Duplex Stabilization and Energy Transfer in Zipper Porphyrin-DNA
Duplex Stabilization and Energy Transfer in Zipper Porphyrin-DNA
复制标题
拉链卟啉-DNA 中的双链体稳定性和能量转移
DOI：
10.1002/ange.200805657
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发表时间：
2009
影响因子：
--
通讯作者：
Nguyen T
中科院分区：
文献类型：
--
作者：
Nguyen T
The use of functionalized DNA in the construction of new materials for potential nanotechnological applications is becoming more and more widespread.[1] In particular, the site-specific incorporation of fluorophores or metal complexes into DNA has led to the creation of supramolecular arrays with promising properties in optoelectronics. Both the interior [2] and exterior [3] of the DNA or RNA duplex are being used for attachment of modifications, and DNA proves to be a versatile supramolecular scaffold to create helical arrays of functional entities. Since our initial proposal to use DNA as a scaffold for porphyrin arrays [4] as compared to noncovalent assemblies,[5] we have studied both tetraphenylporphyrin (TPP) and diphenylporphyrin (DPP)-substituted DNA [6] and found significant differences in the thermal stability and the electronic properties of the multiporphyrin systems.[7, 8] The attachment of substituents on one strand has an especially profound impact on the stability of the DNA duplex. In contrast to this one-strand modification, individual porphyrins,[9, 10] metal-chelating ligands,[11] and pyrene–perylene systems [12] have been attached to both complementary strands, which leads to new supramolecular systems after hybridization. The design of longer zipper arrays based on an RNA or DNA scaffold, which have been reported by the groups of Wengel,[13] Leumann,[14] Häner,[15] and Wagenknecht,[16] is also very intriguing. Herein, we report that mixed porphyrin arrays can be created through a zipper-like arrangement by modifying both complementary strands, which can lead to a stabilization of the DNA duplex and resonance energy transfer between the chromophores after hybridization.The two porphyrin-modified deoxyuridines, in which a diphenylporphyrin (dU2HDPP, 1) or a tetraphenylporphyrin (dU2HTPP, 2) are attached to the 5-position of the nucleobase, can be incorporated into DNA using standard solid-phase synthesis (Scheme 1). The destabilization of the DNA duplex in the one-strand-modified DNA is highly dependent on the nature, the number and the sequence of the porphyrin modification. In all cases we found a leveling of the
