Facile synthesis of magnetic iron oxide nanoparticles and their characterization

Magnetic iron oxide nanoparticles are synthesized by suitable modification of the standard synthetic procedure without use of inert atmosphere and at room temperature. The facile synthesis procedure can be easily scaled up and is of important from industrial point of view for the commercial large scale production of magnetic iron oxide nanoparticles. The synthesized nanoparticles were characterized by thermal, dynamic light scattering, scanning electron microscopy and transmission electron microscopy analyses.     

Thermally induced changes in the magnetic properties of iron oxide nanoparticles under reducing and oxidizing conditions

Application of iron oxide nanoparticles in the fields of water purification, biomedicine or chemistry often requires controlled magnetic properties that can be modified by changing temperature and redox conditions. Therefore, this work investigates the changes in the magnetic properties of iron oxide nanoparticles in the FeOOH − Fe₂O₃ − Fe₃O₄ system (i.e. hematite, goethite, lepidocrocite, maghemite and magnetite) at heating under reducing and oxidizing conditions. The results show that heat treatment of hematite and goethite in the presence of a reducing agent (5% starch) leads to their conversion into high magnetic magnetite. The starting temperature of transformation is approximately 350 °C for both samples. The magnetization increases to 86 Am²/kg for hematite reduced at 700 °C and to 88 Am²/kg for goethite reduced at 900 °C. An intense reaction occurs within the first 10 min and then the conversion process decelerates. Thermal treatment of lepidocrocite under both oxidizing and reducing conditions leads to an increase in magnetization due to the formation of maghemite and magnetite, respectively. Regardless of the redox conditions, the formation of magnetic phase begins at a temperature of 250 °C and is associated with the formation of maghemite from lepidocrocite. Under oxidizing conditions, the magnetization begins to decrease at 350 °C, which is associated with the conversion of maghemite to hematite. On the contrary, under reducing conditions, the magnetization of lepidocrocite increases up to 900 °C, which is associated with the formation of magnetite. Maximum values of magnetization are 36 Am²/kg for maghemite obtained at 350 °C, and 88 Am²/kg for magnetite obtained at 900 °C from lepidocrocite. With the help of conventional heating, the magnetic properties of IONs can be altered by phase transformations in the FeOOH − Fe₂O₃ − Fe₃O₄ system. Temperature and redox conditions are the two most important factors controlling the transformation pathways and the magnetic properties of the resulting IONs.     

Improvement in the dispersion stability of iron oxide nanoparticles in highly concentrated brine solution using encapsulation with polymer-polymer crosslinked shells

In this study, the dispersion stability of superparamagnetic iron oxide nanoparticles (IONPs) under high salinity was investigated. In our previous study, the stable dispersion of IONPs in 5 wt% NaCl solution was achieved under neutral and basic conditions through the functionalization of IONPs using sulfonated phenolic resin (SPR). However, under acidic conditions, the SPR shell dissociated from the IONP surface, resulting in the loss of dispersion stability. To overcome this limitation, crosslinking with polyvinyl alcohol (PVA) was implemented. The sulfonate groups in the SPR and hydroxyl groups in PVA can form a bond by removing water and consequently a crosslinked structure is formed between SPR and PVA. The stability of the dispersion was evaluated using visual observation of sedimentation and size measurements of the sample for a week. It was found that the dispersion was highly stable in brine, containing up to 10 wt% NaCl, at pH 4. The shell/core structure of the highly crosslinked SPR-PVA was verified using EDS mapping of the S elements in the SPR-IONP sample. The change in the shell structure through the crosslink reaction was characterized using thermogravimetric analysis and Fourier transform infrared spectroscopy.     

Recent progress on magnetic iron oxide nanoparticles: synthesis,surface functional strategies and biomedical applications

Abstract

This review focuses on the recent development and various strategies in the preparation, microstructure, and magnetic properties of bare and surface functionalized iron oxide nanoparticles (IONPs); their corresponding biological application was also discussed. In order to implement the practical in vivo or in vitro applications, the IONPs must have combined properties of high magnetic saturation, stability, biocompatibility, and interactive functions at the surface. Moreover, the surface of IONPs could be modified by organic materials or inorganic materials, such as polymers, biomolecules, silica, metals, etc. The new functionalized strategies, problems and major challenges, along with the current directions for the synthesis, surface functionalization and bioapplication of IONPs, are considered. Finally, some future trends and the prospects in these research areas are also discussed.     

