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Intermolecular Interactions and Chiral Recognition in Water

Research Project

Project/Area Number 10440211
Research Category

Grant-in-Aid for Scientific Research (B).

Allocation TypeSingle-year Grants
Section一般
Research Field 機能・物性・材料
Research InstitutionDoshisha University

Principal Investigator

KANO Koji  Doshisha University, Department of Molecular Science and Technology, Faculty of Engineering, Professor, 工学部, 教授 (60038031)

Project Period (FY) 1998 – 2000
Project Status Completed (Fiscal Year 2000)
Budget Amount *help
¥11,800,000 (Direct Cost: ¥11,800,000)
Fiscal Year 2000: ¥4,000,000 (Direct Cost: ¥4,000,000)
Fiscal Year 1999: ¥4,000,000 (Direct Cost: ¥4,000,000)
Fiscal Year 1998: ¥3,800,000 (Direct Cost: ¥3,800,000)
Keywordscyclodextrin / charged cyclodextrins / Coulomb interactions / thermodynamics / entropy gain / dehydration / hydrogen bonding / porphyrin complex / トリスフェナントロリン金属錯体 / 不斉認識 / エントロピー変化 / キラルフェロセン / 面不斉認識 / 水溶性ポルフィリン / 結合定数 / 錯生成速度 / 錯体解離速度 / ストップドフロー / 水-有機混合溶媒 / 熱力学的パラメータ / β-シクロデキストリン / テトラヘリセンジカルボン酸 / エンタルピー変化 / 二次元NMR / ヘリシティー / 自由エネルギー変化
Research Abstract

Complexation of p-methylbenzoate (p-CH_3-Ph-CO_2^-) and alkanoate anions (CnCO_2^-) with cyclodextrins (CDs) through hydrogen bonding in an aprotic polar solvent, DMSO-d_6, has been studied by means of ^1H NMR spectroscopy. Although undissociated p-methylbenzoic acid, p-CH_3-Ph-CO_2H, does not interact with CDs, p-CH_3-Ph-CO_2^- is bound to native CDs such as α-, β-, and γ-CDs with fairly large binding constants (K) through hydrogen-bonding interactions. Addition of small amounts of D_2O suppresses the formation of the hydrogen-bonded complexes, suggesting that hydrogen-bonding interactions between simple host having dense OH groups as hydrogen-bond donors and guest having the CO_2^- group as a hydrogen-bond acceptor hardly occur in aqueous solution.
Thermodynamic parameters for complexation of polyvalent cyclodextrin cation and anion with oppositely charged guests have been determined in D_2O containing 0.02 M NaCl by means of ^1H NMR spectroscopy. Protonated heptakis (6-amino-6-deoxy) … More -β-CD (per-NH_3^+-β-CD) forms stable inclusion complexes with monovalent guest anions. The enthalpy (ΔH) and entropy changes (ΔS) for complexation of per-NH_3^+-β-CD with p-methylbenzoate anion (p-CH_3-Ph-CO_2^-) are 3.8±0.7 kJ mol^<-1> and 88.6±2.2 J mol^<-1>K^<-1>, respectively. The thermodynamic parameters clearly indicate that dehydration from both the host and guest ions accounts for the entropic gain in inclusion process of p-CH_3-Ph-CO_2^- into the per-NH_3^+-β-CD cavity. The acetate anion is not included into the per-NH_3^+-β-CD cavity, while the butanoate and hexanoate anions form the inclusion complexes. The complexation of the alkanoate anions is entropically dominated. Judging from these results, it may be concluded that Coulomb interactions cooperated with inclusion are required for realizing the large entropic gain due to extended dehydration.
Tetrakis (p-sulfonatophenyl) porphyrin tetraanion (TPPS) forms an extremely stable 1 : 2 inclusion complex of permethylated β-CD (TMe-β-CD)(porphyrin : CD=1 : 2). The K value for this system in water is too large to be determined. Such a system is expected to act as a good model for hemoglobin and/or myoglobin. The we studied the system composed of Fe (III) TPPS and TMe-β-CD.The Fe (III) complex of TPPS also form a very stable 1 : 2 complex of TMe-β-CD in water at pH>5, while the stoichiometry of the CD inclusion complex is altered to 1 : 1 because of the effort of the net charge of the porphyrin ring. The CD-porphyrin complex shows a novel behavior of axial ligation of Cl^- and ClO_4^-. Less

