Magnetite Nanorods Research Articles

Magnetic Assembly of Magnetite/Perovskite Hybrid Nanorods for Circularly Polarized Luminescence

AbstractMagnetic fields are uniquely valuable for creating colloidal nanostructured materials, not only providing a means for controlled synthesis but also guiding their self‐assembly into distinct superstructures. In this study, a magnetothermal process for synthesizing hybrid nanostructures comprising ferrimagnetic magnetite nanorods coated with fluorescent perovskite nanocrystals is reported and their magnetic assembly into superstructures capable of emitting linear and circularly polarized light are demonstrated. Under UV excitation, the superstructures assembled in a liner magnetic field produce linear polarized luminescence, and those assembled in a chiral magnetic field exhibit strong circularly polarized luminescence (CPL) with a glum value up to 0.44 (±0.004). The CPL is believed to originate from the dipolar interaction between neighboring perovskite nanocrystals attached to the chiral assemblies and the chiral‐selective absorption of the perovskite emission by the magnetite phase. The magnetic synthesis and assembly approaches and the resulting distinctive chiral superstructures are anticipated to open up new avenues for designing diverse functional chiroptical devices.

Solvothermally synthesized magnetite nanorods for application in magnetic hyperthermia and photothermia

The development of the multi-functional nanostructures has recently been of particular interest in therapeutic research for various diseases including atherosclerosis, cancer, etc. Indeed, the use of multi-responsive nanostructures that can remotely be activated by different stimuli is a promising strategy to combine the advantages of standalone methods and overcome their intrinsic drawbacks. In this regard, thermal treatment using heat-generating magnetic nanostructures that can remotely respond to a wide range of electromagnetic stimuli is of especial importance, mainly applied through magnetic hyperthermia therapy (MHT) and photothermal therapy (PTT) modalities. In this work, magnetite (Fe3O4) nanorods (MNRs) were synthesized using a one-pot solvothermal process. Adjusting the amount of hexadecylamine capping ligand and the filling percentage of the autoclave, uniformed-sized MNRs of 4·46nm in diameter and 31·09nm in length were prepared and investigated in terms of their heat-generating ability for application in the MHT and PTT. The experimental results show the good heat-generating ability of the MNRs in both modalities with the maximum absorption rate (SAR) values of 228.51 W/g (MHT) and 56.59 W/g (PTT).

Chitosan-coated magnetic nanorods and nanospheres: physicochemical characterizations and potential as methotrexate carriers for targeted drug delivery

Abstract Spherical magnetite nanoparticles were employed in the almost all magnetic based drug delivery studies. But as we all know the shape of employed particles is one of the major deterministic properties that can significantly affect the physicochemical and biological features of nanostructures and so can fluctuate efficiency of drug delivery. However, it is worthy of consideration that so far no study has investigated the effect of the shape of nanoparticles in drug delivery. To some extent this deficiency in publications may be due to the fact that the synthesis of other forms of magnetite nanoparticles is not as developed as spherical nanoparticles. But recent experiments paved the way for the synthesis of magnetite nanoparticles specially magnetite nanorods (MNRs). So, for the first time, in the current experiment magnetite nanospheres (MNSs) and MNRs were compared in the potential for drug delivery. Chitosan is a natural and biocompatible compound that widely employed as coating material for the fabrication of anticancer drug nano-carriers. So in the present study this carbohydrate was chosen as coating material for the magnetic nanostructures. MNSs were synthesized via a co-precipitation reaction, and MNRs were obtained from the chemical reduction of iron oxide hydroxide (FeOOH) nanorods. Both nanostructures were loaded with methotrexate (MTX), and the release of the drug was measured. The chitosan-coated MNSs (C@MNSs) were 7–18 nm in diameter, and the chitosan-coated MNRs (C@MNRs) were 5–21 nm in width and 29–108 nm in length and had a porous structure. The C@MNSs had a magnetic saturation of ∼80 emu/g, whereas that for the C@MNRs was ∼45 emu/g. The synthesized nanostructures exhibited low toxicity and were able to release the drug inside the cells. The findings of this study demonstrate the suitability of C@MNRs as an alternative to spherical nano-carriers for the efficient and contained delivery of anticancer drugs to designated target cells.

