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DOI: 10.1016/j.jmrt.2019.09.034
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Available online 1 October 2019
Tuning hyperthermia efficiency of MnFe2O4/ZnS nanocomposites by controlled ZnS concentration
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D.K. Mondala, C. Borgohainb, N. Paula, J.P. Boraha,
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jpborah@rediffmail.com

Corresponding author.
a Department of Physics, National Institute of Technology Nagaland, Chumukedima, 797103, India
b Central Instrumentation Facility (CIF), Indian Institute of Technology Guwahati, Guwahati, 781039, India
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Tables (2)
Table 1. Structural parameters of MnFe2O4 and ZnS nanoparticles in different samples.
Table 2. The observed value of coercivity (Hc), saturation Magnetization (Ms) and Remanence (Mr) of MnFe2O4 with ZnS 1%, 3% and 5% in the nanocomposites.
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Abstract

Magneto-fluorescence MnFe2O4/ZnS nanocomposite with varying ZnS concentration were successfully synthesized by co-precipitation method. Its structural, morphological, optical and magnetic properties are comprehensively characterized by XRD, HRTEM, FTIR, UV-Vis, Photoluminescence (PL) spectroscopy and VSM techniques. XRD Results indicates that the prepared nanocomposite comprises of cubic Spinel structure of MnFe2O4 and cubic zinc blende structure of ZnS. FTIR analysis exhibits conjugation of ZnS with surface of MnFe2O4 nanoparticles through surfactant PEG. The photoluminescence study shows the shifting of emission peaks due to strong quantum confinement effect and the absorption spectra shows the trend of increasing band gap with increasing concentration of ZnS. Room temperature magnetic study shows that the saturation magnetization increases with increasing ZnS concentration. The prepared nanocomposite investigated for hyperthermia application at different concentration of ZnS. The result infer that the nanocomposite is a promising material for hyperthermia and also heating efficiency can be tuned by changing the ZnS concentration in the MnFe2O4/ZnS nanocomposite.

Keywords:
Nanocomposites
Morphology
Photoluminescence
Quantum confinement
Hyperthermia
Full Text
1Introduction

Opto-magnetic nanocomposites have drawn attention from the research community because of their multifunctional properties and broad range of application in military [1,2], catalysis [3–8], devices [9–15] and others [16–22]. Recently magnetic fluorescence nanocomposites considered as one of the most promising therapeutic agent due to its exciting magnetic and optical properties and their potential range of photo-catalysis and biomedical application such as targeted drag delivery [23], magnetic resonance imaging [24], diagnosis [25], tissue engineering [26], mediator to convert electromagnetic energy into heat energy, when expose to A.C magnetic field [27–30]. Spinel Metal ferrite (MFe2O4 where M = Mn, Ni, Co, Zn etc) nanoparticles are superior for hyperthermia owing to their tunability, biocompatibility, chemical stability [31]. Among the ferrites, MnFe2O4 is a decent candidate which has been widely used as MRI contrast agent, targeted drug delivery and magnetic hyperthermia agent [32–34]. MnFe2O4 nanoparticles shows mixed spinel structure due to their Mn2+and Fe3+ ions distribution over tetrahedral A site and octahedral B site (Mn2+ Fe3+)A (Mn2+ Fe3+)BO4. This cataion distribution leads exchange interaction between two sites which increase the saturation magnetization of MnFe2O4 nanoparticles. Due to fascinating size dependent electronic and optical properties, II-VI semiconductor structures have attracted increasing attention [35,36]. Among this semiconductor group ZnS (direct band gap 3.68 eV) is an excellent contestant due to its significant optical properties like high photo stability, active size dependent physio-chemical properties, cell imaging, tuneable and narrow emission spectra motivated worldwide enthusiasms of scientists [37–39].

