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Karbala International Journal of Modern Science xx (2015) 1e11
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Studies on interaction of ribonucleotides with zinc ferrite

nanoparticles using spectroscopic and microscopic techniques
Md. Asif Iqubal, Rachana Sharma, Kamaluddin*
Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee 247 667, UK, India
Received 30 May 2015; revised 22 June 2015; accepted 30 June 2015

Abstract

Interaction of ribonucleotides with zinc ferrite nanoparticles (~15 nm) prepared by the solegel method was studied at physi-
ological pH (~7.0). Ultra-violet (UVeVis), Fourier transform infrared (FT-IR), Raman spectroscopy and field emission scanning
electron microscopy (FE-SEM) and atomic force microscopy (AFM) were employed to investigate the interaction of ribonucle-
otides with zinc ferrite surface. Langmuir and Freundlich adsorption models were used to describe the equilibrium isotherms in the
concentration range of 1.0
104 M4.0
104 M of ribonucleotides. The maximum adsorption capacity determined for 50 -GMP,
50 -AMP, 50 -UMP, 50 -CMP was 22.37 mg/g, 17.42 mg/g, 16.03 mg/g and 14.03 mg/g, respectively. Langmuir model was found to
show the best fit for experimental data. Adsorption kinetics were studied by pseudo-first order and pseudo-second order kinetic
models, and the adsorption process was best described by the pseudo-second order kinetic model. FE-SEM images clearly showed
that ribonucleotide adheres onto the zinc ferrite nanoparticles surface. AFM analysis demonstrated that the root mean square
roughness (Rms, Sq) and average roughness (Sa) increased from 0.98 nm to 1.80 and 0.67 nme1.38 nm, respectively following
exposure to ribonucleotide. FT-IR spectroscopy revealed that the zinc ferrite nanoparticles interact strongly with the phosphate,
carbonyl and amino groups of ribonucleotides. Raman spectra of 50 -AMP-zinc ferrite adduct showed the participation of amino and
a phosphate group with zinc ferrite nanoparticles surface.
© 2015 The Authors. Published and hosting by Elsevier B.V. on behalf of University of Kerbala. This is an open access article under
the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Keywords: Ribonucleotides; Adsorption; AFM; FT-IR; FE-SEM

1. Introduction amount of nucleic acids is released in natural envi-

Adsorption of nucleic acids and their components
on mineral matrices are especially interesting in
respect of several scientific issues. After the death of
organism and subsequent cell lysis a significant
* Corresponding author. Tel.: þ91 1332 285796; fax: þ91 1332
285146.
E-mail addresses: kamalfcy@gmail.com, kamalfcy@iitr.ac.in (
Kamaluddin).
Peer review under responsibility of University of Kerbala.
ronment, mainly in soil [1e3]. The released nucleic
acids are adsorbed onto mineral surfaces and preserved
in the natural environment. Mineral surface protects
them from UV-mediated or enzymatic degradation
[4e8]. This preserved nucleic acid further can be taken
up by the microorganisms for horizontal gene transfer
or transfection [9e11]. Several important biomedical
experiments involving nucleic acidemineral interac-
tion have been carried out in recent past [12e17].
Apart from this the adsorption of nucleic acids and

