Chapter 6 Magnetic nanoparticles
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1 Chapter 6 Magnetic nanoparticles Magnetic nanoparticles (MNPs) are a class of nanoparticle which can be manipulated using magnetic field gradients. Such particles commonly consist of magnetic elements such as iron, nickel and cobalt and their chemical compounds. Magnetic nanoparticle clusters which are composed of a number of individual magnetic nanoparticles are known as magnetic nanobeads with a diameter of nanometers. The magnetic nanoparticles have been the focus of much research recently because they possess attractive properties which could see potential use in catalysis including nanomaterial-based catalysts, biomedicine, magnetically tunable colloidal photonic crystals, magnetic resonance imaging, magnetic particle imaging, data storage, environmental remediation, nanofluids, and optical filters. Figure 6.1: Diagram of a magnetic nanoparticle 53
2 Properties of magnetic nanoparticles The physical and chemical properties of magnetic nanoparticles largely depend on the synthesis method and chemical structure. In most cases, the particles range from 1 to 100 nm in size and may display superparamagnetism. Types of magnetic nanoparticles 1- Oxides: (ferrites) Ferrite nanoparticles or iron oxide nanoparticles (iron oxides in crystal structure of maghemite or magnetite) are the most explored magnetic nanoparticles up to date. Once the ferrite particles become smaller than 128 nm they become superparamagnetic which prevents self agglomeration since they exhibit their magnetic behavior only when an external magnetic field is applied. The magnetic moment of ferrite nanoparticles can be greatly increased by controlled clustering of a number of individual superparamagnetic nanoparticles into superparamagnetic nanoparticle clusters, namely magnetic nanobeads. With the external magnetic field switched off, the remanence falls back to zero. Just like non-magnetic oxide nanoparticles, the surface of ferrite nanoparticles is often modified by surfactants, silica, silicones or phosphoric acid derivatives to increase their stability in solution. 54
3 2- Ferrites with a shell The surface of a maghemite or magnetite magnetic nanoparticle is relatively inert and does not usually allow strong covalent bonds with functionalization molecules. However, the reactivity of the magnetic nanoparticles can be improved by coating a layer of silica onto their surface. The silica shell can be easily modified with various surface functional groups via covalent bonds between organo-silane molecules and silica shell. In addition, some fluorescent dye molecules can be covalently bonded to the functionalized silica shell. Figure 6.2: Maghemite magnetic nanoparticle cluster with silica shell Ferrite nanoparticle clusters with narrow size distribution consisting of superparamagnetic oxide nanoparticles (~ 80 maghemite superparamagnetic nanoparticles per bead) coated with a silica shell have several advantages over metallic nanoparticles: Higher chemical stability (crucial for biomedical applications) Narrow size distribution (crucial for biomedical applications) 55
4 Higher colloidal stability since they do not magnetically agglomerate Magnetic moment can be tuned with the nanoparticle cluster size Retained superparamagnetic properties (independent of the nanoparticle cluster size) Silica surface enables straightforward covalent functionalization 3- Metallic Metallic nanoparticles may be beneficial for some technical applications due to their higher magnetic moment whereas oxides (maghemite, magnetite) would be beneficial for biomedical applications. This also implies that for the same moment, metallic nanoparticles can be made smaller than their oxide counterparts. On the other hand, metallic nanoparticles have the great disadvantage of being pyrophoric and reactive to oxidizing agents to various degrees. This makes their handling difficult and enables unwanted side reactions, which makes them less appropriate for biomedical applications. Colloid formation for metallic particles is also much more challenging. 4- Metallic with a shell The metallic core of magnetic nanoparticles may be passivated by gentle oxidation, surfactants, polymers and precious metals. In an oxygen environment, Co nanoparticles form an anti-ferromagnetic CoO layer on the surface of the Co nanoparticle. Recently, work has explored the synthesis and exchange bias effect in these Co core CoO shell nanoparticles with a gold outer shell. Nanoparticles with a magnetic core consisting either of elementary Iron or Cobalt with a nonreactive shell 56