Several groups have investigated various types of magnetic luminescence nanocomposites adopting different methods to analyse its optical and magnetic properties. He et al. [40] reported lanthanide doped nanoparticles to prepare Fe3O4@LaF3:CeTb opto-magnetic nanoparticles. Acharya et al. [41] succeeded to visualise recognition of targeted cancer cells by a multifunctional magneto-fluorescent nanocomposites. Cui et al. [42] develop a fluorescent magnetic nanoprobe for vivo targeted imaging and hyperthermia therapy of prostate cancer and showed highly selective targeting, fluorescent imaging and magnetic resonance imaging of the prostate cancer cells and solid tumours under vitro alternating magnetic field irradiation.

Here in our work, we synthesis a MnFe2O4/ZnS magnetic fluorescence bi-functional nanocomposites by co-precipitation method, considering MnFe2O4 as a core and its surface is functionalised by organic polymer PEG and ZnS used as a shell. We have investigated structural, morphological, optical and magnetic properties of the nanocomposites. In this work we have reported the moderate hyperthermic efficiency of the nanocomposite and also study the effect of the concentration of ZnS in the nanocomposite to optimized heating efficiency.

2Experimental studies2.1Synthesis of MnFe2O4 nanoparticles

MnFe2O4 magnetic nanoparticles were synthesis by a simple co-precipitation technique using hydrolysis of Mn2+ and Fe3+ salts of molar ratio 1:2. The aqueous solution of precursor materials MnCl2.4H2O and 2FeCl3 were prepared at room temperature. A NaOH solution of 2.0 M was added drop-wise to Mn2+ and Fe3+ mixture under continuous stirring till the pH level of the solution reached 7–8. After this, the prepared solution was stirred for 30 min at 100 ℃. The obtained black coloured solution then sonicate for half an hour at 50 ℃ and then cooled the solution up to room temperature. The black precipitate solution were vacuum pumped and the obtained precipitate washed 5 times by de-ionised water, then dried for 8 h at 100 ℃. The solid product reduce to powder. The obtained powder again heated at 200 ℃ for 4 h.

2.2Synthesis of ZnS nanoparticles

ZnS nanoparticles were synthesised by co-precipitation method where Zinc acetate [Zn (CH3COO)2] of 0.2 M and sodium sulphide [Na2S.9H2O] of 0.2 M were taken separately, then dissolved in 50 ml of de-ionised water and stirred for 30 min. With the Zinc acetate solution, the sodium sulphide solution was added drop wise under stirring at 70 ℃ until the pH value of the solution reached up to 7–8. The solution then cooled to room temperature. The obtained white precipitate washed several times by de-ionised water and then dried at 80 ℃ for 6 h. As prepared MnFe2O4 nanoparticles and PEG4000 were mixed separately in 25 ml of de-ionised water at stoichiometric ratio and then satired both the solution for 20 min. The mixed solutions stired at 50 ℃ for 30 min.The solution is then sonicate for 90 min at 50 ℃ and cooled it. The black coloured solution centrifuged at 3000 r.p.m for 15 min and the obtained black precipitate washed 4 times then dried at 60 ℃ for 12 h. The acquired solid product grinds to powder.

2.3Synthesis of MnFe2O4@ZnS 1%, 3% and 5%

MnFe2O4/PEG and ZnS at the wt. percentage of 1% of MnFe2O4/PEG are dissolving separately in 25 ml of de-ionised water. After mixing both the solution satired continuously for half an hour at 50 ℃ and the resulting solution sonicate for 90 min at 50 ℃. The obtained precipitate centrifuge at the rate of 2000 r.p.m for 10 min and then washed 5 times by de-ionised water. The acquired black precipitate dried at 60 ℃ for 12 h and then grinds to powder. Similarly the sample for ZnS 3% and 5% also prepared.

