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Keywords: Pure and Ag substituted cobalt ferrite nanoparticles (NPs) having the composition (1−x)CoFe2O4: xAg
Nanoparticles (x = 0.0, 0.2) were synthesized by a novel honey assisted combustion method in order to investigate their
Honey assisted synthesis structural and magnetic properties along with their antibacterial activity. XRD patters confirm the spinel phase
Structural analysis of CoFe2O4 and the presence of silver (Ag) nanoparticles in the spinel network. The incorporation of Ag in
Magnetic properties
CoFe2O4 spinel structure enhanced the size of the unit cell, resulting to higher value of lattice parameter (a)
compared to the pure CoFe2O4. The sintering process promoted the growth of the crystallite sizes (D). The
crystallite sizes of the synthesized and annealed powders were found in the range of 24–41 nm. From the EDX
studies, it seemed that the distribution of Ag nanoparticles was non-uniform. The saturation magnetization
(Ms) and coercivity (Hc) of the powders were influenced by annealing as well as with the substitution of Ag.
The highest value of saturation magnetization (60 emu/g) was obtained by the CoFe2O4 nanoparticles with the
coercivity value 1358 Oe. The saturation magnetization and coercivity of Ag doped CoFe2O4 were less than
that of pure CoFe2O4. The present cobalt ferrite nanoparticles and Ag doped cobalt ferrite nanoparticles have
shown good antibacterial activities. But Ag doped cobalt ferrite nanoparticles seems to be the potential can-
didates for effective antibacterial activity. The structural and magnetic results along with the results of an-
tibacterial activities are reported in the present manuscript.
1. Introduction ferrite NPs. But honey assisted combustion route has been believed to
be reliable to synthesize ultrafine ferrite NPs with narrow size dis-
In recent years, the research towards the magnetic NPs is of growing tribution [4,5]. Therefore, honey assisted combustion method has been
interest due to their potential utility in biomedicine applications. The adopted to prepare un-doped and Ag doped cobalt ferrite NPs.
functionalization of ferrite NPs can be found in a wide variety of ap- Even now, the fundamental research on spinel nanoparticles has
plications including biomedical applications like targeted drug de- been explored due to their versatile utility as photo catalysts in waste
livery, cancer treatment through hyperthermia, magnetic resonance water treatment as well as for their antibacterial activities. Bacterial
imaging, etc. [1–3]. The physical properties of ferrite nanoparticles are microbes E. Coli, S. Auresus can be frequently found in waste water,
very important to find the suitability for application. These properties flood water that are responsible for skin diseases. In particular, Candide
are mainly structure sensitive like the size and shape of the NPs as well microbe species are the human effective microorganisms causing in-
as processing conditions adopted for the preparation of ferrite nano- fections to nails, skin and mucosal surfaces. Silver (Ag) is a well-known
particles. Therefore, to attain definite recital, different wet chemical chemical agent which can affectively useful for antibacterial activity. In
methods as well as physical methods have been reported to produce the recent studies, silver (Ag) substituted and silver (Ag) coated ferrite
⁎
Corresponding authors.
E-mail addresses: ranjueaswar@gmail.com (E.R. Kumar), srinivas.chintoju75@gmail.com (C. Srinivas), nsuri22@gmail.com (N. Suriyanarayanan).
https://doi.org/10.1016/j.jmmm.2018.09.039
Received 23 August 2018; Received in revised form 6 September 2018; Accepted 8 September 2018
Available online 08 September 2018
0304-8853/ © 2018 Elsevier B.V. All rights reserved.
M.K. Satheeshkumar et al. Journal of Magnetism and Magnetic Materials 469 (2019) 691–697
nanoparticles were prepared in order to understand and improve the concentrated (100–500 mg) CoFe2O4 and AgCoFe2O4 nanoparticles
antibacterial activity of silver (Ag). Okasha et al. [6] experimented on sonicated in distilled water were pipetted on to individual inoculated
the effect of Ag doping in MgFe2O4 and reported a development in its agar plates and then incubated at 37 °C for 24 h before that the mi-
electrical and thermal conductivity. Kooti et al. [7] studied the biolo- croorganisms were cultured into nutrient broth medium and incubated
gical activity of AgCoFe2O4 nanocomposite. CoFe2O4 is a famous spinel at 37 °C for 2 to 5 h. Each strain was swabbed uniformly on to agar
ferrite which has reasonable saturation magnetization, high coercivity plates and 6 mm diameter wells were made in to which nanoparticles
and very high magneto-crystalline anisotropy. It can be found in bio- were loaded. The standard antibiotic streptomycin was also loaded as
medical applications like magnetic hyperthermia, targeted drug de- control to monitor any contamination during testing. Zones of inhibi-
livery and bactericides [8–10].The substitution of Ag in CoFe2O4 spinel tion surrounding the coated samples were measured by vernier caliper
structure or coating of Ag to CoFe2O4 ferrite nanoparticles provides a as a parameter of antibacterial property of the synthesized CoFe2O4 and
new composite material possessing good physical properties and anti- the AgCoFe2O4.
microbial active nature.
