Under the right process conditions, nanoparticles can cluster together to form defined, dispersed structures, which can be termed supraparticles. Controlling the size, shape, and morphology of such entities is a central step in various fields of science and technology, ranging from colloid chemistry and soft matter physics to powder technology and pharmaceutical and food sciences. These diverse scientific communities have been investigating formation processes and structure/property relations of such supraparticles under completely different boundary conditions. On the fundamental side, the field is driven by the desire to gain maximum control of the assembly structures using very defined and tailored colloidal building blocks, whereas more applied disciplines focus on optimizing the functional properties from rather ill-defined starting materials. With this review article, we aim to provide a connecting perspective by outlining fundamental principles that govern the formation and functionality of supraparticles. We discuss the formation of supraparticles as a result of colloidal properties interplaying with external process parameters. We then outline how the structure of the supraparticles gives rise to diverse functional properties. They can be a result of the structure itself (emergent properties), of the colocalization of different, functional building blocks, or of coupling between individual particles in close proximity. Taken together, we aim to establish structure-property and process-structure relationships that provide unifying guidelines for the rational design of functional supraparticles with optimized properties. Finally, we aspire to connect the different disciplines by providing a categorized overview of the existing, diverging nomenclature of seemingly similar supraparticle structures.
A process is reported to obtain a nanoparticle sol from co-precipitated iron oxide particles without using any surfactant. The sol - a true ferrofluid - is not only stable over a wide range of pH but also in physiological solutions. This is a decisive step towards biomedical applications where nanoparticle agglomeration could so far only be prevented by using unwanted surfactants.
The maximum magnetisation (saturation magnetisation) obtainable for iron oxide nanoparticles can be increased by doping the nanocrystals with non-magnetic elements such as zinc. Herein, we closely study how only slightly different synthesis approaches towards such doped nanoparticles strongly influence the resulting sub-nano/atomic structure. We compare two co-precipitation approaches, where we only vary the base (NaOH versus NH), and a thermal decomposition route. These methods are the most commonly applied ones for synthesising doped iron oxide nanoparticles. The measurable magnetisation change upon zinc doping is about the same for all systems. However, the sub-nano structure, which we studied with Mössbauer and X-ray absorption near edge spectroscopy, differs tremendously. We found evidence that a much more complex picture has to be drawn regarding what happens upon Zn doping compared to what textbooks tell us about the mechanism. Our work demonstrates that it is crucial to study the obtained structures very precisely when "playing" with the atomic order in iron oxide nanocrystals.
A smart optical composite material with dynamic isotropic and anisotropic optical properties by combination of luminescence and high reflectivity was developed. This combination enables switching between luminescence and angle-dependent reflectivity by changing the applied wavelength of light. The composite is formed as anisotropic core/shell particles by coating superparamagnetic iron oxide-silica microrods with a layer of the luminescent metal-organic framework (MOF) [Eu(BDC)]·2DMF·2HO (BDC = 1,4-benzenedicarboxylate). The composite particles can be rotated by an external magnet. Their anisotropic shape causes changes in the reflectivity and diffraction of light depending on the orientation of the composite particle. These rotation-dependent optical properties are complemented by an isotropic luminescence resulting from the MOF shell. If illuminated by UV light, the particles exhibit isotropic luminescence while the same sample shows anisotropic optical properties when illuminated with visible light. In addition to direct switching, the optical properties can be tailored continuously between isotropic red emission and anisotropic reflection of light if the illuminating light is tuned through fractions of both UV and visible light. The integration and control of light emission modes within a homogeneous particle dispersion marks a smart optical material, addressing fundamental directions for research on switchable multifunctional materials. The material can function as an optic compass or could be used as an optic shutter that can be switched by a magnetic field, e.g., for an intensity control for waveguides in the visible range.
Magnetic
particle spectroscopy (MPS) is used in this work to obtain
a magnetic fingerprint signal from anisotropic supraparticles, i.e.,
microrods assembled from superparamagnetic iron oxide nanoparticles.
Exceeding its intended purpose of nanoparticle characterization for
biomedical magnetic particle imaging, it is shown that MPS is capable
of resolving structural differences between the anisotropic alignment
of individual nanoparticles and its isotropic counterpart. Additionally,
orientation-dependent MPS signal variations of anisotropic supraparticles
are identifiable. This finding enables the detection of cold-chain
breaches (for instance, during delivery of a product that needs to
be cooled all of the time) by recording the initial and final MPS
signals of microrod samples integrated into the container of a frozen
product.
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