3Characterization

A powder X-ray diffractometer (Rigaku, RINT 2500 TRAX-III) using Cukα radiation (wavelength λ = 1.5406 Å) was used to take the XRD spectra of the samples to identify the phase. The morphology of the materials was studied by a high resolution transmission electron microscope (HRTEM) of (JEOL. Model: JEM 2100). To observed the vibrational spectra of synthesised materials A Cary 630 Fourier transform infrared (FT-IR) (Agilent Technology) was used. The recorded Photoluminescence (PL) spectra of the samples were examined by fluorescence spectrometer [Thermospectronic AMINCO Bowman (series 2)]. A double beam spectrometer (HITACHI-U3210) in the range of 200–800 nm was used to record the absorption spectra of all the samples at a resolution of 0.1 nm wavelength. The magnetic parameters were studied by Vibrating Sample Magnetometer (VSM) (Model: 7410 series).

3.1Induction heating

The Easy Heat 8310, Ambrell make, UK with a coil diameter of 8 turns was used to study the induction heating efficiency of pure MnFe2O4 and MnFe2O4/ZnS nanocomposites at different weight percentage. The 2 mg mass of each sample was suspended in 1 ml of distilled water, were sonicated for 15 min for suitable suspension, and then placed at the centre of the water cooled induction coil. The frequency of A.C magnetic field was fixed at 336 kHz and the current were kept constant at two different values 250 Å and 350 Å. The magnetic field was evaluated from the relation

where N is the number of turns of the induction coil, z is the distance from the centre of the coil on z-axis, ‘a’ is the radius of the coil and I is the current.

4Results and discussion4.1Structural and morphological studies

XRD patterns of MnFe2O4/ZnS nanocomposites at different weight percentage of ZnS (1%, 3%, 5%) are displayed in Fig. 1. All the samples shows the diffraction peaks corresponding to the lattice planes (311),(331),(511),(440) and (531), which match well with the standard JCPDS (card no.73–1964) and confirms the single phase cubic spinel structure of MnFe2O4. The diffraction peaks be in tune with the lattice planes (111) and (311) for the samples signify, cubic zinc blende ZnS structure JCPDS (card no.80-0020). The signature of cubic spinel structure of MnFe2O4 and cubic zinc blende structure of ZnS for the synthesised samples were confirms from the diffractrograms. Again, MnO impurity peaks accord with the lattice plane (200) has appeared in all the spectra. The existence of impurities in the precursor material may be the possible cause for the MnO peak in the nanocomposites.

Fig. 1.

XRD spectra of MnFe2O4 nanocomposites at different concentrations of ZnS (1%, 3%, 5%).

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The average crystalline size and the micro strain of the samples were further calculated from Williamson–Hall (W–H) equation [43].

where β is the FWHM of diffraction peak, θ is the diffraction angle, D is the average crystalline size and ε is the effective micro strain.

Table 1 shows that the crystallite size of MnFe2O4 nanoparticles increases from 9.53 nm to 41.2 nm after surface modification of the nanoparticles by PEG. It has been reported that the increase of crystallite size due to the more binding affinity of the organic molecules of the surfactant to the surface of nanoparticles which provides stability of the nanoparticles for further growing of crystals. The organic molecules produce a steric effect at the interface of the nanoparticles which disturbed the effective particle to particle contact and reduce the Brownian motion of the nanoparticles [44]. On the other hand crystallite size of the MnFe2O4 nanoparticles in MnFe2O4/ZnS nanocomposite decreases after incorporation of ZnS which can be ascribed as the change of morphology of synthesized nanoparticles were found to converges from irregular shaped nanoparticles to the regular nanospheres which is consistent with the result acquired by Kavas et al. [45]. As the weight percentage of the ZnS in the nanocomposites increases crystallite size of the MnFe2O4 nanoparticles further increases in the nanocomposites, which can be attributed to the large nucleation growth of ZnS nanoparticles on various sites of the core MnFe2O4 nanoparticles and multiple interfacial strain also may be the possible cause of increase of the crystallite size. On the other way crystallite size of ZnS decreases due to occurrence of large deformation of the periodic lattice of ZnS crystals, when Zn2+ ions of ionic radius (0.74 Å) replaced by Mn2+ ions of ionic radius (0.80 Å) induce lattice strain takes place in ZnS lattice [46].

Table 1.

Structural parameters of MnFe2O4 and ZnS nanoparticles in different samples.

