besides, we will also use this type of bisNHC-modified chiral Au clusters in asymmetric catalysis. The direct reduction of ketones and kinetic resolution of alcohols will be chosen as the reactions. Due to the high quantum yield of [Au13(bisNHC)5Cl2]Cl3, we will apply this type of bis-NHC Au13 nanocluster in cell imaging, which will be of great importance in biology.
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