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Dual orthogonal functionality in a single material is highly desirable in many fields such as bio-imaging, sensing, coating or diagnostic and therapy. However, combining two different functionalities in a precise and controlled way is still a challenging task.
Here we present how simply dual functional hybrid nanoparticles consisting of a silica core with a fluorescent and a thermoresponsive polymeric layers can be prepared. As a first step of this work, silica core particles were coated by a fluorescent layer using surface-initiated reversible addition-fragmentation chain transfer polymerization. Afterwards, the fluorescent silica nanoparticles were completely enclosed in a switchable protective coating made of thermoresponsive poly(N-isopropylacrylamide). The thermoresponsive poly(N-isopropylacrylamide) changes its properties with varying the surroundings temperature and this behavior is reversible and controllable. To the best of our knowledge these types of hybrid dual functional core-shell-shell nanoparticles have not yet been prepared, despite the prospect of many potential applications.
Due to the adsorption of biomolecules, the control of the biodistribution of nanoparticles is still one of the major challenges of nanomedicine. Poly(2-ethyl-2-oxazoline) (PEtOx) for surface modification of nanoparticles is applied and both protein adsorption and cellular uptake of PEtOxylated nanoparticles versus nanoparticles coated with poly(ethylene glycol) (PEG) and non-coated positively and negatively charged nanoparticles are compared. Therefore, fluorescent poly(organosiloxane) nanoparticles of 15 nm radius are synthesized, which are used as a scaffold for surface modification in a grafting onto approach.
With multi-angle dynamic light scattering, asymmetrical flow field-flow fractionation, gel electrophoresis, and liquid chromatography-mass spectrometry, it is demonstrated that protein adsorption on PEtOxylated nanoparticles is extremely low, similar as on PEGylated nanoparticles. Moreover, quantitative microscopy reveals that PEtOxylation significantly reduces the non-specific cellular uptake, particularly by macrophage-like cells. Collectively, studies demonstrate that PEtOx is a very effective alternative to PEG for stealth modification of the surface of nanoparticles.
Dual orthogonal functionality in a single material is highly desirable in many fields such as bio-imaging, sensing, coating or diagnostic and therapy. However, combining two different functionalities in a precise and controlled way is still a challenging task.
Here we present how simply dual functional hybrid nanoparticles consisting of a silica core with a fluorescent and a thermoresponsive polymeric layers can be prepared. As a first step of this work, silica core particles were coated by a fluorescent layer using surface-initiated reversible addition-fragmentation chain transfer polymerization. Afterwards, the fluorescent silica nanoparticles were completely enclosed in a switchable protective coating made of thermoresponsive poly(N-isopropylacrylamide). The thermoresponsive poly(N-isopropylacrylamide) changes its properties with varying the surroundings temperature and this behavior is reversible and controllable. To the best of our knowledge these types of hybrid dual functional core-shell-shell nanoparticles have not yet been prepared, despite the prospect of many potential applications.
The controlled synthesis of supramolecular aggregates formed by the self-assembly of dendritic amphiphiles is a challenging task. Conventional batch-based techniques such as the solvent injection method or the film hydration method typically go along with a lack of control over mixing and thus over size, morphology and size distribution.
The micromixer technology is a promising method for the controlled preparation of supramolecular assemblies as it allows control of mixing at microscale level. In addition, such microfluidic systems benefit from a high mixing efficiency, a low mixing time as well as from a reproducible and continuous synthesis.
Herein, we report on the microfluidic-controlled self-assembly of several dendritic amphiphiles and the impact of the mixing parameters on the self-assembly process.
Dendron-based macromolecules and supramolecular architectures for medical diagnosis and therapy
(2015)
Dendron-based macromolecules and supramolecular architectures for medical diagnosis and therapy
(2015)
Dendron-based macromolecules and supramolecular architectures for medical diagnosis and therapy
(2015)
The protein corona, which forms on the nanoparticle's surface in most biological media, determines the nanoparticles physicochemical characteristics. The formation of the protein corona has a significant impact on the biodistribution and clearance of nanoparticles in vivo. Therefore, the ability to influence the formation of the protein corona is essential to most biomedical applications, including drug delivery and imaging. In this study, we investigate the protein adsorption on nanoparticles with a hydrodynamic radius of 30 nm and a coating of thermoresponsive poly(2-isopropyl-2-oxazoline) in serum. Using multiangle dynamic light scattering (DLS) we demonstrate that heating of the nanoparticles above their phase separation temperature induces the formation of agglomerates, with a hydrodynamic radius of 1 µm. In serum, noticeably stronger agglomeration occurs at lower temperatures compared to serum-free conditions. Cryogenic transmission electron microscopy (cryo-TEM) revealed a high packing density of agglomerates when serum was not present. In contrast, in the presence of serum, agglomerated nanoparticles were loosely packed, indicating that proteins are intercalated between them. Moreover, an increase in protein content is observed upon heating, confirming that protein adsorption is induced by the alteration of the surface during phase separation. After cooling and switching the surface back, most of the agglomerates were dissolved and the main fraction returned to the original size of approximately 30 nm as shown by asymmetrical flow-field flow fractionation (AF-FFF) and DLS. Furthermore, the amounts of adsorbed proteins are similar before and after heating the nanoparticles to above their phase-separation temperature. Overall, our results demonstrate that the thermoresponsivity of the polymer coating enables turning the corona formation on nanoparticles on and off in situ. As the local heating of body areas can be easily done in vivo, the thermoresponsive coating could potentially be used to induce the agglomeration of nanoparticles and proteins and the accumulation of nanoparticles in a targeted body region.