Applications of Ferrites in Biomedical and Environmental Fields
Applications of Ferrites in Biomedical and Environmental Fields
Applications of Ferrites in Biomedical and Environmental Fields
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Abstract
1. Introduction
There are many small organic molecules that are commonly used as stabilizing
and functionalizing agents like amines and thiols for modification of the surface
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Functionalized Ferrites for Therapeutics and Environmental Pollution Management
DOI: http://dx.doi.org/10.5772/intechopen.1002336
Figure 1.
Different materials used for ferrite functionalization.
of ferrites. One such example is ethanolamine, which can modify the ferrite NP
surfaces in a simple one-step process [13, 14]. The surface amine groups lower the
hydrodynamic diameter (HDD) of the functionalized CoFe2O4 MNPs and facilitate
their usage in biomedical applications [13]. The hardly basic nature of -NH2 groups of
MgFe2O4-NH2 adsorbent helps in the selective chemisorption of different heavy metal
ions (Pb2+, Cu2+, and Zn2+) via a complexation reaction [14]. For thiol functionaliza-
tion, a mixture of tetraethyl orthosilicate (TEOS) and (3-mercaptopropyl)-trime-
thoxysilan is much desired by many researchers [15, 16]. It includes the silica coating
of the ferrite core to which the -SH group is attached. Like amine functionalization,
the heavy metal adsorption process of thiol-functionalized ferrites is influenced by
the Lewis acid-base interactions [15].
Folic acid (FA) is a poorly water-soluble biologically important molecule. Its
overexpression in the vast majority of cancer cells gives the FA-modified nanopar-
ticles a better chance for internalization into the body and enhances the efficacy
of targeted delivery of drug molecules. FA functionalization facilitates the pH-
responsive release of the cationic anticancer drug doxorubicin (DOX) from cobalt
ferrite magnetic nanoparticles (CFMNPs). At basic pH, FA is converted into folate
ions and immobilizes a higher amount of DOX molecules. The acidic environment
of cancer cells stimulates the breaking of this electrostatic interaction and enables
the burst release of the DOX molecules [8]. FA is widely used for rendering cancer
cell targetability to different anticancer drug nanocarriers [8, 17, 18]. Citric acid
has been readily used in the synthesis of biocompatible magnetic fluids (BMFs)
for enhanced colloidal stability of the nanoparticles [19, 20]. Citrate-coated cobalt
(cit-CF) and nickel ferrite (cit-NF) nanoparticles exhibit a dose-dependent radiation
cytotoxicity against MCF-7 cancerous cells and are considered a suitable radiosen-
sitizer for cancer treatment [21]. Oleic acid (OA) is a type of fatty acid that is used
as a surfactant and forms a dense protective shell layer around the nanoparticle
surface during its functionalization process. In addition to its ambiphilic nature, OA
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Applications of Ferrites
electrodes exhibit larger liner range (3 × 10−2 to 8 mM), shorter response time (4 s),
and enhanced sensitivity (23 nA/mM) [32]. Chitosan-functionalized CaFe2O4 MNPs
possess 88.2% immobilization efficiency for ampicillin, which is mainly attributed
to the electrophilic interactions of the protonated amino groups of CH moiety with
ampicillin [33]. Moreover, Datna et al. reported that CH-coated CoFe2O4 MNPs
exhibit stronger antimicrobial activity for both the Gram-negative P. aeruginosa and
Gram-positive E. faecalis and E. coli than the uncoated ones [34]. Conducting poly-
mers; such as polyaniline (PANI) and polypyrrole (PPy) comprise a useful group of
materials for ferrite functionalization due to their tunable electrical properties and
high physical flexibility. Experiments showed that the diamagnetic PANI coating
enhances the electromagnetic shielding ability of MnZn ferrite (MZF) and NiMnZn
ferrite (NiMZF) [35]. Sadeghinia et al. showed that the PANI filaments in the PANI/
perlite-barium ferrite nanoparticles (PANI/PBF-NPs) cause a decrease in their surface
areas and an increase in the pore volume. Thus, PANI contributes to the improve-
ment of the electrical charge storage capability of the composite [36]. The extended
p-conjugation of PANI with single- and double-bond alteration is responsible for its
semiconducting nature that can facilitate the electrochemical properties of different
spinel ferrites [37, 38]. Yan et al. showed that due to the dielectric loss of PANI/PPY
coating, the saturation magnetization of the PANI(PPY)-BaFe12O19/Ni0.8Zn0.2Fe2O4
ferrite decreases while increasing its electrical conductivity [39].
