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Research Papers

Synthesis of Zn-Doped Manganese Ferrite Nanoparticles Via Coprecipitation Method for Magnetic Resonance Imaging Contrast Agent OPEN ACCESS

[+] Author and Article Information
Firooz Salehpour

Professor
Department of Neurosurgery,
Tabriz University of Medical Sciences,
Tabriz, Iran
e-mail: firoozsalehpour@hotmail.com

Ainaz Khorramdin

Department of Material Sciences
and Engineering,
Shiraz University of Technology,
Shiraz, Iran
e-mail: a.khorramdin@sutech.ac.ir

Hooman Shokrollahi

Assistant Professor
Department of Material Sciences
and Engineering,
Shiraz University of Technology,
Shiraz, Iran
e-mail: shokrollahi@sutech.ac.ir

Arastoo Pezeshki

Department of Material Sciences
and Engineering,
Shiraz University of Technology,
Shiraz, Iran
e-mail: Draraspz@yahoo.com

Farhad Mirzaei

Department of Neurosurgery,
Tabriz University of Medical Sciences,
Tabriz, Iran

Nader D. Nader

Professor
Department of Anesthesiology,
University at Buffalo
252 Farber Hall,
South Campus,
Buffalo, NY 14214
e-mail: nnader@buffalo.edu

1Corresponding author.

Manuscript received August 1, 2014; final manuscript received February 13, 2015; published online March 11, 2015. Assoc. Editor: Roger Narayan.

J. Nanotechnol. Eng. Med 5(4), 041002 (Nov 01, 2014) (6 pages) Paper No: NANO-14-1052; doi: 10.1115/1.4029855 History: Received August 01, 2014; Revised February 13, 2015; Online March 11, 2015

Two different preparations of biocompatible magnetic nanoparticles (MNPs), both (MnFe2O4 and Mn0.91Zn0.09Fe2O4) coated with methoxy polyethylene glycol aldehyde (m-PEG-CHO) were prepared through coprecipitation method. The prepared powder was reanalyzed for material structure with an X-ray diffractometer (XRD) and for particle size using a transition electron microscope (TEM). Magnetic saturation (MS) and coercivity (HC) of the formed particles were examined by a vibrating sample magnetometer (VSM). Surface structure of the samples was characterized by Fourier transform infrared spectroscopy (FTIR). Biocompatible ferrofluids were intravenously injected into four rabbits. Then the magnetic resonance (MR) images of brain were obtained by magnetic resonance imaging (MRI) experiments before and after intravenous injection of ferrofluids. The MNPs demonstrate super paramagnetic behavior with a spinel structure measuring 30–40 nm in size. Doping of these magnetite nanoparticles with zinc resulted in decreases in crystallite size from 24.23 nm to 21.15 nm, the lattice parameter from 8.45 Å to 8.43 Å and the coercivity from 41.20 Oe to 13.07 Oe. On the other hand, saturation magnetization increased from 50.12 emu/g to 57.36 emu/g following zinc doping. Image exposure analysis revealed that the reduction of MR signal intensity for zinc-doped magnetite nanoparticles was more than nondoped nanoparticles (shorter T2 relaxation time) thereby making the images darker.

FIGURES IN THIS ARTICLE
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Mn–Zn ferrites MNPs have been formally described in 1947 and gained more interest over the past few years for their use in magnetic data storage technology as well as their biomedical utilization [1,2]. Early investigators predicted a bright future for Mn–Zn in electronic industry because of their superior electrical and magnetic properties [3]. Mn–Zn ferrites belong to a class of soft magnetic materials with a great ability for magnetic penetration. Main characteristics of these nanoparticles are their high electrical resistance and saturation magnetization [4,5]. Saturation magnetization of these ferrite particles increases by addition of zinc (doping) to the ferrite nucleus [6]. MNPs are widely used in the field of electronics and electrics such as deflection yoke rings, computer memory chips, magnetic recording heads, microwave devices, transducers, and transformers [7-10]. Apart from these applications, nanosized Mn–Zn ferrites have potential usage in ferrofluid technology, enzyme and protein immobilization, and magnetically guided drug delivery [11-13].

