TOP > 研究報告検索 > 単一分子・原子レベルの反応制御 超臨界流体溶媒を用いた反応の制御と新反応の開拓

単一分子・原子レベルの反応制御 超臨界流体溶媒を用いた反応の制御と新反応の開拓

研究報告コード R990004268
掲載日 2001年2月6日
研究者
  • 梶本 興亜
研究者所属機関
  • 京都大学大学院理学研究科
研究機関
  • 京都大学大学院理学研究科
報告名称 単一分子・原子レベルの反応制御 超臨界流体溶媒を用いた反応の制御と新反応の開拓
報告概要 炭酸ガスおよび水の超臨界流体は化学反応を起こす反応媒体として非常に有利な諸性質を持つ。超臨界流体の特異な性質は流体中にある反応分子の溶媒和に起因している。本研究では,様々な状況下(温度・密度・流体種類など)で超臨界流体中での反応分子の溶媒和の挙動を探り,溶媒和の制御による反応そのものの制御を目的としている。これまでに炭酸ガスと水中での溶媒和の挙動を,紫外・可視・赤外吸収スペクトルやフェムト秒励起レーザを用いて解明してきた。例えば,かなり低密度の流体中でも反応分子周囲には流体のクラスタが発達し,液相に近い状態の出現することや,このクラスタが時間と共に大きく揺らいでいることなどを明らかにした。主な研究成果を次に示した。
1)超臨界流体中でのエネルギー散逸,
2)異性化反応に対する動的溶媒効果,
3)超臨界水中のC1化合物の元反応(還元反応の全体像の解明,図1,
4)超臨界水中でのポリフェノールの有機反応機構。
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研究分野
  • 無触媒反応
  • 光化学一般
  • 反応工学,反応速度論
  • 反応操作(単位反応)
関連発表論文 1. Ishida, T., Fujimura, Y., Fujiwara, T., and Kajimoto, O. (1998) ""Excited state dynamics of 9,9'-bianthryl clusters with H2O and Ar."" Chem. Phys. Lett., 288, 433-440.
2. Kobayashi, T., and Kajimoto, O. (1998) ""Benzonitrile and its van der Waals complexes studied in a free jet. III. Enhancement of the intersystem crossing rate in the benzonitrile dimer and other complexes."" Res, Chem. Intermed., 24(7), 785-802.
3. Kajimoto, O. (1998) ""Energy Transfer."" Funcitonality of Molecular Systems, S. Nagakura, ed., Springer-Verlag Tokyo, Tokyo, 110-126.
4. 梶本興亜,「超臨界流体中の溶媒和と反応の物理化学」,超臨界流体反応方の基礎と展開(碇屋隆雄編),シーエムシー,1-16 (1998).
5. 梶本興亜,「環境に優しい超臨界流体」,化学,Vol.53, No.10, 37-42 (1998).
6. Hara, K. and Kometani, N. (1998) ""High Pressure Studies on Excited Intramolecular Charge-Transfer Reactions and Solvation Dynamics."" Rev. High Pressure Sci. Technol. 7, 1219-1221.
7. Bulgarevich, D. S. and Hara, K. (1998) ""High Pressure Studies on Excited Intramolecular Charge-Transfer Reactions and Solvation Dynamics."" Rev. High Pressure Sci. Technol. 7, 1256-1258.
8. Yoshimura, Y. (1998) ""Mean force acting on a thin hard needle in a hard disk fluid."" J. Phys. Soc. Jpn. 67, 890-898 .
9. Kimura, Y., Takebayashi, Y., and Hirota, N. (1998) ""Effect of the solvent density and species on the back-electron transfer rate in the hexamethylbenzene/tetracyanoethylene charge-transfer complex."" J. Chem. Phys. 108, 1485-1498.
10. Kimura, Y., Sugihara, K., Ooe, H., M. Terazima, and Hirota, N.(1998) ""Solvent Density Dependence of the Photolysis Quantum yield in Supercritical Fluids."" Rev. High Pressure Sci. and Technol. 7, 1259-1261.