Silica-coated magnetic nanorods with zwitterionic surface functionalization to overcome non-specific protein adsorption

Anisotropic magnetic nanoparticles are receiving growing interest for biomedical applications due to their interesting properties, particularly for MRI and magnetic hyperthermia. In this work, a two-step, relatively simple synthesis pathway of magnetite nanorods was optimised. A ligand from the catechol family, known for its high iron oxide surface affinity, was used to transfer them into aqueous phase. The magnetite nanorods were then coated with a layer of fluorescent silica, whose surface was functionalised in two ways: either by short poly(ethylene glycol) (PEG) chains or by sulfobetaine zwitterionic molecules. A wide range of techniques were used to thoroughly characterise their physical structure, magnetic properties and dispersion characteristics. Finally, a study of the adsorption of a fluorescent model protein revealed that zwitterionic sulfobetaine molecules were more effective than PEG chains in limiting the non-specific adsorption of this protein.

Enhancement of Magnetic Surface-Enhanced Raman Scattering Detection by Tailoring Fe3O4@Au Nanorod Shell Thickness and Its Application in the On-site Detection of Antibiotics in Water.

Surface-enhanced Raman scattering (SERS) has become a promising method for the detection of contaminants or biomolecules in aqueous media. The low interference of water, the unique spectral fingerprint, and the development of portable and handheld equipment for in situ measurements underpin its predominance among other spectroscopic techniques. Among the SERS nanoparticle substrates, those composed of plasmonic and magnetic components are prominent examples of versatility and efficiency. These substrates harness the ability to capture the target analyte, concentrate it, and generate unique hotspots for superior enhancement. Here, we have evaluated the use of gold-coated magnetite nanorods as a novel multifunctional magnetic-plasmonic SERS substrate. The nanostructures were synthesized starting from core-satellite structures. A series of variants with different degrees of Au coatings were then prepared by seed-mediated growth of gold, from core-satellite structures to core-shell with partial and complete shells. All of them were tested, using a portable Raman instrument, with the model molecule 4-mercaptobenzoic acid in colloidal suspension and after magnetic separation. Experimental results were compared with the boundary element method to establish the mechanism of Raman enhancement. The results show a quick magnetic separation of the nanoparticles and excellent Raman enhancement for all the nanoparticles both in dispersion and magnetically concentrated with limits of detection up to the nM range (∼50 nM) and a quantitative calibration curve. The nanostructures were then tested for the sensing of the antibiotic ciprofloxacin, highly relevant in preventing antibiotic contaminants in water reservoirs and drug monitoring, showing that ciprofloxacin can be detected using a portable Raman instrument at a concentration as low as 100 nM in a few minutes, which makes it highly relevant in practical point-of-care devices and in situ use.

Combined Magnetic Hyperthermia and Photothermia with Polyelectrolyte/Gold-Coated Magnetic Nanorods.

Magnetite nanorods (MNRs) are synthesized based on the use of hematite nanoparticles of the desired geometry and dimensions as templates. The nanorods are shown to be highly monodisperse, with a 5:1 axial ratio, and with a 275 nm long semiaxis. The MNRs are intended to be employed as magnetic hyperthermia and photothermia agents, and as drug vehicles. To achieve a better control of their photothermia response, the particles are coated with a layer of gold, after applying a branched polyethyleneimine (PEI, 2 kDa molecular weight) shell. Magnetic hyperthermia is performed by application of alternating magnetic fields with frequencies in the range 118-210 kHz and amplitudes up to 22 kA/m. Photothermia is carried out by subjecting the particles to a near-infrared (850 nm) laser, and three monochromatic lasers in the visible spectrum with wavelengths 480 nm, 505 nm, and 638 nm. Best results are obtained with the 505 nm laser, because of the proximity between this wavelength and that of the plasmon resonance. A so-called dual therapy is also tested, and the heating of the samples is found to be faster than with either method separately, so the strengths of the individual fields can be reduced. Due to toxicity concerns with PEI coatings, viability of human hepatoblastoma HepG2 cells was tested after contact with nanorod suspensions up to 500 µg/mL in concentration. It was found that the cell viability was indistinguishable from control systems, so the particles can be considered non-cytotoxic in vitro. Finally, the release of the antitumor drug doxorubicin is investigated for the first time in the presence of the two external fields, and of their combination, with a clear improvement in the rate of drug release in the latter case.