Gadolinium is commonly used in its ionized form as a commercially available contrast medium. This is a heavy metal and easily filtered by the kidneys due to its smaller size. Free gadolinium ions toxicity in both human and different animal models is mediated through interfering with calcium-ion channels. Nephrogenic systemic fibrosis has been reported following clinical uses of gadolinium ions for MRI [14]. Additionally, gadolinium image enhancement is mainly useful for T1 phase of MRI. Since brain tissue enhancement is more prominent during T2 phase, therefore synthesis of a magnetic particle with this property is advantageous. Additionally, polyglycation and coating these particles will theoretically decrease the ability of the particle to freely pass into the nephron and therefore may reduce their nephrotoxicity.

Superparamagnetic characteristics of Mn–Zn ferrite nanoparticles are responsible for proton relaxation in tissues and therefore make these particles suitable for MRI contrast enhancement [15]. These nanoparticles induce large magnetic moments altering the magnetic field in a tissue over time and space, thus creating a large magnetic heterogeneity through which water molecules scatter. Dephasing of the magnetic moments of protons is responsible for creating data for MR images (T2 relaxation times) [16].

During the preparation, storage and application of MR contrast agents, the durability of the colloid is important. However, due to the high ratio of surface to volume and magnetization, these MNPs are prone to accumulate in water or tissue fluid, which limits their application. To reduce aggregation and enhance the biocompatibility between MNPs and water or tissue fluid, the coating of polymer onto MNPs surface is required [17]. Superparamagnetic iron oxide agents have been coated with polymers such as dextran or PEG, in order to enhance their dispersion and increase their stability [18-20]. Superparamagnetic enhancers like most of the diamagnetic materials have only an insignificant effect on the MR signals.

In the present investigation, m-PEG was coated on the surface of zinc-doped and plain MnFe2O4 MNPs using the coprecipitation method. The effects of Zn substitution on particle size and magnetic properties of the modified MNPs, especially MS and coercivity (HC), were studied. In addition, each MNP product was intravenously injected into a rabbit and the quality of the MR image enhancement was assessed both before and after the contrast injection.

Nanoparticle Synthesis, Aldehydization, and PEG Coating.

Manganese ferrofluid MNPs were prepared by using coprecipitation method. The metal salt precursors, ferric (III) chloride hexahydrate (FeCl3.6H2O, 99%, Merck, Germany), manganese (II) nitrate tetrahydrate (Mn(NO3)2.4H2O, 99%, Merck, Germany) were dissolved in distilled water at 0.1 M and 0.05 M concentrations, respectively. The molar ratio of metal salts solution [Fe3+]/[Mn2+] was 4:1 (10 ml and 5 ml) to maintain the stoichiometry of the spinel ferrite. The solutions were blended at 65–70 °C and then added into a boiling sodium hydroxide (NaOH 0.69 M) solution. The reaction was carried out at 85 °C for 2 hr at pH of 12, under the nitrogen atmosphere (Eq. (1)).

Zinc Doping.

The concentration of Zn for doping was determined through several optimization experiments. Various amount of Zn ranging from 0% to 18% were initially used for doping process. The specific saturation magnetization (Ms) increased and coercively (HC) decreased peaking when the nanoferites were dopped with 9% Zn. However, with additional increases of Zn doping, Ms further decreased and HC increased which were the inappropriate. Therefore, the optimum Zn doping of MNPs was selected at 9% and was used for injection and imaging in presence of a magnetic field. For preparation of Mn0.91Zn0.09Fe2O4 nanoparticles, 0.09% of 5 ml manganese nitrate solution (0.09 × 5 = 0.45 ml) was replaced by zinc chloride tetrahydrate (ZnCl2.4H2O) solution and the same procedure was followed (Eq. (2)).

Precipitation and formation of nanoferrites took place by the conversion of metal salts into hydroxides, which occurred immediately, followed by transformation of hydroxides into ferrites (Eqs. (3) and (4)). The solution was maintained at 85 °C for 2 hr. This duration was necessary to ensure the transformation of hydroxides into a spinel ferrite in which dehydration and atomic rearrangement were included. Fine particles were collected by using centrifuge (2000 g × 15 min) three times. The particles were then washed several times with distilled water, followed by an acetone rinse and dried at room temperature:Display Formula

