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.
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DOI:
10.1039/c5ob01681a
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发表时间:
2016-01-07
影响因子:
3.2
通讯作者:
Stulz E
Stulz E
中科院分区:
化学3区
文献类型:
--
作者:
Singleton DG;Hussain R;Siligardi G;Kumar P;Hrdlicka PJ;Berova N;Stulz E

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LNA-porphyrin building blocks were used to create stable zipper-porphyrin DNA arrays, which were analysed in detail with CD spectroscopy and thermodynamic studies. 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 ΔΔS and ΔΔH values, and less ordered duplexes with small positive ΔΔS 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.