Report

(4 results)
  • 2000 Annual Research Report   Final Research Report Summary
  • 1999 Annual Research Report
  • 1998 Annual Research Report
  • Research Products

    (38 results)

All Other

All Publications (38 results)

  • [Publications] K.Kano: "Chiral Recognition of Cationic Dipeptides by an Anioic β-Cyclodextrin"Chirality. (印刷中).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] S.Negi: "Effects of Anions in Subphases on a Langmuir Monolayer of N, N-Dimethyl-I-octadecanamine."Bull.Chem.Soc.Jpn.. 73. 977-984 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Kano: "Chiral Recognition of Ru(phen)_3^<2+> by Anionic Cyclodextins"Chem.Lett.. 698-699 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Kano: "Complexation of Polyuatent Cyclodextrin Ions with Oppositely Charge 2 Guests : Eutropically Favorable Complexation duets Dehydration"Chem.Eur.J.. 6. 2705-2713 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Kano: "Factors Influencing Self-Aggregation Tendencies of Cationic Porphyrins in Aqueous Solution"J.Am.Chem.Soc.. 122. 7494-7502 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Kitae: "Chiral Recognition of Phenylacetic Acid Derivatives by Aminated Cyclodextrins"J.Incl.Phenom.Macrocyl.Chem.. 33. 345-359 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Kano: "Recognition of Planar Chirality by Cyclodextrins"Chem.Lett.. 1337-1338 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Kitae: "Chiral recognition of α-amino acids by charged Cyclodextrins through Cooperative Work of Coulomb interaction and inclusion"J.Chem.Soc.,Perkin Trans.2. 207-212 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Kano: "Recognition of Helicity by Native Cyclodextrins. Highly Enantioselective Compleration of Tetrahelicene Dicarboxylic Acid with β-cyclodextrin"Chem.Lett.. 151-152 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] S.Negi: "Chiral Recognition of 1-(4-Quinolye) ethanol by Permethylated α-Cyclodextrin"J.Chem.Res.(M). 3268-3296 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Kano: "Molecular Recognition and Inclusion"Kluwer Academic Publishers. 7 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Kano: "Chiral Recognition of Cationic Dipeptides by an Anionic β-Cyclodextrin"Chirality. (in print).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] S.Negi: "Effects of Anions in Subphases on a Langmuir Monolayer of N, N-Dimethyl-1-octadecanamine"Bull.Chem.Soc.Jpn.. 73. 977-984 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Kano: "Chiral Recognition of Ru (phen)_3^<2+> by Anionic Cyclodextrins"Chem.Lett.. 698-699 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Kano: "Complexation of Polyvalent Cyclodextrin Ions with Oppositely Charged Guests : Entropically Favorable Complexation due to Dehydration"Chem.Eur.J.. 6. 2705-2713 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Kano: "Factors Influencing Self-Aggregation Tendencies of Cationic Porphyrins in Aqueous Solution"J.Am.Chem.Soc.. 122. 7494-7502 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Kitae: "Chiral Recognition of Phenylacetic Acid Derivatives by Aminated Cyclodextrins"J.Incl.Phenom.Macrocyl.Chem.. 33. 345-359 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Kano: "Recognition of Planar Chirality by Cyclodextrins"Chem.Lett.. 1337-1338 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] T.Kitae: "Chiral recognition of α-amino acids by charged cyclodextrins through cooperative work of Coulomb interaction and inclusion"J.Chem.Soc., Perkin Trans.. 2. 207-212 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Kano: "Interactions of Porphyrins with Cyclodextrins. Porphyrins as Probes for Studying Inclusion Phenomena"Molecular Recognition and Inclusion, A.W.Coleman, Ed., Kluwer Academic Publishers, the Nethwelands. 191-196 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] K.Kano: "Recognition of Helicity by Native Cyclodextrins. Highly Enantioselective Complexation of Tetrahelicene Dicarbolylic Acid with β-Cyclodextrin"Chem.Lett.. 151-152 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] S.Negi: "Chiral Recognition of 1-(4-Quinolyl) ethanol by Permethylated α-Cyclodextrin"J.Chem.Res.(M). 3268-3296 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] S.Negi: "Optical Resolution of (L)-1-Aryl-1-alkanols using Enantioselective Transesterification by Lipases"Enantiomer. 5. 63-70 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] S.Negi: "Effects of Anions in Subphases on a Langmuir Monolayer of N_1N-Dimethyl-1-octadecamine"Bull.Chem.Soc.Jpn.. 73. 977-984 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] K.Kano: "Factors Influencing Self-Aggregation Tendencies of Cationic Porphyrins in Aqueous Solution"J.Am.Chem.Soc.. 122. 7494-7502 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] K.Kano: "Chiral Recognition of Ru(phen)_3^<2+> by Anionic Cyclodextrins"Chem.Lett.. 698-699 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] K.Kano: "Complexation of Polyvalent Cyclodextrin Ions with Oppositely Charged Guests"Chem.Eur.J.. 6. 2705-2713 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] T.Kitae: "Chiral Recognition of Phenylacetic Acid Derivatives by Aminated Cyclodextrins"J.Incl. Phenom.Macrocycl.Chem.. 33. 345-359 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] K.Kano: "Recognition of Planar Chirality by Cyclodextrins"Chem.Lett.. 1337-1338 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] S.Negi: "Optical Resolution of (±)-1-Aryl-1-alkanals Using Enantioselective Transesterification by Lipases"Enantiomer. (印刷中).

