Study on the chemical co-precipitation synthesized CoFe2O4 nanoparticle for magnetocaloric performance in the vicinity of superparamagnetic blocking temperature.

Nanoscaled magnetic cobalt ferrite (CoFe2O4) of approximately size 17 nm was synthesized via the co-precipitation method and then annealed at 600 °C. The resultant materials were taken for various magnetic characterizations. The X-ray diffraction pattern confirms the formation of the fcc type of cubic crystal structure. The ferrimagnetic phenomenon of the specimen was confirmed by the hysteresis loop, which is comparable to the slow relaxation sextet pattern of the MÓ§ssbauer study. Isomer shift, quadrupole splitting, hyperfine field, and Fe3+ occupancy of various sites are also investigated from mÓ§ssbauer spectroscopy. The frequency-dependent initial permeability has a comparatively high value up to a certain frequency range and then decreases drastically, whereas the imaginary part of complex permeability decreases sharply with the increase of frequency. The temperature-dependent magnetization ensures the presence of a superparamagnetic blocking temperature of 433 K. In the study of the magnetocaloric effect, isothermal magnetization measurements were carried out around the superparamagnetic blocking temperature, revealing a maximum entropy change of ΔSmax = 1.32 J/kg K and a relative cooling power (RCP) of 52.22 J/kg (H = 1.5 T) through the Maxwell approach. These outcomes emphasize the potential of CoFe2O4 NPs for magnetic refrigeration at reduced temperatures with lower applied magnetic fields.

Mesoporous Fe3O4/SiO2/poly(2-carboxyethyl acrylate) composite polymer particles for pH-responsive loading and targeted release of bioactive molecules.

pH-responsive polymer microspheres undergoing reversible changes in their surface properties have been proved useful for drug delivery to targeted sites. This paper is aimed at preparing pH-responsive polymer-modified magnetic mesoporous SiO2 particles. First, mesoporous magnetic (Fe3O4) core-particles are prepared using a one-pot solvothermal method. Then, magnetic Fe3O4 particles are covered with a C[double bond, length as m-dash]C functional mesoporous SiO2 layer before seeded emulsion polymerization of 2-carboxyethyl acrylate (2-CEA). The composite polymer particles are named Fe3O4/SiO2/P(2-CEA). The average diameters of the Fe3O4 core and Fe3O4/SiO2/P(2-CEA) composite polymer particles are 414 and 595 nm, respectively. The mesoporous (pore diameter = 3.41 nm) structure of Fe3O4/SiO2/P(2-CEA) composite polymer particles is confirmed from Brunauer-Emmett-Teller (BET) surface analysis. The synthesized Fe3O4/SiO2/P(2-CEA) composite polymer exhibited pH-dependent changes in volume and surface charge density due to deprotonation of the carboxyl group under alkaline pH conditions. The change in the surface properties of Fe3O4/SiO2/P(2-CEA) composite polymer particles following pH change is confirmed from the pH-dependent sorption of cationic methylene blue (MB) and anionic methyl orange (MO) dye molecules. The opening of the pH-responsive P(2-CEA) gate valve at pH 10.0 allowed the release of loaded vancomycin up to 99% after 165 min and p-acetamido phenol (p-AP) up to 46% after 225 min. Comparatively, the amount of release is lower at pH 8.0 but still suitable for drug delivery applications. These results suggested that the mesoporous Fe3O4/SiO2 composite seed acted as a microcapsule, while P(2-CEA) functioned as a gate valve across the porous channel. The prepared composite polymer can therefore be useful for treating intestine/colon cancer, where the pH is comparatively alkaline.

Effect of particle size and composition on local magnetic hyperthermia of chitosan-Mg1-xCoxFe2O4 nanohybrid.

