Cem L. Altan

Effect of Surface Modification on Magnetization of Iron Oxide Nanoparticle Colloids

Magnetic iron oxide nanoparticles have numerous applications in the biomedical field, some more mature, such as contrast agents in magnetic resonance imaging (MRI), and some emerging, such as heating agents in hyperthermia for cancer therapy. In all of these applications, the magnetic particles are coated with surfactants and polymers to enhance biocompatibility, prevent agglomeration, and add functionality. However, the coatings may interact with the surface atoms of the magnetic core and form a magnetically disordered layer, reducing the total amount of the magnetic phase, which is the key parameter in many applications. In the current study, amine and carboxyl functionalized and bare iron oxide nanoparticles, all suspended in water, were purchased and characterized. The presence of the coatings in commercial samples was verified with X-ray photoelectron spectroscopy (XPS). The class of iron oxide (magnetite) was verified via Raman spectroscopy and X-ray diffraction. In addition to these, in-house prepared iron oxide nanoparticles coated with oleic acid and suspended in heptane and hexane were also investigated. The saturation magnetization obtained from vibrating sample magnetometry (VSM) measurements was used to determine the effective concentration of magnetic phase in all samples. The Tiron chelation test was then utilized to check the real concentration of the iron oxide in the suspension. The difference between the concentration results from VSM and the Tiron test confirmed the reduction of magnetic phase of magnetic core in the presence of coatings and different suspension media. For the biocompatible coatings, the largest reduction was experienced by amine particles, where the ratio of the effective weight of magnetic phase reported to the real weight was 0.5. Carboxyl-coated samples experienced smaller reduction with a ratio of 0.64. Uncoated sample also exhibits a reduction with a ratio of 0.6. Oleic acid covered samples show a solvent-depended reduction with a ratio of 0.5 in heptane and 0.4 in hexane. The corresponding effective thickness of the nonmagnetic layer between magnetic core and surface coating was calculated by fitting experimentally measured magnetization to the modified Langevin equation.

Enhancement of thermal conductivity upon application of magnetic field to Fe3O4 nanofluids

Enhancement of thermal conductivity of fluids upon addition of nanoparticles has been previously observed. In this study, Fe3O4 magnetite particles were used and thermal conductivity enhancements both in water and in heptane with increasing volume fraction have been shown. Upon measuring thermal conductivity under externally applied magnetic field, it has been shown experimentally that thermal conductivity can be further increased even at low concentrations and low magnetic field strengths in both fluids. Theoretical calculations are presented to support the effect of magnetic field on the thermal conductivity enhancement. This enhancement is attributed to the thermomagnetic convection which due to a temperature gradient, results in a non-uniform magnetic body force resulting in more efficient thermal conductance.

The effect of Fe3O4 nanoparticles on the thermal conductivities of various base fluids

Conventional heat transfer fluids have intrinsically poor heat transfer properties compared to solids. Enhancing the efficiency of heat transfer is of great interest for various industrial applications. Suspending solid particles in a fluid increases the thermal conductivity of the resulting suspension and enhances the heat transfer properties. In this work, changes in thermal conductivities of fluids upon the addition of magnetic nanoparticles have been investigated. Fe(3)O(4) nanoparticles are synthesized using different synthesis methods and are suspended in various oils. The effect of the base fluid and the type of magnetic particle on the thermal conductivity is investigated in detail. Up to 28% increase in the thermal conductivity is obtained with 2.5 wt% magnetic particles in hexane. The thermal conductivity enhancement is found to depend on the particle concentration, method of preparation and base fluid. The enhancements obtained are higher than those estimated using any theoretical model present in the literature.

Partial Oxidation as a Rational Approach to Kinetic Control in Bioinspired Magnetite Synthesis

Biological systems show impressive control over the shape, size and organization of mineral structures, which often leads to advanced physical properties that are tuned to the function of these materials. Such control is also found in magnetotactic bacteria, which produce-in aqueous medium and at room temperature-magnetite nanoparticles with precisely controlled morphologies and sizes that are generally only accessible in synthetic systems with the use of organic solvents and/or the use of high-temperature methods. The synthesis of magnetite under biomimetic conditions, that is, in water and at room temperature and using polymeric additives as control agents, is of interest as a green production method for magnetic nanoparticles. Inspired by the process of magnetite biomineralization, a rational approach is taken by the use of a solid precursor for the synthesis of magnetite nanoparticles. The conversion of a ferrous hydroxide precursor, which we demonstrate with cryo-TEM and low-dose electron diffraction, is used to achieve control over the solution supersaturation such that crystal growth can be regulated through the interaction with poly-(α,β)-dl-aspartic acid, a soluble, negatively charged polymer. In this way, stable suspensions of nanocrystals are achieved that show remanence and coercivity at the size limit of superparamagnetism, and which are able to align their magnetic moments forming strings in solution as is demonstrated by cryo-electron tomography.

