Effects on the aromatic character of DNA/RNA nucleobases due to its adsorption onto graphene

Abstract

In the last years, experimental/theoretical studies have shown that graphene has a strong affinity toward nucleobases, serving as a promising nanomaterial for self-assembly, sensing, and/or sequencing of DNA/RNA constituents. Then, a complete picture of the properties of the nucleobase-graphene systems is required for its use in technological applications. This work describes a detailed quantum chemical analysis of the aromaticity of adsorbed nucleobases on graphene, comparing between aromaticity indexes based on magnetic, geometry, electron density, and electron delocalization properties of graphene-nucleobase systems. Contrary to the stated by magnetic-based aromaticity criteria (such as nucleus-independent chemical shifts), it is proved that the aromatic character of nucleobases is not increased/decreased upon binding on graphene. Therefore, magnetic aromaticity criteria are not recommended to analyze aromaticity in related systems, unless a fragmented scheme be adopted. Finally, these results are expected to expand the knowledge about the understanding of biomolecules-graphene interactions.

Probing the Interaction of Nucleobases and Fluorophore‐Tagged Nucleobases with Graphene Surface: Adsorption and Fluorescence Studies

“…The fluorophore tagged nucleobases adsorbed to the graphene surface showed enhanced aromaticity on individual rings i.e, NICS (1) and NICS (1) ZZ values turns to be more negative (Table ). This aromaticity trend is in good agreement with the previous reports . The detection of dye‐labeled nucleic acids using fluorescence has now a common technique in chemistry and biology laboratories.…”

“…The literature reports reveal that the stability trend varies with the choice of methods. Recently, Cortes‐Arriagada and Ortega investigated the aromaticity of the adsorbed nucleobases on the graphene surface and the physisorption stability follows the trend: G>A≈C>T, which is in agreement with the calculated results …”

“…The nucleobases are aromatic in nature, hence, the aromatic behavior in such bases can be diagnosed upon binding with graphene and carbon nanotube surfaces. There are reports on the aromatic behavior of nucleobases while binding with the graphene surfaces . The aromaticity of nucleobases adsorbed on the graphene surface was examined using nucleus‐independent chemical shift (NICS) using the same level of theory.…”

“…Recently, Cortes-Arriagada and Ortega investigated the aromaticity of the adsorbed nucleobases on the graphene surface and the physisorption stability follows the trend: G > A � C > T, which is in agreement with the calculated results. [54] The interaction of nucleobases with carbon nanotubes (CNT) and graphene surface using ONIOM level (M06-2X/6-31G*:AM1) of theory in the gas phase is G > A > T > C. [37] Recently, the binding of nucleobases with graphene surface (C 48 H 18 ) have investigated where the trend follows the order as G > A > T > C. [36] In general, the interaction of guanine with the graphene surface is relatively stronger compared to the other nucleobases as obtained with the computational methods in the gas phase.…”

“…[20][21][22] Computational and exper-imental studies have been investigated on the interaction of the graphene layer with the nucleobases. [21][22][23][24][25][26][27][28][29][30][31][32][33][34] From these reports, the order of stability in nucleobase-graphene systems is commonly sorted as Guanine (G) > Adenine (A) � Cytosine (C) � Thymine (T) > Uracil (U). [27,[35][36][37][38] The stability of (C, A, and T) is largely dependent on different theoretical methodologies.…”