In this study, Mg1-xCoxFe2O4 (0≤x ≤ 1 with ∆x = 0.1) or MCFO nanoparticles were synthesized using a chemical co-precipitation method and annealed at 200, 400, 600, and 800°C respectively to investigate the structural properties of the materials by X-ray diffractometer (XRD), transmission electron microscopy (TEM), and Fourier-transform infrared spectroscopy (FTIR). Controlled annealing increased particle size for each value of x. The aim was to investigate how specific loss power (SLP) and maximum temperature (Tmax) during local magnetic hyperthermia were affected by structural alterations associated with particle size and composition. The lattice parameter, X-ray density, ionic radius, hopping length, bond length, cation-cation distance, and cation-anion distance increase with an increase in Co2+ content. Raman and FTIR spectroscopy reveal changes in cation distribution with Co2+ content and particle size. Magnetic properties measured by the physical property measurement system (PPMS) showed saturation magnetization (Ms), coercivity (Hc), remanent magnetization (Mr/Ms), and anisotropy constant (K1) of the Mg1-xCoxFe2O4 nanoparticles increase with Co2+ content and particle size. When exposed to an rf magnetic field, the nanohybrids experienced an increase in both the SLP (specific loss power) and Tmax (maximum temperature) as the particle size initially increased. However, these values reached their peak at critical particle size and subsequently decreased. This occurs since a modest increase in anisotropy, resulting from the presence of Co2+ and larger particle size, facilitates Néel and Brownian relaxation. However, for high anisotropy values and particle size, the Néel and Brownian relaxations are hindered, leading to the emergence of a critical size. The critical size increases as the Co2+ content decreases, but it decreases as the Co2+ content increases, a consequence of higher anisotropy with the increase in Co2+. Additionally, it is noteworthy that the maximum temperature (Tmax) rises as the concentration of nanohybrids grows, but the specific loss power (SLP) decreases. An increased concentration of chitosan-MCFO nanohybrids inhibits both the Néel and Brownian relaxation processes, reducing specific loss power.

Enhanced specific loss power of hematite-chitosan nanohybrid synthesized by hydrothermal method.

We used a hydrothermal technique to develop nano-scale α-Fe2O3 particles and functionalized them with chitosan. An X-ray diffraction study revealed α-Fe2O3 nanoparticles were of single-phase, lattice constants were a = 5.07 Å and c = 13.68 Å, and the grain size was 27 nm. The presence of lattice fringes in the HRTEM image confirmed the crystalline nature of the α-Fe2O3. The Mössbauer spectra reveal a mixed relaxation state, which supports the PPMS studies. Zero-field cooled studies revealed the existence of a Morin transition and blocking temperature. The z-average value of the coated particles by DLS was between 218 and 235 nm, PDI ranged from 0.048 to 0.119, and zeta potential was +46.8 mV. We incubated the Vero and HeLa cell lines for 24 h to study the viability of the nanohybrids at different concentrations. Hyperthermia studies revealed the maximum temperature and specific loss power attained by the hematite-chitosan nanohybrid solution of a concentration between 0.25-4 mg ml-1. The Tmax at the lowest and highest concentrations of 0.25 and 4 mg ml-1 were 42.9 and 48.3°C, while the SLP were 501.6 and 35.5 W g-1, which are remarkably high when the maximum magnetization of α-Fe2O3 nanoparticles was as small as 1.98 emu g-1 at 300 K.

Correction: Efficacy of surface-functionalized Mg1-x Co x Fe2O4 (0 ≤ x ≤ 1; Δx = 0.1) for hyperthermia and in vivo MR imaging as a contrast agent.

[This corrects the article DOI: 10.1039/D2RA00768A.].

Efficacy of surface-functionalized Mg1-x Co x Fe2O4 (0 ≤ x ≤ 1; Δx = 0.1) for hyperthermia and in vivo MR imaging as a contrast agent.

Surface-functionalized Mg1-x Co x Fe2O4 (0 ≤ x ≤ 1; Δx = 0.1) can be an exciting candidate as an MRI contrast agent and for thermotherapeutic applications. The figure-of-merit, T 2, relaxivity, r 2, of MRI and specific loss power, SLP, of hyperthermia depend on the structural and magnetic properties of the nanoparticles. We synthesized cobalt-substituted magnesium ferrite Mg1-x Co x Fe2O4 (0 ≤ x ≤ 1 with Δx = 0.1) nanoparticles using a chemical co-precipitation method. The lattice parameter and average crystallite size increase with the increase in cobalt content. The force-constant of FTIR of the tetrahedral sites increases, and that of the octahedral sites decreases with an increase in cobalt content. The room temperature Mössbauer spectra of Mg1-x Co x Fe2O4 show that the Mössbauer absorption area of the A site decreases, and the Mössbauer absorption area of the B site increases with x. The Mössbauer spectra and M-H hysteresis loops at room temperature confirmed that a transition from fast relaxation (superparamagnetic) to mixed slow/fast (superparamagnetic/ferrimagnetic) relaxation occurs with changing cobalt content. The cobalt ion tends to occupy the octahedral B site, which makes the A-B interaction stronger; therefore, we see the above transition. Cytotoxicity experiments on HeLa cells revealed that both chitosan and chitosan-coated magnesium cobalt ferrite nanoparticles are biocompatible. In the Mg1-x Co x Fe2O4 series, both r 2 and SLP increase with x because of the increase in magnetization and anisotropy.

