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ferrite NPs. But honey assisted combustion route has been believed to
ABSTRACT
be reliable to synthesize ultrafine ferrite NPs with narrow size dis
In recent years, the research towards the magnetic NPs is of
Pure and Ag substituted cobalt ferrite nanoparticles (NPs) having the composition
growing interest due to their potential utility in biomedicine applications.
(1−x)CoFe2O4: xAg (x = 0.0, 0.2) were synthesized by a novel honey assisted
combustion method in order to investigate their structural and magnetic properties The functionalization of ferrite NPs can be found in a wide variety of ap
along with their antibacterial activity. XRD patters confirm the spinel phase of plications including biomedical applications like targeted drug de livery,
CoFe2O4 and the presence of silver (Ag) nanoparticles in the spinel network. The cancer treatment through hyperthermia, magnetic resonance imaging,
incorporation of Ag in CoFe 2O4 spinel structure enhanced the size of the unit cell, etc. [1–3]. The physical properties of ferrite nanoparticles are very
resulting to higher value of lattice parameter (a) compared to the pure CoFe2O4. important to find the suitability for application. These properties are
The sintering process promoted the growth of the crystallite sizes (D). The mainly structure sensitive like the size and shape of the NPs as well as
crystallite sizes of the synthesized and annealed powders were found in the range processing conditions adopted for the preparation of ferrite nano
of 24–41 nm. From the EDX studies, it seemed that the distribution of Ag particles. Therefore, to attain definite recital, different wet chemical
nanoparticles was non-uniform. The saturation magnetization (Ms) and coercivity methods as well as physical methods have been reported to produce
(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 ⁎
Corresponding authors.
magnetization and coercivity of Ag doped CoFe 2O4 were less than that of pure
tribution [4,5]. Therefore, honey assisted combustion method has been that are responsible for skin diseases. In particular, Candide microbe
adopted to prepare un-doped and Ag doped cobalt ferrite NPs. Even species are the human effective microorganisms causing in fections to
now, the fundamental research on spinel nanoparticles has been nails, skin and mucosal surfaces. Silver (Ag) is a well-known chemical
explored due to their versatile utility as photo catalysts in waste water agent which can affectively useful for antibacterial activity. In the recent
treatment as well as for their antibacterial activities. Bacterial microbes studies, silver (Ag) substituted and silver (Ag) coated ferrite
E. Coli, S. Auresus can be frequently found in waste water, flood water
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
tional analysis through EDX.
nanoparticles were prepared in order to understand and improve the TEM micrographs and selected-area electron diffraction (SAED)
antibacterial activity of silver (Ag). Okasha et al. [6] experimented on have been recorded with the help of Technai G20-stwin HRTEM
the effect of Ag doping in MgFe2O4 and reported a development in its working at an accelerating voltage of 200 kV.
electrical and thermal conductivity. Kooti et al. [7] studied the biolo gical Lakeshore model 7410 Vibrational Sample Magnetometer was
activity of AgCoFe2O4 nanocomposite. CoFe2O4 is a famous spinel used to obtain the hysteresis loops at room temperature.
ferrite which has reasonable saturation magnetization, high coercivity
and very high magneto-crystalline anisotropy. It can be found in bio 2.3. Antibacterial test
medical applications like magnetic hyperthermia, targeted drug de
livery and bactericides [8–10].The substitution of Ag in CoFe2O4 spinel Antibiotic susceptibility tests for the CoFe2O4 and the Ag doped
structure or coating of Ag to CoFe2O4 ferrite nanoparticles provides a CoFe2O4 were carried out against Staphylococcus aureus (ATCC
new composite material possessing good physical properties and anti 25923); Escherichia coli (ATCC 25922) and Candida ablicans (ATCC
microbial active nature. 10231) using well diffusion method on Mueller–Hinton agar plates. The
NPs with antibacterial activity can be found in huge applications like various
food processing and packaging, textile industry, biomedical de vices
and water disinfection [11–13]. Among the various ferrites, cobalt and
Ag doped cobalt ferrite is of special class of interest due to their unique
physical, magnetic properties along with their wider scope of
biomedical applications. Therefore, in the present study, honey
assisted combustion route has been adopted to prepare CoFe2O4 and
Ag doped CoFe2O4NPs with a chemical equation (1–x) CoFe2O4: xAg
(x = 0.0, 0.2), assuming an advancement in the biological ac tivity. The
present work deals with the structural, morphological and magnetic
characterization of undoped and Ag doped CoFe2O4 NPs synthesized
and it also aims to identify the action of these NPs in suitable biological
applications.
a d h k l = + + 2 2 2 (1)
Table 1
Structural and magnetic properties of (1–x)CoFe2O4: xAg (x = 0.0, 0.2) -
Sample A (as burnt CoFe 2O4), Sample B (annealed CoFe2O4), Sample C(as burnt
Ag-CoFe2O4) and Sample D (annealed Ag-CoFe 2O4).
