Introducing structural flexibility into porphyrin-DNA zipper arrays
Introducing structural flexibility into porphyrin-DNA zipper arrays
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DOI：
10.1039/c0ob00535e
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发表时间：
2011-01-01
影响因子：
3.2
通讯作者：
Stulz, Eugen
中科院分区：
文献类型：
--
作者：
Brewer, Ashley;Siligardi, Guiliano;Stulz, Eugen
一个更灵活的核苷酸构建块合成新的DNA为基础的卟啉拉链阵列描述。将卟啉取代基和2'-脱氧尿嘧啶之间的刚性乙炔连接改为更灵活的含有连接的丙炔酰胺，部分地增加了双相稳定性。CD光谱揭示了卟啉之间不同的电子相互作用，这取决于所使用的连接剂的类型。分子模型表明，在DNA的主要凹槽内，卟啉的相对取向有很大的变化。卟啉可以在合成后用不同的金属进行金属化，如锌、钴和铜。除CD光谱外，金属化后的光谱特征不会发生剧烈变化，金属配合物的稳定性高度依赖于金属的性质。CD谱分析表明，卟啉锌在高温下快速脱金属。用SAXS测定球状结构表明，由2到4个螺旋束组成的分子组装在高浓度溶液中占主导地位（>= 50 μ M），而在较低浓度(
A more flexible nucleotide building block for the synthesis of new DNA based porphyrin-zipper arrays is described. Changing the rigid acetylene linker between the porphyrin substituent and the 2'-deoxyuridine to a more flexible propargyl amide containing linkage leads in part to an increased duplex stability. The CD spectra reveal different electronic interactions between the porphyrins depending on the type of linker used. Molecular modelling suggests large variation of the relative orientation of the porphyrins within the major groove of the DNA. The porphyrins can be metallated post-synthetically with different metals as shown with zinc, cobalt and copper. The spectroscopic features do not alter drastically upon metallation apart from the CD spectra, and the stability of the metal complex is highly dependent on the nature of the metal. As shown by CD spectroscopy, the zinc porphyrin is rapidly demetallated at high temperatures. Globular structure determination using SAXS indicates that a molecular assembly comprised of a two to four helical bundle dominates in solution at higher concentrations (>= 50 mu M) which is not observed by spectroscopy at lower concentrations (