NPs with antibacterial activity can be found in huge applications 3. Results and discussion
like food processing and packaging, textile industry, biomedical de-
vices and water disinfection [11–13]. Among the various ferrites, 3.1. X-Ray diffraction studies
cobalt and Ag doped cobalt ferrite is of special class of interest due to
their unique physical, magnetic properties along with their wider XRD technique has been used to confirm the formation of phase in
scope of biomedical applications. Therefore, in the present study, as-burnt and annealed samples of cobalt and Ag doped cobalt ferrite
honey assisted combustion route has been adopted to prepare CoFe2O4 NPs. The respective XRD patterns are depicted in Fig. 2. The diffraction
and Ag doped CoFe2O4NPs with a chemical equation (1–x) CoFe2O4: peaks identified at the diffraction angles nearer to 30.19°, 35.55°,
xAg (x = 0.0, 0.2), assuming an advancement in the biological ac- 37.15°, 43.24°, 53.34°, 57.14°, 62.69° and 74.03o in all XRD patterns are
tivity. The present work deals with the structural, morphological and indexed with the miller indices (2 2 0), (3 1 1), (2 2 2), (4 0 0), (4 2 2),
magnetic characterization of undoped and Ag doped CoFe2O4 NPs (5 1 1), (4 4 0) and (5 3 3). These are consistent with the JCPDS card no.
synthesized and it also aims to identify the action of these NPs in 75-0894 belonging to Fd3m space group with cubic spinel structure.
suitable biological applications. The diffraction peaks in the patterns (c) and (d) are noticed nearly at
the diffraction angles 38.09°, 44.39oand 64.69°, and are labeled as
2. Experimental procedure and characterization techniques (1 1 1), (2 0 0) and (2 2 0) comparing with the silver X-ray spectrum.
This observation confirms the presence of silver (Ag) nanoparticles in
2.1. Sample preparation the spinel ferrite network. The indexed diffraction planes are consistent
with JCPDS card no.004-0783 belonging to Fm3m space group with
Analytical grade cobalt nitrate (Co(NO3)26H2O), silver nitrate (Ag cubic structure. An interesting observation has been made from the
(NO3)2) and ferric nitrate (Fe(NO3)29H2O) are used as precursors to XRD patterns. The pure cobalt ferrite (CoFe2O4) both as-burnt and
synthesize CoFe2O4 and Ag doped CoFe2O4 ferrite NPs. These materials annealed samples seem to be free from the formation of secondary
are weighed in stoichiometric amounts along with freshly extracted phases, where in the silver (Ag) substituted cobalt ferrite secondary
honey from bees foraged on eucalyptus trees. In this typical experiment, phases of α–Fe2O3 (JCPDS card no.87-1166) are found which are in-
solutions of 0.5mol Co(NO3)26H2O, 1mol Fe(NO3)29H2O were slowly dexed in the XRD patterns. Generally, the methods of preparation,
added (1:2 ratio) to the honey solution (30 ml of fresh honey +20 ml of nature of additives, and optimum conditions for the preparation of
distilled water). They severely mixed for 1 h and finally ferrite powder ferrites are the factors that predominately affect the spinel structure of
was obtained by heating the mixed solution to 100 °C. The obtained ferrites and the formation of secondary phases. The literature reports
ferrite powder was milled in an agate mortar into a fine powder and a [14] disclose that the formation of secondary phases in Mn-ferrite and
portion of the powder was heat treated at 600 °C in the air atmosphere. Mn-substituted ferrites are phenomenal due to oxidation of Mn2+which
The same method was repeated to prepare Ag doped CoFe2O4 NPs (0.1 depends upon the local oxygen environment. A comprehensive analysis
mol Ag(NO3)2 + 0.4 mol Co(NO3)26H2O). The as prepared samples and of the formation of these secondary phases in different ferrite systems
sintered samples are characterized for structural, magnetic and anti- was reported in our previous publication [15]. In the present ferrite
bacterial studies. The pictorial diagram of method preparation is shown systems, the presence of Ag in the spinel structure seems to be affecting
in Fig. 1. the Fe3+ and O2– environments resulting to the formation of secondary
phases. The lattice constant (a) for cubic spinel structure was calculated
2.2. Characterization techniques using the formula [16]
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M.K. Satheeshkumar et al. Journal of Magnetism and Magnetic Materials 469 (2019) 691–697
Table 1
Structural and magnetic properties of (1–x)CoFe2O4: xAg (x = 0.0, 0.2) -
Sample A (as burnt CoFe2O4), Sample B (annealed CoFe2O4), Sample C(as burnt
Ag-CoFe2O4) and Sample D (annealed Ag-CoFe2O4).