Sample name  Crystallite size of MnFe2O4 from W-H plot (nm)  Crystallite size of ZnS from W-H plot (nm)  Lattice constant of MnFe2O4 Nelson Riley plot (Å)  Lattice constant of ZnS Nelson Riley plot (Å) 
MnFe2O4  9.53 ± 0.002  --  8.51  -- 
MnFe2O4 /PEG  41.2 ± 0.001  ---  8.509  --- 
MnFe2O4/ZnS (1%)  6.00 ± 0.006  6.6 ± 0.010  8.509  5.344 
MnFe2O4/ZnS (3%)  6.87 ± 0.010  4.1 ± 0.001  8.509  5.343 
MnFe2O4/ZnS (5%)  8.55 ± 0.016  3.74 ± 0.002  8.509  5.343 

The HRTEM images of 1% and 3% nanocomposites as shown in the Fig. 2. MnFe2O4 and ZnS nanoparticles are almost quasi spherical in shape and the average size of the MnFe2O4 nanoparticles are almost 6–6.5 nm whereas ZnS nanoparticles are ranges from 4.8 to 5.4 nm. The SAED pattern of 1% and 3% of ZnS in MnFe2O4 nanocomposites are viewed in Fig. 2(a) and 2(c) corresponds to the reflections from the crystal planes (311), (222), (440), (331) of MnFe2O4 and (111), (311) of cubic zinc blend structure which is match with diffraction planes indexed from the XRD diffractogram. Fig. 2(d) shows the d-spacing of (311) planes of MnFe2O4 and (111) planes of ZnS. The EDAX spectrum of sample 3% as shown in Fig. 3 illustrates the stoichiometric ratios of the nanoparticles in the nanocomposites. The inset shows the weight % of different elements in the nanocomposites.

Fig. 2.

HRTEM image of MnFe2O4/ZnS nanocomposite with (a) 1% ZnS and the inset shows its SAED patterns (b) Enlarge view of 1% nanocomposites (c) 3% ZnS and the inset shows its SAED patterns (d) d-spacing of (111) plane of ZnS and (311) plane of MnFe2O4 in nanocomposites.

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Fig. 3.

EDAX spectrum of nanocomposites with 3% ZnS and the inset shows the weight % of different elements in the nanocomposites.

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4.2FTIR analysis

The FTIR spectra of uncoated MnFe2O4, MnFe2O4/PEG, MnFe2O4/ ZnS @1%, 3% and 5% nanocomposites as shown in Fig. 4.The absorbance peak at 2118 cm−1 assigned to C–H bending from PEG.

Fig. 4.

FITR spectra of MnFe2O4, MnFe2O4/PEG nanocomposites at different concentration of ZnS (1%, 3%, 5%).

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The broad peak 3330 cm−1 due to the −OH group vibrations specify the absorption of water molecules in the surface of nanoparticles [47]. The bands stretching mode at the centered on 1186 cm−1 arising from CO, COC stretches of MnFe2O4 nanoparticles in PEG [48].The absorption peak at 821 attributed to CH bending vibration and CO stretching in PEG. The peak at 1100 cm−1 signifies the characteristic stretching vibration of COC from PEG and characteristic bands of SO42− which indicate the hydrophilic group (SO4) of ZnS interact with the surface of MnFe2O4 nanoparticles due to the interaction of the vibrating sulphide ions, Rema Devi et al. [49] and Kuppayu et al. [50] also reported the same result. The FTIR spectra confirms the coating of PEG on the surface of MnFe2O4 nanoparticles and the incorporation of ZnS on the surface MnFe2O4 nanoparticles through surfactant PEG and form the MnFe2O4/ZnS nanocomposites.

4.3Photoluminescence study

Photoluminescence spectra of pristine ZnS and MnFe2O4/PEG @ ZnS 1%, 3% and 5% nanocomposites at room temperature under excitation wavelength 260 nm as shown in the Fig. 5. The de-convoluted emission peaks centred 303, 351 and 360 nm for pure ZnS as shown in Fig. 5(a). The emission peak at 303 nm due to band to band transition of electrons in ZnS crystals almost remain at the same peak position in all samples.

