Strong Positive Allosterism which Appears in Molecular Recognition with Cerium(IV) Double Decker Porphyrins: 'Correlation between the Number of Binding Sites and Hill Coefficients

Masato Ikeda, Masayuki Takeuchi, Atsushi Sugasaki, Andrew Robertson, Tomoyuki Imada, Seiji Shinkai

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Abstract

Cerium(IV) double decker porphyrins bearing one-to-four pairs of 4-pyridyl groups (3a, 3a′, 3bp, 3bd, 3c, and 3d) were synthesized from tetraarylporphyrins bearing mono-, bis-, tris-, and tetrakis(4-pyridyl) groups. In 3b bearing two pairs of 4-pyridyl groups, there exist two isomers in which the 4-pyridyl groups are either proximal or distal (3bp and 3bd, respectively). In a mixed solvent of dichloromethane: ethyl acetate (30:1 v/v), 3a′ bearing one pair of 4-pyridyl groups and three pairs of phenyl groups did not interact with any dicarboxylic acids whereas 3d bearing four pairs of 4-pyridyl groups interacted only with dicarboxylic acid guests with a dimethylene spacer [e.g., BOC-L-aspartic acid (L-4) and (1R,2R)-cyclohexane-1,2-dicarboxylic acid ((1R,2R)-5)]. Interestingly, the complexation process monitored by CD spectroscopy showed a positive homotropic allosterism which satisfied the Hill equation giving constants K = 2.63×1011M-4 and n = 3.9 for L-4 and K = 2.75×109 M-4 and n = 4.0 for (1R,2R)-5. The continuous variation plots (Job plots) also supported the formation of the 1:4 3d/dicarboxylic acid guest complexes. The results consistently indicate that four pairs of 4-pyridyl groups in 3d allosterically bind these guests. In 3d, the two porphyrin rings can still rotate, but once the rotation is suppressed by the first guest binding, the subsequent binding of the second, third and fourth guests can occur cooperatively. This is the origin of the present positive homotoropic allosterism. A similar positive homotropic allosterism was also observed for 3bp and 3bd with n = 1.5 and 1.7, respectively and 3c with n = 3.0. The X-ray crystallographic study of the 3d·[(1R,2R)-5]4 complex showed that the two porphyrin planes are warped outward to relax the electrostatic repulsion and chirally twisted. The two carboxylic acid groups form intermolecular hydrogen bonds (but not intramolecular bridge-type hydrogen bonds) with the pyridyl groups because of the close packing effect of rigid host 3d and rigid guest (1R,2R)-5. In conclusion, this is a rare example of positive homotropic allosterism in an artificial system which is frequently seen in nature where the biological events must be efficiently regulated in response to signals.

Original languageEnglish
Pages (from-to)321-345
Number of pages25
JournalSupramolecular Chemistry
Volume12
Issue number3
DOIs
Publication statusPublished - Jan 1 2000

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Bearings (structural)
Cerium
Molecular recognition
Porphyrins
Dicarboxylic Acids
Binding Sites
Hydrogen bonds
Methylene Chloride
Carboxylic Acids
Complexation
Aspartic Acid
Isomers
Electrostatics
Spectroscopy
X rays

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Strong Positive Allosterism which Appears in Molecular Recognition with Cerium(IV) Double Decker Porphyrins : 'Correlation between the Number of Binding Sites and Hill Coefficients. / Ikeda, Masato; Takeuchi, Masayuki; Sugasaki, Atsushi; Robertson, Andrew; Imada, Tomoyuki; Shinkai, Seiji.

In: Supramolecular Chemistry, Vol. 12, No. 3, 01.01.2000, p. 321-345.

Research output: Contribution to journalArticle

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abstract = "Cerium(IV) double decker porphyrins bearing one-to-four pairs of 4-pyridyl groups (3a, 3a′, 3bp, 3bd, 3c, and 3d) were synthesized from tetraarylporphyrins bearing mono-, bis-, tris-, and tetrakis(4-pyridyl) groups. In 3b bearing two pairs of 4-pyridyl groups, there exist two isomers in which the 4-pyridyl groups are either proximal or distal (3bp and 3bd, respectively). In a mixed solvent of dichloromethane: ethyl acetate (30:1 v/v), 3a′ bearing one pair of 4-pyridyl groups and three pairs of phenyl groups did not interact with any dicarboxylic acids whereas 3d bearing four pairs of 4-pyridyl groups interacted only with dicarboxylic acid guests with a dimethylene spacer [e.g., BOC-L-aspartic acid (L-4) and (1R,2R)-cyclohexane-1,2-dicarboxylic acid ((1R,2R)-5)]. Interestingly, the complexation process monitored by CD spectroscopy showed a positive homotropic allosterism which satisfied the Hill equation giving constants K = 2.63×1011M-4 and n = 3.9 for L-4 and K = 2.75×109 M-4 and n = 4.0 for (1R,2R)-5. The continuous variation plots (Job plots) also supported the formation of the 1:4 3d/dicarboxylic acid guest complexes. The results consistently indicate that four pairs of 4-pyridyl groups in 3d allosterically bind these guests. In 3d, the two porphyrin rings can still rotate, but once the rotation is suppressed by the first guest binding, the subsequent binding of the second, third and fourth guests can occur cooperatively. This is the origin of the present positive homotoropic allosterism. A similar positive homotropic allosterism was also observed for 3bp and 3bd with n = 1.5 and 1.7, respectively and 3c with n = 3.0. The X-ray crystallographic study of the 3d·[(1R,2R)-5]4 complex showed that the two porphyrin planes are warped outward to relax the electrostatic repulsion and chirally twisted. The two carboxylic acid groups form intermolecular hydrogen bonds (but not intramolecular bridge-type hydrogen bonds) with the pyridyl groups because of the close packing effect of rigid host 3d and rigid guest (1R,2R)-5. In conclusion, this is a rare example of positive homotropic allosterism in an artificial system which is frequently seen in nature where the biological events must be efficiently regulated in response to signals.",
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AU - Takeuchi, Masayuki

