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
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.
Maghemite nanoparticle cluster with silica shell.
TEM image of a maghemite magnetic nanoparticle cluster with silica shell.
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.
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)
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
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.
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 made of graphene have been synthesized recently.
The advantages compared to ferrite or elemental nanoparticles are:
Higher stability in acidic and basic solution as well as organic solvents
Chemistry on the graphene surface via methods already known for carbon nanotubes