高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (2): 279.doi: 10.7503/cjcu20180673
收稿日期:
2018-10-08
出版日期:
2019-02-10
发布日期:
2018-11-26
作者简介:
联系人简介: 刘海英, 女, 博士, 副教授, 主要从事理论计算与模拟化学方面的研究. E-mail:
基金资助:
CHENG Yingying, LIU Haiying*(), TIAN Yigeng, LIU Zhongqi, LI Qingxin
Received:
2018-10-08
Online:
2019-02-10
Published:
2018-11-26
Contact:
LIU Haiying
E-mail:ss_liuhy@ujn.edu.cn
Supported by:
摘要:
利用密度泛函理论并结合非平衡态格林函数方法, 研究了腺嘌呤A的碳2位氨基修饰对DNA导电性的影响. 结果表明, 形成的双氨基嘌呤D可以与胸腺嘧啶T通过3个氢键进行配对, 由于氨基修饰形成了新的氢键, 使配对碱基D和T之间的结合比AT更紧密. 修饰后体系的能隙和电离能大大降低, 紫外吸收光谱在一定程度上会发生红移, 并增加了一些电荷转移跃迁. 计算的沿氢键方向的横向电荷输运和沿DNA链方向的纵向电荷输运性质, 证明了氨基的取代修饰可以很好地提高DNA的电荷输运性质. 揭示了DNA导电性增强是由于修饰调整了碱基对DT的最高占据轨道(HOMO)能级, 使之较天然碱基对AT更靠近GC的HOMO, 从而降低了空穴在DNA中迁移的势垒.
中图分类号:
TrendMD:
程颖颖, 刘海英, 田宜耕, 刘仲奇, 李清新. 腺嘌呤的氨基修饰增强DNA导电性的理论研究. 高等学校化学学报, 2019, 40(2): 279.
CHENG Yingying,LIU Haiying,TIAN Yigeng,LIU Zhongqi,LI Qingxin. Theoretical Study on Enhancement Effect of Amino Modification of Adenine on Conductivity of DNA†. Chem. J. Chinese Universities, 2019, 40(2): 279.
Fig.2 Schematic illustration of two-probe systems in charge transport calculation(A) The transverse charge transport model; (B) the longitudinal charge transport model.
Base and base pair | VIP/eV | AIP/eV | Edef/eV | Eb/eV |
---|---|---|---|---|
A | 8.30 | 8.11 | 0.19 | - |
D | 7.59 | 7.30 | 0.29 | - |
G | 7.94 | 7.68 | 0.26 | - |
AT | 7.87 | 7.70 | 0.17 | 0.46(0.52[ |
DT | 7.16 | 6.90 | 0.26 | 0.55 |
GC | 7.28 | 6.92(6.90[ | 0.36 | 1.00 |
Table 1 Comparison of the adiabatic ionization potentials(AIP), vertical ionization potentials(VIP), deformation energies(Edef) and binding energies(Eb)
Base and base pair | VIP/eV | AIP/eV | Edef/eV | Eb/eV |
---|---|---|---|---|
A | 8.30 | 8.11 | 0.19 | - |
D | 7.59 | 7.30 | 0.29 | - |
G | 7.94 | 7.68 | 0.26 | - |
AT | 7.87 | 7.70 | 0.17 | 0.46(0.52[ |
DT | 7.16 | 6.90 | 0.26 | 0.55 |
GC | 7.28 | 6.92(6.90[ | 0.36 | 1.00 |
Base pair | EHOMO/eV | ELUMO/eV | Egap/eV | VIP/eV |
---|---|---|---|---|
GAG | -6.35 | -0.86 | 5.49 | 6.89 |
GDG | -5.89 | -0.95 | 4.94 | 6.40 |
Table 2 Comparison of HOMO-LUMO gaps, VIP of three-layer stacked base pairs GAG and GDG, calculated by M06-2X/B3LYP*
Base pair | EHOMO/eV | ELUMO/eV | Egap/eV | VIP/eV |
---|---|---|---|---|
GAG | -6.35 | -0.86 | 5.49 | 6.89 |
GDG | -5.89 | -0.95 | 4.94 | 6.40 |
Fig.6 Absorption spectra of AT(a) and DT(b) in the ultraviolet region between 200 and 310 nm determined from the CIS resultsBlack and red solid triangles represent positions assigned to π→π* charge-transfer transition of AT and DT, respectively. H-0: HOMO, L+0: LUMO, L+3: LUMO+3, other markers are similar, and percentages represent proportions of transitions.
Fig.8 Energy levels of AT and DT junctions for the transverse transport model in the energy region of -4.0―4.0 eV under 0 and 0.5 V biasesThe average Fermi level is set as zero.
Fig.10 Transmission spectra of 3-layer stacked GAG(A) and GDG(B) junctions at zero bias for the longitudinal electronic transport modelThe dotted dots on the top of each picture represent the molecular projected self-consistent Hamiltonian(MPSH) eigenvalue positions. The solid dots represent the occupied molecular orbital energies and the hollow dots correspond to the unoccupied molecular orbital energies.
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