Fig. 5.

Gaussian fitting PL spectra of (a) pure ZnS (b) 1% (ZnS) (c) 3% (ZnS) (d) 5% (ZnS) of MnFe2O4 nanocomposites.

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The peaks at 351 nm attributed to the characteristics defect level (sulphur vacancy) emission of ZnS which is shifted to 343 and 348 nm (blue shift), when the amount of ZnS in the sample increases [51]. This shifting of peak towards lower wavelength region signifies the quantum size effect of ZnS nanoparticles due to decreasing of crystallite size which is consistent with our XRD result. In addition, the emission peak at 360 nm of pristine ZnS nanoparticles shifted higher wavelength region in the sample 3% and 5% when the concentration of ZnS increases, is the signature of recombination of electrons with holes in trap state arises by zinc vacancies in ZnS [46].

4.4Optical absorption spectra analysis

The UV-Vis spectra of ZnS nanoparticles for different concentrations in MnFe2O4 /PEG nanocomposites are illustrated in Fig. 6.

Fig. 6.

UV-Vis spectra of (a) ZnS (b) 3% and (c) 5% of ZnS in nanocomposites.

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The absorption peak of ZnS nanoparticles observed within the range of 220 nm to 320 nm for all the samples. The direct band gap energy of ZnS QD was approximated from Tauc plot using the relation [52]

Αhν = A( hν - Eg)n
where α represents the absorption coefficient, α = 4 πk/λ (k is the absorption index), hν is the photon energy, A is a constant, λ is the wavelength, and n = 2 for the allowed direct band gap (Eg). The inset depicts that there is a increasing trend of direct band gap value of ZnS nanoparticles are 3.91, 4.06 and 4.10 eV, respectively, with increasing concentration of ZnS. The increase of band gap reveals the quantum confinement effect owing to decreasing of crystallite size of ZnS nanoparticles, which is a reasonable agreement with XRD analysis.

The change of band gap can be used to estimate the crystallite size (r) using the effective mass approximation by Brus equation, given by [53].

where μ is reduced electron-hole effective mass, me* and mh* are the effective masses of electron and holes in ZnS, respectively (me* = 0.34mo and mh* = 0.23mo, where mo = 9.11 × 10−19 kg is the free electron mass). The size of the ZnS nanoparticles for all condition estimated to be 5.25–5.13 nm which is matching with the TEM result.

4.5Magnetic analysis

Magnetic properties of both bare MnFe2O4 and MnFe2O4/PEG with different concentration of ZnS at room temperature are shown in the Fig. 7. The magnetic parameters for all samples are listed in Table 2. The value of saturation magnetization of pure MnFe2O4 recorded as 0.311 emu/g which is lower than bulk MnFe2O4 (80 emu/g).The cause of lower magnetic saturation can be ascribed as large spin disorder of surface nanoparticles as well as surface effect of the nanoparticles [54]. It is also found that the maximum value of saturation magnetization (Ms) is 0.424 (emu/g) recorded for the sample 3%, higher than the pure MnFe2O4 nanoparticle. The saturation magnetization (Ms) of the nanocomposites increases as the quantity of ZnS increases. In spinel ferrite, tetrahedral sites are antiferromagneticaly coupled with the octahedral sites. As the concentration of ZnS in the nanocomposites increases, an enormous amount of nonmagnetic Zn2+ ions of ionic radius 0.74 Å in the MnFe2O4/PEG/ZnS nanocomposites take over the tetrahedral site (A) of the MnFe2O4 nanoparticles and force the Fe3+ ions of ionic radius 0.60 Å to migrates from tetrahedral site to octahedral site. Thus, the magnetization of the octahedral site (B) increases than the tetrahedral site (A). Hence, the net saturation magnetization of the nanocomposites increases than the uncoated MnFe2O4 nanoparticles [55,56].

Fig. 7.

