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芳香族氨基酸与石墨烯及单壁碳纳米管相互作用的理论研究

A theoretical study on the interaction of aromatic amino acids with graphene and single walled carbon nanotube.

作者信息

Rajesh Chinagandham, Majumder Chiranjib, Mizuseki Hiroshi, Kawazoe Yoshiyuki

机构信息

RMC, Bhabha Atomic Research Centre, Mumbai 400 094, India.

出版信息

J Chem Phys. 2009 Mar 28;130(12):124911. doi: 10.1063/1.3079096.

Abstract

In this study we have investigated the interaction of phenylalanine (Phe), histidine (His), tyrosine (Tyr), and tryptophan (Tryp) molecules with graphene and single walled carbon nanotubes (CNTs) with an aim to understand the effect of curvature on the non-covalent interaction. The calculations are performed using density functional theory and the Moller-Plesset second-order perturbation theory (MP2) within linear combination of atomic orbitals-molecular orbital (LCAO-MO) approach. Using these methods, the equilibrium configurations of these complexes were found to be very similar, i.e., the aromatic rings of the amino acids prefer to orient in parallel with respect to the plane of the substrates, which bears the signature of weak pi-pi interactions. The binding strength follows the trend: His<Phe<Tyr<Tryp. Although the qualitative trend in binding energy is almost similar between the planar graphene and rolled nanotube structure but they differ in terms of the absolute magnitude. For the nanotube, the binding strength of these molecules is found to be weaker than the graphene sheet. To get an insight about the nature of these interactions, we have calculated the polarizability of the aromatic motifs of the amino acids. Remarkably, we find excellent correlation between the polarizability and the strength of the interaction; the higher the polarizability, greater is the binding strength. Moreover, we have analyzed the electronic densities of state spectrum before and after adsorption of the amino acid moieties. The results reveal that the Fermi level of the free CNT is red-shifted by the adsorption of the amino acids and the degree of shift is consistent with the trend in polarizability of these molecules.

摘要

在本研究中,我们研究了苯丙氨酸(Phe)、组氨酸(His)、酪氨酸(Tyr)和色氨酸(Tryp)分子与石墨烯及单壁碳纳米管(CNT)之间的相互作用,旨在了解曲率对非共价相互作用的影响。计算采用密度泛函理论以及线性组合原子轨道 - 分子轨道(LCAO - MO)方法中的莫勒 - 普莱塞特二阶微扰理论(MP2)。使用这些方法,发现这些配合物的平衡构型非常相似,即氨基酸的芳香环倾向于相对于基底平面平行排列,这体现了弱π - π相互作用的特征。结合强度遵循以下趋势:His<Phe<Tyr<Tryp。尽管平面石墨烯和卷曲纳米管结构之间结合能的定性趋势几乎相似,但它们在绝对值方面存在差异。对于纳米管,发现这些分子的结合强度比石墨烯片弱。为了深入了解这些相互作用的本质,我们计算了氨基酸芳香基序的极化率。值得注意的是,我们发现极化率与相互作用强度之间存在极好的相关性;极化率越高,结合强度越大。此外,我们分析了氨基酸部分吸附前后的电子态密度谱。结果表明,自由碳纳米管的费米能级因氨基酸的吸附而发生红移,且红移程度与这些分子的极化率趋势一致。

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