1989 Fiscal Year Annual Research Report

不飽和アシル鎖を含む脂質および関連長鎖化合物の構造多形と相転移挙動

Research Project

Project/Area Number	63470010
Research Institution	OSAKA UNIVERSITY
Principal Investigator	小林雅通大阪大学, 理学部, 教授 (40028147)
Co-Investigator(Kenkyū-buntansha)	金子文俊大阪大学, 理学部, 助手 (70214468) 田代孝二大阪大学, 理学部, 助手 (60171691)
Keywords	不飽和脂肪酸 / 不飽和グリセリド / 結晶多形(ポリモルフ) / 層状多形(ポリタイプ) / 相転移 / 分子運動 / 振動スペクトル / X線構造解析
Research Abstract	リン脂質およびグリセリドは生体組織に広く分布し生理活性を担う重要な物質であるが、その主成分の長鎖アシル基のほゞ半数は不飽和アシル鎖で占められ、生体膜に流動性を付与し機能を活性化するのに役立っている。不飽和アシル鎖の示す特有な機能を分子レベルで解明する研究の一環として前年度に続き一連の不飽和脂肪酸、不飽和トリグリセリドの多形構造とその熱力学的安定性および固相転移の分子機構について、赤外・ラマン分光、X線解析、DSCを用いて考察した。不飽和脂肪酸は極めて複雑な結晶多形を示すが、各結晶相の単結晶試料を作り前年度のエルシン酸γ、γ_1、ペトロセリン酸低融点(LM)相に加えてペトロセリン酸高融点(HM)相の結晶構造を決定した。LM相ではアシル鎖はO_〓型副格子をとり、これまでnーアルカンや飽和脂肪酸で見出した2層ポリタイプ構造を形成すること、HM相はオレフィン基配座の異なる2種類の二量体よりなり、メチル基側の鎖はM_<11>型、カルボキシル基側の鎖はO_〓型副格子をとることを明らかにした。いずれもas型不飽和アシル鎖の凝集構造としては初めて見出されたものである。不飽和アシル鎖に特徴的なγ【double arrow】α、γ_1【double arrow】α_1可逆相転移は分子層界面も構成するメチル基側アルキル基の部分融解によるものであるが、エルシン酸についてこの相転移に伴うスペクトル変化の詳細を調べ、無秩序相であるα、α_1中に存在するゴ-シュ形の割合や空間群対称の乱れについて考察した。2ー位に不飽和アシル鎖をもつトリグリセリドの多形構造の研究も進めた。長鎖分子系の固相転移に伴なう分子変位を知る目的でステアリン酸単結晶のB(Mon)→C(Mon)、B(Orth11)→C(Mon)、E(Mon)→C(Mon)、およびE(Orth11)→C(Mon)ポリモルフ/ポリタイプ複合相転移を振動分光、X線回折で追跡し分子層内で大きな分子回転を伴なう協同的な分子変位が起っていることを確認した。

Research Products
(21 results)

All Other

All Publications (21 results)