M-H curve of pure MnFe2O4,1%, 3% and 5% of ZnS in nanocomposites.

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Table 2.

The observed value of coercivity (Hc), saturation Magnetization (Ms) and Remanence (Mr) of MnFe2O4 with ZnS 1%, 3% and 5% in the nanocomposites.

Sample name  Coercivity (Hc) (G)  Saturation Magnetization (Ms) (emu/g)  Remanence (Mr) (emu/g) 
MnFe2O4  122.65  0.311  0.80 × 10−2 
(ZnS) 1%  130.12  0.347  0.85 × 10−2 
(ZnS) 3%  89.66  0.424  0.80 × 10−2 
(ZnS) 5%  150.49  0.409  1.14 × 10−2 
4.6Induction heating curve analysis

The heat generation by the magnetic nanoparticles in A.C magnetic field for hyperthermia application can be analysed as the variation of temperature as a function of time measured. The temperature variation curves with time for the samples MnFe2O4, MnFe2O4@ZnS 1%, 3% and 5% for different concentrations (2 mg/ml, 4 mg/ml, 6 mg/ml, 8 mg/ml and 10 mg/ml) in presence of AC magnetic field at frequency 336 kHz for current 250A at an amplitude of H = 161 G as shown in the Fig. 8.

Fig. 8.

(a) Induction heating curves of MnFe2O4 with concentration (2, 4, 6 and 8 mg/ml)(b) 1% (ZnS) with concentration (2, 6, 8 and 10) mg/ml (c) 3% (ZnS) with concentration (2, 4, 6, 8 and 10) mg/ml (d) 5% (ZnS) with concentration (2, 4, 6, 8 and 10) mg/ml at frequency 336 kHz, current 250 A and field amplitude H = 161G.

(0.52MB).

The temperature variation with time for each sample was observed for 30 min. The above graphs demonstrate that the maximum saturation temperature attain by the samples increases as the concentration increases. The maximum temperature 45 0C attain by the sample 3% of concentration 4 mg/ml, 6 mg/ml and 10 mg/ml as shown in the Fig. 8(c) which is very close to the hyperthermic threshold temperature 45.67 °C [57]. We set the safety limit as C=H.f = 6 × 109 Am−1s−1 for all the samples in this experiments as suggested by Hergt et al. [58]. In most of the samples other than 3% with different concentration could not reach up to the threshold temperature for effective hyperthermia therapy. We observed little fluctuations in the heating curves of some samples, which may be occurred owing to the aberrant particles size distribution and the decreases of magnetic moments of each MnFe2O4 nanoparticles because of increasing time span in AC magnetic field with raising ambient temperature. Similar result also observed by seongate Bae et al. [59] for NiFe2O4 nanoparticles.

Fig. 9 illustrates the induction heating curves of pure MnFe2O4 and MnFe2O4s/ZnS nanocomposites having different concentration of ZnS in presence of AC magnetic field at frequency 336 kHz with amplitude H = 226 G for the current of I = 350 A. In this analysis we observed that the heating curves for most of the samples reach the maximum saturation temperature of 45 °C. When the amplitude of the AC magnetic field increases, the magnetization of nanoparticles also increases linearly according to the linear response theory (LRT) hence the power dissipation of the nanoparticles also increases [60]. In addition, the power dissipation by the nanoparticles is also depends on their size. Since the Neel and Brownian relaxation losses governed by the size of the magnetic nanopartiles, which may directly affects, the heat dissipation power of the nanoparticles.

Fig. 9.

(a) Induction heating curves of MnFe2O4 with concentration (2, 4, 6 and 8) mg/ml (b) 1% (ZnS) with concentration (2, 6, 8 and10) mg/ml (c) 3% (ZnS) with concentration (2, 4, 6, 8 and 10) mg/ml (d) 5% (ZnS) with concentration (2, 4, 6, 8 and 10) mg/ml at frequency 336 kHz, current 350 A and field amplitude H = 262 G.

(0.56MB).