(1)Mn2++2Fe2++8OH-Mn(OH)2×2Fe(OH)3
Display Formula
(2)(1-x)Mn2++xZn2++2Fe3++8OH-(1-x)Mn(OH)2×xZn(OH)2×xFe(OH)3
Display Formula
(3)Mn(OH)2×2Fe(OH)3MnFe2O4·nH2O
Display Formula
(4)(1-x)Mn(OH)2×xZn(OH)2×2Fe(OH)3Mn(1-x)ZnxFe2O4·nH2O

m-PEG polymers were changed to their aldehyde derivatives in the presence of dimethyl sulfoxide (DMSO) and acetic anhydride as previously described [21]. Briefly, 0.5 ml acetic anhydride was added to 1 g m-PEG in 5 ml DMSO including 6% chloroform under nitrogen atmosphere. The reaction combination was mixed for 24 hr at room temperature and then was added to 50 ml cold diethyl ether. The precipitate was filtered with a paper filter. The precipitation process from chloroform solution was repeated two more times with diethyl ether until a white powder was produced. A schematic illustration for the formation of the m-PEG-CHO chain is displayed in Fig. 1(a).

PEGis a hydrophilic, water-soluble, and biocompatible polymer that can be prepared with a wide range of sizes and terminal functional groups [22]. PEG coating improves the dispersity and blood circulation time of the MNPs after binding [23]. In order to prepare m-PEG-MNPs and m-PEG aldehyde (10 mg) was dissolved in deionized water (2 ml). Then MNPs (10 mg) was added to the above solution and after 2 min bath sonication and 2 hr of magnetic mixture. Subsequently, the purified particles were obtained by spinning (5600 g × 15 min) three times followed by washing with deionized water and freeze drying for further measurements as previously described. Formation of m-PEG-coated MNPs is shown in Fig. 1(b).

X-Ray Diffractometry.

The crystal structure of the powders was characterized by an XRD (Bruker®, Billerica, MA), which utilizes Cu-K α radiation. The relative intensity (I/I0) was measured over the range of the diffraction angle θ from 30 deg to 75 deg. Based on the width and the position of the (311 nm) peak, the mean size of the crystals was estimated by using Scherrer's equationDisplay Formula

(5)DXRD=kλβcosθ

where DXRD is the mean dimension of the crystallites, K is Scherrer constant taken to be 0.94, λ is the X-ray wavelength (λ = 1.54 Å), β is the broadening of the peak width of half-maximum, and θ is the Bragg diffraction angle. The lattice parameter was calculated using the Bragg equationDisplay Formula

(6)d=ah2+k2+l2

where “d” is the lattice distance, “a” is lattice parameter, and “h,” “k,” and “l” are plane indexes.

Transmission Electron Microscopy.

The surface morphology and the particle size for Mn0.91Zn0.09Fe2O4 MNPs, m-PEG-coated Mn0.91Zn0.09Fe2O4 MNPs and MnFe2O4 MNPs and were examined by a transmission electron microscope (LE-O906 Zeiss®, Oberkochen, Germany). The mean crystallite sizes for MnFe2O4 and Mn0.91Zn0.09Fe2O4 MNPs, calculated from Scherrer's formula were in good agreement with those from the transmission electron micrographs.

FTIR Spectrometry and Vibrating Sample Magnetometry.

The infrared spectra were recorded over the range of 400–4000 per centimeter on a FTIR spectrometer (Shimadzo-8400 series, Dubai, UAE) following the protocol provided by the user's manual. The specific saturation magnetization (MS) and coercively (HC) of MNPs were measured using a VSM (JDAW-2000D, Microsense®, Lowell, MA) at room temperature in a maximum field of 15 kOe.

Animal Preparation, Injection, and MR Imaging.

The MR imaging were performed using a MRI (Gold-Seal Signa Excite®, GE Healthcare, Pittsburg, PA) with a magnetic field of 1.5 Tesla. T2-weighted images were obtained before and 1 hr after intravenous injection of MNPs suspension. Four male white New Zealand rabbits were anesthetized with intraperitoneal injection of ketamine (20 mg/kg body weight). Before injection of contrast suspension, parallel MR images of the brain were obtained. Two rabbits received 4 ml of MnFe2O4 suspension injected through the great auricular vein. Two other rabbits received 4 ml of Mn0.91Zn0.09Fe2O4 via the same route within 1 min. Contrast-enhanced images of the brain were immediately obtained from both rabbits by MR scanning both in T1 and T2 phases. To further investigate the potential usage of the ferrofluids in MR imaging, T2 transverse relaxation time was measured using the MR spectrometer in field strength of 1.5 Tesla.