http://dx.doi.org/10.1016/j.kijoms.2015.06.001
2405-609X/© 2015 The Authors. Published and hosting by Elsevier B.V. on behalf of University of Kerbala. This is an open access article under
the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Please cite this article in press as: M.A. Iqubal et al., Studies on interaction of ribonucleotides with zinc ferrite nanoparticles using spectroscopic
and microscopic techniques, Karbala International Journal of Modern Science (2015), http://dx.doi.org/10.1016/j.kijoms.2015.06.001
 + MODEL
2 Md.A. Iqubal et al. / Karbala International Journal of Modern Science xx (2015) 1e11
their components on mineral surfaces may have
important rule on the origin of life issue, where mineral
surfaces concentrate the nucleic acid components from
dilute oceans [18e21]. Several minerals such as
olivine, pyrite, calcite, hematite and rutile [22], zinc
oxide [23], alumina [24,25], manganese oxides [26],
metal octacyanomolybdates [27], natural zeolite [28],
clays [29e34] have been employed to study the
adsorption of nucleic acid and their components.
Spinel ferrites a group of minerals having the gen-
eral formula MIIFeIII2 O4 where M may be Zn, Ni, Co,
Cu, etc., are a special class of compounds having high
magnetic properties. Ferrite nanoparticles are particu-
larly useful in biomedicine for nucleic acid separation,
gene detection, as contrast agent and biosensors
[35,36]. Zinc ferrite mineral (ZnFe2O4) has attracted
an increasing attention due to possessing excellent
electrical, optical and magnetic properties. This
important material can be used in areas devoted to
hyperthermia [37], MRI contrast agent [38], gas sen-
sors [39], catalyst [40], etc. Although several minerals
have been tested for the adsorption of nucleic acid,
only a few literature are available involving metal
ferriteenucleic acid interactions. Magnetite, cobalt
ferrite and silica-magnetite composite have been used
as an effective adsorbent for the isolation of genomic
DNA molecules [41,42]. Pershina et al., (2009) studied
the interaction between DNA and cobalt nano ferrite
particles using FTIR spectroscopy [43]. Recent work
involving adsorption of DNA on Fe3O4 nanoparticles
has been carried out by Ghaemi and Absalan (2014)
[44]. To the best of our knowledge spinel metal ferrites
has not been tested to study the adsorption of nucleo-
tides (monomeric unit of nucleic acid) that prompted
us to investigate the interaction between nucleotides
and zinc ferrite nanoparticles.
In the present work we report the interaction be-
tween ribonucleotides (50 -AMP, 50 -GMP, 50 -UMP and
50 -CMP) and zinc ferrite nanoparticles under physio-
logical pH (~7.0) using spectroscopic and microscopic
techniques. This study involving magnetic nano-
particleenucleic acid interaction may be of high
importance because of the influence of nano materials
on biosystems and further the mechanism of interac-
tion can be used to develop bio-nano composites.
2. Experimental
2.1. Materials
Zinc(II) nitrate (Zn(NO3)2.6H2O) was purchased
from E. Merck, Citric acid (C6H8O7.H2O) from
Please cite this article in press as: M.A. Iqubal et al., Studies on interaction of ribonucleotides with zinc ferrite nanoparticles using spectroscopic
and microscopic techniques, Karbala International Journal of Modern Science (2015), http://dx.doi.org/10.1016/j.kijoms.2015.06.001
RANKEM, Ethylene glycol (C2H6O2) from Sisco
Research Laboratory, India, Iron(III) nitrate
(Fe(NO3)3.9H2O) and disodium salts of ribonucleo-
tides were purchased from SigmaeAldrich. The re-
agents were used without further purification.
Millipore water was used throughout the studies.
Graphs are plotted and smoothened in Origin Pro 8.1
software.
2.2. Apparatus and measurements
X-ray powder diffraction analysis of samples was
carried out using a Brucker AXS D8 advanced X-ray
diffractometer (Cu-Ka, l ¼ 0.1540 nm). Ultra-
violetevisible (UVeVis) absorption spectra of the
samples were recorded in the wavelength range of
200e800 nm with a resolution of 0.1 nm in a quartz
cuvette by using a Shimadzu UV-16001 spectropho-
tometer. The infrared spectra of samples were recorded
using a KBr pressed disk technique by a Fourier
transform infrared spectrometer (PerkineElmer),
operating in the range of 400e4000 cm1. About 10
mg of sample with 200 mg of KBr were ground in an
agate mortar until a homogenous mixture was ob-
tained. Then this mixture was hydraulic pressed to
form disc pellets. Spectra were recorded with a scan-
ning speed of 2 mm/s with resolution of 2 cm1.
Raman spectra of the samples were recorded using a
RENISHAW in Via Raman spectrophotometer with