Samples a D Ms Hc Mr S = Mr/Ms
(Å) (nm) (emu/g) (Oe) (emu/g)
doped CoFe2O4 are 24.1 nm and 40.9 nm. The crystallite sizes of the
prepared and the annealed Ag doped CoFe2O4 are 27.5 nm and 39.3 nm.
The improvement of crystallinity of ferrite NPs has been clearly iden-
tified by increasing the sharpness of the diffraction peaks under an-
nealing treatment which can be expected due to Oswald ripening. It was
observed that the crystallite size of ferrite NPs in the prepared Ag doped
CoFe2O4 is greater than that of the prepared un-doped CoFe2O4.
Whereas, the crystallite size of ferrite NPs in the annealed Ag doped
CoFe2O4 is less than that of the annealed un-doped CoFe2O4. With the
heat treatment, the size of Ag nanoparticles is increased. These bigger
Ag nanoparticles in the annealed Ag doped CoFe2O4 may be acted as
resistive centers at the grain boundaries to obstruct the release of sur-
face energy needed for the crystallite growth.
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M.K. Satheeshkumar et al. Journal of Magnetism and Magnetic Materials 469 (2019) 691–697
Fig. 3. EDX spectra of Pure and Ag substituted cobalt ferrite nanoparticles: (a) as-prepared cobalt ferrite, (b) 600 °C annealed cobalt ferrite, (c) as-prepared Ag-cobalt
ferrite (d) 600 °C annealed Ag-cobalt ferrite.
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M.K. Satheeshkumar et al. Journal of Magnetism and Magnetic Materials 469 (2019) 691–697
Fig. 4. SEM micrograms of Pure and Ag substituted cobalt ferrite nanoparticles: (a) as-prepared cobalt ferrite, (b) 600 °C annealed cobalt ferrite, (c) as-prepared Ag-
cobalt ferrite (d) 600 °C annealed Ag-cobalt ferrite.
VSM results, it can be observed that the coercivity (Hc) is decreased in abundant aspects like magnetocrystalline anisotropy, microstrain, size
pure the CoFe2O4, but it is increased in the Ag doped CoFe2O4 with the distribution and magnetic domain size [22–24]. The variation of Hc in
heat treatment. The above oscillation of Hc may be influenced by the pure CoFe2O4 can be explained in the following way; in the multi
Fig. 5. TEM and HR-TEM images of as-prepared pure and Ag substituted cobalt ferrite nanoparticles.
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M.K. Satheeshkumar et al. Journal of Magnetism and Magnetic Materials 469 (2019) 691–697
Fig. 8. Antimicrobial activity of CoFe2O4 and AgCoFe2O4 against (A) & (B)
Staphylococcus aureus, (C) & (D) Escherichia coli, (E) & (F)Candida albicans.
study, it can be observed that the width of the hysteresis loop is de-
creased with the substitution of Ag in the spinel structure of CoFe2O4.
This indicates that the nature of magnetization is transforming from the
ferromagnetic order to superparamagnetic order with the substitution
of Ag, resulting the decrease of magnetocrystalline anisotropy. The
decrease of magnetocrystalline anisotropy is the probable reason for the
low of Hc in the Ag doped CoFe2O4 when compared with the pure
CoFe2O4 in the present studies. The isotropic nature of present ferrite
samples is evident by noticing with low value of squareness ratio which
is in the range of 0.29 to 0.37.
Table 3
Inhibitory activity of CoFe2O4 and AgCoFe2O4.
Sample Microbes Zone of inhibition in mm
CoFe2O4 E.coli 7.5 ± 0.20 8.0 ± 0.7 8.5 ± 0.04 9.0 ± 0.8 9.5 ± 0.04 18.66 ± 0.47
S.aureus 9.0 ± 0.41 9.5 ± 0.01 8.5 ± 0.01 8.75 ± 0.20 10.0 ± 0.41 18.66 ± 0.47
C.albicans 8.0 ± 0.08 9.5 ± 0.62 10.05 ± 0.23 12.5 ± 0.01 15.0 ± 0.07 27.8 ± 0.16
AgCoFe2O4 E.coli 8.0 ± 0.08 8.5 ± 0.06 9.3 ± 0.23 10.5 ± 0.01 10.5 ± 0.08 18.66 ± 0.47
S.aureus 6.5 ± 0.06 6.8 ± 0.04 7.5 ± 0.01 7.86 ± 0.20 8.5 ± 0 19.03 ± 0.12
C.albicans 8.0 ± 0.04 8.5 ± 0.31 8.93 ± 0.09 16.13 ± 0.18 20.03 ± 0.47 29.17 ± 0.23
696
M.K. Satheeshkumar et al. Journal of Magnetism and Magnetic Materials 469 (2019) 691–697
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