PCCP

View Article Online

PAPER View Journal
Published on 06 March 2018. Downloaded by Maharaja Sayajirao University of Baroda on 20/03/2018 11:39:35.

Nucleobases-decorated boron nitride

nanoribbons for electrochemical biosensing:
Cite this: DOI: 10.1039/c7cp08145f
a dispersion-corrected DFT study†
Shweta D. Dabhi,a Basant Roondheb and Prafulla K. Jha *b

Received 5th December 2017,
Accepted 2nd March 2018
DOI: 10.1039/c7cp08145f
rsc.li/pccp
Understanding the interactions between biomolecules and boron nitride nanostructures is key for their
use in nanobiotechnology and medical engineering. In this study, we investigated the adsorption of
nucleobases adenine (A), guanine (G), cytosine (C), thymine (T) and uracil (U) over armchair and zigzag
boron nitride nanoribbons (BNNR) using density functional theory to define the applicability of BNNR for
the sensing of nucleobases and DNA sequencing. To appropriately account for dispersion, the van der
Waals forces (DFT-D2)-type method developed by Grimme was also included in the calculations. The
calculated adsorption energy suggests the following order of adsorption for A-BNNR and Z-BNNR with
the nucleobases: G 4 T 4 A 4 U 4 C and G 4 C 4 A 4 T 4 U, respectively. The origin of the
binding of the different nucleobases with BNNR was analysed and p–p stacking was found to be respon-
sible. In addition, the electronic properties, density of states and work function significantly vary after
adsorption. These analyses indicate different binding natures for different nucleobases and BNNRs. Thus,
this study demonstrates that BNNR can be applied as biosensors for the detection of nucleobases, which
are constituents of DNA and RNA. Furthermore, analysis of electronic properties and adsorption energies
will play a key role in targeted drug delivery, enzyme activities and genome sequencing. Our results
indicate that BNNRs have better adsorption capacity than graphene and boron nitride nanotubes.

1. Introduction result in exceptional properties such as thermal stability, and

A thrust in the development of technology began after the discovery
of graphene.1–3 Graphene, a monoatomic thick layer of carbon
atoms, possesses extraordinary hidden properties, which are excep-
tionally different from its bulk counterparts. Due to graphene,
researchers were inspired to explore other materials in their 2D-
confined form. Subsequently, intense efforts of researchers led to
the development of new 2D material boron nitride sheet analogues
to graphene.4 Boron nitride (BN) has boron and nitrogen in equal
proportions, which belong to groups 13 and 15 in the periodic
table, respectively. BN has three different isomers: 3D cubic boron
nitride (c-BN), 2D hexagonal boron nitride sheet (h-BN), and 1D
boron nitride nanotube (BNNT) and boron nitride nanoribbon
(BNNR), similar to carbon.5
BNNR is a special case of boron nitride nanostructures (BNNs)
that have received attention due to their edge structures, which
a
Department of Physics, Maharaja Krishnakumarsinhji Bhavnagar University,
Bhavnagar-364 001, India
b
Department of Physics, Faculty of Science, The M. S. University of Baroda,
Vadodara-390 002, India. E-mail: prafullaj@yahoo.com,,
pk.jha-phy@msubaroda.ac.in
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c7cp08145f
electronic, optical, and magnetic properties, all of which are
superior to those of graphene nanoribbons (GNR)6 and therefore,
led to important applications. The experimental isolation of BNNR
was difficult although they were theoretically predicted in 2007.
However, Zeng et al., with the help of arc plasma etching, a
method previously used to produce GNR from CNT, succeeded
in the isolation of BNNR.7 However, Erickson et al.8 suggested a
more efficient process to form BNNR from BNNT: if potassium
metal is vaporized and intercalated on BNNT, it helps to split the
BNNT longitudinally to form BNNR with a high aspect ratio.
BNNR has different types of edges such as armchair BNNR
(A-BNNR), zigzag BNNR (Z-BNNR) and chiral, which are similar
to GNR, but their properties are tremendously different from
that of GNR due to nature of the bonding between B–N. BNNR
have hexagonal rings, which form basal planes, where each B
atom is bonded to three N atoms in the plane and vice versa.
The strong directional bonding between adjacent coplanar
atoms shows charge localization closer to the N atom than
the B atom and depending on the radii assumed for each atom,
each B atom loses 1 to 2 electrons to its three neighbouring N
atoms. The electrons in the p-orbitals are also localized closer
to the N atoms than the B atoms.9 Remarkable changes in the
electronic as well as in the magnetic properties of BNNR has

This journal is © the Owner Societies 2018 Phys. Chem. Chem. Phys.