X-ray diffraction patterns of the nanoparticles confirmed the formation of a mix and normal spinel structure with the most intense peak corresponding to the (311) reflection plane. A similar pattern was observed for both MnFe2O4 and Mn0.91Zn0.09Fe2O4 MNPs (Fig. 2). Values for the lattice distance were calculated from the X-ray diffraction patterns. The calculated lattice parameters for MnFe2O4 and Mn0.91Zn0.09Fe2O4 MNPs by using Bragg's equation (Eq. (6)) were 8.45 Å and 8.43 Å, respectively. XRD analysis has been done for crystal phase investigation only and the (PEG) coating does not affected the crystal structure of the magnetic core.

The particle size was measured by Scherer's formula using half width of the peak of maximum intensity (311) plane. The average crystallite size of MnFe2O4 ferrite MNPs reduces from 24.23 nm to 21.15 nm by Zn doping. These values were well indexed to the mixed and normal spinel structure of MnFe2O4 and Mn0.91Zn0.09Fe2O4 MNPs, respectively. Particle size and morphology were further examined and confirmed by transmission electron microscopy. As is shown in Fig. 3, neither the size nor the shape of either MNP does change significantly following polyethylene glycation. Furthermore, TEM images indicate that most of the particles are spherical and quasi-spherical and the average size measured for various particles ranges between 30 and 40 nm, which is in a good agreement with the results obtained from X-ray diffraction analysis.

FTIR spectroscopy results have been depicted in Fig. 4. The observed peak at the 580 cm−1 position is the characteristic absorption of a Fe–O bond. The absorption peak at about 3450 cm−1 indicated the presence of nondissociated hydroxyl groups (−OH) of aldehyde additions. The peak that was observed at 1740 cm−1 was related to aldehyde carbonyl (HC = O) group, and the band present at almost 3500 cm−1 suggested the presence of nondissociated hydroxyl groups (−OH) of aldehyde-PEG. Additional useful diagnostic band was the C–H stretch at 2900 cm−1 that is seen with PEG core only. The broad peak seen at about 1400–1500 cm−1 in Fig. 4 (arrows) pointed out the C–O–C ether bond stretching vibrations characteristic of PEG chains, which suggested successful attachment of PEG moieties to MNPs.

As displayed in Fig. 5, MnFe2O4 and Mn0.91Zn0.09Fe2O4 MNPs show a typical superparamagnetic behavior. While the substitution Zn (nonmagnetic ion) increased Ms from 50.32 emu/g to 57.36 emu/g, it resulted in the reduction of HC from 41.20 Oe to 13.07 Oe. The saturation magnetization of the PE Gylated Mn0.91Zn0.09Fe2O4 and MnFe2O4 MNPs were slightly lower than the uncoated MNPs 52.27 emu/g (a drop from 57.36 emu/g) and 48.84 emu/g (a drop from 50.32 emu/gm), respectively.

The MRI images of the brain were obtained from four rabbits before and after they were injected with respective MNPs. The sequence parameter (TR/TE) for m-PEG-coated MnFe2O4 and Mn0.91Zn0.09Fe2O4 injected suspensions was 3400/81 ms (T2-weighted) and 400/8.6 ms (T1-weighted), respectively. The quality of the images was good both before and after injection of nanoparticles. Numbers 2, 3, and 4 are hyper in the image B, and is hypo in A. Since B was taken after injection, so there was truly an enhancement. There was a difference of intensity decrement after injection of MNPs (Figs. 6(b) and 6(d)). When the injected MNPs spread in the brain tissue, as seen in (Figs. 6(b) and 6(d), 1–7), T1 weighted intensity was enhanced by MNPs, while there was a reduction in signal intensity of a neighboring lymph node. The decrement of signal intensity following Mn–MNP was more than that seen after injection of Zn–MNP.