Substituting paramagnetic Co2+ ions with diamagnetic Zn2+ in the CoFe2O4 lattice
profoundly impacts the magnetic aspects of the Co1 − xZnxFe2O4 compound. The
as-synthesized mixed ferrite exhibits increased saturation magnetization and reduced
anisotropy constant due to the dilution of spin moments by the Zn2+ ions [40]. Zn
doping essentially improves the photocatalytic efficiency of ferrite NPs by lowering
the band gap and reducing the recombination of photogenerated electrons and holes
[41, 42]. Gold nanoparticles (Au NPs) possess rich surface chemistry for facilitat-
ing the healthcare-related application sectors. Au coating of ferrite NPs hinders
the oxidation of the magnetic core and acts as a convenient platform for further
surface functionalization. Juan et al. fabricated glyco-ferrites for MRI contrast agent
application using bimetallic superparamagnetic XFe2O4@Au (X = Fe, Mn, and Co)
nanocrystals. During the synthesis process, the Au shell forms stable thiol-Au bonds
with the neoglycoconjugates [43]. Au NPs render biocompatibility along with tunable
plasmonic characteristics to the superparamagnetic MgFe2O4. Such optical properties
allow the easy detection of tissue and blood in the near-infrared (NIR) region for
potential hyperthermia and drug delivery application [44].
interactions between magnetic nanoparticles and in that way facilitate their aqueous
dispersibility and biocompatibility for biomedical and bioengineering applications.
The presence of abundant silanol groups at the silica-coated ferrite NP surfaces enables
the scope for easy processability for multifunctional nanocomposite synthesis [47].
Banalata et al. tailored the mesoporous silica-coated superparamagnetic manganese
ferrite (MSN) with 3-aminopropyl triethoxysilane (APTES) for amine functionaliza-
tion, which is schematically shown in Figure 2. Next, the H2N-MSN particles were
conjugated with FA for targeted delivery of the anticancer drug, doxorubicin (DOX).
The residual amine groups on the FA-MSN were labeled with the fluorescent dye
rhodamine-B-isothiocyanate (RITC) for their cell internalization and detection.
Hence, this functionalized entity can serve for cancer diagnosis and treatment [47].
Ferrite-decorated graphene oxide (GO) nanocomposites are well dispersed in
aqueous/physiological media and biocompatible in nature due to the high density of
oxygen-containing groups, such as carboxylic, hydroxyl, and epoxide groups on the
surfaces and edges of GO. The unique mechanical, electrical, and surface characteristics
Figure 2.
Step-by-step synthesis of silica-coated manganese ferrite for DOX delivery (MSN). Copyright: Journal
of colloid and Interface science [47].
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Functionalized Ferrites for Therapeutics and Environmental Pollution Management
DOI: http://dx.doi.org/10.5772/intechopen.1002336
Ferrite NPs decorated on CNTs possess excellent electrical, thermal, and mechani-
cal properties. CoFe2O4 modified acid-functionalized multiwalled carbon nanotubes
(MWCNT-COOH) are effective RhB adsorbent. Increasing MWCNT-COOH content
from 29 to 75% increases the presence of active sites for electrostatic interactions and
eventually increases the adsorption capacity from 5.165 to 42.68 mg g−1 [50]. On the
other hand, Huixia et al. demonstrated the biomedical applications of MWCNT/CoFe2O4
nanocomposite. The strong supramolecular π–π stacking interaction between DOX and
the side walls of CNTs results in its high loading capacity (about 75.2%). Moreover, a
high T2 relaxivity, low cytotoxicity, and pH-responsive drug release ability showcase the
nanocomposite’s potential as synergistic cancer diagnostic and chemotherapeutic agent
[51]. Yan et al. coated the magnetoelectric multiwall carbon nanotubes (MWCNTs)/
Fe–Ni alloy/NF particles with 3,4-ethylenedioxythiophene and pyrrole (PPy-PEDOT)
copolymers in a complex core–shell structure. The conducting network of MWCNTs and
PPy-PEDOT nanofiller improves the impedance matching and interfacial polarization,
making a promising microwave absorber for electromagnetic pollution remediation [52].
