Size-controlled magnetic nanoparticles with lecithin for biomedical applications

Lecithin-adsorbed magnetic nanoparticles were prepared by three-step process that the thermal decomposition was combined with ultrasonication. Experimental parameters were three items—molar ratio between Fe(CO)₅ and oleic acid, keeping time at decomposition temperature and lecithin concentration. As the molar ratio between Fe(CO)₅ and oleic acid, and keeping time at decomposition temperature increased, the particle size increased. However, the change of lecithin concentration did not show the remarkable particle size variation.     

Patterned magnetite films prepared via soft lithography and thermal decomposition

A method for the fabrication of patterned magnetite (Fe₃O₄) films is presented. We first prepared an ordered 2D array of Fe(acac)₃ through a selective deposition technique on patterned self-assembled monolayers. Using thermal decomposition at elevated temperature (300 °C), we transformed the patterned Fe(acac)₃ into patterned Fe₃O₄ films in a short reaction time. These patterned films have been confirmed by using optical photographs, field emission scanning electron microscopy and atomic force microscopy.     

Ferrofluids of magnetic multicore nanoparticles for biomedical applications

For a variety of magnetically based biomedical applications, it is advantageous to use sedimentation stable suspensions of relatively large (d>20 nm) magnetic core-shell nanoparticles. Water-based suspensions of multicore nanoparticles were prepared by coating of the particles (synthesized by means of a modified alkaline precipitation method) with a carboxymethyldextran shell. The resulting ferrofluids were structurally and magnetically characterized. It was found that these fluids show a specific heating power of about 60 W/g (f=400 kHz, H=10 kA/m). This value was increased up to 330 W/g by a simple fractionation method based on centrifugation. Finally, the cellular uptake of the multicore nanoparticles was demonstrated.     

Aqueous immune magnetite nanoparticles for immunoassay

Immune magnetite nanoparticles (MNPs) are prepared by four successive reactions, which are MNPs preparation, silica-coating, surface modification with amino group, and conjugation with bio-molecule, respectively. The crystal structure and morphology of intermediate products are characterized by XRD, TEM and AFM. Qualitative and quantitative assays for amino group on the MNPs’ surface are made by FTIR and Organic Element Assay. Ultraviolet–visible absorption spectrum can indirectly illustrate the quantity of bio-molecule conjugated with MNPs. In addition, specific combination and nonspecific combination of immune MNPs are measured by commercial RIA box. The results show that the size of MNPs prepared is 10 ± 5 nm, and silica-coated MNPs with spinel structure have quasi-spherical morphology. Infrared absorption bands of –NH₂ are appeared around 3380–3200 cm⁻¹ and 1650–1510 cm⁻¹, and the amino group content is 0.5 μmol –NH₂ per mg MNPs. The specific immune combination of immune MNPs is up to 75%, and nonspecific combination is under 5%.     

Sonochemical coating of magnetite nanoparticles with silica

Magnetite nanoparticles were coated with silica through the hydrolysis and condensation of tetraethyl orthosilicate (TEOS) under ultrasonic irradiation. The ultrasonic irradiation was used to prevent the agglomeration of the magnetite particles and accelerate the hydrolysis and condensation of TEOS. TEM, DLS, XRF, VSM, TG and sedimentation test were used to characterize the silica-coated magnetite particles. The dispersibility of silica-coated magnetite particles in aqueous solution was improved significantly and the agglomerate particle size was decreased to 110 nm. It was found that the agglomerate particle size of silica-coated magnetite particles was mainly decided by the coating temperature and the pH value in the silica-coating process. The weight ratio of silica in silica-coated magnetite particles was mainly decided by the pH value in the silica-coating process. The dispersibility of silica-coated magnetite particles was mainly decided by the agglomerate particle size of the suspension. The oxidation of magnetite particles in air was limited through the coated silica. The magnetism of silica-coated magnetite particles decreased slightly after silica-coating.     

Synthesis of magnetite nanoparticles for AC magnetic heating

Magnetite particles with different average diameter (D_m) suitable for magnetic fluid hyperthermia (MFH) were synthesized by controlled coprecipitation technique. In this method, the reaction pH was stabilized using the pH buffer and the average particle diameter decreased with increasing reaction pH. The size-dependent magnetic behavior of the magnetite nanoparticles was studied and the optimum size range required for magnetic fluid hyperthermia (MFH) has been arrived at. Among the samples studied, the maximum specific absorption rate of 15.7 W/g was recorded for the magnetite sample with D_m of 13 nm, when exposed to an AC magnetic field strength of 3.2 kA/m and a frequency of 600 kHz. The AC magnetic properties suggested that the size distribution of the sample was bimodal with average particle size less than ∼13 nm.     