4 cm1 resolution. An argon ion laser operating at
514.5 nm was used as the excitation source having
laser power of 1 mW an and acquisition time of 30 s.
The zeta potential of the zinc ferrites nanoparticles was
measured at different pH (i.e., pH ¼ 3, 5, 7, 9, 11)
using Malvern Zeta Sizer Nano ZS90. The pH of the
solutions was adjusted by adding dilute hydrochloric
acid (0.01 M) or sodium hydroxide (0.01 M). The
experiments were carried out by dispersing 5 mg of
zinc ferrite in 50 mL of 10 mM NaCl solution and
sonicated for 10 min. Surface morphological images of
the samples were carried out using a FEI Quanta 200F
scanning electron microscope operating at 20 kV. The
sample is first made conductive for current by smear-
ing the sample on a conducting carbon tape and then
gold sputtered for 100 s in a high vacuum chamber.
Elemental compositions of the samples were also
analyzed using an energy dispersive X-ray analysis
(EDX) facility attached with the FE-SEM. Surface
topography of the samples was analyzed by recording
2D images on a NTEGRE (NT-MDT) atomic force
microscope (AFM) equipped with NOVA software.
The textural characteristics of the samples were
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Md.A. Iqubal et al. / Karbala International Journal of Modern Science xx (2015) 1e11
determined from N2 adsorption isotherms at 77 K
using a Nova 2200e (Quantachrome) instrument. Prior
to analysis, samples were kept at 150  C for 2 h. He-
lium gas was used for dead measurements. The BET
(Brunauer, Emmet and Teller) equation was used to
calculate the specific surface area of porous solids from
pressure measurements [45].
P=VðPo  PÞ ¼ 1=Vm C þ C  1=Vm ðP=Po Þ
where P/Po is relative pressure, V is the adsorbed gas
quantity, Vm is the monolayer adsorbed gas quantity
and C is BET constant. A linear plot of P/V(PoeP) vs.
P/Po was used to find out the value of surface area of
samples from the slope and intercept. The classical pore
size model developed by Barret, Joyner and Halenda
(BJH) in 1951, which is based on the Kelvin equation
and corrected for multilayer adsorption, is most widely
used for calculations of the pore size distribution over
the mesopore and part of the macropore range [46]. The
Nova 2200e (quantachrome) instrument allows to
measure the BJH pore size distribution data
automatically.
The magnetic hysteresis loop of zinc ferrite was
obtained by using a vibrating-sample magnetometer
(PAR 155). Approximately 50 mg powder samples
were put in a diamagnetic plastic straw and packed into
a minimal volume for magnetic measurements.
2.3. Synthesis of zinc ferrite nanoparticles
The nanosized zinc ferrite was prepared according
to a modified version of a previously reported proce-
dure [47,48]. In a typical synthesis of zinc ferrite
stoichiometric amounts of Zn(NO3)2.6H2O (0.005 mol,
1.48 g) and Fe(NO3)3.9H2O (0.01 mol, 4.04 g) were
dissolved in a minimum amount of Millipore water
with constant stirring at 80e90  C. After complete
dissolution of the metal salts, citric acid (0.015 mol,
3.15 g) was added, followed by 10 mL of ethylene
glycol to the solution. The solution was stirred until gel
formation. The obtained gel was subjected to thermal
treatment at 400  C for 2 h in a muffle furnace.
2.4. Adsorption studies
All glasswares were cleaned in an aqueous HCl bath
and rinsed with Millipore water prior to use. Stock
solutions of the ribonucleotides were prepared from
crystalline powder as supplied and the pH was adjusted
to the desired value (pH ¼ 7.0) by adding
0.01 mol dm3 HCl or 0.01 mol dm3 NaOH. The pH
Please cite this article in press as: M.A. Iqubal et al., Studies on interaction of ribonucleotides with zinc ferrite nanoparticles using spectroscopic
and microscopic techniques, Karbala International Journal of Modern Science (2015), http://dx.doi.org/10.1016/j.kijoms.2015.06.001
3
was measured before and after the adsorption reaction
and it was found to be stable within 0.1 units over the
time of adsorption. In the adsorption experiment 25 mg
of zinc ferrite was added in 5 mL of ribonucleotide
solution (ranging from 1.0
104 M4.0
104 M)
in a 25 mL glass tube followed by shaking at room
temperature for 2 min on a Vortex shaker (Spinix).
After 24 h the samples were centrifuged at 4000 rpm
for 10 min and the supernatant was analyzed for
ribonucleotide concentration by UVeVisible spectro-
photometry at their characteristic values of lmax which
was 259 nm for 50 -AMP, 252 nm for 50 -GMP, 272 nm
for 50 -CMP and 262 nm for 50 -UMP. Each adsorption
experiment was performed in triplicate. The adsorbed
amount of ribonucleotides at equilibrium, Xe (mg/g)
was calculated by the following expression:


Xe ¼ Ci  Ceq
M
V
1000=m mg
where,
Xe ¼ amount (mg) of adsorbate adsorbed on 1 g of
adsorbent
Ci and Ceq ¼ initial and equilibrium concentration
of ribonucleotide solution, respectively.
V ¼ volume of the adsorbate solution
M ¼ molecular weight of adsorbate
m ¼ amount (mg) of adsorbent used
The equilibrium concentration of ribose nucleotide
and the amount adsorbed were used to obtain the
adsorption isotherms. The solid residue was dried for
24 h at 30  C and analyzed with FT-IR, FE-SEM,
AFM, XRD, and Raman spectroscopy to know the
nature of adsorption.
2.5. Kinetic studies
Kinetic studies were performed by placing 25 mg of
adsorbent in a glass tube containing a fixed concen-
tration (3.0
104 M) of ribonucleotides at pH 7 for
33 h. At different time intervals concentration of ri-
bonucleotides was measured by UVeVisible spectro-
photometry. Each kinetic study was performed for
three times.
3. Results and discussions
3.1. Characterization of zinc ferrite nanoparticles
Figure S1 (in Supplementary Section) shows the
XRD pattern of the zinc ferrite after calcination at
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temperature 400  C. The experimental XRD data agree

closely with the standard values given in the JCPDS
data card (01-1108) confirming the single cubic phase
spinel formation of zinc ferrite. The average crystallite
size of zinc ferrite was found to be 14.89 nm which has
been calculated using the DebyeeScherrer equation as
given below:
D ¼ ð0:89
lÞ=ðb
cosqÞ

where D is the crystallite size, l is the wavelength of X-

ray radiation (0.1540 nm for Cu-Ka radiation), b is the
full width at half maximum and q is the diffraction
angle. The values of the lattice parameter ‘a’ was
calculated from the most prominent peak in the XRD of
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
zinc ferrite by using the formula a ¼ d h2 þ k2 þ l2 ,
where h, k and l are the Miller indices of the crystal
plane (311) and ‘d’ is the interplanar spacing
(0.2544 nm) obtained by the XRD pattern. The X-ray
density of zinc ferrite was calculated using the equation,
rx ¼ 8M=Na3

where M ¼ the molecular weight of zinc ferrite

(241.07 g/mol); Na is the Avogadro constant; ‘a’ is the
lattice parameter. The obtained lattice parameter
(8.437 Å) and X-ray density (5.345 g/cm3) are in good
agreement with the reported value, i.e. 8.43 Å, and
5.346 g/cm3, respectively [49]. TEM was used to find
out the morphology and particle size of synthesized zinc
ferrite particles. TEM (Fig. 1A) confirms particle size
and was used to find out to the morphology of the
particles and the size distribution.
FTIR spectra (Figure S2) of zinc ferrite showed two
fundamental absorption peaks at 546 cm1 and
434 cm1. The existence of these characteristic peaks
confirmed the presence of spinel type structure. The
stronger absorption peak (546 cm1) was due to vi-
bration mode between tetrahedral metal ion and oxy-
gen complex while the weaker absorption peak
(434 cm1) was attributed to stretching vibration be-
tween octahedral metal ion and oxygen complex [50].
In the Raman spectrum (Figure S3) of zinc ferrite
peaks at 217 cm1, 260 cm1, 360 cm1, 469 cm1
were observed as characteristic frequency modes of the
octahedral sites (FeO6) whereas peak at 658 cm1 is
attributed to the motion of oxygen atoms in tetrahedral
(ZnO4) environment.
Magnetic characteristics of a material are a crucial
property which is determined by recording magneti-
zation curve at room temperature using a Vibrating
Sample Magnetometer (PAR 155 VSM). The hystere-
sis loops of zinc ferrite illustrated the magnetic
Fig. 1. (A) TEM image and corresponding particle size distribution
curve in inset; (B) Zeta potential curve of zinc ferrite nanoparticles at
different pH (i.e., pH ¼ 3, 5, 7, 9, 11) using 10 mM NaCl as
electrolyte.
behavior. The parameters such as saturation magneti-
zation (Ms) and coercivity (Hc) were deduced from the
magnetic curve (Figure S4). The saturation magneti-
zation and coercivity values were observed to be 2.1
emu/g and 8.0 Oe, respectively for zinc ferrite which is
a typical behavior of soft ferrites.
3.2. Surface properties of zinc ferrite
The Zeta potential indicates the global charge of the
particles, and is calculated from the electrophoretic
mobility. Fig. 1B shows the effect of pH on the zeta
potential of zinc ferrite nanoparticles. The point of zero
charge (pzc) describes the definite pH value at which
the electrical charge density on a particular surface is
zero. Point of zero charge value of zinc ferrite was
found to be 9.3 as can be seen from Fig. 1(B). So the
surface charge of zinc ferrite is positive at pH values
lower than pzc, neutral at pzc, and negative at pH
values higher than it. As indicated by the pzc of zinc
ferrite, the net surface charge at pH 7 is positive, which