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Applications of Ferrites
This process is used in thin-film formation mainly for the uniform distribution
of the functionalizing materials in the polymer matrix. It is a convenient laboratory-
friendly process in which polymer film adhesion with the reinforcing material (i.e.,
ferrite NPs in this case) is achieved by dispersing the polymer and NPs in a common
solvent medium. Next, the evaporation of the solvent leaves out the desired polymer-
functionalized nanocomposite [57]. The inclusion of multicomponent CuFe2O4/
Cu2O/CuO NPs in the polymethyl methacrylate (PMMA) matrix was carried out for
enhanced antibacterial properties. The NPs-PMMA dispersion in acetone solution
cast on a slide resulted in an antibiofilm nanocomposite [58]. Jay et al. synthesized
CH-functionalized nanostructured NiFe2O4 (n-NiFe2O4-CH) thin film onto the
indium tin oxide (ITO) glass substrate via this simple method [59].
Also known as inorganic sol-gel coating that occurs via successive hydrolysis and
polycondensation of the precursor material (sol) into a three-dimensional continuous
network (gel). This method is preferable due to better control over nanoparticle size
and stability and coating homogeneity [60]. Ashkan et al. synthesized zinc silicate-
coated superparamagnetic zinc ferrite composite using the sol-gel method. In this
work, a simple tuning of pH value into the basic medium of the reacting solution
paved the way for Zn2+ and Si4+ ion adsorption onto the cetyltrimethylammonium
bromide (CTAB)-modified surfaces of ZnFe2O4 nanoparticles. After that, the interme-
diate CTAB layer was eliminated with the help of ethanol solution yielding zinc silicate
shell over the ZnFe2O4 core. Figure 3 shows the rough surface texture and microspher-
ical size (100–300 nm) of the synthesized zinc silicate-ZnFe2O4 composite [61].
The sol-gel technique was utilized to yield a uniform coating of nanocrystalline
TiO2 shell around the CoFe2O4 MNPs core. Wuyou et al. induced the heterogeneous
nucleation of TiO2 via a slow and gradual supersaturation of Ti(OC3H7)4 ethanol in
1:10 water–ethanol suspension of CoFe2O4 [62].
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Functionalized Ferrites for Therapeutics and Environmental Pollution Management
DOI: http://dx.doi.org/10.5772/intechopen.1002336
Figure 3.
The FESEM micrographs of ZnFe2O4 (a) and zinc silicate-ZnFe2O4 (b). Copyright: Ceramics international [61].
The Stöber method is a facile process for uniform silica coating on a nanoparticle
surface through a sol-gel strategy. In simple words, ammonia-mediated hydrolysis of tet-
raethoxysilane (TEOS) yields silanol monomers at the nanoparticle surface. After that,
the neighboring silanol monomers are condensed into a siloxane network cluster [63].
Likewise, Kooti et al. utilized this method to coat CoFe2O4 with SiO2. The inert silica
layer was later used for anchoring a molybdenum Schiff base onto the complex surface
in order to enhance the catalytic activity for the oxidation of alkene. Figure 4 shows the
step-by-step reactions that occurred during the functionalization process [64].
TDD means the focused transportation of therapeutic agents into the diseased
tissue without affecting other organs adversely. The enhanced permeability and reten-
tion (EPR) effect of the drug-conjugated nanocarrier system is a very crucial factor
for TDD [65]. Ferrite NPs with their intrinsic responsiveness toward the external
Figure 4.
Schematic illustration of the Mo-salenSi@Si-CoFe2O4 MNP preparation. Copyright: Catalysis letters [64].
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Applications of Ferrites
Figure 5.
Time-dependent DOX release profile of FA-coated cobalt ferrite MNPs at (a) pH = 5.5 and (b) pH = 7 as
a function of time under temperatures 37 and 44°C in phosphate buffer solution. Copyright: Chemphyschem [8].
4.2 Bioimaging
The magnetic spinel structure of ferrite NPs helps to shorten the spin-spin relax-
ation time (T2-weighted) of surrounding water protons. This improves the contrast of
the magnetic resonance (MR) image while real-time imaging of biological functions.