We have successfully synthesized manganese-based nanoparticles that can be used as magnetic contrast material to improve the diagnostic power of MRI. Through multiple examinations, we characterized both morphology and size of these nanoparticles as well as their magnetic properties. Furthermore, we demonstrated that substitution of Zinc in these nanoparticles while it reduces the magnetic coercivity, it does neither affect their particle size nor reduce their diagnostic power. Within clinical terms of application, the decrement of signal intensity that is seen in T2 weighted MRI scanning following Mn-MNP was more than that seen after injection of Zn–MNP.

Zinc substitution also known as Zn doping was achieved by coprecipitation method in our experiments resulted small shifting of the reaction peaks to larger angles. This switch was due to the fact that the divalent ion radius of Zn (0.74 Å) was slightly smaller than that of Mn (0.80 Å), which caused lattice parameter to shrink. The calculated lattice parameters for both MnFe2O4 and Mn0.91Zn0.09Fe2O4 MNPs corresponded well to those previously reported by Arulmurugana et al. [24] and Elahi et al. [25].

As anticipated, both MNPs showed a typical superparamagnetic behavior. Although the coercivity decreased by Zn substitution, the MS of MNPs increased by doping. The substitution of nonmagnetic Zn ion with preferential tetrahedral site occupancy resulted in the reduction of the exchange interaction between tetrahedral and octahedral sites. Zinc ion had a strong effect on the magnetic properties of ferrites and especially decreased the coercivity. For this reason it has widely been used as a common component in ferrite nanoparticles especially in Mn-based MNPs. We additionally showed that the average crystallite size of MnFe2O4 ferrite MNPs reduced only modestly following Zn doping. This was probably due to the reaction condition, which favored the formation of new nuclei and prevented further growth of particles. Therefore, it was conceivable to conclude that the Zn concentration might have provided an effective means to control the particle size.

Further, structural characterization of the MNPs by FTIR spectroscopy showed a corresponding peaks for the aldehyde carbonyl (HC = O) group and hydroxyls groups on the surface of MnFe2O4 and Mn0.91Zn0.09Fe2O4 MNPs [26]. The absorption peak, which was recorded at 3400 cm−1, could be ascribed to the hydroxyl moieties, indicating the presence of large numbers of hydroxyl groups on the surface of MnFe2O4 and Mn0.91Zn0.09Fe2O4 MNPs. Additional useful diagnostic band in our report was the peak that corresponded to the C–H stretch PE glycated MNPs which was previously described by others [27,28].

Since the specific surface area (surface-to-volume ratio) was large and the surface energy was high, both MnFe2O4 and Mn0.91Zn0.09Fe2O4 MNPs were likely to aggregate during drying. This condition was confirmed by the presence of some aggregates in our preparations. Therefore, we carried out m-PEG coating of and magnetic nucleus formation, simultaneously. Since the nuclear formation process was faster than the growth process, the aggregation was reduced and the particle dispersion was improved after m-PEG coating (Fig. 3(d)).

Polyethylene glycation has offered a solution to many pharmacokinetic problems related to fast clearance as it prevents the uptake of the active substance by the reticulo-endothelial system. PEG is generally considered nontoxic and is useful in stabilizing its active ingredients in otherwise destabilizing environments [29]. PEG covalently attaches to the MNPs surface and becomes functional by targeting ligands, imaging reporter molecules, or therapeutic agents attached to the other end [30,31].

Polyethylene glycation process was completed and collected using high ionic strength (>100 mM) solvents that shielded from MNPs during this process as previously described. High concentrations of MNPs solutions were prepared to minimize the distance between neighboring particles. High ionic strength of the solvents reduced the time required for synthesis while maintaining a neutral (±5 mV) zeta potential [32]. Polyethylene glycation did not substantially change the size, morphology, or the magnetic properties of the particles. We noticed a slight decrease in saturation magnetization of Mn0.91Zn0.09Fe2O4 and MnFe2O4 MNPs PEG coating. This was due to the existence of the diamagnetic layer of PEG in the polyethylene glycated MNPs [5,33]. Although, the size of the particle may not significantly change with PEG coating, the alteration of surface charges of MNPs, will theoretically decrease the availability of free ions and subsequent interstitial uptake and tissue toxicity. Further pharmacokinetics and pharmacodynamics studies are needed following intravenous injection of these MNPs to address this important issue.