In Vivo Toxicity Studies of Chitosan-Coated Cobalt Ferrite Nanocomplex for Its Application as MRI Contrast Dye.

Cobalt ferrite nanoparticle (CFN) has received attention in magnetic resonance imaging (MRI) as a promising contrast agent due to its higher saturation magnetization and magneto-crystalline anisotropy. However, the in vitro cytotoxicity of CFN has raised concern for its biomedical application as a diagnostic agent. The coating of CFN by a biocompatible polymer such as chitosan (CH) might lessen the biocompatibility concern. Therefore, in this study, we examined the applicability of chitosan-coated cobalt ferrite nanoparticle (CCN) as an MRI contrast dye and investigated its biocompatibility in vivo. Phantom MRI images revealed that the relaxivity of CCN was 121 (±8) mM-1s-1, indicating the potential of CCN as a T2-weighted contrast agent. A single intravenous (iv) administration of CCN (10 mg/kg) improved the contrast of magnetic-resonance-imaging-based angiography (MRA) and brain-MRI in male albino Wistar rats compared to the control. Furthermore, toxicity studies dependent on dose (1-20 mg/kg) and time (1-28 days) in male albino Wistar rats confirmed the in vivo biocompatibility of CCN. The physical, hematological, biochemical, and histopathological observation assured that a single iv injection of CCN up to 20 mg/kg was well adjusted with liver, kidney, heart, and brain functions. The findings of the current study consolidate CCN as a promising candidate for MRI contrast dye.

Improved specific loss power on cancer cells by hyperthermia and MRI contrast of hydrophilic Fex Co1-x Fe2 O4 nanoensembles.

Ferrite-based ferri/superparamagnetic nanoparticles can be rapidly heated by an external alternating magnetic field (AMF) to induce tissue necrosis of the adjacent microenvironment, but in addition provide magnetic resonance imaging (MRI) contrast utilizing enhanced water relaxivity. Here we characterized nanoensembles of Fe-Co mixed spinel ferrites (i.e. Fex Co1-x Fe2 O4 , where x ranges from 0.2 to 0.8) synthesized by chemical co-precipitation. With nanoensembles of increasing Co content the saturation magnetization improved, while lattice parameter remained relatively constant. MRI water (transverse) relaxivity at 11.7 T was also boosted with increasing Co content. Efficiency of AMF-induced heating was quite comparable for the nanoensembles with either chitosan or polyethylene glycol (PEG) coating except for PEG-coated Fe0.2 Co0.8 Fe2 O4 , which was twice as less efficient as others. While toxicity of the nanoensembles with either coating examined on 9L tumor cell cultures showed no significant differences, upon AMF exposure (i.e. heat-induced necrosis) Fex Co1-x Fe2 O4 composition with different values of x showed quite dramatic effects on cell death of tumor cells with both coatings. This study lays the ground work for further characterization of other mixed spinel ferrites, and in addition we expect that chitosan and PEG coated Fex Co1-x Fe2 O4 of all the compositions will have good potential for preclinical applications in vivo. Copyright © 2016 John Wiley & Sons, Ltd.

Thermo-therapeutic applications of chitosan- and PEG-coated NiFe2O4 nanoparticles.

