Quantum chemical calculations reveal that the binding energy of the carbon nanotube (CNT) and DNA/RNA nucleobase complexes is controlled by the curvature of the carbon nanotube. Graphene not only has higher affinity but also appears to be best suited to differentiate various nucleobases compared with carbon nanotubes. The dispersion-corrected DFT and M06-2X functionals are in excellent agreement with the experimental observations. Interestingly, nucleus-independent chemical shift (NICS) calculations indicate substantial enhancement of aromaticity for all nucleobases upon binding to graphene and CNT.

The potential application of carbon nanomaterials in biology and medicine increases the necessity to understand the nature of their interactions with living organisms and the environment. The primary forces of interaction at the nano-bio interface are mostly noncovalent in nature. Quantifying such interactions and identifying various factors that influence such interactions is a question of outstanding fundamental interest in academia and industry. In this Account, we have summarized our recent studies in understanding the noncovalent interactions of carbon nanostructures (CNSs), which were obtained by employing first-principles calculations on various model systems representing carbon nanotubes (CNTs) and graphene. Bestowed with an extended sp(2) carbon network, which is a common feature in all of these nanostructures, they exhibit π-π interactions with aromatic molecules (benzene, naphthalene, nucleobases, amino acids), cation-π type of interactions with metal ions, anion-π interactions with anions, and other XH···π type of interactions with various small molecules (H2O, NH3, CH4, H2, etc.). CNTs are wrapped-up forms of two-dimensional graphene, and hence, it is interesting to compare the binding abilities of these two allotropes that differ in their curvature. The chirality and curvature of CNSs appear to play a major role in determining the structural, energetic, and functional properties. Flat graphene shows stronger noncovalent interactions than the curved nanotubes toward various substrates. Understanding the interactions of CNSs with organic molecules and biomolecules has gained a great deal of research interest because of their potential applications in various fields. Aromatic hydrocarbons show a strong propensity to interact with CNSs via the π-π mode of interaction rather than CH···π interaction. As DNA sequencing appears to be one of the most important potential applications of carbon nanomaterials, the study of CNS-nucleobase interactions has become quite important. The nucleobases are physisorbed on the surface of CNSs in the order G > T ≈ A > C > U, exhibiting π-π-stacking type of interaction. These interactions become stronger as the curvature of the CNSs decreases. It is also indispensable to study the interaction of nanomaterials with proteins and especially with amino acids at a molecular level to understand the drug delivery mechanism of CNSs. We have shown that the CNSs interact with small molecules by means of physisorption and thus show potential for sensor applications. The prime requisite for the exploitation of these CNSs in nanoelectronics is the tunable energy gap. We have revealed that metal ion doping modulates the HOMO-LUMO energy gap of the nanotubes significantly and thus provides a handle to tune the electronic and conductivity properties of CNTs. Moreover, metal ions tend to selectively bind with nanotubes of different chirality such as armchair and zigzag nanotubes. The reduction of planar hydrocarbon materials by lithium atoms has also been studied very systematically. We als...

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A Tröger’s base functionalized luminescent nanoscale Zn(II) coordination polymer (TB-Zn-CP) is synthesized and used as selective fluorescence sensor for phenolic nitroaromatics in water.