The MR images of brains obtained before and after injections of MNPs produced strong magnetic moments that partially amplified the magnetic field and made magnetic field heterogeneous. Thus, when water molecules passed through the heterogeneous magnetic field, the strong magnetic moment accelerated the diphasing of protons and caused contrast-type enhancement. The major limitation of this study was the fact that a clinical device was used to obtain MR images. The magnetic field of this device is limited to 1.5 Tesla, which results in suboptimal resolution of the MR images in smaller animals. The best pictures obtained from the four animals were selected to be the representation of the MR imaging before and after injection of the nanoparticles. The resultant shortening of T2 phase caused a switch in relaxation (compatible to those of T1 phase) and, therefore, decreased T2 MR intensity. In fact, shortening the T2 relaxation time was due to the superparamagnetic effect of MnFe2O4 and Mn0.91Zn0.09Fe2O4 MNPs. This reason for this difference was mainly due to larger saturation magnetization (stronger magnetic moment) of Zn–MNP (55.16 emu/g) when compared to Mn–MNP (47.23 emu/g), which causes more loss of homogeneity in magnetic field.

In summary, from chemical synthesis and physical characterization of nanoparticles, the following conclusions are achieved. The m-PEG covered MnFe2O4 and Mn0.91Zn0.09Fe2O4 MNPs were prepared through the coprecipitation method. The surface of MnFe2O4 and Mn0.91Zn0.09Fe2O4 MNPs covered with m-PEG can decrease the combination of MNPs and help to form a fix colloid suspension in water. Doping of optimal content of Zn, reduce the coercivity and mean crystallite size, but increases the saturation magnetization. Superparamagnetic MnFe2O4 and Mn0.91Zn0.09Fe2O4 MNPs solubilized in water with the help of m-PEG copolymer. MRI study in vivo implies when the MNPs dispersed in the brain tissue, T2 transverse relaxation time is shortened and T2 MR intensity is decreased, subsequently. Therefore, we speculate that the use of digital subtraction may improve the quality of imaging and the diagnostic power of the MRI after injection of these MNPs as potential contrast materials. Additionally, with the use of devices with stronger magnetic field, the quality of contrast enhancement is expected to increase.

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Figures

Grahic Jump Location
Fig. 1

Preparation of nanoparticles: (a) aldehydization (m-PEG-CHO) and (b) polyethylene glycation processes

Grahic Jump Location
Fig. 2

X-Ray diffraction patterns recorded for MnFe2O4 MNPs (a) and Mn0.91Zn0.09Fe2O4 MNP (b) powders. Average particle size was calculated and reported using Scherrer's formula (Eq. (5)). Additionally, the average lattice parameter and distance were calculated with a precision of 0.01% using the Bragg equation (Eq. (6)).

Grahic Jump Location
Fig. 3

Transmission electron microscopy of Mn0.91Zn0.09Fe2O4 MNPs (a), m-PEG-coated Mn0.91Zn0.09Fe2O4 MNPs (b), MnFe2O4 MNPs (c), and MnFe2O4 m-PEG-coated MNPs (d). The range both for coated and uncoated MNPs was 30–40 nm.

Grahic Jump Location
Fig. 4

The heating ratios (transmittance percentage) were measured over the range of infrared spectrum. The figure shows the FTIR spectra for Mn0.91Zn0.09Fe2O4-m-PEG-coated (a); MnFe2O4-m-PEG-coated (b); MNPs; Mn0.91Zn0.09Fe2O4 (c); MnFe2O4 (d); MNPs and PEG core by itself (e)

Grahic Jump Location
Fig. 5

Magnetization curves measured Ms = 57.36 emu/g for Mn0.91Zn0.09Fe2O4 MNPs (a); Ms = 28.32 emu/g for m-PEG-coated-Mn0.91Zn0.09Fe2O4 MNPs (b); Ms = 50.12 emu/g for MnFe2O4 MNPs (c); and Ms = 19.21 emu/g for m-PEG-coated-MnFe2O4 MNPs (d)

Grahic Jump Location
Fig. 6

Magnetic resonance signals intensity of rabbit brain in T2-weighted sequences before (a and c) and 1 hr after intravenous injection of m-PEG-coated-Mn0.91Zn0.09Fe2O4 suspension (b) and m-PEG-coated-MnFe2O4 suspension (d). For full details, please refer to the text.

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