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Tetranucleotides as a scaffold for diporphyrin arrays

Tetranucleotides as a scaffold for diporphyrin arrays
Tetranucleotides as a scaffold for diporphyrin arrays
The incorporation of porphyrin-substituted nucleosides into tetranucleotides using phosphoramidite chemistry on solid support is reported. Both diphenyl and tetraphenyl porphyrin nucleosides were used as building blocks. This method allows the synthesis of chiral homo- and heteroporphyrinic arrays, where the composition and thus the physical properties of the array can be modulated simply by reprogramming the DNA synthesizer. The porphyrin arrays are initially isolated in the free-base form. Remetallation to give the zinc-porphyrins can be achieved using standard procedures in solution. The UV-vis spectra of the arrays are reproducible by a superposition of the absorbance spectra of the individual porphyrins, indicating an undisturbed electronic ground state of the porphyrins in the arrays. The same is true for the steady-state emission spectra of the homoporphyrinic arrays, which are not influenced by the presence of the nucleotide strand. In the mixed porphyrin arrays, large differences in the excited-state properties compared to an equimolar mixture of the building blocks are observed by means that the emission of the diphenyl porphyrin moiety is quenched to a large extent, and the overall emission is dominated by the tetraphenyl porphyrin. The covalent connection of the porphyrins via the DNA-derived backbone therefore substantially alters the excited-state and energy-transfer properties of mixed porphyrin systems. The circular dichroism (CD) spectra show induced negative cotton effects in the region of the porphyrin B-band absorption, which is due to the attachment of the chromophores to the chiral oligonucleotide backbone. Addition of a complementary tetra-adenosine did not alter any of the spectroscopic properties, neither in chloroform nor in acetonitrile solutions. Therefore, it can be concluded that no duplex is formed, which is corroborated by H-1 NMR spectroscopy.
porphyrin, modified nucleotides, phosphoramidite, heteroporphyrinic arrays, homoporphyrinic arrays, energy transfer zinc porphyrin host, energy-transfer, chiral recognition, exciton migration, building-blocks, single dna, cd, oligonucleotides, nanotechnology, spectroscopy
0033-4545
2003-2014
Bouamaied, Imenne
9938a8f5-740f-4c9c-9285-8a16a43a5fe5
Fendt, Leslie-Anne
4d792d3c-b84e-4ff4-bd59-ca56b0d3ddf7
Wiesner, Markus
6301a8c9-3896-4403-b477-f665ab78cb17
Häussinger, Daniel
5e90e1cc-8447-42ea-9e29-35f41883c030
Amiot, Nicolas
43e27be1-78da-4040-8f3a-d316bb4a02be
Thöni, Sandra
f7e8f927-defc-4c9c-863e-7b8275cc632d
Stulz, Eugen
9a6c04cf-32ca-442b-9281-bbf3d23c622d
Bouamaied, Imenne
9938a8f5-740f-4c9c-9285-8a16a43a5fe5
Fendt, Leslie-Anne
4d792d3c-b84e-4ff4-bd59-ca56b0d3ddf7
Wiesner, Markus
6301a8c9-3896-4403-b477-f665ab78cb17
Häussinger, Daniel
5e90e1cc-8447-42ea-9e29-35f41883c030
Amiot, Nicolas
43e27be1-78da-4040-8f3a-d316bb4a02be
Thöni, Sandra
f7e8f927-defc-4c9c-863e-7b8275cc632d
Stulz, Eugen
9a6c04cf-32ca-442b-9281-bbf3d23c622d

Bouamaied, Imenne, Fendt, Leslie-Anne, Wiesner, Markus, Häussinger, Daniel, Amiot, Nicolas, Thöni, Sandra and Stulz, Eugen (2006) Tetranucleotides as a scaffold for diporphyrin arrays. Pure and Applied Chemistry, 78 (11), 2003-2014. (doi:10.1351/pac200678112003).

Record type: Article

Abstract

The incorporation of porphyrin-substituted nucleosides into tetranucleotides using phosphoramidite chemistry on solid support is reported. Both diphenyl and tetraphenyl porphyrin nucleosides were used as building blocks. This method allows the synthesis of chiral homo- and heteroporphyrinic arrays, where the composition and thus the physical properties of the array can be modulated simply by reprogramming the DNA synthesizer. The porphyrin arrays are initially isolated in the free-base form. Remetallation to give the zinc-porphyrins can be achieved using standard procedures in solution. The UV-vis spectra of the arrays are reproducible by a superposition of the absorbance spectra of the individual porphyrins, indicating an undisturbed electronic ground state of the porphyrins in the arrays. The same is true for the steady-state emission spectra of the homoporphyrinic arrays, which are not influenced by the presence of the nucleotide strand. In the mixed porphyrin arrays, large differences in the excited-state properties compared to an equimolar mixture of the building blocks are observed by means that the emission of the diphenyl porphyrin moiety is quenched to a large extent, and the overall emission is dominated by the tetraphenyl porphyrin. The covalent connection of the porphyrins via the DNA-derived backbone therefore substantially alters the excited-state and energy-transfer properties of mixed porphyrin systems. The circular dichroism (CD) spectra show induced negative cotton effects in the region of the porphyrin B-band absorption, which is due to the attachment of the chromophores to the chiral oligonucleotide backbone. Addition of a complementary tetra-adenosine did not alter any of the spectroscopic properties, neither in chloroform nor in acetonitrile solutions. Therefore, it can be concluded that no duplex is formed, which is corroborated by H-1 NMR spectroscopy.

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More information

Published date: 2006
Keywords: porphyrin, modified nucleotides, phosphoramidite, heteroporphyrinic arrays, homoporphyrinic arrays, energy transfer zinc porphyrin host, energy-transfer, chiral recognition, exciton migration, building-blocks, single dna, cd, oligonucleotides, nanotechnology, spectroscopy

Identifiers

Local EPrints ID: 44391
URI: http://eprints.soton.ac.uk/id/eprint/44391
ISSN: 0033-4545
PURE UUID: 30e6fac5-4e09-4446-b2b3-b6d0c2865a12
ORCID for Eugen Stulz: ORCID iD orcid.org/0000-0002-5302-2276

Catalogue record

Date deposited: 01 Mar 2007
Last modified: 10 Dec 2019 01:43

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