Abdalla S, Obaid A, Al-Marzouki F M
Department of Physics, Faculty of Science, King Abdulaziz University Jeddah, P.O. Box 80203, Jeddah, 21589, Saudi Arabia.
Department of Chemistry, Faculty of Science, King Abdulaziz University Jeddah, P.O. Box 80203, Jeddah, 21589, Saudi Arabia.
Nanoscale Res Lett. 2017 Dec;12(1):316. doi: 10.1186/s11671-017-2076-y. Epub 2017 Apr 27.
Deoxyribonucleic acid (DNA) is one of the best candidate materials for various device applications such as in electrodes for rechargeable batteries, biosensors, molecular electronics, medical- and biomedical-applications etc. Hence, it is worthwhile to examine the mechanism of charge transport in the DNA molecule, however, still a question without a clear answer is DNA a molecular conducting material (wire), semiconductor, or insulator? The answer, after the published data, is still ambiguous without any confirmed and clear scientific answer. DNA is found to be always surrounded with different electric charges, ions, and dipoles. These surrounding charges and electric barrier(s) due to metallic electrodes (as environmental factors (EFs)) play a substantial role when measuring the electrical conductivity through λ-double helix (DNA) molecule suspended between metallic electrodes. We found that strong frequency dependence of AC-complex conductivity comes from the electrical conduction of EFs. This leads to superimposing serious incorrect experimental data to measured ones.
At 1 MHz, we carried out a first control experiment on electrical conductivity with and without the presence of DNA molecule. If there are possible electrical conduction due to stray ions and contribution of substrate, we will detected them. This control experiment revealed that there is an important role played by the environmental-charges around DNA molecule and any experiment should consider this role.
We have succeeded to measure both electrical conductivity due to EFs (σ ) and electrical conductivity due to DNA molecule (σ ) independently by carrying the measurements at different DNA-lengths and subtracting the data. We carried out measurements as a function of frequency (f) and temperature (T) in the ranges 0.1 Hz < f < 1 MHz and 288 K < T < 343 K. The measured conductivity (σ ) portrays a metal-like behavior at high frequencies near 1 MHz. However, we found that σ was far from this behavior because the conduction due to EFs superimposes σ , in particular at low frequencies. By measuring the electrical conductivity at different lengths: 40, 60, 80, and 100 nm, we have succeeded not only to separate the electrical conduction of the DNA molecule from all EFs effects that surround the molecule, but also to present accurate values of σ and the dielectric constant of the molecule ε' as a function of temperature and frequency. Furthermore, in order to explain these data, we present a model describing the electrical conduction through DNA molecule: DNA is a classical semiconductor with charges, dipoles and ions that result in creation of localized energy-states (LESs) in the extended bands and in the energy gap of the DNA molecule.
This model explains clearly the mechanism of charge transfer mechanism in the DNA, and it sheds light on why the charge transfer through the DNA can lead to insulating, semiconducting, or metallic behavior on the same time. The model considers charges on DNA, in the extended bands, either could be free to move under electric field or localized in potential wells/hills. Localization of charges in DNA is an intrinsic structural-property of this solitaire molecule. At all temperatures, the expected increase in thermal-induced charge is attributed to the delocalization of holes (or/and electrons) in potential hills (or/and potential wells) which accurately accounts for the total electric and dielectric behavior through DNA molecule. We succeeded to fit the experimental data to the proposed model with reasonable magnitudes of potential hills/wells that are in the energy range from 0.068 eV.
脱氧核糖核酸(DNA)是用于各种器件应用的最佳候选材料之一,如用于可充电电池的电极、生物传感器、分子电子学、医学和生物医学应用等。因此,研究DNA分子中的电荷传输机制是很有价值的。然而,一个尚未得到明确答案的问题是:DNA是分子导电材料(导线)、半导体还是绝缘体?根据已发表的数据,答案仍然不明确,没有任何得到证实的清晰科学答案。人们发现DNA总是被不同的电荷、离子和偶极所包围。当测量通过悬浮在金属电极之间的λ-双螺旋(DNA)分子的电导率时,这些周围的电荷以及由于金属电极(作为环境因素(EFs))产生的电屏障起着重要作用。我们发现交流复电导率的强烈频率依赖性来自于环境因素的导电。这导致将严重错误的实验数据叠加到测量数据上。
在1MHz频率下,我们进行了第一个对照实验,测量有无DNA分子时的电导率。如果存在由于杂散离子和基底贡献而产生的可能导电情况,我们将检测到它们。这个对照实验表明DNA分子周围的环境电荷起着重要作用,任何实验都应考虑这一作用。
我们通过在不同DNA长度下进行测量并减去数据,成功地分别测量了由于环境因素产生的电导率(σ )和由于DNA分子产生的电导率(σ )。我们在0.1Hz<f<1MHz和288K<T<343K的频率和温度范围内进行了测量。测得的电导率(σ )在接近1MHz的高频下呈现出类似金属的行为。然而,我们发现σ 并非如此,因为环境因素的导电叠加在σ 上,特别是在低频时。通过测量40、60、80和100nm不同长度下的电导率,我们不仅成功地将DNA分子的导电与围绕该分子的所有环境因素的影响区分开来,还给出了σ 的准确值以及分子的介电常数ε'作为温度和频率的函数。此外,为了解释这些数据,我们提出了一个描述通过DNA分子导电的模型:DNA是一种经典半导体,其电荷、偶极和离子导致在扩展能带和DNA分子的能隙中产生局域能态(LESs)。
该模型清楚地解释了DNA中的电荷转移机制,并揭示了为什么通过DNA的电荷转移会同时导致绝缘、半导体或金属行为。该模型考虑了DNA上的电荷,在扩展能带中,这些电荷要么可以在电场下自由移动,要么定域在势阱/势垒中。DNA中电荷的定域是这种单分子的固有结构特性。在所有温度下,热诱导电荷的预期增加归因于势垒(或/和势阱)中空穴(或/和电子)的离域,这准确地解释了通过DNA分子的总电行为和介电行为。我们成功地将实验数据与所提出的模型进行了拟合,势垒/势阱的合理幅度在0.068eV的能量范围内。