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Increased duplex stabilization in porphyrin-LNA zipper arrays with structure dependent exciton coupling

Increased duplex stabilization in porphyrin-LNA zipper arrays with structure dependent exciton coupling
Increased duplex stabilization in porphyrin-LNA zipper arrays with structure dependent exciton coupling
Porphyrins were attached to LNA uridine building blocks via rigid 5-acetylene or more flexible propargyl-amide linkers and incorporated into DNA strands. The systems show a greatly increased thermodynamic stability when using as little as three porphyrins in a zipper arrangement. Thermodynamic analysis reveals clustering of the strands into more ordered duplexes with both greater negative ??S and ??H values, and less ordered duplexes with small positive ??S differences, depending on the combination of linkers used. The exciton coupling between the porphyrins is dependent on the flanking DNA sequence in the single stranded form, and on the nature of the linker between the nucleobase and the porphyrin in the double stranded form; it is, however, also strongly influenced by intermolecular interactions. This system is suitable for the formation of stable helical chromophore arrays with sequence and structure dependent exciton coupling.
1477-0520
1-9
Singleton, Daniel G.
6c251bf3-8ca7-478d-8870-b39705b1c5fc
Hussain, Rohanah
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Siligardi, Giuliano
ebce490a-2faa-4b98-9703-ae0d6f8e46c2
Kumar, Pawan
e6fd8cbe-4d33-49e3-bc00-99d8b1ffe428
Hrdlicka, Patrick J.
c77cd9dc-1654-4502-9909-70fd745564e0
Berova, Nina
344c6eda-4f7f-4f05-9d77-0753016c7bf3
Stulz, Eugen
9a6c04cf-32ca-442b-9281-bbf3d23c622d
Singleton, Daniel G.
6c251bf3-8ca7-478d-8870-b39705b1c5fc
Hussain, Rohanah
d46302e5-4734-4f59-9ac1-bc7b1f62693c
Siligardi, Giuliano
ebce490a-2faa-4b98-9703-ae0d6f8e46c2
Kumar, Pawan
e6fd8cbe-4d33-49e3-bc00-99d8b1ffe428
Hrdlicka, Patrick J.
c77cd9dc-1654-4502-9909-70fd745564e0
Berova, Nina
344c6eda-4f7f-4f05-9d77-0753016c7bf3
Stulz, Eugen
9a6c04cf-32ca-442b-9281-bbf3d23c622d

Singleton, Daniel G., Hussain, Rohanah, Siligardi, Giuliano, Kumar, Pawan, Hrdlicka, Patrick J., Berova, Nina and Stulz, Eugen (2015) Increased duplex stabilization in porphyrin-LNA zipper arrays with structure dependent exciton coupling. Organic & Biomolecular Chemistry, 1-9. (doi:10.1039/C5OB01681A).

Record type: Article

Abstract

Porphyrins were attached to LNA uridine building blocks via rigid 5-acetylene or more flexible propargyl-amide linkers and incorporated into DNA strands. The systems show a greatly increased thermodynamic stability when using as little as three porphyrins in a zipper arrangement. Thermodynamic analysis reveals clustering of the strands into more ordered duplexes with both greater negative ??S and ??H values, and less ordered duplexes with small positive ??S differences, depending on the combination of linkers used. The exciton coupling between the porphyrins is dependent on the flanking DNA sequence in the single stranded form, and on the nature of the linker between the nucleobase and the porphyrin in the double stranded form; it is, however, also strongly influenced by intermolecular interactions. This system is suitable for the formation of stable helical chromophore arrays with sequence and structure dependent exciton coupling.

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Accepted/In Press date: 18 September 2015
e-pub ahead of print date: 22 September 2015
Organisations: Chemistry

Identifiers

Local EPrints ID: 383495
URI: http://eprints.soton.ac.uk/id/eprint/383495
ISSN: 1477-0520
PURE UUID: 893a8a6d-1303-452e-bea6-cf2338f1fac1
ORCID for Eugen Stulz: ORCID iD orcid.org/0000-0002-5302-2276

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Date deposited: 17 Nov 2015 11:50
Last modified: 05 Nov 2019 01:47

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Contributors

Author: Daniel G. Singleton
Author: Rohanah Hussain
Author: Giuliano Siligardi
Author: Pawan Kumar
Author: Patrick J. Hrdlicka
Author: Nina Berova
Author: Eugen Stulz ORCID iD

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