Catalytic Formation of Luminescent Complex Clusters Based on Autonomous Strand Exchange Reaction of DNA
Catalytic Formation of Luminescent Complex Clusters Based on Autonomous Strand Exchange Reaction of DNA
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DOI：
10.1021/acsabm.9b00326
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发表时间：
2019-07-15
影响因子：
4.7
通讯作者：
Ihara, Toshihiro
中科院分区：
文献类型：
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作者：
Kitamura, Yusuke;Nozaki, Akihiro;Ihara, Toshihiro
DNA可以作为灵活的界面，将特定的反应物伙伴，如生物分子和其他修饰在DNA上的功能分子紧密连接在一起，以增加它们的有效浓度。在这里，我们专注于DNA结构的动态可编程性，其基础是由引发者DNA触发的序列特定的自主链交换反应，即DNA回路，以实现提供物理和化学信号的催化反应。在分析应用中，以DNA为模板形成的发光稀土(Ln)络合物与所述的放大系统相结合。乙二胺四乙酸(螯合剂)和1，10-菲咯啉(增敏剂)连接到组装的DNA末端形成发光络合物，为稀土离子[Ln(III)]的吸附提供了合适的微环境。对于DNA环路，我们利用杂交链反应和催化发夹组装分别构建了线形和十字形DNA结构，作为Ln簇形成的支架。这两个系统都是为在DNA支架上通过添加引发剂而组成DNA末端相对的每个位置形成复杂结构而设计的。通过对反应条件的优化，得到了Tb(III)配合物的放大发光，这表明在加入引发剂DNA后形成了大量的配合物。稀土络合物簇合物的形成可以简单地由双链杂交的热力学控制，而双链杂交的热力学可以合理地控制DNA的长度和序列、浓度、温度和离子强度等参数。通过选择具有所需颜色的Ln离子，可以很容易地改变Ln团簇的发射颜色。这项技术背后的原理很简单，因此，它可以通过用其他功能分子和材料取代稀土络合物配体来应用于各种催化DNA模板反应。
DNAs can act as flexible interfaces for arranging particular reactant partners such as biomolecules and other functional molecules modified on DNAs in close proximity to increase their effective concentrations. Here, we focused on dynamic programmability of the DNA structure based on sequence-specific autonomous strand exchange reactions triggered by an initiator DNA, i.e., DNA circuits, to achieve a catalytic reaction providing physical and chemical signals. For analytical applications, DNA-templated formation of luminescent lanthanide (Ln) complexes was combined with the described amplification system. An appropriate microenvironment for the accommodation of a lanthanide ion [Ln(III)] was constitutively generated by ethylenediaminetetraacetic acid (a chelator) and 1,10-phenanthroline (a sensitizer) tethered to the ends of assembled DNAs to form a luminescent complex. For DNA circuits, we used hybridization chain reaction and catalytic hairpin assembly to construct linear and cruciform DNA structures, respectively, as scaffolds of Ln cluster formation. Both systems were designed for complex formation at every site where the ends of constituent DNAs faced each other on the DNA scaffolds by addition of an initiator. After optimization of the reaction conditions, amplified luminescence of a Tb(III) complex was obtained, which implies formation of a large number of complexes after addition of the initiator DNA. The formation of lanthanide complex clusters can be simply governed by the thermodynamics of duplex hybridization, which can be rationally controlled by well-established parameters such as the DNA length and sequence, concentration, temperature, and ionic strength. The emission color of the Ln cluster can be easily changed by choosing Ln ions with the desired color. The principle behind this technique is simple; therefore, it can be applied to various catalytic DNA-templated reactions by replacing lanthanide complex ligands by other functional molecules and materials.