Paper
been observed depending on the type of atom at the edge from
B and N and their passivation by hydrogen atoms.10,11 Qi et al.12
studied the effect of strain on the electronic properties of
Z-BNNR and reported that the band gap of Z-BNNR can be
tailored by axially applied strain. These properties makes BNNR
a good candidate for use in electronics, spintronics and sensing
Published on 06 March 2018. Downloaded by Maharaja Sayajirao University of Baroda on 20/03/2018 11:39:35.
applications.13–15 Furthermore, their high surface to volume
ratio and non-cytotoxicity makes them a good candidate for
biosensing applications.
In the past few decades, researchers have started focusing
on the centre of biological systems i.e., deoxyribonucleic acid
(DNA) and ribonucleic acid (RNA) since they are the key
components of the genome. Due to the importance of these
biological systems, it is necessary to understand the interaction
of the nucleobases that form these systems and the nano-
structures.16–22 Nucleobases, with purine as their base compound,
are the basic building blocks of nucleotides, which carry all the
genetic information. Dewasigamini et al.23 provided a brief
account on the sensing phenomena of carbon nanotubes (CNT)
to nucleobases. Their findings indicated an inverse relationship
between the binding mechanism and the curvature of the nano-
structure and they concluded that it is significant in case of
graphene than CNT. Recently, Zhi et al.24 reported that BN
nanostructures interact strongly with nucleobases, which they
attributed to the dissimilar atoms in the BN nanostructures in
contrast to graphene, in which only one type of atom is present.
The studies reported by Ciofani et al.25 and Chen et al.26 revealed
the good cytocompatibility of BNNT in living cells. Furthermore,
the studies reported by Liu et al.27 and Zhang and Wang28 on the
interaction of nucleobases with BN nanopores indicated that BN
nanopores are a good candidate for DNA and genome sequencing,
respectively. In addition, other studies have demonstrated
the interaction between h-BN and nucleobases.29–31 Lin et al.29
and Lee et al.30 performed calculations for single nucleobases,
while Ding et al.31 considered a pair of nucleobases. Transition
metal dichalcogenides (TMDs) have also recently attracted
interest for the design of novel biosensing platforms because
of their multidimensional structures and structure-dependent
unique electronic, electrocatalytic, and optical properties.32
Jin et al.33 reported the improved sensing of MoS2 by modify-
ing its surface with Au for the detection of DNA. These
studies enhanced our understanding to demonstrate that
BNNs can be used in many potential applications, particularly
nanobiomedical applications.34–38 The electronic and mag-
netic properties of BNNR indicate that BNNR are magnetic
semiconductors with a width dependent band gap making
them very different to h-BN and graphene.39,40
Thus, considering the nature of the interactions between
nucleobases and BNNR, it is very important to obtain an atomic
level understanding of the various applications of these hybrid
systems.41,42 In the present study, our main aim was to inves-
tigate the binding mechanism of the nucleobases and BNNR
together with the influence of their geometry in binding due
to different chiralities (Z-BNNR and A-BNNR). We studied
the adsorption, charge transfer and electronic properties of
BNNR with 10 Å-width BNNRs functionalized by adenine (A),
Phys. Chem. Chem. Phys.
View Article Online
PCCP
thymine (T), guanine (G), cytosine (C) and uracil (U) nucleobases.
The atomic-level dispersion mechanism of the interaction of
the nucleobases adsorbed on BNNR was revealed through state
of the art ab initio calculations based on density functional
theory. Moreover, understanding the nanobiointerface was
crucial to study the impact of nanomaterials on living cells
and human health and was also helpful in illuminating future
sequencing designs.
2. Computational methods
All calculations were performed under the framework of density
functional theory (DFT) based on the first principles method.
The ground state optimization was carried out through a total
energy minimization process utilizing the ultrasoft (US) projected
augmented wave (PAW) Rappe–Rabe–Kaxiras–Joannopoulos (RRKJ)
pseudopotential combined with a suitable generalized gradient
approximation (GGA) as the exchange–correlation functional imple-
mented in the Quantum Espresso (QE) simulation package.43 The
single particle functions were expanded in a plane wave basis set
with kinetic energy and charge density cutoffs of 60 Ry and 600 Ry,
respectively, which were sufficient to obtain a good convergence.
Higher values of charge density cutoffs were necessary due to the
ultrasoft pseudopotentials. The Brillouin zone (BZ) integration
was sampled on uniform Monkhorst and Pack44 k-point grids
1  16  1 in size, which we found to well-describe the binding
and electronic properties (the convergence plots are provided in
Fig. S1, ESI†). This k-point mesh guaranteed a violation of
charge neutrality less than 0.009e, indicating adequate conver-
gence of the calculations. The average bond length between
boron and nitrogen for the ground state configuration of
pristine BNNR was 1.48 Å. A comparative analysis of the
interaction with five nucleobases was carried out by structural
optimization and obtaining the adsorption energy and density
of states (DOS) plots. It has been emphasized in the literature
that a precise quantum mechanical description of the inter-
action of a molecule with a nanosurface requires accounting for
dispersion forces.45 Therefore, it is important to choose a
suitable computational method that considers the correct
description of long-range electron correlation. The present
study shows the results using Grimme’s dispersion correction
(DFT-D2)46 to incorporate the long-distance van der Waals
interaction, i.e., B2.7 Å between the adsorbent and the adsorbate.
The adsorption energy, Ead, was calculated according to the
following equation:
Ead = E(BNNR + nucleobase) {E(BNNR) + E(nucleobase)} (1)
where E(BNNR + nucleobase) is the total energy of the BNNRs
adsorbed by the nucleobase (adenine (A), thymine (T), guanine
(G), cytosine (C) and uracil (U)), E(BNNR) is the total energy of the
adsorbent nanoribbon and E(nucleobase) is the total energy of the
nucleobase (A, T, G, C and U) obtained from its fully optimized
geometry. According to this definition, Ead o 0 indicates the
exergonic nature of the adsorption.
This journal is © the Owner Societies 2018