Deterioration in effective thermal conductivity of aqueous magnetic nanofluids

Common heat transfer fluids have low thermal conductivities, which decrease their efficiency in many applications. On the other hand, solids have much higher thermal conductivity values. Previously, it was shown that the addition of different nanoparticles to various base fluids increases the thermal conductivity of the carrier fluid remarkably. However, there are limited studies that focus on the thermal conductivity of magnetic fluids. In this study, thermal conductivity of magnetic nanofluids composed of magnetite nanoparticles synthesized via co-precipitation and thermal decomposition methods is investigated. Results showed that the addition of magnetite nanoparticles decreased the thermal conductivity of water and ethylene glycol. This decrease was found to increase with increasing particle concentration and to be independent of the synthesis method, the type of surfactant, and the interfacial thermal resistance.

The polymerisation of oligo(ethylene glycol methyl ether) methacrylate from a multifunctional poly(ethylene imine) derived amide: a stabiliser for the synthesis and dispersion of magnetite nanoparticles

A facile synthetic route to poly(ethylene imine)-graft-poly(oligo(ethylene glycol methyl ether)) (PEI-graft-POEGMA) functionalised superparamagnetic magnetite nanoparticles is described. The polymerisation of OEGMA from a model molecular amide demonstrated the feasibility of POEGMA synthesis under mild ATRP conditions (20 °C in ethanol) albeit with low initiator efficiencies. DFT studies suggest that the amide functionality is intrinsically of lower activity than ester functional monomers and initiators for atom transfer polymerisation (ATRP) as a consequence of higher bond dissociation energies and bond dissociation free energies (BDFE). However these studies further highlighted that use of an appropriate solvent could reduce the free energy of dissociation thereby reducing the relative difference in BDFE between the ester and amide groups. A commercial branched PEI sample was functionalised by reaction with 2-bromo-2-methylpropanoyl bromide giving an amide macroinitiator suitable for the atom transfer radical polymerisation (ATRP) of oligo(ethylene glycol methyl ether) methacrylate. The resulting PEI-graft-POEGMA copolymers were characterised by SEC, FT-IR and 1H and 13C NMR spectroscopy. PEI-graft-POEGMA coated magnetite nanoparticles were synthesised by a basic aqueous co-precipitation method and were characterised by transmission electron microscopy, thermogravimetric analysis and vibrating sample magnetometry and dynamic light scattering. These copolymer coated magnetite nanoparticles were demonstrated to be effectively stabilised in an aqueous medium. Overall the particle sizes and magnetic and physical properties of the coated samples were similar to those of uncoated samples.

The effect of functionalized silver nanoparticles over the thermal conductivity of base fluids

Thermal conductivities of nanofluids are expected to be higher than common heat transfer fluids. The use of metal nanoparticles has not been intensely investigated for heat transfer applications due to lack of stability. Here we present an experimental study on the effect of silver nanoparticles (Ag NPs) which are stabilized with surfactants, on the thermal conductivity of water, ethylene glycol and hexane. Hydrophilic Ag NPs were synthesized in aqueous medium with using gum arabic as surfactant and oleic acid/oleylamine were used to stabilize Ag NPs in the organic phase. The enhancement up to 10 per cent in effective thermal conductivity of hexane and ethylene glycol was achieved with addition of Ag NPs at considerably low concentrations (i.e. 2 and 1 per cent, by weight, for hexane and ethylene glycol respectively). However, almost 10 per cent of deterioration was recorded at effective thermal conductivity of water when Ag NPs were added at 1 per cent (by wt). Considerable amount of Gum Arabic in the me...

Magnetic nanoparticles and cancer

Abstract Cancer, being the number one cause of death, is a disease that becomes even more widespread as the population’s life expectancy increases. Chemotherapy drugs that are designed to destroy the cancer cells, inevitably kill also the healthy cells. Without being targeted or controlled release, these drugs are administered in high doses which make them highly toxic. Magnetic nanoparticles (MNPs) are currently being investigated for their versatile use in drug targeting, therapy, and diagnostics. In this chapter the toxicity of magnetic particles and types of MNPs and their synthesis methods are shortly summarized. As different types of MNPs are employed in this research field, we focused the chapter to magnetite (Fe3O4) nanoparticles. Research in the field of magnetic drug delivery is summarized based on the type of magnetic carrier. Hyperthermia, which is the destruction or reduction of tumor by procuring heat at the tumor site, can be achieved by the application of an external magnetic field, inducing heat generation around the MNPs. This makes MNPs invaluable in cancer therapy, and the type of MNPs along with suitable coatings and targeting ligands used in hyperthermia are summarized. Cancer diagnostics is another field where MNPs find diverse use. MNPs are employed as contrast agents in magnetic resonance imaging (MRI), not only to image the existing tumors but also for post therapy monitoring in stem cell transplantation. By summarizing the work done in this field, MNPs, with ease of surface modification, low toxicity, and magnetic properties are shown to have great potential in novel therapies against cancer.