11. Kimura, Y., Takebayashi, Y., and Hirota, N. (1998) ""Electron-Transfer Rate in the Charge Transfer Complex in the Supercritical Fluids."" Rev. High Pressure Sci. and Technol. 7, 1230-1232.
12. Yamaguchi, T., Kimura, Y., and Hirota, N. (1998) ""Molecular dynamics simulation of solute diffusion in Lennard-Jones fluids."" Mol. Phys. 94, 527-537.
13. Yamaguchi, T., Kimura, Y., and Hirota, N. (1998) ""Solvation state selective excitation in resonance Raman spectroscopy. I. Experimental study on the C=N and the C=O stretching modes of phenol blue."" J. Chem. Phys. 109, 9075-9083.
14. Yamaguchi, T., Kimura, Y., and Hirota, N. (1998) ""Solvation state selective excitation in resonance Raman spectroscopy. II. Theoretical calculation."" J. Chem. Phys. 109, 9084-9095.
15. Matubayasi, N., Wakai, C., and Nakahara, M. (1998) ""NMR Study of Water Structure in Supercritical Conditions."" Rev. High Pressure Sci. Technol., 7, 1112-1114.
16. Tennoh, T., Enomoto, H., Wakai, C., and Nakahara, M. (1998) ""Supercritical Water Cracking and Washing of Used Polymer."" Rev. High Pressure Sci. Technol., 7, 1429-1431.
17. Muko^yama, A. and Yoshimura, Y.(1999) ""Shear viscosity of a fluid composed of infinitely-thin hard needles."" Molecular Simulation, 21, 367-375.
18. Yamasaki, Y., Enomoto, H., Yamasaki, N., and Nakahara, M. (1999) ""Methanol Formation from Dichloromethane under Hydrothermal Conditions"" Chem. Lett. 1999, 83-84.
19. Kajimoto, O., (1999) ""Solvation in supercritical fluids: Its effects on energy transfer and chemical reactions,"" Chem. Rev., 99, 355-389.
20. Kimura, Y., Yamaguchi, T., and Hirota, N.(1999) “Vibrational energy relaxation rates in the S2 state of azulene in nitrogen and carbon dioxide.”Chem. Phys. Lett. 303, 223-228.
21. Yamaguchi, T., Kimura, Y.,, and Hirota, N. (1999) “The role of the attractive and the repulsive interactions in the nonpolar solvation dynamics in simple fluids from the gas-like to the liquid-like densities.”J. Chem. Phys. 111, 4169-4185.
22. Kimura, Y., and Hirota, N. (1999) “Effect of solvent density and species on static and dynamicfluorescence Stokes shifts of Coumarin 153”J. Chem. Phys. 111, 5474-5484.
23. Ooe, H., Kimura, Y.,, Terazima, M., and Hirota, N. (1999)“Photo-dissociation quantum yield of iodine in the low-, medium-, and high-density fluids studied by the transient grating method.” J. Phys. Chem. A, 103, 7730-7741.
24.  Matubayasi, N., Wakai, C., and Nakahara, M., (1999) ""Structural Study of Supercritical Water. II. Computer simulations"" J. Chem. Phys., 110, 8000-8011.
25. Tsujino, Y., Wakai, C., Matubayasi, N., and Nakahara, N., (1999) ""Noncatalytic Cannizzaro-type Reaction of Formaldehyde in Hot Water,"" Chem. Lett., 287-288.
26. Shigeta, T., and Nitta, T., (1999) ""Monte Carlo Simulation Study of Entrainer Effect on Distribution Equilibrium between Supercritical Fluids and Slitpores,"" J. Chem. Eng. Japan, 32, 150-152 .
27. 中原勝、「超臨界水の基礎と高分子化学への応用」Cellulose Commun., 6, 60-66 (1999).