Recent progress on magnetic iron oxide nanoparticles: synthesis,surface functional strategies and biomedical applications

This review focuses on the recent development and various strategies in the preparation, microstructure, and magnetic properties of bare and surface functionalized iron oxide nanoparticles (IONPs); their corresponding biological application was also discussed. In order to implement the practical in vivo or in vitro applications, the IONPs must have combined properties of high magnetic saturation, stability, biocompatibility, and interactive functions at the surface. Moreover, the surface of IONPs could be modified by organic materials or inorganic materials, such as polymers, biomolecules, silica, metals, etc. The new functionalized strategies, problems and major challenges, along with the current directions for the synthesis, surface functionalization and bioapplication of IONPs, are considered. Finally, some future trends and the prospects in these research areas are also discussed.     

M2 macrophage-targeted iron oxide nanoparticles for magnetic resonance image-guided magnetic hyperthermia therapy

Tumor-associated macrophages (TAMs) play an important role in tumor development and progression.In particular,M2 TAMs can promote tumor growth by facilitating tumor progression and malignant behav-iors.Selectively targeted elimination of M2 TAMs to inhibit tumor progression is of great significance for cancer treatment.Iron oxide nanoparticles based magnetic hyperthermia therapy (MHT) is a classical approach to destroy tumor tissue with deep penetration depth.In this study,we developed a typical M2 macrophage-targeted peptide (M2pep) functionalized superparamagnetic iron oxide nanoparticle(SPIO) for magnetic resonance imaging (MRI)-guided MHT in an orthotopic breast cancer mouse model,The obtained multifunctional SPIO-M2pep with a hydrodynamic diameter of 20 nm showed efficient targeting capability,high transverse relaxivity (149 mM-1 s-1) and satisfactory magnetic hyperthermia performance in vitro.In vivo studies demonstrated that the SPIO-M2pep based MRI can monitor the distri-bution of nanoparticles in tumor and indicate the suitable timing for MHT.The M2 macrophage-targeted MHT significantly reduced the tumor volume and the population of pro-tumoral M2 TAMs in tumor.In addition,the SPIO-M2pep based MHT can remodel the tumor immune microenvironment (TIME).The multifunctional SPIO-M2pep with M2 macrophage-targeting ability,high magnetic hyperthermia effi-ciency,MR imaging capability and effective role in remodeling the TIME hold great potential to improve clinical cancer therapy outcomes.     

Sol-gel自燃烧法制备纳米锰铁氧体的相变与电磁性能研究

以柠檬酸盐为络合剂，通过sol-gel自燃烧的合成方法制备了锰铁氧化物纳米晶体。采用FT-IR、DSC-TG、XRD、TEM、波导等方法对产物以及产物的电磁性能进行了表征．结果表明，在前驱体中，金属离子与柠檬酸以络合物的形式存在。凝胶在225℃完成自燃烧反应，生成了尖晶石型MnFe2O4纳米氧化物。在保温处理过程中，尖晶石型MnFeaO4纳米氧化物在602℃发生了相变反应，由AB2O4型转变为ABO3型氧化物。尖晶石型MnFe2O4纳米晶体在8～12GHz的测试条件下具有介电损耗与磁损耗，在转变为钙钛矿氧化物以后，由于超交换作用的消失，在测试条件下FeMnO3纳米晶体不再具有电磁损耗。     

多糖涂覆的氧化铁纳米粒子的合成及其药物递送应用研究进展

近年来,氧化铁纳米粒子(Iron Oxide Nanoparticles,IONPs)由于具有超顺磁性、生物相容性、比表面积大、易分离等特点而备受科学界关注.然而,裸露的IONPs容易聚集和氧化而失去其应有的特性,采用多糖进行涂覆不仅能提高IONPs的稳定性和生物相容性,还能通过多糖与其他生物活性物质结合,赋予INOPs新的功能.多糖涂覆的IONPs充分结合了多糖的生化特性与磁芯的理化特性,在药物递送中展现出巨大的应用潜力.本文综述了多糖涂覆IONPs的合成方法、合成过程的影响因素、多糖与IONPs的结合机理及其在药物递送中的应用,最后对多糖涂覆的IONPs的合成及其在药物递送方面的应用进行了总结和展望.     