Samples a D Ms Hc Mr S = Mr/Ms
(Å) (nm) (emu/g) (Oe) (emu/g)
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.
and the Ag doped) show that the shapes of the ferrite nanoparticles are
nearly spherical and polyhedron. The distribution of particles of
Table 2
different sizes have been revealed from the histograms and the
Elemental compositions of (1–x)CoFe2O4: xAg (x = 0.0, 0.2) - Sample A(as
average particle sizes for the as-burnt cobalt ferrite and the Ag doped
burnt CoFe2O4), Sample B (annealed CoFe2O4), Sample C(as burnt
cobalt ferrite are found to be 25.2 nm and 28.4 nm respectively. The
Ag-CoFe2O4) and Sample D (annealed Ag-CoFe 2O4).
agglomeration of Ag na noparticles on the ferrite nanoparticles may be
Samples Co:Fe Fe:O Ag resulted a bigger par ticle size in the Ag doped CoFe2O4. Similar
Sample A 0.57 0.48 – Sample B 0.52 0.42 – Sample C 0.5 0.47 1.15 Sample D 0.56 studies have been reported in the literature [17]. The average particle
0.49 0.94 sizes estimated from histo grams are consistent with the crystallite size
Destimated from the XRD analysis. The superimposition of bright spots
observed in the SAED pattern of the ferrite sample recorded through a
transmission electron microscope is an indicative of polycrystalline
3.3. SEM and TEM studies nature of ferrite samples [16] that is supporting the particle distribution
as observed from XRD and TEM.
Morphology of the undoped and the Ag doped CoFe2O4 nano
particles annealed at 600 °C were investigated using scanning electron
microscopy (SEM), and corresponding micrograms are shown in Fig. 4.
The morphological changes in samples due to doping and annealing
are clearly evident from the nature of SEM micrograms. The particle
size and shape of the as-burnt samples of the undoped and the Ag
doped cobalt ferrite NPs have been recorded using transmission
electron mi croscopy (TEM). TEM images and histograms are
presented in Fig. 5.TEM images of the as-burnt sample (the undoped
3.4. Magnetic studies
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.
abundant aspects like magnetocrystalline anisotropy, microstrain, size
distribution and magnetic domain size [22–24]. The variation of Hc in
VSM results, it can be observed that the coercivity (Hc) is decreased in
the pure CoFe2O4 can be explained in the following way; in the multi
pure the CoFe2O4, but it is increased in the Ag doped CoFe2O4 with the
heat treatment. The above oscillation of Hc may be influenced by
Fig. 5. TEM and HR-TEM images of as-prepared pure and Ag substituted cobalt ferrite nanoparticles.
695
M.K. Satheeshkumar et al. Journal of Magnetism and Magnetic Materials 469 (2019) 691–697
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
that the AgCoFe2O4 Nps are quite effective than the CoFe2O4 against
aureus, Escherichia coli and Candida ablicans tested with the zone of Escherichia coli and Candida ablicans. This is due to the fact that the
inhibition greater than 7 mm. Generally, getting 7 mm inhibition zone antimicrobial activity of AgCoFe2O4 depends on the amount of Ag+ ions
diameter due to testing material represents the good antibacterial ac released which can cause cell distortion and death of bacterial species
tivity against to bacteria which is under testing [21]. Highly con [28]. Thus the CoFe2O4 and the AgCoFe2O4 were found to in hibit all
centrated nanoparticles produce greatest antimicrobial action up to tested pathogenic bacteria and fungus including Staphylococcus
10–20 mm of diameter. The antimicrobial activity was compared with aureus and Escherichia coli and Candida ablicans.