[Publications] Kiyotaka SATO: "Stability,Occurrence and Step Morphology of Polymorphs and Polytypes of Stearic Acid I.Stability and Occurrence" J.Cryst.Growth. 87. 236-242 (1988)
[Publications] Kimio INAOKA: "Stability,Occurrence and Step Morphology of Polymorphs and Polytypes of Stearic Acid II.Mono-1amellar Step Morphology and Composite Polymorphic/Polytypic Transformation" J.Cryst.Growth. 87. 243-250 (1988)
[Publications] Masamichi KOBAYASHI: "Molecular Motions of n-Alkane Chains in Urea Adducts Studied by Raman Band Profiles" Rept.Progr.Polym.Phys.Jpn.31. 477-480 (1988)
[Publications] Masao SUZUKI: "Polymorphic Behavior of Erucic Acid" J.Am.Oil Chem.Soc.65. 1942-1947 (1988)
[Publications] 小林雅通: "高分子・長鎖分子結晶における分子運動" 化学. 43. 342-343 (1988)
[Publications] Masamichi KOBAYASHI: "Molecular and Crystal Structures of Lipids and Related Compounds" J.Dispersion Sci.Tech.10. 319-350 (1989)
[Publications] Fumitoshi KANEKO: "Polymorphic Structure and Phase Transitions of Mono-unsaturated Fatty Acids" Proc.ISF-JOCS World Congress. 1. 531-535 (1988)
[Publications] Fumitoshi KANEKO: "Structure and Phase Transition Behavior of Stearic Acid E-Form" Proc.ISF-JOCS World Congress. 1. 536-541 (1988)
[Publications] Masamichi KOBAYASHI: "Molecular Motions of n-Alkane Chains in Urea Adducts:Potential Barrier Heights and Lattice Vibrations of Host Channels" Rept.Progr.Polym.Phys.Jpn.32. 419-422 (1989)
[Publications] Kiyotaka SATO: "Structure and Transformation in Polymorphism of Petroselinic Acid(cis-ω12-octadecenoic acid)" J.Phys.Chem.(1989)
[Publications] 小林雅通: "長鎖状分子および高分子の構造、転移、物性" 海外高分子研究. 36. 42-46 (1990)
[Publications] Fumitoshi KANEKO: "Crystal Structure of Stearic Acid E-Form" Acta Crystallogr.C. (1989)
[Publications] Fumitoshi KANEKO: "Vibrational Spectroscopic Study on γ→α Phase Transition of cis-monounsaturated Fatty Acids:Palmitoleic and Erucic Acids" J.Phys.Chem.(1990)
[Publications] Fumitoshi KANEKO: "Crystal Structure of petroselinic acid Low-melting Phase" Acta Crystallogr.C. (1990)
[Publications] Fumitoshi KANEKO: "Crystal Structure of Petroselinic Acid High-melting Phase" Acta Crystallogr.(1990)
[Publications] Kohji TASHIRO: "Structural Study on Phase Transition in Ferroelectric Liquid Crystal:Temperature Dependence of Infrared and Raman Spectra" Rept.Progr.Polym.Phys.Jpn.32. 415-418 (1989)
[Publications] Kohji TASHIRO: "X-ray Structure Analyses and Vibrational Spectral Measurements of the Model Compounds of the Liquid-Crystalline Arylate Polymers[1]Finding out the Raman Bands Characteristic of the Twisted Biphenyl Structure in Association with the Solid-to-Liquid Crystalline Phase Transition" J.Am.Chem.Soc.(1990)
[Publications] Kohji TASHIRO: "Structural Study on Phase Transition in Ferroelectric Liquid Crystal[II]The Structural Changes Revealed by X-ray Diffraction Measurements" Rept.Progr.Polym.Phys.Jpn.(1990)
[Publications] Masamichi KOBAYASHI: "Vibrational Spectroscopic Aspects of Polymorphism and Phase Transition of Fats and Fatty Acids in“Crystallization and Polymorphism of Fats and Fatty Acids"(Eds.N.Garti & K.Sato)" Marcel Dekker,New York, 140-187 (1988)
[Publications] Masamichi KOBAYASHI: "Application of Raman Microprobe Technique to the Study of Organic Polymers and Long-chain Compounds in“Vibrational Spectra and Structures Vol.17B"(Eds.H.D.Bist,J.R.Durig,and J.F.Sullivan)." Elsevier,Amsterdam, 369-397 (1989)
[Publications] 小林雅通: "いのちと暮しのケミ・スト-リ-、第11章" 化学同人, 173-192 (1989)

1989 Fiscal Year Annual Research Report

不飽和アシル鎖を含む脂質および関連長鎖化合物の構造多形と相転移挙動

Principal Investigator

小林 雅通 大阪大学, 理学部, 教授 (40028147)

Research Products

[Publications] Kiyotaka SATO: "Stability,Occurrence and Step Morphology of Polymorphs and Polytypes of Stearic Acid I.Stability and Occurrence" J.Cryst.Growth. 87. 236-242 (1988)

