“Complete” Thermocontrol of Ion Permeation Through Ternary Composite Membranes Composed of Polymer/liquid Crystal/amphiphilic Crown Ethers

Seiii Shinkai, Shinichiro Nakamura, Kouii Ohara, Shinji Tachiki, Osamu Manabe, Tisato Kajiyama

研究成果: ジャーナルへの寄稿記事

20 引用 (Scopus)

抄録

Composite membranes composed of polymer (polycarbonate (PC))/liquid crystal (N-(4-eth-oxybenzylidene)-4'-butylaniline (EBBA))/amphiphilic crown ethers (la, 2a, and 2b) have been prepared. The DSC study established that la (single-chain amphiphile) is dispersed homogeneously in the PC/EBBA composite membrane, whereas 2a and 2b (double-chain amphiphiles) exist as phase-separated aggregates in the membrane. Also prepared were ternary composite membranes containing natural ionophores such as X-537A (lasalocid) or monensin, which were dispersed homogeneously in the PC/EBBA composite membrane. Above Tkn(crystal-nematic liquid crystal phase transition temperature of EBBA), ion permeation through these composite membranes was very fast (19-34-fold compared with the conventional membranes). This is due to the high fluidity of EBBA forming a continuous phase in the composite membrane. Permeation of K+ion through PC/EBBA/la and PC/EBBA/natural ionophore was observed below and above TKN, and the Arrhenius plots consisted of two straight lines intersecting at TKN.This indicates that carrier-mediated K+permeation is directly affected by the molecular motion of the liquid crystal phase. Surprisingly, K+permeation through PC/EBBA/2a and PC/EBBA/2b was “completely” suppressed below TKNand increased with increasing transport temperature above Tkn.Furthermore, Cs+, which forms sandwich-type complexes with 18-crown-6 and its analogues, could permeate through PC/EBBA/2a but not at all through PC/EBBA/la above TKN.The difference in the permeation mechanism between PC/EBBA/la and PC/EBBA/2a is discussed in relation to the dispersion state of the crown ethers. The Arrhenius thermodynamic parameters show a good en-thalpy-entropy compensation relationship expressed by Ea= 5.42 log A + 50.4, but the permeability coefficient for K+(PK+) was affected more significantly by the log A term. Finally, the PC/EBBA/2a membrane, which exhibits an all-or-nothing change in the ion permeability, was applied to the reversible thermocontrol of K+permeation and to the temperature-dependent “catch-and-release” of K+ion. This is the first example for “complete” thermocontrol of ion permeation through the polymer composite membrane.

元の言語英語
ページ(範囲)21-28
ページ数8
ジャーナルMacromolecules
20
発行部数1
DOI
出版物ステータス出版済み - 1 1 1987
外部発表Yes

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polycarbonate
Crown Ethers
Crown ethers
Composite membranes
Liquid crystal polymers
Polycarbonates
Permeation
Ions
Lasalocid
Ionophores
Liquid Crystals
Amphiphiles
Membranes
Liquid crystals
liquid crystal polymer
Polymers

All Science Journal Classification (ASJC) codes

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry

これを引用

“Complete” Thermocontrol of Ion Permeation Through Ternary Composite Membranes Composed of Polymer/liquid Crystal/amphiphilic Crown Ethers. / Shinkai, Seiii; Nakamura, Shinichiro; Ohara, Kouii; Tachiki, Shinji; Manabe, Osamu; Kajiyama, Tisato.

:: Macromolecules, 巻 20, 番号 1, 01.01.1987, p. 21-28.