Please cite this article in press as: M.A. Iqubal et al., Studies on interaction of ribonucleotides with zinc ferrite nanoparticles using spectroscopic
and microscopic techniques, Karbala International Journal of Modern Science (2015), http://dx.doi.org/10.1016/j.kijoms.2015.06.001
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Md.A. Iqubal et al. / Karbala International Journal of Modern Science xx (2015) 1e11 5

Fig. 2. (A) Adsorption isotherms and (B) Langmuir plots of ribonucleotides at pH~7.0 on zinc ferrite; each point is the mean ± S.D., n ¼ 3.

is beneficial for adsorbing the negatively charged
ribonucleotides.
3.3. Adsorption data modeling
The adsorption isotherm models are usually used to
investigate the interaction between the absorbent and
the adsorbate when the adsorption process reaches
equilibrium. Adsorption isotherms describe how the
adsorbates interact with the adsorbent at constant
temperature. In this work, the adsorption isotherm
studies were conducted by varying the initial concen-
tration of ribonucleotides from
1.0
104 M4.0
104 M while the adsorbent
mass (25 mg) was kept constant at pH 7.0 for 24 h. The
equilibrium isotherms for the adsorption of ribonu-
cleotides by zinc ferrite are shown in Fig. 2A. With the
increasing initial concentration of ribonucleotides, the
equilibrium adsorption capacity for ribonucleotides
increases gradually until the equilibrium condition is
reached. The percent binding for all the four ribonu-
cleotides corresponding to the saturation point of
adsorption isotherm was calculated and listed in
Table 1.
The percent binding of purine nucleotides (50 -AMP,
0
5 -GMP) was found higher than the pyrimidine nu-
cleotides (50 -CMP, 50 -UMP) probably due to the pres-
ence of larger amounts of p electrons in the double-
ring purines as compared to the single-ring pyrimi-
dines. The Langmuir and Freundlich isotherm models
are often used to describe the equilibrium adsorption
isotherms. The Langmuir model suggests that adsorp-
tion occurs on a homogeneous surface with no inter-
action between adsorbed molecules [51]. The
linearized form of Langmuir model is given as:
 
Ceq Xe ¼ Ceq Xm þ 1=Xm kL
where
Xe ¼ equilibrium adsorption capacity (mg/g)
Xm ¼ maximum adsorption capacity (mg/g)
KL ¼ Langmuir adsorption constant (L/mol)
A straight line plot (Fig. 2B) was obtained upon
plotting Ceq/Xe vs. Ceq and thus the Langmuir
adsorption isotherm was found to be obeyed. The
essential characteristics of the Langmuir isotherm can
be expressed in terms of a dimensionless constant

Table 1
Percent binding and adsorption isotherms constants of ribonucleotides on the surface of zinc ferrite.
Ribonucleotide % bindinga Langmuir Freundlich
Xm (mg/g) KL
10 (L/mol)
4
RL R 2
KF (mg/g) n R2
50 -AMP 64.71 ± 2.37 17.42 6.52 0.048 0.99 191.52 3.55 0.95
50 -GMP 74.43 ± 3.38 22.37 5.32 0.058 0.99 547.30 2.75 0.95
50 -UMP 58.65 ± 3.51 16.03 3.63 0.084 0.99 289.45 2.87 0.94
50 -CMP 58.58 ± 3.31 14.30 4.01 0.076 0.99 266.93 2.88 0.98
a
The value of percent binding represents the mean ± S.D. (n ¼ 3).

Please cite this article in press as: M.A. Iqubal et al., Studies on interaction of ribonucleotides with zinc ferrite nanoparticles using spectroscopic
and microscopic techniques, Karbala International Journal of Modern Science (2015), http://dx.doi.org/10.1016/j.kijoms.2015.06.001
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separation factor RL which is given by the following
equation
RL ¼ 1=ð1 þ KL Co Þ
where Co is the initial concentration of ribonucleotides
solution. The values of RL indicate the type of isotherm
to be reversible (RL ¼ 0), favorable (0 ˂ RL ˂ 1), linear
(RL ¼ 1) or unfavorable (RL ˃ 1). In the present case for
all the ribonucleotide studied the RL values were in the
range of 0e1 suggested the favorable adsorption (Table
1). Freundlich equilibrium isotherm is an empirical
equation which is used for the description of multilayer
adsorption with interaction between adsorbed mole-
cules [52].