Microwave-assisted synthesis and magnetic studies of cobalt oxide nanoparticles

An efficient microwave-assisted route has been used to synthesize nanoparticles of cobalt oxide. The particles were well characterized by transmission electron microscopy (TEM) which showed that the average diameter of the particles is around 6 nm. X-ray diffraction (XRD) studies further confirmed the formation of the spinel Co₃O₄. Purity of the products was detected by Fourier transform infrared spectroscopy (FTIR) combined with thermal gravimetric analysis (TG/DTG). The magnetic measurements revealed a small hysteresis loop at room temperature indicating a weak ferromagnetic nature of the synthesized Co₃O₄ nanoparticles. The magnetic moment of the particles was measured to be 4.27 μ_eff.     

One-step hydrothermal process to prepare highly crystalline Fe3O4 nanoparticles with improved magnetic properties

Hydrothermal process was successfully used to synthesize Fe₃O₄ powder using ferrous chloride (FeCl₂) and diamine hydrate (H₄N₂·H₂O) as starting materials by carefully controlling the reaction conditions. The as-prepared Fe₃O₄ sample was characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM), and its magnetic properties were evaluated on a vibrating sample magnetometer (VSM). The nanoscale (40 nm) Fe₃O₄ powder obtained at 140 °C for 6 h possessed a saturation magnetization of 85.8 emu/g, a little lower than that of the correspondent bulk Fe₃O₄ (92 emu/g). It is suggested that the well-crystallized Fe₃O₄ grains formed under appropriate hydrothermal conditions should be responsible for the increased saturation magnetization in nanosized Fe₃O₄.     

Superparamagnetic iron oxide nanoparticles assembled magnetic nanobubbles and their application for neural stem cells labeling

Micro/nanobubbles for use as ultrasound contrast agents have been fabricated with different shell materials.When various biomedical nanoparticles have been embedded in the shells of bubbles,the composite structures have shown promising applications in multi-modal imaging,drug/gene delivery,and biomedical sensing.In this study,we developed a new gas-liquid interface self-assembly method to prepare magnetic nanobubbles embedded with superparamagnetic iron oxide nanoparticles(SPIONs).The diameter of the generated assembled nanobubbles was 227.40±87.21 nm with a good polydispersity index(PDI)of 0.29.Under the condition of 150 compression cycles,the nanobubble concentration could reach about 6.12×10⁹/mL.Transmission electron microscopy(TEM)and scanning electronic microscopy(SEM)demonstrated that the assembled nanobubbles had a hollow gas core with SPIONs adsorbed on the surface.Ultrasound(US)imaging and magnetic resonance imaging(MRI)experiments indicated that the assembled magnetic nanobubbles exhibited good US and MR contrast capabilities.Moreover,the assembled magnetic nanobubbles were used to label neural stem cells under ultrasound exposure.After 40 s US exposure,the magnetic nanobubbles could be delivered into cells with 2.80 pg Fe per cell,which could be observed in the intracellular endosome by TEM.Compared with common incubation methods,the ultrasound exposure method did not introduce the potential cytotoxicity of transfection reagents and the efficiency was about twice as high as the efficiency of incubation.Therefore,the assembled magnetic nanobubbles prepared through the pressure-driven gas-liquid interface assembly approach could be a potential US/MRI dual model imaging nanocarrier for regenerative applications.     

