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Cytosine substituted calix[4]pyrroles: neutral receptors for 5'-guanosine monophosphate

Cytosine substituted calix[4]pyrroles: neutral receptors for 5'-guanosine monophosphate
Cytosine substituted calix[4]pyrroles: neutral receptors for 5'-guanosine monophosphate
The synthesis and characterization of two cytosine-substituted calix[4]pyrrole conjugates, bearing the appended cytosine attached at either a ?- or meso-pyrrolic position, is described. These systems were tested as nucleotide-selective carriers and as active components of nucleotide-sensing ion-selective electrodes at pH 6.6. Studies of carrier selectivity were made using a Pressman-type model membrane system consisting of an initial pH 6.0 aqueous phase, an intervening dichloromethane barrier containing the calix[4]pyrrole conjugate, and a receiving basic aqueous phase. Good selectivity for the Watson-Crick complementary nucleotide, 5'-guanosine monophosphate (5'-GMP), was seen in the case of the meso-linked conjugate with the relative rates of through-membrane transport being 7.7:4.1:1 for 5'-GMP, 5'-AMP, and 5'-CMP, respectively. By contrast, the ?-substituted conjugate, while showing a selectivity for 5'-GMP that was enhanced relative to unsubstituted calix[4]pyrrole, was found to transport 5'-CMP roughly 4.5 times more quickly than 5'-GMP. Higher selectivities were also found for 5'-CMP when both the ?- and meso-substituted conjugates were incorporated into polyvinyl chloride membranes and tested as ion selective electrodes at pH 6.6, whereas near-equal selectivities were observed for 5'-CMP and 5'-GMP in the case of unsubstituted calix[4]pyrroles. These seemingly disparate results are consistent with a picture wherein the meso-substituted cytosine calix[4]pyrrole conjugate, but not its ?-linked congener, is capable of acting as a ditopic receptor, binding concurrently both the phosphate anion and nucleobase portions of 5'-GMP to the calixpyrrole core and cytosine "tails" of the molecule, respectively, with the effect of this binding being most apparent under the conditions of the transport experiments.
ion-selective electrodes, anion-binding, molecular recognition, nucleotide monophosphates, enhanced transport, liquid membrane, sapphyrin, nucleosides, 1, 4, 7, 10-tetraazacyclododecane, complexation, calixpyrrole, anion binding
0027-8424
4848-4853
Sessler, Jonathan L.
d793ea76-a3a2-4ce1-a8d5-aca7d3307fbe
Král, Vladimir
5d78b97d-203c-4fd9-9a4e-fb788cd78cd1
Shishkanova, Tatiana V.
7de89e0c-027d-4424-94a4-5160797e943e
Gale, Philip A.
c840b7e9-6847-4843-91af-fa0f8563d943
Sessler, Jonathan L.
d793ea76-a3a2-4ce1-a8d5-aca7d3307fbe
Král, Vladimir
5d78b97d-203c-4fd9-9a4e-fb788cd78cd1
Shishkanova, Tatiana V.
7de89e0c-027d-4424-94a4-5160797e943e
Gale, Philip A.
c840b7e9-6847-4843-91af-fa0f8563d943

Sessler, Jonathan L., Král, Vladimir, Shishkanova, Tatiana V. and Gale, Philip A. (2002) Cytosine substituted calix[4]pyrroles: neutral receptors for 5'-guanosine monophosphate. Proceedings of the National Academy of Sciences of the United States of America, 99 (8), 4848-4853. (doi:10.1073/pnas.062633799).

Record type: Article

Abstract

The synthesis and characterization of two cytosine-substituted calix[4]pyrrole conjugates, bearing the appended cytosine attached at either a ?- or meso-pyrrolic position, is described. These systems were tested as nucleotide-selective carriers and as active components of nucleotide-sensing ion-selective electrodes at pH 6.6. Studies of carrier selectivity were made using a Pressman-type model membrane system consisting of an initial pH 6.0 aqueous phase, an intervening dichloromethane barrier containing the calix[4]pyrrole conjugate, and a receiving basic aqueous phase. Good selectivity for the Watson-Crick complementary nucleotide, 5'-guanosine monophosphate (5'-GMP), was seen in the case of the meso-linked conjugate with the relative rates of through-membrane transport being 7.7:4.1:1 for 5'-GMP, 5'-AMP, and 5'-CMP, respectively. By contrast, the ?-substituted conjugate, while showing a selectivity for 5'-GMP that was enhanced relative to unsubstituted calix[4]pyrrole, was found to transport 5'-CMP roughly 4.5 times more quickly than 5'-GMP. Higher selectivities were also found for 5'-CMP when both the ?- and meso-substituted conjugates were incorporated into polyvinyl chloride membranes and tested as ion selective electrodes at pH 6.6, whereas near-equal selectivities were observed for 5'-CMP and 5'-GMP in the case of unsubstituted calix[4]pyrroles. These seemingly disparate results are consistent with a picture wherein the meso-substituted cytosine calix[4]pyrrole conjugate, but not its ?-linked congener, is capable of acting as a ditopic receptor, binding concurrently both the phosphate anion and nucleobase portions of 5'-GMP to the calixpyrrole core and cytosine "tails" of the molecule, respectively, with the effect of this binding being most apparent under the conditions of the transport experiments.

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More information

Published date: 16 April 2002
Keywords: ion-selective electrodes, anion-binding, molecular recognition, nucleotide monophosphates, enhanced transport, liquid membrane, sapphyrin, nucleosides, 1, 4, 7, 10-tetraazacyclododecane, complexation, calixpyrrole, anion binding
Organisations: Chemistry

Identifiers

Local EPrints ID: 19849
URI: http://eprints.soton.ac.uk/id/eprint/19849
ISSN: 0027-8424
PURE UUID: 7a793bdb-8a5f-461e-a41a-862e2f976d85
ORCID for Philip A. Gale: ORCID iD orcid.org/0000-0001-9751-4910

Catalogue record

Date deposited: 22 Feb 2006
Last modified: 09 Jan 2022 03:03

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Contributors

Author: Jonathan L. Sessler
Author: Vladimir Král
Author: Tatiana V. Shishkanova
Author: Philip A. Gale ORCID iD

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