28. 中原勝、松林伸幸、「超臨界水の構造と物性」、電気化学と工業物理化学、67、988-993 (1999).
29. 梶本興亜、「超臨界流体をミクロに見る」、現代化学、No.3、25-31 (1999).
30. Hara, K., Ito, N., and Kajimoto, O. (1999) ""High pressure studies of the Kramers turnover behavior for the excited state isomerization of 2-alkenylanthracene in alkane."" J. Chem. Phys., 110(3), 1662-1668.
31. Mukoyama A. and Yoshimura, Y. (1999) ""Shear viscosity of a fluid composed of infinitely-thin hard needles"" Molecular Simulation, 21, 367.
32. Yoshimura, Y. (1999) ""Molecular association in a one-dimensional square-well fluid"" J. Phys. Soc. Jpn. 68, 1917-1931.
33. 網田富士嗣、梶本興亜 「高圧力実験装置入門」高圧力の化学と技術, 9 (4), 308-313
34. Ito, N., Kajimoto, O., and Hara, K. (2000) ""Picosecond time-resolved fluorescence depolarization of p-terphenyl at high pressures,"" Chem. Phys. Lett, 318, 118-124.
35. Fujiwara, T., Egashira, K., Ohshima, Y., and Kajimoto, O. (2000) ""Effects of a solvent molecule on the torsional potential of 9,9'-bianthryl,"" Phys. Chem. Chem. Phys., 2, 1365-1373.
36. Mitsui, M., Ohshima, Y., Ishiuchi, S., Sakai, M. and Fujii, M. (2000) ""Structural characterization of the acridine?(H2O)n (n = 1?3) clusters by fluorescence-detected infrared spectroscopy."" Chem. Phys. Lett. 317, 211?219.
37. Takahashi, H., Hori, T., Wakabayashi, T., and Nitta, T., (2000) ""A Density Functional Study for Hydrogen Bond Energy by Employing Real Space Grids,"" Chemistry Letters, 222-223.
38. Takebayashi, Y., Kimura, Y., and Ohba, M. (2000)“Density dependence of solvation properties in polar dumbbell fluids from gaseous to liquid densities”J. Chem. Phys. 112, 4662-4675.
39. Kimura, Y., Yamaguchi, T., and Hirota, N. (2000) ""Photo-excitation dynamics of Phenol Blue."" PCCP, 2, 1415-1420.
40. Yoshimura, Y. (2000) ""Solvophobic interaction between hard spheres in a square-well fluid"", J. Phys. Soc. Jpn. 69, 1084-1092
41. Fujiwara, T., Fujimura, Y., Kajimoto, O. ""9,9'-bianthryl and its van der Waals complexes studied by rotational coherence spectroscopy: Structure and excited sate dynamics."" J. Chem. Phys. in press
42. Nitta, T. and Furukawa, S. ""Simulation Performance of a Non-Equilibrium Molecular Dynamics Method using Density Difference as Driving Force."" Molecular Simulation, in press.
43. Kitahama, Y., Kimura, Y., and Hirota, N., “An analysis of S-T0 mixing polarization of CIDEP in terms of the Lennard-Jones fluids: 1-hydroxy-1-methylethyl radical in 2-propanol”Bull. Chem. Soc. Jpn, in press.
44. Yamaguchi, T., Kimura, Y., and Hirota, N. “Vibrational energy relaxation of azulene in the S2 state. I: Solvent species dependence.” J. Chem. Phys. in press.
研究制度
  • 戦略的基礎研究推進事業、研究領域「単一分子・原子レベルの反応制御」研究代表者 梶本 興亜(京都大学大学院理学研究科)/科学技術振興事業団
研究報告資料
  • 梶本 興亜. 単一分子・原子レベルの反応制御 超臨界流体溶媒を用いた反応の制御と新反応の開拓. 戦略的基礎研究推進事業 平成10年度 研究年報,1999. p.365 - 368.

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