lnXe ¼ 1=n lnCeq þ lnKF
where KF and n are the Freundlich constants related to
the adsorption capacity and intensity, respectively. The
values of n are 3.55, 2.75, 2.87 and 2.88 from Freund-
lich plots (in Supplementary Section Figure S5) for 50 -
AMP, 50 -GMP, 50 -UMP and 50 -CMP, respectively
(Table 1). It is generally stated that values of n in the
range 2e10 represent better, 1e2 moderately difficult,
and less than 1 poor adsorption, respectively [53]. In our
case values of n were found to lie in the range of 2e4
suggested the favorable adsorption of ribonucleotides
on zinc ferrite surface. Both models describe the
favorable adsorption of ribonucleotides but according
to the correlation coefficient (R2) as given in Table 1,
Langmuir model was found better than that of
Freundlich model. The Langmuir and Freundlich
adsorption constants and correlation coefficient (R2)
values are summarized in Table 1.
3.4. Kinetics models
The adsorption behavior of the ribonucleotides to-
ward zinc ferrite at different time intervals is shown in
Fig. 3A. The results indicate that a fast adsorption
process occurs during the first 12 h and reaches equi-
librium within 24 h. The pseudo-first and pseudo-
second order models were used to examine the ki-
netics of the adsorption process of the ribonucleotides.
The pseudo-first-order kinetic model [54] is expressed
by Eq.
lnðXe  Xt Þ ¼ lnXe  k1 t
where Xe and Xt are the amount adsorbed (mg/g) at
equilibrium and at time t(h), respectively. k1 is the rate
constant (h1) of pseudo-first-order equation. The
linear plot of ln(XeXt) vs. t is given in the supple-
mentary section (Figure S6).
The linear form of the pseudo-second order rate
equation [55] can be represented as,


t=Xt ¼ 1 k2 Xe2 þ t=Xe
where k2 denotes the rate constant in g/(mg h) for
pseudo-second order kinetic model. The values of k2
and Xe were determined from the slope and intercept of
the pseudo-second order kinetics plot (Fig. 3B). The
rate constant and the correlation coefficient of each
model are listed in Table 2. To evaluate the suitability of
different models, the correlation coefficient R2 was
introduced. The comparison of the two models based on
R2, the pseudo-second-order kinetic model fits the
experimental data more accurately than pseudo first
order. This was mainly supposed to be due to the actual
heterogeneous distribution of ribonucleotides on nano-
particles surface. Pseudo second order model implies
that chemisorption took place during the adsorption
process [54].
3.5. Spectroscopic investigation of ribonucleotides
upon adsorption
3.5.1. Fourier transform infrared spectroscopy (FT-IR)
A 25 mg of zinc ferrite was placed in 25 mL glass
tube containing 4.0
104 M of ribonucleotides so-
lution. The pH of the solution was adjusted to ~7 with
0.01 M NaOH. The tube contents were left for 24 h at
room temperature. The supernatant was decanted and
residue obtained was dried at 30  C. In order to analyze
the interaction of ribonucleotides with zinc ferrite
nanoparticles FT-IR spectra of ribonucleotides and ri-
bonucleotides adduct adsorbed on zinc ferrite were
recorded under identical experimental conditions.
Under the experimental condition (pH ¼ 7.0) the sur-
face of zinc ferrite nanoparticles is positively charged
as indicated by its determined pzc value (9.3). At the
experimental pH ribonucleotides are likely to be pre-
sent in its dianionic form as suggested by the pka2
values of 50 -AMP (6.1), 50 -GMP (6.1), 50 -UMP (6.4)
and 50 -CMP (6.3). The nature of the interaction be-
tween ribonucleotides and zinc ferrite is mainly elec-
trostatic involving positively charged surface of zinc
ferrite and negatively charged atoms in the phosphate
groups, via the p electrons of the aromatic ring, and/or
via the lone pair of electrons on the N and O atoms.
Such type of electrostatic interaction was further
confirmed by infrared spectroscopic results as dis-
cussed below.

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and microscopic techniques, Karbala International Journal of Modern Science (2015), http://dx.doi.org/10.1016/j.kijoms.2015.06.001
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Md.A. Iqubal et al. / Karbala International Journal of Modern Science xx (2015) 1e11 7

Fig. 3. (A) Time-dependent adsorption of ribonucleotides on zinc ferrite at pH 7 for 33 h; (B) Pseudo-second order kinetic model of ribonu-
cleotides on zinc ferrite; each point is the mean ± S.D., n ¼ 3.

