2003 Fiscal Year Annual Research Report

多核種高温拡散NMRプローブの開発と超臨界水溶液のダイナミクスの解析

Research Project

Project/Area Number	15205004
Research Category	Grant-in-Aid for Scientific Research (A)
Research Institution	Kyoto University
Principal Investigator	中原勝京都大学, 化学研究所, 教授 (20025480)
Co-Investigator(Kenkyū-buntansha)	若井千尋京都大学, 化学研究所, 助手 (40293948) 岡村恵美子京都大学, 化学研究所, 助手 (00160705) 松林信幸京都大学, 化学研究所, 助教授 (20281107)
Keywords	拡散定数 / 高分解能NMR / 超臨海水 / イオン / 輸送現象 / 窒化アルミ / 高温高圧 / 電気伝導度
Research Abstract	本研究の目的は、高温高圧極端条件にある超臨界水・水溶液の拡散現象を直接観察・解析する方法論を開拓・確立することである。この目的のために、電荷の有無に関わらず、どのような原子核種・化学種に対しても適用可能で、400℃以上の高温でも安定で精密に作動する高温拡散NMRプローブを世界に先駆けて開発した。これまで、超臨界水溶液の輸送現象の系統的な解析は、電気伝導度測定にほぼ限られてきた。しかし、電気伝導度測定は、イオン性の溶質に対してのみ適用可能である。また、超臨界水中では、イオンの会合度が増大するために、高精度の測定・解析は非常に困難であり、分子レベルの知見は得られない。本研究で開発した高温拡散NMRプローブによって、超臨界水溶液の拡散現象の系統的な解析が可能となった。500MHzの高磁場下での測定によって、Debye-Huckel理論の守備範囲であるサブmMのオーダーでの拡散係数決定を行うことができ、また、測定可能な分子種の制限を取り除いた。本年度に開発した高温拡散NMRプローブの最大のポイントは、ラジオ波を当てて観測するサンプル部分の上下に、直熱ヒーターを対称に配置し、熱伝導性が高く非磁性の金によって熱を伝導したことである。これまでは、サンプル部の下部から熱した窒素ガスを吹き付けて温度を上昇させていた。当然、温度分布は上下非対称である。今回の設計によって、温度の均一性は大きく向上した。さらに、NMRサンプル管として、通常のガラスや石英ではなく、熱伝導性に優れたサファイアや窒化アルミ材を採用することで、更なる温度均一性を達成した。また、測定核種が高周波・低周波1種類づつ(通常は、^1Hと^<13>C)となっていたものを、今回の設計ではtunableとし、^1H核から^<14>N核までを1本のプローブで測定できるようにした。

Research Products

(17 results)

All Other

All Publications (17 results)

[Publications] Y.Nagai, C.Wakai, N.Matsubayasi, M.Nakahara: "Noncatalytic Cannizzaro-type Reaction of Acetaldehyde in Supercritical Water"Chemistry Letters. 32. 310-311 (2003)
[Publications] N.Matubayasi, M.Nakahara: "Theory of solutions in the energy representation. III. Treatment of the molecular flexibility"Journal of Chemical Physics. 119. 9686-9702 (2003)
[Publications] Y.Takebayashi, S.Yoda, T.Shigeta, K.Otake, M.Nakahara: "Dipolar Hydration Anomaly in the Temperature Dependence : Crbonyl and Nitrile Solutes Studied by ^<13>C NMR Chemical Shifts"Journal of Physical Chemistry B. 107. 9847-9852 (2003)
[Publications] T.Kimura, N.Matsubayasi, M.Nakahara: "Side-Chain Conformational Thermodynamics of Aspartic Acid Residue in the Peptides and Achatin-1 in Aqueous Solution"Biophysical Journal. 86. 1124-1137 (2004)
[Publications] T.Yamaguchi, N.Matsubayasi, M.Nakahara: "NMR Study on the Reorientational Relaxation in Supercritical Alcohols"Journal of Physical Chemistry A. 108. 1319-1324 (2004)
[Publications] C.Wakai, S.Morooka, N.Matsubayasi, M.Nakahara: "Carbon-Carbon Bond Formation in Glycolic Acid Generated Spontaneously from Dichloromethane in Hot Water"Chemistry Letters. 33. 302-303 (2004)
[Publications] S.Yoshida, K.Takewaki, K.Miwa, C.Wakai, M.Nakahara: "Desulfurization of Thiophene in Alkaline Supercritical Water Studied by ^1H and ^<13>C NMR"Chemistry Letters. 33. 330-331 (2004)
[Publications] Y.Usui, C.Wakai, N.Matsubayasi, M.Nakahara: "Synthesis of Dimethyl Ether from Supercritical Methanol in the Presence of Aluminum"Chemistry Letters. 33. 394-395 (2004)
[Publications] Y.Nagai, N.Matsubayasi, M.Nakahara: "Hot Water Induces an Acid-Catalyzed Reacrion in its Undissociated Form"Bulletin of the Chemical Society of Japan. 77(in press). (2004)
[Publications] Y.Nagai, N.Matsubayasi, M.Nakahara: "Noncatalytic Disproportionation and Decarbonylation Reactions of Benzaldehyde in Supercritical Water"Chemistry Letters. 33(in press). (2004)
[Publications] C.Wakai, K.Yoshida, Y.Tsujino, N.Matsubayasi, M.Nakahara: "Effect of Concentration, Acid, Temperature, and Metal on Competitive Reaction Pathways for Decarbonylation and Decarboxylation of Formic Acid in Hot Water"Chemistry Letters. 33(in press). (2004)
[Publications] S.Morooka, C.Wakai, N.Matsubayasi, M.Nakahara: "Acid-Catalyzed Hydrothermal Formation of Carbon-Carbon Bond in Glycolic Acid from a Series of Formaldehyde Producers"Chemistry Letters. 33(in press). (2004)
[Publications] Y.Takebayasi, S.Yoda, T.Shigeta, K.Otake, T.Sako, M.Nakahara: "Acetone hydration in supercritical water.13C-NMR spectroscopy and Monte Carlo simulation"Journal of Chemical Physics. 120(in press). (2004)
[Publications] T.Kimura, E.Okamura, N.Matsubayasi, K.Asami, M.Nakahara: "NMR Study on the Binding of Neuropeptide Achatin-I to Phospholipid Bilayer : The Equilibrium, Location, and Peptide Conformation"Biophysical Journal. 86(in press). (2004)
[Publications] 中原勝: "超臨海水の構造と物性"熱測定. 31. 14-22 (2004)
[Publications] 岡村恵美子, 中原勝: "膜"化学. 59. 66-67 (2004)
[Publications] 中原勝: "化学便覧基礎編II"丸善(日本化学会編). II127-II129, II144-II149 (2004)