Citric-acid-coated magnetite nanoparticles for biological applications

Water-based magnetic fluids, generally intended for biomedical applications, often have various coating molecules that make them stable and compatible with biological liquids. Magnetic fluids containing iron oxide particles have been prepared by a co-precipitation method, using citric acid as stabilizer. The magnetic particles of the magnetic fluids were obtained by chemical precipitation from ferric ( FeCl₃) and ferrous salts ( FeSO₄ or FeCl₂) in alkali medium (ammonia hydroxide). Citric acid was used to stabilize the magnetic-particle suspension. Physical tests were performed in order to determine various microstructural and rheological features. Transmission electron microscopy was the main investigation method for assessing the magnetic-particle size. The dimensional distribution of the magnetic-particle physical diameter was analyzed using the box-plot statistical method while infrared absorption spectra were used to study the colloidal particle structure. The magnetic-fluid density (picnometric method), viscosity (capillary method) and surface tension (stalagmometric method) were measured using standard methods.     

Characterization of magnetite nanoparticles for SQUID-relaxometry and magnetic needle biopsy

Magnetite nanoparticles (Chemicell SiMAG-TCL) were characterized by SQUID-relaxometry, susceptometry, and TEM. The magnetization detected by SQUID-relaxometry was 0.33% of that detected by susceptometry, indicating that the sensitivity of SQUID-relaxometry could be significantly increased through improved control of nanoparticle size. The relaxometry data were analyzed by the moment superposition model (MSM) to determine the distribution of nanoparticle moments. Analysis of the binding of CD34-conjugated nanoparticles to U937 leukemia cells revealed 60,000 nanoparticles per cell, which were collected from whole blood using a prototype magnetic biopsy needle, with a capture efficiency of >65% from a 750 μl sample volume in 1 min.     

Sonochemical synthesis of versatile hydrophilic magnetite nanoparticles

Hydrophilic magnetite nanoparticles in the size range 30-10 nm are easily and rapidly prepared under ultrasonic irradiation of Fe(OH)₂ in di- and tri-ethylene glycol/water solution with volume ratio varying between 7:3 and 3:7.Structural (XRD) and morphological (SEM) characterization reveal good crystalline and homogeneous particles whereas, when solvothermally prepared, the particles are inhomogeneous and aggregated. The sonochemically prepared particles are versatile, i.e. well suited to covalently bind molecules because of the free glycol hydroxylic groups on their surface or exchange the diethylene or triethylene glycol ligand. They can be easily transferred in hydrophobic solvents too.Room-temperature magnetic hysteresis properties measured by means of Vibrating Sample Magnetometer (VSM) display a nearly superparamagnetic character.The sonochemical preparation is easily scalable to meet industrial demand.     

EPR spectroscopy and imaging of TEMPO-labeled magnetite nanoparticles

The article presents results of a study of TEMPO-labeled polymer coated superparamagnetic iron(II,III) oxide nanoparticles using both Electron Paramagnetic Resonance (EPR) spectroscopy and Electron Paramagnetic Resonance imaging technique (EPRI). The X-band (9.4 GHz) EPR spectroscopy was used to investigate the behavior of TEMPO-labeled polymer coated magnetite nanoparticles in different conditions (temperature and orientation in magnetic field). The broad line, which comes from the core of Fe₃O₄ nanoparticles, shows anisotropy. This signal broadens with decreasing temperature, its intensity increases with increasing temperature and the g factor decreases with increasing temperature. The shape of the signal from nitroxide radical strongly depends on temperature. When temperature is higher than 200 K, a narrow triplet appears, but when it is lower than 200 K the signal consists of broad asymmetric lines. Analysis of the signal allowed characterization of the motion of the spin label attached to nanoparticles. Values of anisotropy parameter ɛ and rotational correlation time τ_c were calculated for TEMPO in the fast rotation regime.The ability of TEMPO-labeled PEG coated magnetite nanoparticles to diffuse within the hydrogel medium was also investigated. The EPR imaging of nanoparticles diffusion in hydrogel was made at room temperature using an EPR L-band (1 GHz) spectrometer. EPRI has been proved effective for evaluation of changes in the spatial distribution of nanoparticles in the sample.     

