Project/Area Number |
16074208
|
Research Category |
Grant-in-Aid for Scientific Research on Priority Areas
|
Allocation Type | Single-year Grants |
Review Section |
Science and Engineering
|
Research Institution | Nagoya University |
Principal Investigator |
WATANABE Yoshihito Nagoya University, Research Center for Materials Science, Professor (10201245)
|
Co-Investigator(Kenkyū-buntansha) |
NAKAJIMA Hiroshi Nagoya University, Graduate School of Science, Associate Professor (00283151)
UENO Takafumi Nagoya University, Graduate School of Science, Assistant Professor (70332179)
|
Project Period (FY) |
2004 – 2007
|
Project Status |
Completed (Fiscal Year 2007)
|
Budget Amount *help |
¥59,000,000 (Direct Cost: ¥59,000,000)
Fiscal Year 2007: ¥10,500,000 (Direct Cost: ¥10,500,000)
Fiscal Year 2006: ¥31,000,000 (Direct Cost: ¥31,000,000)
Fiscal Year 2005: ¥10,500,000 (Direct Cost: ¥10,500,000)
Fiscal Year 2004: ¥7,000,000 (Direct Cost: ¥7,000,000)
|
Keywords | Ferritin / Suzuki coupling / myoglobin / palladium / oraganometal complex / biocalalyst / metalloprotein / artificial protein / 結晶構造 / 還元反応 / 金属クラスター / Pdクラスター / 有機金属酵素 / 合金 / コア・シェル構造 / ナノクラスター / ヘムオキシゲナーゼ / 電子伝達 / 酸化還元 / ヘム / 水素結合 |
Research Abstract |
Last year, we have specified the amino acid residues responsible for capturing Pd2+ ions on the interior surface of ap-ferritin by X-ray crystal structural studies. In addition, we have examined the residues which ligate to Au3+ ions and found that some of the Au ion binding sites in apo-ferritin are different from those of Pd ions with different coordi-nation structures. On the basis of these observation, we have prepared two type of metal nano-clusters, i.e., alloy and core/shell as shown in Schem 1. In the co-reduction, Au and Pd ions coexist in the apo-ferritin cage. The number of each ion in the cage is regulated by the affinity of each ions to its specific amino acid residues. Consequently, the alloy nano-particle was composed of 133 Au atoms and 165 Pd atoms ((AuPd)・apo-ferritin). On the other hand, we have successfully prepared Au-core/Pd-shell([Au] (Pd)) and Pd-core/Au-shell ([Pd] (Au)) types of nano-particles composed of 201 Au atoms/305 Pd atoms and 169 Au atoms/65Pd atoms, respectively. Among those apo-ferritin composites, [Au] (Pd) apo-ferritin shows the highest catalytic activity for the hydrogenation of olefins. In a separate experiment, we have examined a possible incorporation of organometallic compounds such as [Pd(allyl)C1]2 and [Rh(norbornadiene)C1]2 in apo-ferritin. The crystal structure of Pd(allyl)・apo-ferritin clearly shows that the allyl group ligates to Pd ion in apo-ferritin.
|