PCCP
3. Results and discussion
The full structural optimization of both boron nitride nano-
ribbons, namely, armchair BNNR (A-BNNR) and zigzag BNNR
(Z-BNNR) and all the considered nucleobases, namely, adenine
(A), thymine (T), guanine (G), cytosine (C) and uracil (U) was
first performed individually. Fig. 1(a–e) present the optimized
Published on 06 March 2018. Downloaded by Maharaja Sayajirao University of Baroda on 20/03/2018 11:39:35.
structure of the nucleobases adenine, thymine, guanine, cyto-
sine and uracil. Fig. 2(a–f) show the optimized geometries of
pristine A-BNNR and nucleobase-adsorbed A-BNNRs, while the
optimized geometries of Z-BNNR and the nucleobase-adsorbed
Fig. 1 Optimized structure of the nucleobases: (a) adenine, (b) guanine, (c) cytosine, (d) thymine and (e) uracil. The blue, green, red, and yellow balls
represent nitrogen, carbon, oxygen and hydrogen, respectively.
Fig. 2 (a) Pristine A-BNNR and A-BNNR with nucleobases (b) A, (c) G, (d) C, (e) T and (f) U (top and side view). The pink and blue balls represent boron and
nitrogen atoms, respectively.
This journal is © the Owner Societies 2018
View Article Online
Paper
Z-BNNRs are shown in Fig. 3(a–f). The initial configurations are
provided in the ESI,† with parallel and perpendicular orienta-
tions shown in Fig. S2–S5 and the energy comparison of the
parallel and perpendicular configurations provided in Table S1
(ESI†). Both pristine BNNRs have local minima as can be seen
from the phonon density of states presented in Fig. S6 of the
ESI.† The finite (real) value of the phonon DOS at zero wave-
number confirms that all the phonon modes are real in the
entire Brillouin zone (BZ) as DOS requires calculation of
phonons in entire BZ.47,48 The adsorbed nucleobase molecules
on both BNNRs were explored with different orientations by
Phys. Chem. Chem. Phys.
 View Article Online

Paper PCCP
Published on 06 March 2018. Downloaded by Maharaja Sayajirao University of Baroda on 20/03/2018 11:39:35.

Fig. 3 (a) Pristine Z-BNNR and Z-BNNR with nucleobases (b) A, (c) G, (d) C, (e) T and (f) U (top and side view).