The binding of the ribonucleotides on zinc ferrite spinel lattice of the zinc ferrite. Beside phosphate
was observed through ˃C]O, NH2 and PO2 3 groups as group considerable shifting in ˃C]O frequencies from
indicated by a shift in frequencies due to these groups 1680 cm1, 1681 cm1 to 1694 cm1, 1692 cm1 was
along with a change in the nature of their bands. Small observed in case of both 50 -GMP and 50 -UMP,
shifting of pyrimidine and imidazole ring vibrational respectively, while significant change in frequency of
frequencies in ribonucleotides was also observed upon NH2 group was noted in 50 -CMP from 1688 cm1 to
interaction with zinc ferrite. The characteristic peaks of 1674 cm1. The FT-IR spectra of the ribonucleotides
ribonucleotides before and after adsorption are sum- (50 -GMP, 50 -UMP and 50 -CMP) upon adsorption were
marized in Table S1 (see Supplementary Section). given in the supplementary section (Figure S7).
Fig. 4A shows the FT-IR spectra of 50 -AMP and 50 -
AMP adsorbed on zinc ferrite at pH 7. The infrared 3.6. Raman spectroscopy
spectrum of 50 -AMP shows all of its characteristic
peaks as reported in literature [56]. Upon interaction Raman spectra of 5ˈ-AMP and interacting sample
with zinc ferrite, the ʋNH2 peak (1645 cm1) is shifted are given in Fig. 5(B). The band at 1635 cm1 in the
to 1656 cm1, which showed the involvement of the Raman spectrum of 50 -AMP is assigned as a scissoring
NH2 groups in adsorption process. The strong peaks of mode of NH2 [57], shifted towards higher frequencies
1
ʋ(PO23 ) antisymmetric (1032 cm ) and ʋ(PO3 )
2
(1643 cm1) on the adsorption that indicates interac-
1
symmetric (979 cm ) shifted to the frequency tion of amino group with the nanoparticle surface. The
1078 cm1 and 991 cm1, strongly suggest that shifts of the band corresponding to symmetric
interaction is taking place through the phosphate [ʋs(PO2 2
3 )] and asymmetric [ʋas(PO3 )] oscillation of
moiety of 50 -AMP with zinc ferrite. The fact that there phosphate group from 988, 1065 cm1 to 1017,
was no significant change in the infrared frequencies 1072 cm1, respectively suggest the participation of
(546 cm1, 434 cm1) of zinc ferrite upon adsorption PO2
3 group in interaction with the nanoparticle sur-
suggested that the ribonucleotides do not affect the face. The change in intensity ratios of the symmetric
and asymmetric oscillation (ʋs/ʋas) of PO2 3 group
Table 2
from 4.35 to 1.17 for 50 -AMP and interacting sample
Comparison of rate constants calculated based on first-order and
second-order kinetic models. respectively, confirms the involvement of phosphate
group in the formation of bionanocomposite [58]. A
Kinetic model 50 -AMP 50 -GMP 50 -UMP 50 -CMP
small shifting in Raman modes involving vibrations of
Pseudo first order
both pyrimidine and imidazole ring is also observed.
R2 0.97 0.99 0.98 0.98
k1 (h1) 0.1786 0.1468 0.9408 0.2202
Xe (mg/g) 15.46 18.52 12.96 13.20 3.7. Field emission scanning electron microscopy
Pseudo second order (FE-SEM)
R2 0.99 0.99 0.99 0.99
k2 g/(mg h) 0.0264 0.03026 0.0444 0.0378
FE-SEM was employed to observe the attachment
Xe (mg/g) 17.09 19.90 14.47 15.50
of ribonucleotides on zinc ferrite surface. The SEM

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and microscopic techniques, Karbala International Journal of Modern Science (2015), http://dx.doi.org/10.1016/j.kijoms.2015.06.001
 + MODEL
8 Md.A. Iqubal et al. / Karbala International Journal of Modern Science xx (2015) 1e11

Fig. 4. (A) FT-IR; (B) Raman spectra of 50 -AMP and 50 -AMP adsorbed on zinc ferrite.

images of 50 -AMP, zinc ferrite nanoparticles and
adsorption adduct were given in Fig. 5. The surface in
50 -AMP consists of some sort of curl-slice
morphology whereas zinc ferrite has spherical like
morphology. After the adsorption of 50 -AMP surface
of adduct becomes blunt. It is obvious from the SEM
images that 50 -AMP molecule appeared to adhere on
the surface of zinc ferrite. In the EDX spectrum
(Fig. 5D) presence of sodium, phosphorous, carbon
and nitrogen in adsorption adduct in addition to the
elements present in zinc ferrite also confirm the
adsorption of 50 -AMP on the surface of zinc ferrite.
Further the SEM EDX mapping image as shown in
the supporting information clearly demonstrated the
presence of C, N, Na and P in adsorption adduct
(Figure S8).