Mesocrystalline Ordering and Phase Transformation of Iron Oxide Biominerals in the Ultrahard Teeth of Cryptochiton stelleri

Biological organisms naturally synthesize complex, hierarchical, multifunctional materials through mineralization processes at ambient conditions and under physiological pH. One such example is the ultrahard and wear‐resistant radular teeth found in mollusks, which are used to scape against the rock to feed on algae. Herein, the biologically controlled structural development of the hard, outer magnetite‐containing shell of the chitin teeth is revealed. Specifically, the formation of a series of mesocrystalline iron oxide phases, templated by chitin‐binding proteins, is identified. The initial domains, consisting of ferrihydrite mesocrystals with a spherulite‐like morphology, undergo a solid‐state phase transformation to form magnetite while maintaining mesocrystallinity, likely via a shear‐induced solid‐state reaction, without any noticeable architectural changes. Subsequent growth via Ostwald ripening leads to nearly single‐crystalline rod‐like elements. In addition, an interpenetrating organic matrix is identified that, at early stages of tooth development, potentially contains iron‐binding proteins that guide the self‐assembly of the mesocrystalline mineral and influence the preferred orientation of the later‐formed magnetite nanorods, which ultimately determines the mechanical behavior of the mature chiton teeth.

Magnetically aligned CNT/magnetite heterogeneous composite membranes for electromagnetic wave shielding and heat dissipation

The miniaturization and integration of next-generation electronic devices are accompanied by a substantial increase in electromagnetic interference (EMI) and heat generation, which requires light and thin EMI shielding materials. Herein, we attempt to tackle this challenge by designing a heterogeneous membrane using carbon nanotubes (CNTs) and magnetite (Fe3O4) nanorods. The polymer-coated Fe3O4 uniformly adsorbs on the surface of the polyaniline (PANi) coated CNTs, forming a self-supporting composite membrane with vertical CNTs under a magnetic field. Due to the entanglement of the CNTs, the vertical alignment is more effective in the top region of the membrane than in the bottom, resulting in an asymmetric structure that is beneficial to EMI absorption. When electromagnetic waves are incident from the top surface, high-absorption electromagnetic shielding is obtained due to multiple attenuations and absorption-reflection losses. The vertical orientation and heterogeneous CNTs network structure of the membrane also enable stable heat dissipation.

Magnetic Stiffening in 3D Cell Culture Matrices.

The mechanical environment of a cell is not constant. This dynamic behavior is exceedingly difficult to capture in (synthetic) in vitro matrices. This paper describes a novel, highly adaptive hybrid hydrogel composed of magnetically sensitive magnetite nanorods and a stress-responsive synthetic matrix. Nanorod rearrangement after application of (small) magnetic fields induces strain in the network, which results in a strong (over 10-fold) stiffening even at minimal (2.5 wt %) nanorod concentrations. Moreover, the stiffening mechanism yields a fast and fully reversible response. In the manuscript, we quantitatively analyze that forces generated by the particles are comparable to cellular forces. We demonstrate the value of magnetic stiffening in a 3D MCF10A epithelial cell experiment, where simply culturing on top of a permanent magnet gives rise to changes in the cell morphology. This work shows that our hydrogels are uniquely suited as 3D cell culture systems with on-demand adaptive mechanical properties.

One dimensional magneto-optical nanocomplex from silver nanoclusters and magnetite nanorods containing ordered mesocages for sensitive detection of PD-L1