changing the distance between the ribbons and the molecule Table 1 Adsorption energy (eV), vertical distance d (Å) of the nucleobases
before concluding the best optimized geometry. We found that from the BNNRs, HOMO–LUMO gap Eg (eV), work function (F) (eV) and
change in work function DF (eV)
the most favourable orientation of the molecules was that
where the heteroatoms in the molecules were facing the HOMO–LUMO Ef Ead WF(F) DF
BNNRs. For h-BN sheet-functionalized guanine, the most System gap (eV) (eV) (eV) d (Å) (eV) (eV)
stable configuration was guanine positioned parallel to the A-BNNR 4.8880 3.059 — — 4.150
nanosheet.49 Therefore, we chose the parallel orientation for A + A-BNNR 3.7280 3.262 0.485 2.9450 4.527 0.377
G + A-BNNR 3.5055 3.999 0.624 2.7450 5.278 1.128
the nucleobases-functionalized BNNRs, which can be seen in C + A-BNNR 3.2518 3.285 0.388 2.7750 4.525 0.375
Fig. 2 and 3. It is noteworthy that the optimized hybrid T + A-BNNR 3.6197 3.532 0.496 2.7255 4.760 0.61
structures show alignment of the hexagonal rings of the U + A-BNNR 3.6056 3.503 0.433 2.9530 4.716 0.566
nucleobases and BNNR different from graphene. This can be Z-BNNR 4.2970 2.925 — — 3.993
attributed to the fact that we maintained the p–p staking, which A + Z-BNNR 3.7115 3.162 0.658 2.8524 4.404 0.411
minimizes the steric repulsion between the molecule and G + Z-BNNR 3.4662 3.274 0.795 2.8102 4.539 0.546
C + Z-BNNR 3.3733 3.192 0.688 2.6140 4.393 0.4
BNNR. The adsorption was physical in nature as the distance T + Z-BNNR 3.5633 3.414 0.648 2.6667 4.620 0.627
between the molecules and BNNRs are large as shown in U + Z-BNNR 3.4887 3.402 0.567 2.9057 4.604 0.611
Table 1. The calculations in the present study were performed
with the incorporation of dispersion corrected DFT (DFT-D2)
which considers the long-range van der Waals (vdW) inter- underestimation of the vdW interaction. Furthermore, our
actions. It should be noted that we used the D2 correction results are relatively in good agreement with the results
instead of the newly introduced D3 correction to DFT50 as the obtained through the PBE+vdW calculations by Lee et al.31
molecules were non-covalently adsorbed on the BNNs. Further- The slight deviation in the adsorption energy can be attributed
more, the D2 and D3 corrections give comparable results in the to the H-site interaction of the molecules with the host sub-
case of non-covalent interactions.51 The adsorption energy strate, which results in less binding compared to that observed
calculated for A, G, C, T and U adsorbed on A-BNNR is Ead = in the CH3-site.31 Fig. 4a presents the adsorption energy plot for
0.485 eV, 0.624 eV, 0.388 eV, 0.496 eV and 0.433 eV, adsorption of A-BNNR/Z-BNNR with the five nucleobases. The
respectively, with a vertical distance d in the range of 2.72–2.95 Å. order of the binding of the molecule over A-BNNR is G 4 T 4
Our results are comparatively better than the results obtained in A 4 U 4 C. However, the binding nature of the molecule over
ref. 31 and 52–54 for h-BN as well as graphene with nucleobases Z-BNNR is in the order G 4 C 4 A 4 T 4 U with the
because those authors employed LDA calculations and adsorption energy Ead of 0.795 eV, 0.688 eV, 0.658 eV,
obtained lower binding energies, which they attributed to the 0.648 eV and 0.567 eV, respectively and vertical distance d

Phys. Chem. Chem. Phys. This journal is © the Owner Societies 2018
 View Article Online

PCCP Paper
Published on 06 March 2018. Downloaded by Maharaja Sayajirao University of Baroda on 20/03/2018 11:39:35.

Fig. 4 (a) Adsorption energy plot for A-BNNR and Z-BNNR with nucleobases. (b) Band gap difference (D Eg) plot for A-BNNR and Z-BNNR with adsorbed
nucleobases.