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AU - Imada, Tomoyuki

AU - Shinkai, Seiji

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N2 - Cerium(IV) double decker porphyrins bearing one-to-four pairs of 4-pyridyl groups (3a, 3a′, 3bp, 3bd, 3c, and 3d) were synthesized from tetraarylporphyrins bearing mono-, bis-, tris-, and tetrakis(4-pyridyl) groups. In 3b bearing two pairs of 4-pyridyl groups, there exist two isomers in which the 4-pyridyl groups are either proximal or distal (3bp and 3bd, respectively). In a mixed solvent of dichloromethane: ethyl acetate (30:1 v/v), 3a′ bearing one pair of 4-pyridyl groups and three pairs of phenyl groups did not interact with any dicarboxylic acids whereas 3d bearing four pairs of 4-pyridyl groups interacted only with dicarboxylic acid guests with a dimethylene spacer [e.g., BOC-L-aspartic acid (L-4) and (1R,2R)-cyclohexane-1,2-dicarboxylic acid ((1R,2R)-5)]. Interestingly, the complexation process monitored by CD spectroscopy showed a positive homotropic allosterism which satisfied the Hill equation giving constants K = 2.63×1011M-4 and n = 3.9 for L-4 and K = 2.75×109 M-4 and n = 4.0 for (1R,2R)-5. The continuous variation plots (Job plots) also supported the formation of the 1:4 3d/dicarboxylic acid guest complexes. The results consistently indicate that four pairs of 4-pyridyl groups in 3d allosterically bind these guests. In 3d, the two porphyrin rings can still rotate, but once the rotation is suppressed by the first guest binding, the subsequent binding of the second, third and fourth guests can occur cooperatively. This is the origin of the present positive homotoropic allosterism. A similar positive homotropic allosterism was also observed for 3bp and 3bd with n = 1.5 and 1.7, respectively and 3c with n = 3.0. The X-ray crystallographic study of the 3d·[(1R,2R)-5]4 complex showed that the two porphyrin planes are warped outward to relax the electrostatic repulsion and chirally twisted. The two carboxylic acid groups form intermolecular hydrogen bonds (but not intramolecular bridge-type hydrogen bonds) with the pyridyl groups because of the close packing effect of rigid host 3d and rigid guest (1R,2R)-5. In conclusion, this is a rare example of positive homotropic allosterism in an artificial system which is frequently seen in nature where the biological events must be efficiently regulated in response to signals.

AB - Cerium(IV) double decker porphyrins bearing one-to-four pairs of 4-pyridyl groups (3a, 3a′, 3bp, 3bd, 3c, and 3d) were synthesized from tetraarylporphyrins bearing mono-, bis-, tris-, and tetrakis(4-pyridyl) groups. In 3b bearing two pairs of 4-pyridyl groups, there exist two isomers in which the 4-pyridyl groups are either proximal or distal (3bp and 3bd, respectively). In a mixed solvent of dichloromethane: ethyl acetate (30:1 v/v), 3a′ bearing one pair of 4-pyridyl groups and three pairs of phenyl groups did not interact with any dicarboxylic acids whereas 3d bearing four pairs of 4-pyridyl groups interacted only with dicarboxylic acid guests with a dimethylene spacer [e.g., BOC-L-aspartic acid (L-4) and (1R,2R)-cyclohexane-1,2-dicarboxylic acid ((1R,2R)-5)]. Interestingly, the complexation process monitored by CD spectroscopy showed a positive homotropic allosterism which satisfied the Hill equation giving constants K = 2.63×1011M-4 and n = 3.9 for L-4 and K = 2.75×109 M-4 and n = 4.0 for (1R,2R)-5. The continuous variation plots (Job plots) also supported the formation of the 1:4 3d/dicarboxylic acid guest complexes. The results consistently indicate that four pairs of 4-pyridyl groups in 3d allosterically bind these guests. In 3d, the two porphyrin rings can still rotate, but once the rotation is suppressed by the first guest binding, the subsequent binding of the second, third and fourth guests can occur cooperatively. This is the origin of the present positive homotoropic allosterism. A similar positive homotropic allosterism was also observed for 3bp and 3bd with n = 1.5 and 1.7, respectively and 3c with n = 3.0. The X-ray crystallographic study of the 3d·[(1R,2R)-5]4 complex showed that the two porphyrin planes are warped outward to relax the electrostatic repulsion and chirally twisted. The two carboxylic acid groups form intermolecular hydrogen bonds (but not intramolecular bridge-type hydrogen bonds) with the pyridyl groups because of the close packing effect of rigid host 3d and rigid guest (1R,2R)-5. In conclusion, this is a rare example of positive homotropic allosterism in an artificial system which is frequently seen in nature where the biological events must be efficiently regulated in response to signals.

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