Heterobimetallic Base Pair Programming in Designer 3D DNA Crystals
Heterobimetallic Base Pair Programming in Designer 3D DNA Crystals
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DOI：
10.1021/jacs.3c05478
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发表时间：
2023-08-02
影响因子：
15
通讯作者：
Vecchioni，Simon
中科院分区：
文献类型：
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作者：
Lu，Brandon;Ohayon，Yoel P.;Vecchioni，Simon
金属介导的DNA（mmDNA）提出了一种途径，工程生物无机和电子行为到DNA设备。许多化学和生物物理力驱动嘧啶碱基对之间的可编程金属螯合。在这里，我们开发了一种晶体学方法，使用三维（3D）DNA张力整体三角形基序，以捕获单金属和多金属结合模式的颗粒变化，环境pH值使用异常散射。利用这种可编程晶体，我们确定了28种生物分子结构来捕获mmDNA反应。我们发现，银（I）在升高的pH水平下结合T-T和U-U对中的占有率增加，并且我们利用这一点来捕获相同碱基对内的银（I）和汞（II），并分离同金属和异金属碱基对模式的滴定点。此外，我们还确定了银（I）和汞（II）的C-C对结构。最后，我们扩展我们的范例，以捕获镉（II）在T-T对与汞（II）在高pH值。在亚纳米尺度的杂原子DNA化学的精确自组装将使原子的设计框架更精细的mmDNA为基础的纳米器件和纳米技术。
Metal-mediated DNA (mmDNA) presents a pathway toward engineering bioinorganic and electronic behavior into DNA devices. Many chemical and biophysical forces drive the programmable chelation of metals between pyrimidine base pairs. Here, we developed a crystallographic method using the three-dimensional (3D) DNA tensegrity triangle motif to capture single- and multi-metal binding modes across granular changes to environmental pH using anomalous scattering. Leveraging this programmable crystal, we determined 28 biomolecular structures to capture mmDNA reactions. We found that silver(I) binds with increasing occupancy in T–T and U–U pairs at elevated pH levels, and we exploited this to capture silver(I) and mercury(II) within the same base pair and to isolate the titration points for homo- and heterometal base pair modes. We additionally determined the structure of a C–C pair with both silver(I) and mercury(II). Finally, we extend our paradigm to capture cadmium(II) in T–T pairs together with mercury(II) at high pH. The precision self-assembly of heterobimetallic DNA chemistry at the sub-nanometer scale will enable atomistic design frameworks for more elaborate mmDNA-based nanodevices and nanotechnologies.