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Interstrand Charge Transport within Metallo-DNA: the Effect Due to Hg(II)- and Ag(I)-Mediated Base Pairs
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2020-03-24 , DOI: 10.1021/acs.jpcc.9b12020 Jakub Šebera 1 , David Řeha 2 , Jiří Fukal 1 , Vladimír Sychrovský 1, 3
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2020-03-24 , DOI: 10.1021/acs.jpcc.9b12020 Jakub Šebera 1 , David Řeha 2 , Jiří Fukal 1 , Vladimír Sychrovský 1, 3
Affiliation
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Metallo-DNA is considered promising in regard to functional molecular electronic elements. From this perspective, the longitudinal charge transport within metallo-DNA is usually studied. By contrast, this work was aimed at the transversal conductance of metallo-DNA, particularly at the effect of Hg and Ag metals on the conductance of base pairs. The charge transport through metal-mediated base pairs involving Hg(II) and Ag(I) metals, deoxythymidine (T) and 4-deoxythiothymidine (Ts), was studied by means of density functional theory (DFT) calculations employing the non-equilibrium Green’s function (NEGF) method and electronic coupling calculations. The calculations showed that the conductance along the base-to-base charge transport pathway was significantly enhanced mainly due to the Hg(II)-mediated linkage. This work further showed that not only the metals within the metallo-base pair but also the substitution of the O4 atom in deoxythymidine by sulfur (the Ts nucleoside) enhanced molecular conductance as in the case of Ts–Ag(I)2–Ts. The bias charge transport for T–Ag(I)2–T was less effective than the transport for a TT mismatched base pair. The Ag orbitals participated in the highest occupied molecular orbital (HOMO) of T–Ag(I)2–T and Ts–Ag(I)2–Ts in contrast to negligible participation of Hg orbitals in the HOMO of T–Hg(II)–T. Therefore, a Coulomb blockade effect can be assumed particularly for Ag-mediated base pairs as was apparent from the plateau obtained for the calculated I/V dependencies. The Ag-mediated base pairs can, thus, be potentially utilized as molecular transistors. In addition, the metallo-base pairs anchored to gold electrodes mediated by sulfur preferred hole transport against the electron transport mechanism. This work highlighted the importance of electronic compatibility between the organic DNA scaffold and a particular metal that is essential for effective charge transport through metallo-base pairs (M-base pairs).
中文翻译：
金属DNA内的链间电荷运输：由于Hg（II）和Ag（I）介导的碱基对的影响。
关于功能分子电子元件，金属DNA被认为是有前途的。从这个角度出发，通常研究金属DNA内部的纵向电荷传输。相比之下，这项工作的目的是金属DNA的横向电导，特别是汞和银金属对碱基对电导的影响。通过使用非平衡的密度泛函理论（DFT）计算研究了涉及Hg（II）和Ag（I）金属，脱氧胸苷（T）和4-脱氧硫代胸苷（Ts）的金属介导的碱基对的电荷传输。格林函数（NEGF）方法和电子耦合计算。计算表明，沿基到基电荷传输路径的电导显着增强，这主要归因于Hg（II）介导的键合。2 –Ts。T-Ag（I）2 -T的偏置电荷传输比TT不匹配的碱基对的传输效率低。Ag轨道参与了T–Ag（I）2 –T和Ts–Ag（I）2 –Ts的最高占据分子轨道（HOMO），而Hg（II）的HOMO可以忽略不计）–T。因此，尤其是对于银介导的碱基对，可以假定库仑封锁效应，这是从计算出的I / V所获得的平台上可以明显看出的依赖性。因此，Ag介导的碱基对可以潜在地用作分子晶体管。另外，锚定在硫介导的金电极上的金属-碱对相对于电子传输机理优选空穴传输。这项工作强调了有机DNA支架与特定金属之间电子兼容性的重要性，这对于通过金属碱基对（M碱基对）进行有效的电荷传输至关重要。
更新日期：2020-03-24
中文翻译：
金属DNA内的链间电荷运输：由于Hg（II）和Ag（I）介导的碱基对的影响。
关于功能分子电子元件，金属DNA被认为是有前途的。从这个角度出发，通常研究金属DNA内部的纵向电荷传输。相比之下，这项工作的目的是金属DNA的横向电导，特别是汞和银金属对碱基对电导的影响。通过使用非平衡的密度泛函理论（DFT）计算研究了涉及Hg（II）和Ag（I）金属，脱氧胸苷（T）和4-脱氧硫代胸苷（Ts）的金属介导的碱基对的电荷传输。格林函数（NEGF）方法和电子耦合计算。计算表明，沿基到基电荷传输路径的电导显着增强，这主要归因于Hg（II）介导的键合。2 –Ts。T-Ag（I）2 -T的偏置电荷传输比TT不匹配的碱基对的传输效率低。Ag轨道参与了T–Ag（I）2 –T和Ts–Ag（I）2 –Ts的最高占据分子轨道（HOMO），而Hg（II）的HOMO可以忽略不计）–T。因此，尤其是对于银介导的碱基对，可以假定库仑封锁效应，这是从计算出的I / V所获得的平台上可以明显看出的依赖性。因此，Ag介导的碱基对可以潜在地用作分子晶体管。另外，锚定在硫介导的金电极上的金属-碱对相对于电子传输机理优选空穴传输。这项工作强调了有机DNA支架与特定金属之间电子兼容性的重要性，这对于通过金属碱基对（M碱基对）进行有效的电荷传输至关重要。
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