commercial antimicrobial agent streptomycin, as a positive control
impregnated on the disc. The antibacterial activity of streptomycin 4. Conclusion
seems to be superior to the present NPs of testing materials. Several
discussions are going on among the researchers about the Co ferrite and Ag substituted Co ferrite nanoparticles have been
antibacterial activity. However, the possible mechanism of antimicrobial synthesized by honey assisted combustion method. Secondary phases
activity for the nanoparticles is due to: (1) interference during cell wall are found in the Ag doped CoFe2O4 that is due to the change in the
synthesis; (2) suppression during protein biosynthesis (translation); (3) environments of Fe3+ and O2– with the substitution of Ag in the spinel
inter ference or disruption of transcription process; and (4) disruption of structure. The substitution of Ag in the spinel structure of cobalt ferrite
primary metabolic pathways [26]. The inactivation of bacterial en seems to be effecting the surface energy needed for the crystallite
zymes by the mechanism that Co ions released from nano clusters in growth. The average particle sizes for the as-burnt cobalt ferrite and
teract with the thiol groups present in bacterial enzymes which results the Ag doped cobalt ferrite are 25.2 nm and 28.4 nm. The substitution
in damage to bacterial DNA and cell death [27]. The results revealed of Ag is changing the magnetic behaviour of the CoFe2O4 from
ferromagnetic order to superparamagnetic order. The changes in
magnetic parameters of the pure CoFe2O4and the Ag doped CoFe2O4
are due to the change of particle sizes/or magnetocrystalline
anisotropy. When compared with the pure CoFe2O4, the Ag doped
CoFe2O4 are exhibiting good anti bacterial activity.
Acknowledgement
References
697
mediated sol-gel combustion, J. Phys. Chem. Sol. 107 (2017) 150–161. [5]
Raghvendra Singh Yadav, Ivo Kuřitka, Jaromir Havlica, Jarmila Vilcakova, Jiri Masilko,
Lukas Kalina, Jakub Tkacz, Miroslava Hajdúchová, Vojtech Enev, Structural, dielectric,
electrical and magnetic properties of CuFe2O4 nanoparticles synthesized by honey
mediated sol–gel combustion method and annealing effect, J. Mater. Sci.: Mater. Elect.
28 (2017) 6245–6261.
[6] N. Okasha, Influence of silver doping on the physical properties of Mg ferrites, J.
Mater. Sci. 43 (12) (2008) 4192–4197.
[7] M. Kooti, S. Gharineh, M. Mehrkhah, A. Shaker, H. Motamedi, Preparation and
antibacterial activity of CoFe2O4/SiO2/Ag composite impregnated with strepto
mycin, Chem. Eng. J. 259 (2015) 34–42.
[8] S.S. Challa, R. Kumar, Faruq Mohammad, Magnetic nanomaterials for hy
perthermia-based therapy and controlled drug delivery, Adv. Drug Deliv. Rev. 63
(9) (2011) 789–808.
[9] S. Amiri, H. Shokrollahi, The role of cobalt ferrite magnetic nanoparticles in med ical
science, Mater. Sci Eng. C 33 (1) (2013) 1–8.
[10] Sajjad Abbasi Pour, Hamid Reza Shaterian, Carboxymethyl cellulose (CMC)-loaded
Co-Cu doped manganese ferrite nanorods as a new dual-modal simultaneous con
trast agent formagnetic resonance imaging and nanocarrier for drug delivery
system, J. Magn. Magn. Mater. 438 (2017) 85–94.
[11] Jayshri V. Pande, Ankush B. Bindwal, Yogesh B. Pakade, Rajesh B. Biniwale,
Application of microwave synthesized Ag-Rh nanoparticles in cyclohexane dehy
drogenation for enhanced H2 delivery, Int. J. Hydrogen Energy 43 (15) (2018)
7411–7423.
[12] S. Krishnakumar, P. Janani, S. Mugilarasi, GanitaKumari, Chemical induced fabri
cation of silver nanoparticles (Ag-NPs) as nanocatalyst with alpha amylase
enzyme for enhanced breakdown of starch, Biocatal. Agricult. Biotechnol. (2018).
[13] Elena Husanu, Cinzia Chiappe, Andrea Bernardini, Synthesis of colloidal Ag nano
particles with citrate based ionic liquids as reducing and capping agents, Colloid.
Surf. A: Physicochem. Eng. Aspect. 538 (2018) 506–512 .