[Publications] Kimio INAOKA: "Stability,Occurrence and Step Morphology of Polymorphs and Polytypes of Stearic Acid II.Mono-1amellar Step Morphology and Composite Polymorphic/Polytypic Transformation" J.Cryst.Growth. 87. 243-250 (1988)

[Publications] Masamichi KOBAYASHI: "Molecular Motions of n-Alkane Chains in Urea Adducts Studied by Raman Band Profiles" Rept.Progr.Polym.Phys.Jpn.31. 477-480 (1988)

[Publications] Masao SUZUKI: "Polymorphic Behavior of Erucic Acid" J.Am.Oil Chem.Soc.65. 1942-1947 (1988)

[Publications] 小林雅通: "高分子・長鎖分子結晶における分子運動" 化学. 43. 342-343 (1988)

[Publications] Masamichi KOBAYASHI: "Molecular and Crystal Structures of Lipids and Related Compounds" J.Dispersion Sci.Tech.10. 319-350 (1989)

[Publications] Fumitoshi KANEKO: "Polymorphic Structure and Phase Transitions of Mono-unsaturated Fatty Acids" Proc.ISF-JOCS World Congress. 1. 531-535 (1988)

[Publications] Fumitoshi KANEKO: "Structure and Phase Transition Behavior of Stearic Acid E-Form" Proc.ISF-JOCS World Congress. 1. 536-541 (1988)

[Publications] Masamichi KOBAYASHI: "Molecular Motions of n-Alkane Chains in Urea Adducts:Potential Barrier Heights and Lattice Vibrations of Host Channels" Rept.Progr.Polym.Phys.Jpn.32. 419-422 (1989)

[Publications] Kiyotaka SATO: "Structure and Transformation in Polymorphism of Petroselinic Acid(cis-ω12-octadecenoic acid)" J.Phys.Chem.(1989)

[Publications] 小林雅通: "長鎖状分子および高分子の構造、転移、物性" 海外高分子研究. 36. 42-46 (1990)

[Publications] Fumitoshi KANEKO: "Crystal Structure of Stearic Acid E-Form" Acta Crystallogr.C. (1989)

[Publications] Fumitoshi KANEKO: "Vibrational Spectroscopic Study on γ→α Phase Transition of cis-monounsaturated Fatty Acids:Palmitoleic and Erucic Acids" J.Phys.Chem.(1990)

[Publications] Fumitoshi KANEKO: "Crystal Structure of petroselinic acid Low-melting Phase" Acta Crystallogr.C. (1990)

[Publications] Fumitoshi KANEKO: "Crystal Structure of Petroselinic Acid High-melting Phase" Acta Crystallogr.(1990)

[Publications] Kohji TASHIRO: "Structural Study on Phase Transition in Ferroelectric Liquid Crystal:Temperature Dependence of Infrared and Raman Spectra" Rept.Progr.Polym.Phys.Jpn.32. 415-418 (1989)

[Publications] Kohji TASHIRO: "Structural Study on Phase Transition in Ferroelectric Liquid Crystal[II]The Structural Changes Revealed by X-ray Diffraction Measurements" Rept.Progr.Polym.Phys.Jpn.(1990)

[Publications] Masamichi KOBAYASHI: "Vibrational Spectroscopic Aspects of Polymorphism and Phase Transition of Fats and Fatty Acids in“Crystallization and Polymorphism of Fats and Fatty Acids"(Eds.N.Garti & K.Sato)" Marcel Dekker,New York, 140-187 (1988)

[Publications] Masamichi KOBAYASHI: "Application of Raman Microprobe Technique to the Study of Organic Polymers and Long-chain Compounds in“Vibrational Spectra and Structures Vol.17B"(Eds.H.D.Bist,J.R.Durig,and J.F.Sullivan)." Elsevier,Amsterdam, 369-397 (1989)

[Publications] 小林雅通: "いのちと暮しのケミ・スト-リ-、第11章" 化学同人, 173-192 (1989)

小林雅通大阪大学, 理学部, 教授 (40028147)