    • Related Report
      1999 Annual Research Report
  • [Publications] S.Negi: "Effects of Anions in Subphases on a Langmuir Monolayer of N,N-Dimethyl-1-Octadecanamine"Bull.Chem.Soc. Jpn.. (印刷中).

    • Related Report
      1999 Annual Research Report
  • [Publications] K.Kano: "Complexation of Polyvalent Cyclodextrin Ions with Opposetely Charged Guests."Chem. Euro. J.. (印刷中).

    • Related Report
      1999 Annual Research Report
  • [Publications] Takashi KITAE: "Chiral recognition of α-amino acids by charged cyclodextrins through cooperative work by Coulomb interaction and inclusion" J.Chem.Soc.,Perkin Trans.2. 207-212 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Koji KANO: "Recognition of helicity by native cyclodextrins. Highly enantioselective complexation of tetrahelicene dicarboxylic acid with β-cyclodextrin" Chem.Lett.151-152 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Shigeru NEGI: "Chiral recognition of 1- (4-quinolyl) ethanol by permethylated α-cyclodextrin" J.Chem.Res. (M). 3268-3296 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Koji KANO: "Chiral recognition of an anionic tetrahelicene by native cyclodextrins. Enantioselectivity dominated by location of a hydrophilic group of the guest in a cyclodextrin cavity" J.Chem.Soc.,Perkin Trans 2. 15-21 (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] Koji KANO: "Interactions of porphyrins with cyclodexins.Porphyins as probes for syudying inclusion phenomena" Molecular Recognition and Inclusion. 印刷中

    • Related Report
      1998 Annual Research Report
  • [Publications] Takashi KITAE: "Chiral recognition of α-phenylasetic acid derivatives by aminated cyclodextrins" J.Incl.Phenom.Mol.Recog.Chem. (Proceeding). 191-196 (1998)

    • Related Report
      1998 Annual Research Report

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Published: 1998-04-01   Modified: 2016-04-21  

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