Methotrexate-conjugated L-lysine coated iron oxide magnetic nanoparticles for inhibition of MCF-7 breast cancer cells

Methotrexate (MTX), a stoichiometric inhibitor of dihydrofolate reductase enzyme, is a chemotherapeutic agent for treating a diversity of neoplasms. In this study, we design and developed a new formulation of MTX that serves as drug carrier and examined its cytotoxic effect in vitro. This target drug delivery system is dependent on the release of the MTX within the lysosomal compartment. The iron oxide magnetic nanoparticles (IONPs) were first surface-coated with L-lysine and subsequently conjugated with MTX through amidation between the carboxylic acid end groups on MTX and the amine groups on the IONPs surface. MTX-conjugated L-lysine coated IONPs (F-Lys-MTX NPs) was characterized by X-ray diffraction, thermogravimetric analysis, differential scanning calorimetry, Fourier transform infrared spectroscopy, vibrating sample magnetometer, and transmission electron microscopy techniques. The cytotoxicity of the void of MTX and F-Lys-MTX NPs were compared to each other by MTT assay of the treated MCF-7 cell lines. The results showed that the ζ-potential of F-Lys-MTX NPs was about ?5.49?mV and the average size was 43.72?±?4.73?nm. Model studies exhibited the release of MTX via peptide bond cleavage in the presence of proteinase K and at low pH. These studies specify that F-Lys-MTX NPs have a very remarkable anticancer effect, for breast cancer cell lines.     

壳聚糖修饰氧化铁磁性纳米颗粒的制备和性能研究

通过共沉淀法制备氧化铁磁性纳米颗粒,用壳聚糖对其表面进行修饰得到样品(CS@MNPs);表征其形貌结构、尺寸、表面基团、表面电荷、磁学性质和在不同介质中的稳定性等。实验结果表明,CS@MNPs具有典型的立方反尖晶石晶体结构;粒径为16.5nm;在生理(pH值7.4)条件下拥有较高的正电荷(10mV);呈现超顺磁性,对驰豫时间T1、T2,尤其是T2*具有很强的响应;在双蒸馏水和含10%新生牛血清的RPMI 1640培养液中具有良好的稳定性,具有作为磁共振造影剂的潜力。     

Effective removal of Zn (II) ions from aqueous solution by the magnetic MnFe2O4 and CoFe2O4 spinel ferrite nanoparticles with focuses on synthesis,characterization, adsorption,and desorption

In this study, the MnFe₂O₄ and CoFe₂O₄ spinel ferrites nanoparticles were synthesized via a practical co-precipitation route to investigate the zinc removal from aqueous solution. The synthesized magnetic adsorbents were characterized by XRD, VSM, FE-SEM, BET, EDS, and DLS analyses. The synthesized adsorbents had a diameter range of 20–80 nm. The specific surface areas of adsorbents were found to be 84.5 and 50.4 m²/g for MnFe₂O₄ and CoFe₂O₄, and the saturation magnetization were 61.39 and 37.54 emu/g, respectively. The effects of initial pH, contact time, metal ion concentration, and temperature on Zn (II) adsorption were precisely investigated. These nanoparticles could remove Zn (II) by following the Langmuir isotherm model at optimum pH = 6, with the high adsorption capacities of 454.5 and 384.6 mg/g for MnFe₂O₄ and CoFe₂O₄, respectively. The results of kinetics studies were well fitted by pseudo-second-order, with the determination coefficients of 0.999 for both adsorbents. The thermodynamics studies showed that the zinc (II) adsorption was an exothermic and spontaneous process. Furthermore, the reusability and the desorption capability of adsorbents were also investigated.     

Structural and magnetic properties of phase controlled iron oxide rods

Iron oxide rods are synthesized by thermal decomposition of iron (II) acetate at 700 °C. The X-ray powder diffraction measurement confirms the hematite (α-Fe₂O₃) phase of iron oxide. We observed that the Morin transition depends on applied magnetic field and shift towards lower temperature with increase in applied magnetic field. The Morin temperature at applied field of 500 and 2000 Oe is observed to be 261.1 and 260.3 K respectively. Magnetization versus magnetic field measurements confirms the antiferromagnetic behavior below Morin transition and weak ferromagnetic behavior above Morin transition.     