5 made of graphene have been synthesized recently. The advantages compared to ferrite or elemental nanoparticles are: Higher magnetization Higher stability in acidic and basic solution as well as organic solvents Chemistry on the graphene surface via methods already known for carbon nanotubes Figure 6.3: Cobalt nanoparticle with graphene shell 57
6 Synthesis of magnetic nanoparticles The established methods of magnetic nanoparticle synthesis include: 1- Co-precipitation Co-precipitation is a facile and convenient way to synthesize iron oxides (either Fe 3 O 4 or γ-fe 2 O 3 ) from aqueous Fe 2+ /Fe 3+ salt solutions by the addition of a base under inert atmosphere at room temperature or at elevated temperature. The size, shape, and composition of the magnetic nanoparticles very much depends on the type of salts used (e.g.chlorides, sulfates, nitrates), the Fe 2+ /Fe 3+ ratio, the reaction temperature, the ph value and ionic strength of the media, and the mixing rate with the base solution used to provoke the precipitation. The co-precipitation approach has been used extensively to produce ferrite nanoparticles of controlled sizes and magnetic properties. A variety of experimental arrangements have been reported to facilitate continuous and large scale co precipitation of magnetic particles by rapid mixing. Recently, the growth rate of the magnetic nanoparticles was measured in real-time during the precipitation of magnetite nanoparticles by an integrated AC magnetic susceptometer within the mixing zone of the reactants. 2- Thermal decomposition Magnetic nanocrystals with smaller size can essentially be synthesized through the thermal decomposition of organometallic compounds in high-boiling organic solvents containing stabilizing surfactants. 58
7 3- Microemulsion Using the microemulsion technique, metallic cobalt, cobalt/platinum alloys, and gold-coated cobalt/platinum nanoparticles have been synthesized in reverse micelles of cetyltrimethlyammonium bromide, using 1-butanol as the cosurfactant and octane as the oil phase. 4- Flame spray synthesis Using flame spray pyrolysis and varying the reaction conditions, oxides, metal or carbon coated nanoparticles are produced at a rate of > 30 g/h. Figure 6.4: Flame spray pyrolysis synthesis technique 59
8 Potential applications of magnetic nanoparticles 1- Medical diagnostics and treatments Magnetic nanoparticles are used in an experimental cancer treatment called magnetic hyperthermia in which the fact that nanoparticles heat when they are placed in an alternative magnetic field is used. Another potential treatment of cancer includes attaching magnetic nanoparticles to free-floating cancer cells, allowing them to be captured and carried out of the body. The treatment has been tested in the laboratory on mice and will be looked at in survival studies. Figure 6.5: Cancer treatment with magnetic nanoparticles Magnetic nanoparticles can be used for the detection of cancer. Blood can be inserted onto a microfluidic chip with magnetic nanoparticles in it. These magnetic nanoparticles are trapped inside due to an externally applied magnetic field as the blood is free to flow through. The magnetic nanoparticles are coated with antibodies targeting cancer 60
9 cells or proteins. The magnetic nanoparticles can be recovered and the attached cancer-associated molecules can be assayed to test for their existence. 2- Waste water treatment Thanks to the easy separation by applying a magnetic field and the very large surface to volume ratio, magnetic nanoparticles have a good potential for treatment of contaminated water. In this method, attachment of EDTA-like chelators to carbon coated metal nanomagnets results in a magnetic reagent for the rapid removal of heavy metals from solutions or contaminated water by three orders of magnitude to concentrations as low as micrograms per Litre. Magnetic nanobeads or nanoparticle clusters composed of FDA-approved oxide superparamagnetic nanoparticles (e.g. maghemite, magnetite) hold much potential for waste water treatment since they express excellent biocompatibility which concerning the environmental impacts of the material is an advantage compared to metallic nanoparticles. Figure 6.6: Waste water treatment with magnetic nanoparticles 61
10 3- Information storage Research is going into the use of using MNPs for magnetic recording media. The most promising candidate for high-density storage is the facecentered tetragonal phase FePt alloy. Grain sizes can be as small as 3 nanometers. If it's possible to modify the MNPs at this small scale, the information density that can be achieved with this media could easily surpass 1 Terabyte per square inch. 62
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