ranging between 2.6 Å and 2.9 Å. The difference in the

adsorption energy can be explained on the basis of the funda-
mentals of van der Waals forces, which are directly propor-
tional to the size and mass of the interacting molecules and
also the chirality of the nanoribbons.55 The vdW contribution
plays an important role in the adsorption energy, which was
observed by Lee et al.31 and also previously by our group.56 The
adsorption energy increases up to B8 to 10 times that obtained
through the normal PBE calculation with the inclusion of vdW
correction. In addition, the stacking is also responsible for
different binding nature.57 The molecules that have p–p stack-
ing with the nanoribbon have higher binding energies because
p–p stacking minimises p-orbital overlapping, which prevents
the molecules from being repelled by the nanoribbon. Another
factor that can contribute to the difference in binding nature is
the total energy and the distance of the molecules from the
BNNRs shifting towards the nanoribbon. The adsorption of the
molecules is physical over both BNNRs due to the large nearest
atom distance (B B 2.8 Å), which eliminates the possibility of
covalent bond formation. The adsorption/desorption mecha-
nism will be more effective if the molecules are weakly bound
on the surface of the nanostructures. Therefore, a noncovalent
type of adsorption is more favourable than covalent binding,
Fig. 5 Electronic density of states for A-BNNR with A, G, C, T and U.
where chemical bond formation and bond breaking take place.
The present results depict that the nucleobases are more
effectively adsorbed on Z-BNNR compared to A-BNNR. This can electronic properties of BNNRs. The calculated total DOS of the
be attributed to the conducting behaviour of the nanoribbons. A-BNNR-nucleobase complexes are shown in Fig. 5. For the
It was earlier predicted that hydrogen passivated A-BNNRs are A-BNNR-nucleobase complexes, a small molecular peak arises
large band gap insulators; however, Z-BNNRs can be semicon- near the valance band maxima at 1.8 eV and at 2 eV in the
ducting as well as semimetallic.11,39 The molecules adsorbed conduction band region in the case of A and at 1.95 eV for C
on both BNNRs affect the electronic properties, which were and at 1.85 eV for G. However, in the case of the T and U
examined by calculating DOS and HOMO–LUMO gap. From the interactions with the nanoribbon, the changes occur in the
present calculations we found that the energy gap between the conduction band region at 2.15 eV and 2.3 eV, respectively.
HOMO and LUMO for the five nucleobases A, G, C, T and U are An additional peak in this region is seen for cytosine. The total
3.8181 eV, 3.5387 eV, 3.3997 eV, 3.6773 eV and 3.9182 eV, DOS plots show that pristine A-BNNR has a large band gap of
respectively. Fig. 4b shows the band gap difference (DEg) plot 4.8880 eV and changes in its band gap occur when nucleobases
between pristine A-BNNR/Z-BNNR and nucleobases adsorbed are adsorbed on its surface. Among all the nucleobases, the adsorp-
A-BNNR/Z-BNNR. The total DOS of both BNNRs functionalized tion of C reduces the band gap of A-BNNR the most (1.63 eV)
with nucleobases shows that these molecules modulate the (see Fig. 4b), while the reduction in the bandgap is 1.16 eV, 1.38 eV,

This journal is © the Owner Societies 2018 Phys. Chem. Chem. Phys.

Paper
Published on 06 March 2018. Downloaded by Maharaja Sayajirao University of Baroda on 20/03/2018 11:39:35.
Fig. 6 Electronic density of states for Z-BNNR with A, G, C, T and U.
1.26 eV and 1.28 eV for the adsorption of A, G, T and U, respectively.
The large band gap modulation of A-BNNR with C is because of its
NH2 group, which helps to reduce the band gap and increase the
conductivity. We can easily identify the additional features in the
DOS of the pristine A-BNNR arising from molecular peaks.
The density of states analysis gives information about the
states contribution of the molecules localized around the top of
Fig. 7 Work function plot of A-BNNR with A, G, C, T and U.
Phys. Chem. Chem. Phys.
View Article Online
PCCP
the valance band and the bottom of the conduction band. In the
case of Z-BNNR, its total DOS is presented in Fig. 6, which depicts a
band gap (4.2970 eV) smaller than that of A-BNNR. The order of the
adsorption energy shows that the guanine binding is superior.
Guanine is the strongest electron donor because of the presence
of an oxygen atom, which tends to bind strongly. Due to the
additional pentagonal ring formed in guanine with C and N atoms
and also due to the presence of an O atom, this molecule exhibits
high polarization. The higher electronegativity of the N and O atoms
induces stronger binding.30,58 In the case of Z-BNNR, its band gap is
modulated between 0.58 and 0.98 eV by the nucleobases. C atom
exhibits a similar impact on Z-BNNR as in the case of A-BNNR. The
band gap of pristine Z-BNNR changes from 4.2970 eV to 3.3733 eV
(change of 0.92 eV). Apart from C and G, the other nucleobases U, T
and A also tailor the band gap to 0.80 eV, 0.73 eV and 0.58 eV,
respectively (see Fig. 4b). The change in the DOS is clearly seen after
the adsorption of the molecules at the top of the valence band and
bottom of the conduction band, where the contribution of the
p-orbital electrons of the molecules creates a peak. However, in
the case of U and T, this contribution is seen only at the bottom of
the conduction band. This helps us to understand the difference
in the binding of these molecules over Z-BNNR. These results
reinforce the fact that the molecules are physically adsorbed on
the nanosurface of both BNNRs, which indicates their suitability for
the targeted delivery of the nucleobases as reversibility can be easily
achieved by desorption.
Further, to understand the interaction of the nucleobases on
BNNR, work function (WF) calculations were carried out
through first principles calculations. The work function is the
amount of energy required to take an electron away from the
Fermi level to the vacuum level and is expressed as
WF(F) = Evac EF (2)
This journal is © the Owner Societies 2018