The heating efficiency of magnetic nanoparticles can be represented by specific loss power (SLP) or specific absorption rate (SAR). The SAR is measured from the initial slope of the temperature variation curve using the following equation [61].

SAR = C (dT/dt) (ms/mm)
where C is the volumetric specific heat capacity of the solvent, (dT/dt) is the initial slope of the temperature variation curve with time, mm is the mass of magnetic materials in the suspension and ms is the mass of suspension.

The variation of SAR values with concentration for different samples as shown in the Fig. 10 and Fig. 12 corresponding to the current I = 250A and 350A, respectively. In both the figures, exhibits that as the concentration increases SAR value decreases. The decreases in SAR can be explained by increasing dipole interaction among the nanoparticles. The substantial anisotropic barrier increases with increasing dipole interaction which may be the possible cause for decreasing SAR value of the samples [62]. But interestingly, it is observed that the SAR value increases as the current increases from 250A to 350A.The restraint of the SAR delineation is its dependence with H2, which provides direct comparison of reported literature values difficult owing to variations in the applied AC field conditions. For further varification, the intrinsic loss power (ILP) can be calculated whereby the SAR is normalized to the strength of AC field and its frequency [63].

ILP = SAR/f.H2
where the SAR value is measured in W kg−1, frequency ‘f’ in kHz and H in G. The ILP values of different samples at different AC magnetic field amplitude as shown in the Fig. 11 and in Fig. 13.

Fig. 10.

Histogram of SAR values of sample (a) MnFe2O4 (b) 1% (c) 3% and (d) 5% of ZnS in nanocomposites at frequency 336 kHz, current 250 A and field amplitude 161G.

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Fig. 12.

Histogram of SAR values of sample (a) 1% (c) 3% and (d) 5% of ZnS in nanocomposites at frequency 336 kHz, current 350 A and field amplitude 262G.

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Fig. 11.

Histogram of ILP values of sample (a) MnFe2O4 (b) 1% (c) 3% and (d) 5% of ZnS in nanocomposites at frequency 336 kHz, current 250 A and field amplitude 161G.

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Fig. 13.

Histogram of ILP values of sample (a) MnFe2O4 (b) 1% (c) 3% and (d) 5% of ZnS in nanocomposites at frequency 336 kHz, current 350 A and field amplitude 262G.

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5Conclusion

In this study, bi-functional magnetic fluorescence MnFe2O4/ZnS nanocomposites were successfully synthesized via co-precipitation method. The XRD studies exhibits the existence of both MnFe2O4 cubical spinel phase and cubic zinc blende phase of ZnS in the nanocomposites with the average crystallite size of ˜7.14 nm for MnFe2O4 and that of ˜4.81 nm for ZnS nanoparticles, respectively, which is relatively smaller than the pristine MnFe2O4 and ZnS nanoparticles. The FTIR spectra demonstrate that the peak at 1100 cm−1 represents the incorporation of ZnS on the surface of MnFe2O4 nanoparticles via characteristic stretching vibration of COC from biocompatible surfactant PEG. The photoluminescence study illustrates the trap level defects (sulphur vacancy) emission in the ZnS nanoparticles shows the blue shift in the nanocomposites due to strong quantum confinement effect. UV-Vis absorption analysis revel the increasing band gap with increasing concentration of ZnS in the nanocomposites with decreasing crystallite size of ZnS nanoparticles due to quantum size effect. In magnetic analysis MnFe2O4/ZnS nanocomposites shows near superparamagnetic properties with maximum magnetic saturation of ˜0.424 emu/g which is greater than pure MnFe2O4 nanoparticles. Magnetization increases with increasing ZnS concentration in the nanocomposites owing to the migration of Fe3+ ions from tetrahedral site to octahedral site. The induction heating analysis shows that the heating efficiency increase as the concentration of ZnS in nanocomposites increases. The MnFe2O4/ZnS magnetic-fluorescent nanocomposites may provide a rousing possibility in magnetic hyperthermia application for the treatment of cancer.

Conflicts of interest

The authors declare no conflicts of interest.

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