Microwave-assisted synthesis of magnetite nanoparticles for MR blood pool contrast agents

Microwave-assisted polyol process was developed for the synthesis of magnetite nanoparticles with precisely controlled size, high crystallinity and high water solubility. The process is simple, time-saving and low energy-consuming due to the advantages of polyols and microwave irradiation combined. The crystal phases of the nanoparticles were determined by transmission electron microscopy, X-ray powder diffraction and Raman spectrum. The coating materials of the nanoparticles were analyzed by Fourier transformed infrared spectroscopy and thermal gravimetric analysis. Precise size tuning enables an easier way to adjust the relaxation properties of the magnetite nanoparticles. The colloid nanoparticles with high longitudinal relaxivity (r₁) and low ratio of transverse relaxivity (r₂) to r₁ have a potential application in magnetic resonance angiography.     

Raman spectroscopy investigation of magnetite nanoparticles in ferrofluids

Raman spectroscopy is used to investigate magnetite nanoparticles dispersed in two types of β-cyclodextrin suspensions. An approach is presented for characterization of the magnetic core in liquid surrounding at room temperature and atmospheric pressure. The effect of elevating laser power on the structural stability and chemical composition of magnetite in the ferrofluids is discussed. The data are compared with data from dry by-products from the fluids. Powder samples undergo total phase transition from magnetite to hematite at laser power of 1.95 mW. The same nanoparticles in the fluid undergo transformation at 9 mW, but no hematite positions appear throughout that investigation. The Raman spectra revealed that the main phase of the magnetic core in the fluids is magnetite. That is indicated by a strong and non-diminishing in intensity peak at 670 cm⁻¹. A second phase is present at the nanoparticle’s surface with Raman spectroscopy unveiling maghemite-like and small fractions of goethite-like structures. The Fourier transform infrared spectroscopy investigations confirm deviations in the surface structure and also point to the fact that the oxidation process starts at an early stage after formation of the nanoparticles. The analyses of the infrared data also show that β-cyclodextrin molecules retain their cyclic character and the coating does not affect the oxidation process once the particles are evicted from the fluids. A Mössbauer spectroscopy measurement on a ferrofluidic sample is also presented.     

Anisotropy-induced quantum critical behavior of magnetite nanoparticles at low temperatures

The classical, thermally driven transition from ferrimagnets to superparamagnets in Fe₃O₄ nanoparticles can be converted into another quantum phase by a transverse microwave magnetic field or by a strong internal anisotropic field. These fields, perpendicular to the Ising axis, can destroy the magnetic long-range order to quantum paramagnets as the fields exceed some critical values. We have exploited the spin resonance spectrometer to determine the dynamic spin susceptibility and the critical exponent γ, which is a power-law dependent spanning of the quantum critical point. Quantum phase transition observed at low temperatures for small magnetite nanoparticles induced by strong surface anisotropic field illustrates the fascinating interplay between thermal and quantum fluctuations in the vicinity of a quantum critical point.     

Novel hybrid nanostructured materials of magnetite nanoparticles and pectin

A novel hybrid nanostructured material comprising superparamagnetic magnetite nanoparticles (MNPs) and pectin was synthesized by crosslinking with Ca²⁺ ions to form spherical calcium pectinate nanostructures, referred as MCPs, which were typically found to be 100-150 nm in size in dried condition, confirmed from transmission electron microscopy and scanning electron microscopy. The uniform size distribution was revealed from dynamic light scattering measurement. In aqueous medium the MCPs showed swelling behavior with an average size of 400 nm. A mechanism of formation of spherical MCPs is outlined constituting a MNP-pectin interface encapsulated by calcium pectinate at the periphery, by using an array of characterization techniques like zeta potential, thermogravimetry, Fourier transformed infrared and X-ray photoelectron spectroscopy. The MCPs were stable in simulated gastrointestinal fluid and ensured minimal loss of magnetic material. They exhibited superparamagnetic behavior, confirmed from zero field cooled and field cooled profiles and showed high saturation magnetization (M_s) of 46.21 emu/g at 2.5 T and 300 K. M_s decreased with increasing precursor pectin concentrations, attributed to quenching of magnetic moments by formation of a magnetic dead layer on the MNPs.     