PCCP
Published on 06 March 2018. Downloaded by Maharaja Sayajirao University of Baroda on 20/03/2018 11:39:35.
Fig. 8 Work function plot of Z-BNNR with A, G, C, T and U.
where Evac denotes the energy of the vacuum level and EF denotes
the energy of the Fermi level. We studied the change in BNNR
without adsorption and the calculated work functions are shown in
Fig. 7 and 8. The peak in the graph corresponds to the position of
the nucleobases and BNNRs. The WF(F) of the pristine BNNRs
drastically changes with the adsorption of A, G, C, T and U. We
observed a large modulation in the work function of A-BNNR. The
calculated values of WF(F) are shown in Table 1. The WF(F) for
guanine with A-BNNR increases to 5.278 eV from 4.150 eV. This large
change in WF(F) (1.128 eV) suggests the charge acceptor behaviour
of guanine on A-BNNR. The WF(F) values of Z-BNNR are lower than
that for A-BNNR due to its non-symmetric structure. The WF(F) for
A-BNNR and Z-BNNR with adsorbed nucleobases are in the follow-
ing order: G 4 T 4 U 4 A E C and T E U 4 G 4 A E C,
respectively. Our results indicate that the WF(F) is distinctly altered
after the adsorption of these nucleobases (through strong physisorp-
tion). As a result, the strong nucleobases-BNNRs interaction affects
the WF of the BNNR. This demonstrates that the WF of materials
can be effectively tuned through adsorption. The obtained results
indicate that BNNRs are good candidates as molecule carriers and
should be explored further for their biomedical applications.
4. Conclusion
In summary, the adsorption behaviour of nucleobases on 1D
nanoribbons of boron nitride with two different chiralities
(Z-BNNR and A-BNNR) was studied using first principles calcu-
lations based on density functional theory with van der Waals
corrections (DFT-D2). The results were compared to those
obtained for nucleobase-adsorbed graphene as well as the
BNNT system. Our results depict that the nucleobases physi-
sorbed on both BNNRs, namely, Z-BNNR and A-BNNR with the
This journal is © the Owner Societies 2018
View Article Online
Paper
interactions in the order of G 4 C 4 A 4 T 4 U and G 4 T 4
A 4 U 4 C, respectively, which are different from the results
obtained for both graphene and BNNT. The adsorption ener-
gies of the BNNR-nucleobase complexes are superior to that of
graphene due to the electron cloud present on the surface
of BNNR. The new features, which can be seen in the DOS of
BNNR due to these nucleobases and also the large change in
the work function, which gives information on the interactions
of BNNR with nucleobases. This reinforces the use of BNNR for
the detection of these biomolecules. Thus, from our results, it
can be concluded that BNNRs may act as superior candidates as
compared to h-BN and graphene systems for the sensing
application of nucleobases as well as DNA sequencing.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
SDD is thankful to the Department of Science and Technology,
India for the INSPIRE senior research fellowship. PKJ is thank-
ful for financial support by a research project from Science and
Engineering Research Board (SERB) (SB/S2/CMP-0005/2013),
Govt. of India. The computations are carried out using high
performance computer cluster provided under DST-FIST program.
References
1 A. K. Geim and K. S. Novoselov, Nat. Mater., 2007, 6, 183–191.
2 A. H. C. Neto, F. Guinea, N. M. R. Peres, K. S. Novoselov and
A. K. Geim, Rev. Mod. Phys., 2009, 81, 109–162.
Phys. Chem. Chem. Phys.