Programmed death ligand 1 (PD-L1) is a typical immune checkpoint protein, whose up-regulation on the membrane of different tumor cells inhibits the immune response of T cells and leads to the escape of tumor cells. In this work, we designed a facile and highly specific surface plasmon resonance (SPR) biosensor to detect PD-L1 in human plasma based on magnetite nanorods containing ordered mesocages (MNOM) and silver nanoclusters (AgNCs). Magneto-optical nanocomplex MNOM@AgNCs with superior magneto-optical properties and high signal-to-noise ratio were fabricated to improve the detection sensitivity owing to the high specific surface area of MNOM and excellent localized SPR of AgNCs. The PD-L1 Antibody on the surface of gold chip and the PD-L1 aptamer on MNOM@AgNCs could realize dual selective recognition of PD-L1, providing the specificity of the sensor and reducing non-specific binding. The SPR sensor showed a good linear range of PD-L1 from 10 ng/mL to 300 ng/mL with the detection limit of 3.29 ng/mL. The practical performance of this immunosensing platform had been successfully verified by clinical samples which included healthy donors and cancer patients. Based on the analysis, the developed immunosensor provided a new strategy for point-of-care detection of PD-L1 and could be used as clinical companion diagnosis of PD-1/PD-L1 inhibitor therapy.

Magnetic anomalies associated with domain wall freezing and coupled electron hopping in magnetite nanorods

Magnetite has fascinated researchers for decades, due to its wide range of applications from spintronics to biomedicine. Despite a large body of works aimed at its magnetic properties, no consensus has been reached on the physical origin of the low temperature magnetic anomalies observed in magnetite. Although, a lot of work has been done in studying magnetite nanoparticles, but studies on the low temperature anomalies in those nanoparticles still remains unresearched. We report on the observation of the low temperature magnetic anomalies in highly crystalline, stoichiometric Fe3O4 nanorods and relate them to the coupled electron hopping relaxation process and domain wall motion. Both DC and AC susceptibility show the presence of a hump around 35 K, which is associated with the relaxation of Fe+2 extra electrons. Radio-frequency transverse susceptibility (TS) measurements indicated a noticeable increase in anisotropy field below ~ 25 K, which is attributed to the rearrangement of Fe+2 electrons in the octahedral sites. TS experiments also revealed the domain wall freezing below ~ 35 K. Our combined DC, AC and TS susceptibility studies shed light on the complex nature of the low-temperature magnetic behavior in nanostructured magnetite.

Synthesis of Magnetite Nanorods from the Reduction of Iron Oxy-Hydroxide with Hydrazine.

Nanowires and nanorods of magnetite (Fe3O4) are of interest due to their varied biological applications but most importantly for their use as magnetic resonance imaging contrast agents. One-dimensional (1D) structures of magnetite, however, are more challenging to synthesize because the surface energy favors the formation of isotropic structures. Synthetic protocols can be dichotomous, producing either the 1D structure or the magnetite phase but not both. Here, superparamagnetic Fe3O4 nanorods were prepared in solution by the reduction of iron oxy-hydroxide (β-FeOOH) nanoneedles with hydrazine (N2H4). The amount of hydrazine and the reaction time affected the phase and morphology of the resulting iron oxide nanoparticles. One-dimensional nanostructures of Fe3O4 could be produced consistently from various aspect ratios of β-FeOOH nanoneedles, although the length of the template was not retained. Fe3O4 nanorods were characterized by transmission electron microscopy, X-ray powder diffraction, X-ray photoelectron spectroscopy, and SQUID magnetometry.

Magnetic-field-assisted synthesis of anisotropic iron oxide particles: Effect of pH.

The synthesis of magnetite (Fe3O4) nanorods using reverse co-precipitation of Fe3+ and Fe2+ ions in the presence of a static magnetic field is reported in this work. The phase composition and crystal structure of the synthesized material were investigated using electron diffraction, Raman spectroscopy, and transmission electron microscopy. It was shown that the morphology of the reaction product strongly depends on the amount of OH− ions in the reaction mixture, varying from Fe3O4 nanorods to spherical Fe3O4 nanoparticles. Fe3O4 nanorods were examined using high-resolution transmission electron microscopy proving that they are single-crystalline and do not have any preferred crystallographic orientation along the axis of the rods. According to the data obtained a growth mechanism was proposed for the rods that consists of the dipole–dipole interaction between their building blocks (small hexagonal faceted magnetite nanocrystals), which are formed during the first step of the reaction. The study suggests a facile, green and controllable method for synthesizing anisotropic magnetic nanoparticles in the absence of stabilizers, which is important for further modification of their surfaces and/or incorporation of the nanoparticles into different media.

Surface Compositional Change of Iron Oxide Porous Nanorods: A Route for Tuning their Magnetic Properties.