The paper reports the thermo-therapeutic applications of chitosan- and PEG-coated nickel ferrite (NiFe2O4) nanoparticles. In this study NiFe2O4 nanoparticles were synthesized by the co-precipitation method, tuning the particle size through heat treatment in the temperature range from 200-800 °C for 3 h. XRD and TEM analysis revealed that the the ultrafine nanoparticles were of size 2-58 nm. Crystallinity of the NiFe2O4 nanoparticles in the as-dried condition with the particle size ∼2-3 nm was confirmed from the presence of a lattice fringe in the HRTEM image. VSM measurements showed that a superparamagnetic/ferromagnetic transition occurs with increasing particle size, which was further confirmed by Mössbauer spectroscopy. The nickel ferrite nanoparticles with optimum particle size of 10 nm were then coated with materials commonly used for biomedical applications, i.e. chitosan and PEG, to form homogeneous suspensions. The hydrodynamic diameter and the polydispersity index (PDI) were analyzed by dynamic light scattering at the physiological temperature of 37 °C and found to be 187 nm and 0.21 for chitosan-coated nanoparticles and 285 nm and 0.32 for PEG-coated ones. The specific loss power of rf induction heating by the set-up for hyperthermia and r 2 relaxivity by the nuclear magnetic resonance were determined. The results of induction heating measurements showed that the temperature attained by the nanoparticles of size 10 nm and concentration of about 20 mg ml(-1) was >70 °C (for chitosan) and >64 °C (for PEG). It has been demonstrated that the required temperature for hyperthermia heating could be tuned by tuning the particle size, shape and magnetization and the concentration of solution. For other potential biomedical applications of the NiFe2O4 nanoparticle solution, e.g. magnetic resonance imaging, the NMR studies yielded the T 1 and T 2 relaxivities as 0.348 and 89 mM(-1) s(-1) respectively. The fact that the T 2 relaxivity is orders of magnitude higher than T 1 indicates that this is suitable as a T 2 contrast agent for magnetic resonance imaging.

Synthesis and characterization of ZnFe2O4 nanoparticles and its biomedical applications.

Biomedical applications of ZnFe2O4 nanoparticle are preferable among all kinds of ferrites due to the compatibility of Zn2+ ions for human bodies. We have followed the soft chemical route to synthesize chitosan and PEG coated ZnFe2O4 nanoparticles and also the chitosan-coated-nanoparticles encapsulated with liposome. X-ray diffraction studies by the Mo Kα target, showed the formation of single phase spinel structure. The lattice parameter turned out to be 8.48Å and grain size ~ 4.8 nm (± 0.1 nm). Similar particle size was observed by transmission electron microscope analysis. HRTEM studies showed the distinct lattice fringes thus confirming the good crystallinity of the synthesized nanoparticles. M-H curve at room temperature showed the prepared sample was superparamagnetic in nature, which is also confirmed by the doublets of Mössbauer spectroscopy. Relaxivity values (r2) of Chitosan and PEG coated ZnFe2O4 nanoparticles are 68 and 76 mM-1s-1 respectively. In order to achieve further biocompatibility the chitosan-coated-nanoparticles were encapsulated with liposome. The r2 relaxivity was found as 54mM-1s-1. MR images obtained from the in vitro experiments based on phantoms demonstrated good contrast enhancement. Induction heating of bare and coated particles was investigated to reveal the self heating temperature rising properties of ZnFe2O4 nanoparticles.

Synthesis, characterization, and nuclear magnetic resonance study of chitosan-coated Mn(1-x)Zn(x)Fe2O4 nanocrystals.

Ultra-fine crystallites of Mn(1-x)Zn(x)Fe2O4 series (0 ≤ x ≤ 1) were synthesized through wet chemical co-precipitation method followed by calcination at 200 °C for 4 hours. Formation of ferrites was confirmed by X-ray diffraction, TEM selected area diffraction (SAD) and Fourier Transform Infra-red Spectroscopy (FTIR). Nanocrystallites of different compositions in the series were coated with biocompatible chitosan in order to investigate their possible application as contrast agent for magnetic resonance imaging (MRI). Chitosan coating examined by FTIR, revealed a strong bonding of chitosan molecules to the surface of the ferrite nanocrystallites. Spin-spin, τ2 relaxivities of nuclear spins of hydrogen protons of the solutions for different ferrites were measured from concentration dependence of relaxation time by nuclear magnetic resonance (NMR). All the compositions Mn(1-x)Zn(x)Fe2O4 of series possess higher values of τ2 relaxivity thus making them suitable as contrast agents for τ2 weighted imaging by MRI.