Paper
3 A. K. Geim, Science, 2009, 324, 1530–1534.
4 M. Terrones, J. C. Charlier, A. Gloter, E. Cruz-Silva, E. Terrés,
Y. B. Li, A. Vinu, Z. Zanolli, J. M. Dominguez, H. Terrones,
Y. Bando and D. Golberg, Nano Lett., 2008, 8, 1026–1032.
5 A. Rubio, J. L. Corkill and M. L. Cohen, Phys. Rev. B:
Condens. Matter Mater. Phys., 1994, 49, 5081–5084.
Published on 06 March 2018. Downloaded by Maharaja Sayajirao University of Baroda on 20/03/2018 11:39:35.
6 M. Topsakal, E. Aktürk and S. Ciraci, Phys. Rev. B: Condens.
Matter Mater. Phys., 2009, 79, 115442.
7 H. Zeng, C. Zhi, Z. Zhang, X. Wei, X. Wang, W. Guo,
Y. Bando and D. Golberg, Nano Lett., 2010, 10, 5049–5055.
8 K. J. Erickson, A. L. Gibb, A. Sinitskii, M. Rousseas, N. Alem
and J. M. Tour, Nano Lett., 2011, 11, 3221–3226.
9 Y. Muramatsu, T. Kaneyoshi, E. M. Gullikson and R. C. C.
Perera, Spectrochim. Acta, Part A, 2003, 59, 1951–1957.
10 F. Zheng, G. Zhou, Z. Liu, J. Wu, W. Duan, B. L. Gu and
S. B. Zhang, Phys. Rev. B: Condens. Matter Mater. Phys., 2008,
78, 205415.
11 L. Lai, J. Lu, L. Wang, G. Luo, J. Zhou, R. Qin, Z. Gao and
W. Mei, J. Phys. Chem. C, 2008, 113, 2273–2276.
12 J. Qi, X. Qian, L. Qi, J. Feng, D. Shi and J. Li, Nano Lett., 2012,
12, 1224–1228.
13 P. Tang, X. Zou, S. Wang, J. Wu, H. Liu and W. Duan,
RSC Adv., 2012, 2, 6192–6199.
14 Y. Han, R. Li, J. Zhou, J. Dong and Y. Kawazoe, Nanotechnology,
2014, 25, 115702.
15 P. Srivastava, N. K. Jaiswal and V. Sharma, Superlattices
Microstruct., 2014, 73, 350–358.
16 F. Ortmann, W. G. Schmidt and F. Bechstedt, Phys. Rev.
Lett., 2005, 95, 186101.
17 E. S. Jeng, A. E. Moll, A. C. Roy, J. B. Gastala and M. S.
Strano, Nano Lett., 2006, 6, 371–375.
18 A. N. Enyashin, S. Gemming and G. Seifert, Nanotechnology,
2007, 18, 245702.
19 S. Gowtham, R. H. Scheicher, R. Pandey, S. P. Karna and
R. Ahuja, Nanotechnology, 2008, 19, 125701.
20 R. R. Johnson, A. T. C. Johnson and M. L. Klein, Nano Lett.,
2008, 8, 69–75.
21 A. Das, A. K. Sood, P. K. Maiti, M. Das, R. Varadarajan and
C. N. R. Rao, Chem. Phys. Lett., 2008, 453, 266–273.
22 M. X. Tu, S. Manohar, A. Jagota and M. Zheng, Nature, 2009,
460, 250–253.
23 D. Umadevi and G. N. Sastry, J. Phys. Chem. Lett., 2011, 2,
1572–1576.
24 C. Zhi, Y. Bando, W. Wang, C. Tang, H. Kuwahara and
D. Golberg, Chem. – Asian J., 2007, 2, 1581–1585.
25 G. Ciofani, V. Raffa, A. Menciassi and A. Cuschieri, Biotechnol.
Bioeng., 2008, 101, 850–858.
26 X. Chen, P. Wu, M. Rousseas, D. Okawa, Z. Gartner, A. Zettl
and C. R. Bertozzi, J. Am. Chem. Soc., 2009, 131, 890–891.
27 S. Liu, B. Lu, Q. Zhao, J. Li, T. Gao, Y. Chen, Y. Zhang, Z. Liu,
Z. Fan, F. Yang, L. You and D. Yu, Adv. Mater., 2013, 25, 4549–4554.
28 L. Zhang and X. Wang, Nanomaterials, 2016, 6, 111–121.
29 Q. Lin, X. Zou, G. Zhou, R. Liu, J. Wu, J. Li and W. Duan,
Phys. Chem. Chem. Phys., 2011, 13, 12225–12230.
30 J. H. Lee, Y. K. Choi, H. J. Kim, R. H. Scheicher and
J. H. Cho, J. Phys. Chem. C, 2013, 117, 13435–13441.