Synthesis and functionalization of magnetite nanoparticles with different amino-functional alkoxysilanes

Superparamagnetic iron oxide (SPIO) nanoparticles show great promise for many biotechnological applications. This paper addresses the synthesis and characterization of SPIO nanoparticles grafted with three different alkoxysilanes: 3-aminopropyl-triethoxysilane (APTES), 3-aminopropyl-ethyl-diethoxysilane (APDES) and 3-aminopropyl-diethy-ethoxysilane (APES). SPIO nanoparticles with an average particle diameter of 10 nm were prepared by chemical sonoprecipitation. As confirmed by Fourier transform infrared (FTIR) spectroscopy, silylation of these nanoparticles occurs through a two-step process. Decreasing the number of alkoxide groups reduced the concentration of free amino groups on the SPIO surface ([SPIO-NH₂]—APTES>APDES>APES). This phenomenon results from steric contributions and the formation of H-bonded amines provided by the ethyl groups present in the APDES and APES molecules. A simulation of SPIO nanoparticles in a saline physiologic solution shows that the ethyl groups impart larger steric stability onto the ferrofluids, which reduces aggregation. The magnetization (M) versus magnetic field (H) curves show that the synthesized iron oxide nanoparticles display superparamagnetic behavior. The zero-field cooling (ZFC) and field cooling (FC) curves show that the changes in the blocking temperature depend on the alkoxysilane-functionalized particle surface.     

Synthesis of magnetite nanoparticles via a solvent-free thermal decomposition route

Superparamagnetic nanoparticles have been widely applied in various bio-medical applications. To date, it is still a challenge to synthesize nanosized Fe₃O₄ particles with controlled size and distribution. In this paper, a novel solvent-free thermal decomposition method is reported for synthesizing Fe₃O₄ nanoparticles. Size and morphology of the nanoparticles are determined by TEM while the structure of the nanoparticles is identified by FTIR, XPS and TGA measurements. Magnetic properties of the obtained particles are determined using VSM and SQUID measurement. The particle size of the Fe₃O₄ can be tailored by adjusting either reaction temperature or time. When the reaction temperature is increased to 330 °C and the reaction time is extended to 4 h, the average particle size of the obtained nanoparticles is ∼9 nm, while Ms value reaches ∼76 emu/g. The as synthesized Fe₃O₄ nanoparticles show well-established superparamagnetic properties with the blocking temperature at around 100 K.     

Preparation of magnetite aqueous dispersion for magnetic fluid hyperthermia

An aqueous magnetic suspension was prepared by dispersing amphiphilic co-polymer-coated monodispersed magnetite nanoparticles synthesized through thermal decomposition of iron acetylacetonate (Fe(acac)₃) in a mixture of oleic acid and oleylamine. The average diameter of narrow-size-distributed magnetite nanoparticles varied between 5 and 12 nm depending on the experimental parameters such as reaction temperature, metal salt concentration and oleic acid/oleylamine ratio. Though the as-synthesized particles were coated with oleate and were dispersible in organic solvent, their surfaces were modified using amphiphilic co-polymers composed of poly(maleic anhydride-alt-1-octadecene) and polyethylene glycol-methyl ether and made dispersible in water. Infrared spectra of the sample indicated the existence of −COOH groups on the surface for further conjugation with biomolecules for targeted cancer therapy.     

Surface characterization of anodized zirconium for biomedical applications

Mechanical properties and corrosion resistance of zirconium make this material suitable for biomedical implants. Its good in vivo performance is mainly due to the presence of a protective oxide layer that minimizes corrosion rate, diminishes the amount of metallic ions released to the biological media and facilitates the osseointegration process.Since the implant surface is the region in contact with living tissues, the characteristics of the surface film are of great interest. Surface modification is a route to enhance both biocompatibility and corrosion resistance of permanent implant materials. Anodizing is presented as an interesting process to modify metal surfaces with good reproducibility and independence of the geometry.In this work the surface of zirconium before and after anodizing in 1 mol/L phosphoric acid solution at a fixed potential between 3 and 30 V, was characterized by means of several surface techniques.It was found that during anodization the surface oxide grows with an inhomogeneous coverage on zirconium surface, modifying the topography. The incorporation of P from the electrolyte to the surface oxide during the anodizing process changes the surface chemistry. After 30 days of immersion in Simulated Body Fluid (SBF) solution, Ca-P rich compounds were present on anodized zirconium.     

Heat dissipation mechanism of magnetite nanoparticles in magnetic fluid hyperthermia

The relative contributions of Néel and Brownian relaxations on magnetic heat dissipation were studied by investigating the physical, magnetic and heating characteristics of magnetite nanoparticle suspensions with average diameters of 12.5 and 15.7 nm. Heating characteristics depended on the dispersion states of particles. The specific absorption rates (SAR) dropped by 27% for the 12.5 nm particles to 16.8×10⁻⁹ W g⁻¹ Oe⁻² Hz⁻¹ and by 67% for the 15.7 nm particles to 9.69×10⁻⁹ W g⁻¹ Oe⁻² Hz⁻¹, when the particle rotation was suppressed by dispersing magnetite nanoparticles in hydro-gel.