2003 Fiscal Year Annual Research Report

多核種高温拡散NMRプローブの開発と超臨界水溶液のダイナミクスの解析

Principal Investigator

中原 勝 京都大学, 化学研究所, 教授 (20025480)

Research Products

[Publications] Y.Nagai, C.Wakai, N.Matsubayasi, M.Nakahara: "Noncatalytic Cannizzaro-type Reaction of Acetaldehyde in Supercritical Water"Chemistry Letters. 32. 310-311 (2003)

[Publications] N.Matubayasi, M.Nakahara: "Theory of solutions in the energy representation. III. Treatment of the molecular flexibility"Journal of Chemical Physics. 119. 9686-9702 (2003)

[Publications] Y.Takebayashi, S.Yoda, T.Shigeta, K.Otake, M.Nakahara: "Dipolar Hydration Anomaly in the Temperature Dependence : Crbonyl and Nitrile Solutes Studied by ^<13>C NMR Chemical Shifts"Journal of Physical Chemistry B. 107. 9847-9852 (2003)

[Publications] T.Kimura, N.Matsubayasi, M.Nakahara: "Side-Chain Conformational Thermodynamics of Aspartic Acid Residue in the Peptides and Achatin-1 in Aqueous Solution"Biophysical Journal. 86. 1124-1137 (2004)

[Publications] T.Yamaguchi, N.Matsubayasi, M.Nakahara: "NMR Study on the Reorientational Relaxation in Supercritical Alcohols"Journal of Physical Chemistry A. 108. 1319-1324 (2004)

[Publications] C.Wakai, S.Morooka, N.Matsubayasi, M.Nakahara: "Carbon-Carbon Bond Formation in Glycolic Acid Generated Spontaneously from Dichloromethane in Hot Water"Chemistry Letters. 33. 302-303 (2004)

[Publications] S.Yoshida, K.Takewaki, K.Miwa, C.Wakai, M.Nakahara: "Desulfurization of Thiophene in Alkaline Supercritical Water Studied by ^1H and ^<13>C NMR"Chemistry Letters. 33. 330-331 (2004)

[Publications] Y.Usui, C.Wakai, N.Matsubayasi, M.Nakahara: "Synthesis of Dimethyl Ether from Supercritical Methanol in the Presence of Aluminum"Chemistry Letters. 33. 394-395 (2004)

[Publications] Y.Nagai, N.Matsubayasi, M.Nakahara: "Hot Water Induces an Acid-Catalyzed Reacrion in its Undissociated Form"Bulletin of the Chemical Society of Japan. 77(in press). (2004)

[Publications] Y.Nagai, N.Matsubayasi, M.Nakahara: "Noncatalytic Disproportionation and Decarbonylation Reactions of Benzaldehyde in Supercritical Water"Chemistry Letters. 33(in press). (2004)

[Publications] C.Wakai, K.Yoshida, Y.Tsujino, N.Matsubayasi, M.Nakahara: "Effect of Concentration, Acid, Temperature, and Metal on Competitive Reaction Pathways for Decarbonylation and Decarboxylation of Formic Acid in Hot Water"Chemistry Letters. 33(in press). (2004)

[Publications] S.Morooka, C.Wakai, N.Matsubayasi, M.Nakahara: "Acid-Catalyzed Hydrothermal Formation of Carbon-Carbon Bond in Glycolic Acid from a Series of Formaldehyde Producers"Chemistry Letters. 33(in press). (2004)

[Publications] Y.Takebayasi, S.Yoda, T.Shigeta, K.Otake, T.Sako, M.Nakahara: "Acetone hydration in supercritical water.13C-NMR spectroscopy and Monte Carlo simulation"Journal of Chemical Physics. 120(in press). (2004)

[Publications] T.Kimura, E.Okamura, N.Matsubayasi, K.Asami, M.Nakahara: "NMR Study on the Binding of Neuropeptide Achatin-I to Phospholipid Bilayer : The Equilibrium, Location, and Peptide Conformation"Biophysical Journal. 86(in press). (2004)

[Publications] 中原 勝: "超臨海水の構造と物性"熱測定. 31. 14-22 (2004)

[Publications] 岡村恵美子, 中原勝: "膜"化学. 59. 66-67 (2004)

[Publications] 中原 勝: "化学便覧 基礎編II"丸善(日本化学会編). II127-II129, II144-II149 (2004)

中原勝京都大学, 化学研究所, 教授 (20025480)

[Publications] 中原勝: "超臨海水の構造と物性"熱測定. 31. 14-22 (2004)

[Publications] 中原勝: "化学便覧基礎編II"丸善(日本化学会編). II127-II129, II144-II149 (2004)