Phys. Chem. Chem. Phys.
View Article Online
PCCP
31 N. Ding, X. Chen, C. M. L. Wu and H. Li, Phys. Chem. Chem.
Phys., 2013, 15, 10767–10776.
32 S. Barua, H. S. Dutta, S. Gogoi, R. Devi and R. Khan,
ACS Appl. Nano Mater., 2018, 1, 2–25.
33 K. Jin, L. Xie, Y. Tian and D. Liu, J. Phys. Chem. C, 2016, 120,
11204–11209.
34 G. Ciofani, V. Raffa, J. Yu, Y. Chen, Y. Obata, S. Takeoka,
A. Menciassi and A. Cuschieri, Curr. Nanosci., 2009, 5, 33–38.
35 G. G. Genchi and G. Ciofani, Nanomedicine, 2015, 10,
3315–3319.
36 Z. Khatti and S. M. Hashemianzadeh, Eur. J. Pharm. Sci.,
2016, 88, 291–297.
37 L. H. Li and Y. Chen, Adv. Funct. Mater., 2016, 26, 2594–2608.
38 C. Wang, S. Li, R. Zhang and Z. Lin, Nanoscale, 2012, 4, 1146–1153.
39 V. Barone and J. E. Peralta, Nano Lett., 2008, 8, 2210–2214.
40 C. H. Park and S. G. Louie, Nano Lett., 2008, 8, 2200–2203.
41 Z. Zhang, H. Huang, X. Yang and L. Zang, J. Phys. Chem.
Lett., 2011, 2, 2897–2905.
42 T. Kar, H. F. Bettinger, S. Scheiner and A. K. Roy, J. Phys.
Chem. C, 2008, 112, 20070–20075.
43 P. Giannozzi, S. Baroni, N. Bonini, M. Calandra, R. Car,
C. Cavazzoni, D. Ceresoli, L. Chiarotti, M. Cococcioni,
I. Dabo, A. Dal Corso, S. Fabris, G. Fratesi, S. de Gironcoli,
R. Gebauer, U. Gerstmann, C. Gougoussis, A. Kokalj,
M. Lazzeri, L. Martin-Samos, N. Marzari, F. Mauri,
R. Mazzarello, S. Paolini, A. Pasquarello, L. Paulatto,
C. Sbraccia, S. Scandolo, G. Sclauzero, A. P. Seitsonen,
A. Smogunov, P. Umari and R. M. Wentzcovitch, J. Phys.:
Condens. Matter, 2009, 21, 395502.
44 H. J. Monkhorst and J. D. Pack, Phys. Rev. B: Condens. Matter
Mater. Phys., 1976, 13, 5188–5192.
45 B. Civalleri, L. Maschio, P. Ugliengo and C. M. Z. Wilson,
Phys. Chem. Chem. Phys., 2010, 12, 6382–6386.
46 S. Grimme, J. Comput. Chem., 2006, 27, 1787–1799.
47 S. K. Gupta, H. R. Soni and P. K. Jha, AIP Adv., 2013,
3, 032117.
48 P. K. Jha, Phys. Rev. B: Condens. Matter Mater. Phys., 2005,
72, 214502.
49 E. C. Anota, Y. Tlapale, M. S. Villanueva and J. A. R.
Márquez, J. Mol. Model., 2015, 21, 215–221.
50 J. B. A. Davis, F. Baletto and R. L. Johnston, J. Phys. Chem. A,
2015, 119, 9703–9709.
51 S. Grimme, J. Antony, S. Ehrlich and H. Krieg, J. Chem. Phys.,
2010, 132, 154104.
52 S. Gowtham, R. H. Scheicher, R. Ahuja, R. Pandey and S. P.
Karna, Phys. Rev. B: Condens. Matter Mater. Phys., 2007, 76, 033401.
53 Q. Lin, X. Zou, G. Zhou, R. Liu, J. Wu, J. Li and W. Duan,
Phys. Chem. Chem. Phys., 2011, 13, 12225–12230.
54 H. H. Gürel and B. Salmankurt, Mater. Res. Express, 2017,
4, 065401.
55 P. Han, K. Akagi, F. F. Canova, H. Mutoh, S. Shiraki, K. Iwaya, P. S.
Weiss, N. Asao and T. Hitosugi, ACS Nano, 2014, 8, 9181–9187.
56 B. Roondhe, S. D. Dabhi and P. K. Jha, Appl. Surf. Sci., 2018,
441, 588–598.
57 K. M. Dethlefs and P. Hobza, Chem. Rev., 2002, 100, 143–168.
58 F. Erkoc and S. Erkoc, THEOCHEM, 2002, 589, 405–411.
This journal is © the Owner Societies 2018