研究成果: ジャーナルへの寄稿記事

Shinkai, Seiii ; Nakamura, Shinichiro ; Ohara, Kouii ; Tachiki, Shinji ; Manabe, Osamu ; Kajiyama, Tisato. / “Complete” Thermocontrol of Ion Permeation Through Ternary Composite Membranes Composed of Polymer/liquid Crystal/amphiphilic Crown Ethers. :: Macromolecules. 1987 ; 巻 20, 番号 1. pp. 21-28.
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abstract = "Composite membranes composed of polymer (polycarbonate (PC))/liquid crystal (N-(4-eth-oxybenzylidene)-4'-butylaniline (EBBA))/amphiphilic crown ethers (la, 2a, and 2b) have been prepared. The DSC study established that la (single-chain amphiphile) is dispersed homogeneously in the PC/EBBA composite membrane, whereas 2a and 2b (double-chain amphiphiles) exist as phase-separated aggregates in the membrane. Also prepared were ternary composite membranes containing natural ionophores such as X-537A (lasalocid) or monensin, which were dispersed homogeneously in the PC/EBBA composite membrane. Above Tkn(crystal-nematic liquid crystal phase transition temperature of EBBA), ion permeation through these composite membranes was very fast (19-34-fold compared with the conventional membranes). This is due to the high fluidity of EBBA forming a continuous phase in the composite membrane. Permeation of K+ion through PC/EBBA/la and PC/EBBA/natural ionophore was observed below and above TKN, and the Arrhenius plots consisted of two straight lines intersecting at TKN.This indicates that carrier-mediated K+permeation is directly affected by the molecular motion of the liquid crystal phase. Surprisingly, K+permeation through PC/EBBA/2a and PC/EBBA/2b was “completely” suppressed below TKNand increased with increasing transport temperature above Tkn.Furthermore, Cs+, which forms sandwich-type complexes with 18-crown-6 and its analogues, could permeate through PC/EBBA/2a but not at all through PC/EBBA/la above TKN.The difference in the permeation mechanism between PC/EBBA/la and PC/EBBA/2a is discussed in relation to the dispersion state of the crown ethers. The Arrhenius thermodynamic parameters show a good en-thalpy-entropy compensation relationship expressed by Ea= 5.42 log A + 50.4, but the permeability coefficient for K+(PK+) was affected more significantly by the log A term. Finally, the PC/EBBA/2a membrane, which exhibits an all-or-nothing change in the ion permeability, was applied to the reversible thermocontrol of K+permeation and to the temperature-dependent “catch-and-release” of K+ion. This is the first example for “complete” thermocontrol of ion permeation through the polymer composite membrane.",
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T1 - “Complete” Thermocontrol of Ion Permeation Through Ternary Composite Membranes Composed of Polymer/liquid Crystal/amphiphilic Crown Ethers

AU - Shinkai, Seiii

AU - Nakamura, Shinichiro

AU - Ohara, Kouii

AU - Tachiki, Shinji

AU - Manabe, Osamu

AU - Kajiyama, Tisato

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N2 - Composite membranes composed of polymer (polycarbonate (PC))/liquid crystal (N-(4-eth-oxybenzylidene)-4'-butylaniline (EBBA))/amphiphilic crown ethers (la, 2a, and 2b) have been prepared. The DSC study established that la (single-chain amphiphile) is dispersed homogeneously in the PC/EBBA composite membrane, whereas 2a and 2b (double-chain amphiphiles) exist as phase-separated aggregates in the membrane. Also prepared were ternary composite membranes containing natural ionophores such as X-537A (lasalocid) or monensin, which were dispersed homogeneously in the PC/EBBA composite membrane. Above Tkn(crystal-nematic liquid crystal phase transition temperature of EBBA), ion permeation through these composite membranes was very fast (19-34-fold compared with the conventional membranes). This is due to the high fluidity of EBBA forming a continuous phase in the composite membrane. Permeation of K+ion through PC/EBBA/la and PC/EBBA/natural ionophore was observed below and above TKN, and the Arrhenius plots consisted of two straight lines intersecting at TKN.This indicates that carrier-mediated K+permeation is directly affected by the molecular motion of the liquid crystal phase. Surprisingly, K+permeation through PC/EBBA/2a and PC/EBBA/2b was “completely” suppressed below TKNand increased with increasing transport temperature above Tkn.Furthermore, Cs+, which forms sandwich-type complexes with 18-crown-6 and its analogues, could permeate through PC/EBBA/2a but not at all through PC/EBBA/la above TKN.The difference in the permeation mechanism between PC/EBBA/la and PC/EBBA/2a is discussed in relation to the dispersion state of the crown ethers. The Arrhenius thermodynamic parameters show a good en-thalpy-entropy compensation relationship expressed by Ea= 5.42 log A + 50.4, but the permeability coefficient for K+(PK+) was affected more significantly by the log A term. Finally, the PC/EBBA/2a membrane, which exhibits an all-or-nothing change in the ion permeability, was applied to the reversible thermocontrol of K+permeation and to the temperature-dependent “catch-and-release” of K+ion. This is the first example for “complete” thermocontrol of ion permeation through the polymer composite membrane.

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