The main problem here is the pharmacokinetic properties (biocompatibility, circula-
tion time in the bloodstream, targetability, etc.) of the contrast agents [67]. Many
researchers have tried to tailor the surface of the ferrite NPs with suitable function-
alities to overcome this situation. PE-HBPG-FA hybrid-encapsulated MnFe2O4 MNPs
are effective T2-weighted MRI contrast agents. This hyperbranched lipopolymer ren-
dered water solubility and biocompatibility, whereas FA introduced tumor cell targe-
tability to the synthesized spinel type MnFe2O4@PE-HBPG-FA MNPs. This composite
exhibited a higher transverse relaxivity value (140.56 mM−1 s−1) than conventional
superparamagnetic iron oxides [17]. Disodium tartrate dihydrate (T)-functionalized
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Functionalized Ferrites for Therapeutics and Environmental Pollution Management
DOI: http://dx.doi.org/10.5772/intechopen.1002336
4.3 Biosensor
compatibility study using osteoblast cell line (MG63) revealed the concentration-
dependent cell viability of the compound. Zn2+ ions are responsible for the antimicro-
bial nature of the complex against both the Gram-positive and Gram-negative bacterial
strains [61]. Glutaric acid-functionalized cobalt ferrite (CoFe2O4-GAPT) MNPs are
efficient agents for the top-down characterization of phosphoproteins during advanced
disease diagnosis. SDS-PAGE analysis of the MNPs incubated pig cardiac phosphopro-
teins, and comparing the results with other non-treated samples showcased that the
GAPT ligands facilitate the specificity and quantification efficacy of the MNPs [73].
Figure 6.
Synthesis of CuFe2O4-2 N-La and comparison of phosphate adsorption efficiency of CuFe2O42N and
CuFe2O4-2 N-La using the Langmuir adsorption isotherms. Copyright: Science of the Total environment [7].
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Functionalized Ferrites for Therapeutics and Environmental Pollution Management
DOI: http://dx.doi.org/10.5772/intechopen.1002336
Figure 7.
Illustration of uranium adsorption by the reduction of U6+ into insoluble U4+ (orange) on the surface of
the nanocrystalline MnFe2O4. Copyright: Journal of Materials Chemistry A [53].
Tudisco et al. anchored the visible light-sensitive TCPP molecules onto the sur-
faces of ferroelectric bismuth ferrite (BFO) MNPs. The resulting organic–inorganic
composite BFO@TCPP is an efficient agent for the photocatalysis of organic dyes
found in industrial wastewaters. TCPP helps enhance the surface-modified MNPs’
catalytic activity by decreasing its band gap than free BFO and inhibiting raid
recombination of the photogenerated electron–hole pairs. Moreover, the TCPP layer
remained intact even after four degradation cyclic runs, indicating the stability and
reusability of the BFO@TCPP particles [74]. TiO2 is arguably one of the best semi-
conducting photocatalysts due to its chemical stability, nontoxicity, and enhanced
photoreactivity. But it suffers from poor separation ability from the treated water.
Wuyou et al. resolved this matter by functionalizing ferromagnetic CoFe2O4 nanopar-
ticles with TiO2 nanocrystals in a core–shell structure. The resulting nanocomposite’s
photocatalytic activity can be increased by increasing the percentage of TiO2 in
TiO2/CoFe2O4 [62]. GO-modified copper ferrite (GO/CuFe2O4) nanocomposite is
another worthy candidate for water remediation. The electron and hole pairs in a
Figure 8.
Photocatalytic degradation mechanism of MG dye onto GO/CuFe2O4. Copyright: Materials today:
Proceedings [75].
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Applications of Ferrites
Figure 9.
Schematic illustration of the p-n heterojunction between PANI and CuFe2O4. Copyright: Sensors and
actuators: B. Chemical [37].
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Functionalized Ferrites for Therapeutics and Environmental Pollution Management
DOI: http://dx.doi.org/10.5772/intechopen.1002336
Similarly, NiFe2O4 MNPs suffer from low power performance despite being
anode materials in pseudocapacitor devices. For this reason, Neha et al. utilized a
covalent functionalization process using aryl diazonium salt to restore the interfacial
stability of the MNPs. The modified NiFe2O4 MNPs showcase strong metal–ligand
bonds that eventually assist their overall magnetic and electrochemical behavior.
Electrochemical studies showed that the diazonium-functionalized pseudocapacitor
electrode exhibits substantially higher specific capacitance (~1279 Fg−1) than bare
NiFe2O4 and (~82–90%) after 2000 cycles [77].
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Applications of Ferrites
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