Syntheses of Macrocyclic Enzyme Models. 8. Conformational Mobility and Molecular Recognition by the Internal Cage of Kyuphane

Yukito Murakami, Jun Ichi Kikuchi, Teruhisa Ohno, Takayuki Hirayama, Yoshio Hisaeda, Hiroshi Nishimura, James P. Snyder, Kosta Steliou, Yukito Murakami, Jun Ichi Kikuchi, Teruhisa Ohno, Takayuki Hirayama, Yoshio Hisaeda, Hiroshi Nishimura, Jun Ichi Kikuchi, James P. Snyder, Kosta Steliou

Research output: Contribution to journalArticle

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Abstract

Temperature-dependent 1 H NMR measurements in CDC13 −CS2 (3:7 v/v) and DMF-d7 in concert with MM2 conformational analysis reveal that the molecular framework of “Kyuphane” (1), a cage-type cubical molecule with six faces each consisting of a 2, 1l,20, 29-tetraaza[3.3.3.3]paracyclophane ring, is significantly more rigid than the corresponding noncage host (2), but still conformationally flexible. A slow rate of interconversion among degenerated conformers of the lowest energy C, conformation accounts for the observed NMR line broadening. Hosts 1 and 2 are soluble in acidic aqueous media below pH 4 and behave as polycationic species. Electrostatic field solvation analysis of the tetraprotonated salt of Kyuphane suggests a square-planar proton placement (11a) to predominate in solution. Line broadening for the tetracation appears to arise from both conformer interconversion and proton exchange. Guest recognition behavior of these hosts under acidic conditions was studied by means of 1 H NMR and fluorescence spectroscopy. Kyuphane demonstrates a pH-dependent guest-binding ability due to changes in the specific microenvironmental polarity of its three-dimensional cavity upon variable protonation of the nitrogen atoms. The host also shows size-sensitive and regioselective molecular discrimination originating from the semirigid geometry of the hydrophobic cavity and the specific protonation geometry. The specific molecular discrimination evidenced by 1 was analyzed by MM2 molecular mechanics and applied to selective transport of hydrophobic molecules between organic phases across an aqueous phase in which 1 was present as a carrier. It is noteworthy that the proton NMR signals of guest molecules naphthalene-2,6-disulfonate, 8-anilinonaphthalene-l-sulfonate, and 6-p-toluidinonaphthalene-2-sulfonate completely disappear upon complexation with Kyuphane, whereas the identical guest naphthalene-2,6-disulfonate shows normal upfield shifts of its NMR proton signals upon complexation with 2.

Original languageEnglish
Pages (from-to)8229-8242
Number of pages14
JournalJournal of the American Chemical Society
Volume113
Issue number22
DOIs
Publication statusPublished - Oct 1 1991

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Molecular recognition
Protons
Enzymes
Nuclear magnetic resonance
Protonation
Naphthalene
Complexation
Molecules
Molecular mechanics
Geometry
Fluorescence Spectrometry
Solvation
Fluorescence spectroscopy
Mechanics
Static Electricity
Nuclear magnetic resonance spectroscopy
Conformations
Ion exchange
Magnetic Resonance Spectroscopy
Nitrogen

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Syntheses of Macrocyclic Enzyme Models. 8. Conformational Mobility and Molecular Recognition by the Internal Cage of Kyuphane. / Murakami, Yukito; Kikuchi, Jun Ichi; Ohno, Teruhisa; Hirayama, Takayuki; Hisaeda, Yoshio; Nishimura, Hiroshi; Snyder, James P.; Steliou, Kosta; Murakami, Yukito; Kikuchi, Jun Ichi; Ohno, Teruhisa; Hirayama, Takayuki; Hisaeda, Yoshio; Nishimura, Hiroshi; Kikuchi, Jun Ichi; Snyder, James P.; Steliou, Kosta.

In: Journal of the American Chemical Society, Vol. 113, No. 22, 01.10.1991, p. 8229-8242.

Research output: Contribution to journalArticle

Murakami, Y, Kikuchi, JI, Ohno, T, Hirayama, T, Hisaeda, Y, Nishimura, H, Snyder, JP, Steliou, K, Murakami, Y, Kikuchi, JI, Ohno, T, Hirayama, T, Hisaeda, Y, Nishimura, H, Kikuchi, JI, Snyder, JP & Steliou, K 1991, 'Syntheses of Macrocyclic Enzyme Models. 8. Conformational Mobility and Molecular Recognition by the Internal Cage of Kyuphane', Journal of the American Chemical Society, vol. 113, no. 22, pp. 8229-8242. https://doi.org/10.1021/ja00022a006
Murakami, Yukito ; Kikuchi, Jun Ichi ; Ohno, Teruhisa ; Hirayama, Takayuki ; Hisaeda, Yoshio ; Nishimura, Hiroshi ; Snyder, James P. ; Steliou, Kosta ; Murakami, Yukito ; Kikuchi, Jun Ichi ; Ohno, Teruhisa ; Hirayama, Takayuki ; Hisaeda, Yoshio ; Nishimura, Hiroshi ; Kikuchi, Jun Ichi ; Snyder, James P. ; Steliou, Kosta. / Syntheses of Macrocyclic Enzyme Models. 8. Conformational Mobility and Molecular Recognition by the Internal Cage of Kyuphane. In: Journal of the American Chemical Society. 1991 ; Vol. 113, No. 22. pp. 8229-8242.
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abstract = "Temperature-dependent 1 H NMR measurements in CDC13 −CS2 (3:7 v/v) and DMF-d7 in concert with MM2 conformational analysis reveal that the molecular framework of “Kyuphane” (1), a cage-type cubical molecule with six faces each consisting of a 2, 1l,20, 29-tetraaza[3.3.3.3]paracyclophane ring, is significantly more rigid than the corresponding noncage host (2), but still conformationally flexible. A slow rate of interconversion among degenerated conformers of the lowest energy C, conformation accounts for the observed NMR line broadening. Hosts 1 and 2 are soluble in acidic aqueous media below pH 4 and behave as polycationic species. Electrostatic field solvation analysis of the tetraprotonated salt of Kyuphane suggests a square-planar proton placement (11a) to predominate in solution. Line broadening for the tetracation appears to arise from both conformer interconversion and proton exchange. Guest recognition behavior of these hosts under acidic conditions was studied by means of 1 H NMR and fluorescence spectroscopy. Kyuphane demonstrates a pH-dependent guest-binding ability due to changes in the specific microenvironmental polarity of its three-dimensional cavity upon variable protonation of the nitrogen atoms. The host also shows size-sensitive and regioselective molecular discrimination originating from the semirigid geometry of the hydrophobic cavity and the specific protonation geometry. The specific molecular discrimination evidenced by 1 was analyzed by MM2 molecular mechanics and applied to selective transport of hydrophobic molecules between organic phases across an aqueous phase in which 1 was present as a carrier. It is noteworthy that the proton NMR signals of guest molecules naphthalene-2,6-disulfonate, 8-anilinonaphthalene-l-sulfonate, and 6-p-toluidinonaphthalene-2-sulfonate completely disappear upon complexation with Kyuphane, whereas the identical guest naphthalene-2,6-disulfonate shows normal upfield shifts of its NMR proton signals upon complexation with 2.",
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