Departments of Chemistry, Biochemistry and Physics, Duke University, Durham, North Carolina 27708, USA.
Center of Biosensor &Bioelectronics, Biodesign Institute, Arizona State University, Tempe, Arizona 85287, USA.
Nat Chem. 2016 Oct;8(10):941-5. doi: 10.1038/nchem.2545. Epub 2016 Jun 20.
Electronic delocalization in redox-active polymers may be disrupted by the heterogeneity of the environment that surrounds each monomer. When the differences in monomer redox-potential induced by the environment are small (as compared with the monomer-monomer electronic interactions), delocalization persists. Here we show that guanine (G) runs in double-stranded DNA support delocalization over 4-5 guanine bases. The weak interaction between delocalized G blocks on opposite DNA strands is known to support partially coherent long-range charge transport. The molecular-resolution model developed here finds that the coherence among these G blocks follows an even-odd orbital-symmetry rule and predicts that weakening the interaction between G blocks exaggerates the resistance oscillations. These findings indicate how sequence can be exploited to change the balance between coherent and incoherent transport. The predictions are tested and confirmed using break-junction experiments. Thus, tailored orbital symmetry and structural fluctuations may be used to produce coherent transport with a length scale of multiple nanometres in soft-matter assemblies, a length scale comparable to that of small proteins.
电子离域在氧化还原活性聚合物中可能会被包围每个单体的环境的不均匀性所破坏。当环境引起的单体氧化还原电位的差异(与单体-单体电子相互作用相比)较小时,离域仍然存在。在这里,我们表明,鸟嘌呤(G)在双链 DNA 支架中传播,在 4-5 个鸟嘌呤碱基上离域。众所周知,在相反的 DNA 链上离域的 G 块之间的弱相互作用支持部分相干的长程电荷输运。这里开发的分子分辨率模型发现,这些 G 块之间的相干性遵循偶数-奇数轨道对称性规则,并预测削弱 G 块之间的相互作用会夸大电阻振荡。这些发现表明了如何利用序列来改变相干和非相干输运之间的平衡。使用断路实验对预测进行了测试和证实。因此,经过精心设计的轨道对称性和结构波动可以用于在软物质组装体中产生具有多个纳米长度尺度的相干输运,该长度尺度与小蛋白质相当。