[14] E. Ranjith Kumar, R. Jaya Prakash, M.S. Seehra, T. Prakash, Sanjay Kumar, Effect
of α–Fe2O3 phase on structural, magnetic and dielectric properties of Mn–Zn ferrite
nanoparticles, J. Phys. Chem. Sol. 74 (2013) 943–949.
[15] S.A.V. Prasad, M. Deepty, P.N. Ramesh, G. Prasad, K. Srinivasarao, Ch. Srinivas,
K. VijayaBabu, E. Ranjith Kumar, N. Krisha Mohan, D.L. Sastry, Synthesis of
MFe2O4 (M=Mg2+, Zn2+, Mn2+) spinel ferrites and their structural, elastic and
electron magnetic resonance properties, Ceram. Int. 44 (2018) 10517–10524.
[16] E. Ranjith Kumar, Ch. Srinivas, M.S. Sheera, M. Deepty, I. Pradeep, A.S. Kamzin,
Particle size dependence of the magnetic, dielectric and gas sensing properties of Co
substituted NiFe2O4 nanoparticles, Sensors Actuat. A: Phys. 279 (2018) 10–16.
[17] Ping Gong, Huimin Li, Xiaoxiao He, Kemin Wang, Hu. Jianbing, Weihong Tan,
Shouchun Zhang, Xiaohai Yang, Preparation and antibacterial activity of
Fe3O4@Ag nanoparticles, Nanotechnology 18 (28) (2007) 1–7.
[18] R. Zhang, L. Sun, Z. Wang, W. Hao, E. Cao, Y. Zhang, Mater. Res. Bull. 98 (2018)
133–138.
[19] S. Mahalakshmi, K. Srinivasa Manja, S. Nithiyanantham, Structural and morpho
logical studies of copper-doped nickel ferrite, J. Supercond. Nov. Magn. 28 (10)
(2015) 3093–3098.
[20] A. Yakubu, Z. Abbas, M. Hashim, A. Fahad, Effect of sintering temperature on
Co0.5Zn0.5Fe2O4 nano-particles evolution and particle size distribution, Adv.
Nanopart. 4 (2015) 37–44.
[21] M. Kooti, S. Saiahi, H. Motamedi, Febrication of silver-coated cobalt ferrite nano
composite and the study of its antibacterial actuvuty, J. Magn. Magn. Mater. 333
(2013) 138–143.
[22] B.G. Toksha, S.E. Shirsath, S.M. Patange, K.M. Jadhav, Structural investigations
and magnetic properties of cobalt ferrite nanoparticles prepared by sol-gel auto
com bustion method, Solid State Commun. 147 (2008) 479–483.
[23] N. Himansulal, Kinetics study on the thermal decomposition of lanthanum oxalate
catalysed by Zn-Cu nano ferrites, Res. J. Mater. Sci. 3 (2) (2015) 1–8. [24] Y. Shen, Y.
Wu, H. Xu, J. Fu, X. Li, Q. Zhao, Y. Hou, Facile preparation of sphere-like copper ferrite
nanostructures and their enhanced visible-light-induced photo catalytic conversion of
benzene, Mater. Res. Bull. 48 (10) (2013) 4216–4222. [25] R. Shukla, R.S. Ningthoujam,
S.S. Umare, S.J. Sharma, Sajith Kurian, R.K. Vatsa, A.K. Tyagi, N.S. Gajbhiye,
Decrease of superparamagnetic fraction at room tem perature in ultrafine CoFe2O4
particles by Ag doping, Hyperfine Interact. 184 (2008) 217–225.
[26] C.H. Shilpa Chakra, K. Venkateswara Rao, Tambur Pavani, Antimicrobial activity of
pure Cu nano particles synthesized by surfactant varied chemical reduction
method, Environ. Nanotechnol. Monitor. Manage. 6 (2016) 88–94.
[27] N.S. Alahmadi, J.W. Betts, F. Cheng, M.G. Francesconi, S.M. Kelly, A. Kornherr,
T.J. Prior, J.D. Wadhawan, Synthesis and antibacterial effects of cobalt–cellulose
magnetic nanocomposites, RSC Adv. 7 (2017) 20020–20026.
[28] Rajdip Bandyopadhyaya, Pritam Biswas, Synergistic antibacterial activity of a
combination of silver and copper nanoparticle impregnated activated carbon for
water disinfection, Environ. Sci. Nano 12 (2017) 1–33.