Dielectric and magnetic properties of ZnCo-substituted X hexaferrites prepared by citrate sol-gel process

Ba₂Zn_2−xCo_xFe₂₈O₄₆ hexaferrites with x=2.0, 1.6, 1.2, 0.8, 0.4 and 0.0 were prepared by citrate sol-gel process. They were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and thermogravimetry-differential scanning calorimetry (TG-DSC). The frequency-response complex dielectric constant and complex permeability of Ba₂Zn_2-xCo_xFe₂₈O₄₆ sintered at 1000-1200 °C had been investigated in the range from 100 MHz to 6 GHz. The pronounced natural resonance phenomena were observed in μ″ spectrum for the samples annealed at 1100 and 1200 °C. The natural resonance frequency of Ba₂Zn_2−xCo_xFe₂₈O₄₆ ferrites was intensively affected by the substitution of Zinc ion and annealing temperature.     

Photoanodic properties of sol-gel-derived iron oxide thin films with embedded gold nanoparticles: effects of polyvinylpyrrolidone in coating solutions

Fe₂O₃ thin films containing dispersed Au nanoparticles were prepared on nesa silica glass substrates, using Fe(NO)₃·9H₂O-HAuCl₄·4H₂O-CH₃COCH₂COCH₃-CH₃OC₂H₄OH solutions containing polyvinylpyrrolidone (PVP). The photoanodic properties were studied in a three-electrode cell with the film sample as the working electrode and an aqueous buffer solution of pH=7 as the supporting electrolyte. The Au particles increased photoanodic quantum efficiency at wavelengths <500-600 nm. Quantum efficiency was further increased by modifying the microstructure of the film electrodes through the addition of PVP. The maximum incident photon to current efficiency (IPCE) of about 20% was achieved in an Au-dispersed film prepared from a solution containing PVP. PVP in coating solutions provided the fired films with an increase in size of the grains and voids between them and in donor density, either of which could contribute to the increased IPCE.     

Preparation and magnetic properties of spindle porous iron nanoparticles

Spindle porous iron nanoparticles were firstly synthesized by reducing the pre-synthesized hematite (α-Fe₂O₃) spindle particles with hydrogen gas. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption/desorption isotherms and vibrating sample magnetometry (VSM). A lattice shrinkage mechanism was employed to explain the formation process of the porous structure, and the adsorbed phosphate was proposed as a protective shell in the reduction process. N₂ adsorption/desorption result showed a Brunauer-Emmett-Teller (BET) surface area of 29.7 m²/g and a continuous pore size distribution from 2 nm to 100 nm. The magnetic hysteresis loop of the synthesized iron particles showed a saturation magnetization of 84.65 emu/g and a coercivity of 442.36 Oe at room temperature.     

Formation, characterization and magnetic properties of carbon-encapsulated iron carbide nanoparticles

Fe₃C nanoparticles encapsulated in carbon shell with a size range of 20–50 nm were obtained in large scale by reacting anhydrous FeCl₃, hexamethylenetetramine and metal Na in an autoclave at 650 °C. Magnetization measurements show that the as-obtained materials display superparamagnetic properties at room temperature. A possible formation mechanism of the core–shell nano-structures was discussed.     

Structural and magnetic properties of glass-ceramics containing silver and iron oxide

Glass-ceramics with a nominal composition of 25SiO₂–(50 − x)CaO–15P₂O₅–8Fe₂O₃–2ZnO–xAg (where x = 0, 2 and 4 mol%) have been prepared. Structural features of glass-ceramics have been investigated using X-ray diffraction (XRD) and scanning electron microscope (SEM) techniques. Magnetic properties were studied using vibrating sample magnetometer and Mössbauer spectroscopy. Ca₃(PO₄)₂, hematite and magnetite are formed as major crystalline phases. The microstructure reveals the formation of 25–30 nm size particles. Mössbauer spectroscopy has shown the relaxation of magnetic particles. Saturation magnetization value is increased with an increase of Ag content up to 4 mol%, which has been attributed to the formation of magnetically ordered particles. The antibacterial response was found to depend on Ag ions concentration in the glass matrix and samples with 4 mol% Ag in glass matrix have shown effective antibacterial activity against Escherichia coli.