Fig. 5. FE-SEM images of (A) 50 -AMP; (B) zinc ferrite; (C) Adsorption adduct and (D) EDX spectrum of adsorption adduct.

Please cite this article in press as: M.A. Iqubal et al., Studies on interaction of ribonucleotides with zinc ferrite nanoparticles using spectroscopic
and microscopic techniques, Karbala International Journal of Modern Science (2015), http://dx.doi.org/10.1016/j.kijoms.2015.06.001
 + MODEL
Md.A. Iqubal et al. / Karbala International Journal of Modern Science xx (2015) 1e11 9

3.8. Atomic force microscopy (AFM)
Atomic force microscopy was employed to inves-
tigate and visualize the change in the surface topog-
raphy resulting from adsorption of ribonucleotides on
zinc ferrite nanoparticle surface. AFM images of zinc
ferrite before and after adsorption show significant
morphological changes (Fig. 6). The roughness of the
film surface is generally characterized by the root
mean square roughness (Rms, Sq) and average rough-
ness (Sa) values. The Rms roughness (Sq) and average
roughness (Sa) as measured by AFM are 0.98 nm,
0.67 nm, respectively, for zinc ferrite, and values were
increased to 1.80 and 1.38 nm after adsorption of 50 -
AMP on zinc ferrite. The increased values of Sq and Sa
indicate the adsorption of 50 -AMP on zinc ferrite
nanoparticle surface.
3.9. Textural characteristics
Figure (S9) shows BET adsorption/desorption iso-
therms of zinc ferrite before and after adsorption of 50 -
AMP. According to the IUPAC classification both the
isotherms are mainly related to the type IV isotherm,
which is a characteristic of mesoporous material. The
BET surface areas of zinc ferrite before and after
adsorption are 28.547 m2 g1 and 21.457 m2 g1 and,
respectively. The considerable decrease in the BET
surface area of zinc ferrite suggests that a considerable
amount of 50 -AMP has been adsorbed to the zinc
ferrite nanoparticle surface. The values of the pore
volume for zinc ferrite before and after adsorption are
0.0169 cc g1 and 0.0147 cc g1, respectively, as
determined using BJH pore size distribution method.
The significant decrease in the pore volume of zinc
ferrite further indicates the adsorption of ribonucleo-
tide onto the zinc ferrite nanoparticle surface.
4. Conclusion
In this study, we have explored the interactions of
ribonucleotides with zinc ferrite nanoparticles surface
using spectroscopic and microscopic techniques. The
percent binding of ribonucleotides on zinc ferrite sur-
face was found in the range of 58%e74%. On the basis
of FT-IR studies of ribonucleotides-zinc ferrite adduct,
we proposed that amino, carbonyl and the phosphate
group of ribonucleotides interact with zinc ferrite
surface. The attachment of ribonucleotides on zinc
ferrite surface was obvious from FE-SEM images of
zinc ferrite before and after adsorption. AFM analysis
revealed that surface roughness was increased after

Fig. 6. AFM images (left) and respective 3D-views (right side) of zinc ferrite before (A) and after (B) adsorption of 50 -AMP.

Please cite this article in press as: M.A. Iqubal et al., Studies on interaction of ribonucleotides with zinc ferrite nanoparticles using spectroscopic
and microscopic techniques, Karbala International Journal of Modern Science (2015), http://dx.doi.org/10.1016/j.kijoms.2015.06.001
 + MODEL
10 Md.A. Iqubal et al. / Karbala International Journal of Modern Science xx (2015) 1e11
adsorption of ribonucleotide on nanoparticle surface.
Our results of this study would provide valuable in-
formation in a wide range of topics including origin of
life, formulation of new material for industrial,
biomedical, agricultural and environmental
applications.
Acknowledgment
This work was financially supported by the Indian
Space Research Organization (ISRO), Bangalore, grant
no: ISRO/RES/2/373/11-12 dated Dec. 5, 2011.
Appendix A. Supplementary data
Supplementary data related to this article can be found
at http://dx.doi.org/10.1016/j.kijoms.2015.06.001.
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