The capability of synthesizing specific nanoparticles (NPs) by varying their shape, size and composition in a controlled fashion represents a typical set of engineering tools that tune the NPs magnetic response via their anisotropy. In particular, variations in NP composition mainly affect the magnetocrystalline anisotropy component, while the different magnetic responses of NPs with isotropic (i.e., spherical) or elongated shapes are mainly caused by changes in their shape anisotropy. In this context, we propose a novel route to obtain monodispersed, partially hollow magnetite nanorods (NRs) by colloidal synthesis, in order to exploit their shape anisotropy to increase the related coercivity; we then modify their composition via a cation exchange (CE) approach. The combination of a synthetic and post-synthetic approach on NRs gave rise to dramatic variations in their magnetic features, with the pores causing an initial magnetic hardening that was further enhanced by the post-synthetic introduction of a manganese oxide shell. Indeed, the coupling of the core and shell ferrimagnetic phases led to even harder magnetic NRs.

Magnetic nanorods for remote disruption of lipid membranes by non-heating low frequency magnetic field

This work presents direct evidence of disordering of liposomal membranes by magnetic nanoparticles during their exposures to non-heating alternating Extremely Low Frequency Magnetic Field (ELF MF). Changes in the lipid membrane structure were demonstrated by the Attenuated total reflection Fourier Transform Infrared and fluorescence spectroscopy. Specifically, about 50% of hydrophobic chains became highly mobile under the action of ELF MF. Magnetic field-induced increase in the membrane fluidity was accompanied by an increase in membrane permeability and release of solutes entrapped in liposomes. The effect of ELF MF on the membrane fluidity was greater in case of 70 × 12 nm magnetite nanorods adsorbed on the liposomes surface compared to liposomes with ~7 nm spherical MNPs embedded within lipid membranes. A physical model of this process explaining experimental data is suggested. The obtained results open new horizons for the development of systems for triggered drug release without dangerous heating and overheating of tissues.

Magnetite Nanorods Stabilized by Polyaniline/Reduced Graphene Oxide as a Sensing Platform for Selective and Sensitive Non‐enzymatic Hydrogen Peroxide Detection

AbstractIn this study, magnetite nanorods stabilized on polyaniline/reduced graphene oxide (Fe3O4@PANI/rGO) was synthesized via a wet‐reflux strategy. The possible formation of Fe3O4@PANI/rGO was morphologically and structurally verified by field emission scanning electron microscopy (FE‐SEM), Fourier transform infrared (FT‐IR) spectroscopy, Raman spectroscopy, X‐ray diffraction (XRD) and X‐ray photoelectron spectroscopy (XPS). Furthermore, the thermal stability of Fe3O4@PANI/rGO was measured by a thermogravimetric analyzer (TGA); the composite had good thermal stability owing to the ceramic nature of Fe3O4. The Fe3O4@PANI/rGO has been applied as a potential sensing platform for electrochemical detection of hydrogen peroxide (H2O2). By the combined efforts of extended active surface area, active carbon support, more catalytic active sites and high electrical conductivity, the Fe3O4@PANI/rGO exhibited an improved performance toward the non‐enzymatic detection of H2O2 in 0.5 M KOH with a fast response time (5 s), high sensitivity (223.7 μA mM−1 cm−2), low limit of detection (4.45 μM) and wide linear range (100 μM–1.5 mM). Furthermore, the fabricated sensor exhibited excellent recovery rates (94.2–104.0 %) during real sample analysis.

Fe3O4 nanorods r-GO sheets nanocomposite visible photo catalyst

Reduced graphene oxide (r-GO) sheets decorated with magnetite (Fe3O4) nanorods were synthesized through wet chemical method at room temperature. X-ray diffraction spectrum of Fe3O4/r-GO nano-composite shows r-GO peak along with few characteristic peaks of magnetite nanoparticles. Scanning electron microscopy confirmed the transformation of Fe3O4 pseudo-spherical morphology into rod shaped over r-GO sheets due to surface to surface interactions and strong alkaline media as dense coverage. UV–vis diffused reflectance spectra of Fe3O4/r-GO composite shows that absorption edge has been shifted towards the higher wavelength because of the presence of Fe3O4 nanoparticles and the partial restoration of pi network upon reduction of GO. The vibrating sample magnetometer (VSM) of various Fe3O4/r-GO composites distinctively represent S-shaped magnetization curves with no coercitivity that supports their super-paramagnetic behavior. Moreover, the hybrid nanostructure Fe3O4/r-GO shows significantly enhanced visible photo catalytic activity for MO degradation due to high surface area of two-dimensional (2D) r-GO sheets and one dimensional (1D) nanostructure of magnetite nanorods that reduces the electron-hole (e−-h+) pair recombination through long distance fast electron transport.

Size-defined synthesis of magnetic nanorods by Salvia hispanica essential oil with electromagnetic excitation properties useful in microwave imagining

Abstract Salvia hispanica (chia) essential oil was applied for successful production of magnetic nanorods. The influence of several parameters, i.e. temperature of the reaction mixture, volume of the S. hispanica essential oil solution, stirring speed of the reaction mixture, and flow rate of the N2 protective gas, on their axial length was studied. A design of experiments (DOE) approach followed by the response surface methodology (RSM) identified the optimal conditions for synthesis of ∼3 nm magnetic nanorods. The granulometric and magnetic properties of these magnetite nanorods were analyzed using transmission electron microscopy (TEM), energy dispersive X-ray scattering (EDX), selected area electron diffraction spectroscopy (SAED), X-ray diffraction (XRD), and superconducting quantum interference device (SQUID) magnetometer. These methods revealed that the produced magnetic nanorods had a crystalline cubic inverse spinel structure with an average axial length of 43.4 ± 20.5 nm, diameter of 3.6 ± 0.9 nm, and aspect ratio of 12.1 ± 5.2 nm, and they suggested the presence of spin glass-like (mictomagnetic) behavior with both ferro- and antiferromagnetic interactions. In addition, attenuated total reflectance Fourier transform infrared spectroscopy (ATR FT-IR) was used to identify functional groups of the organic compounds present in S. hispanica essential oil that were possibly responsible for production and surface functionalization of the magnetite nanorods. The resultant magnetic nanofluid displayed electromagnetic excitation when exposed to microwave radiation, and therefore it could be useful in microwave-imaging of tissues.

Nicotinic Acid Coated Magnetite Nanorods Evaluation by Lipid Profile Analysis and Genetic Tests.

In our present work some biological tests were carried out to assess the biocompatibility of nicotinic acid coated magnetite nanorods. Pure and coated nanorods were injected intraperitoneally to cholesterol fed mice with dose values of 25, 50 mg/Kg. Investigations were done on treated mice with/without exposure to low frequency electromagnetic field (EMF) and samples were collected fourteen days post treatment. Toxicological effects were evaluated using Micronucleus and DNA fragmentation analysis. The results indicated that low dose (25 mg/Kg) nicotinic acid coated nanorods had insignificant toxicological effects in comparison to that of control group. Lipid profile analysis and gene expression of atheroprotective (eNOS) and atherogenic (p65) genes were also investigated. It was found that experimental groups treated with low dose nicotinic acid coated magnetite nanorods and exposed to EMF showed interesting alterations in mice lipid profile. As a result, an insignificant but slight increase in gene expression levels of eNOS and a significant decrease in p65 gene expression were observed. Our study suggests that our proposed magnetic nanosystem in combination with EMF has good biocompatibility and can be a potential drug precursor with therapeutic values.

Theoretical calculation of optical and magneto optical properties of magnetite nanorods

The optical and magneto-optical called Faraday rotation of composites containing isolated Fe3O4 (magnetite) nanorods particles are presented in the wavelength range from 300-700 nm. The results were obtained by using the discrete dipole approximation (DDA) method. The composite materials are constructed by combining Fe3O4 nanorods particles and the material with fixed dielectric constant of 2.25. The Fe3O4 nanorods of different aspect ratio (AR), varied from 3 to 7, were used to embed in the host material. The influence of the orientation of Fe3O4 nanorods comparing with the incident light and number particles on the Faraday rotation spectrum were also presented. The absorption cross-section spectra of Fe3O4 nanorods were able to be observed only when the main axis was aligned parallel to the polarization direction and perpendicular with the direction propagation of excited light.