Controlling the Interparticular Distances of Extended Non-Close-Packed Colloidal Monolayers.

A versatile method for the preparation extended, well-ordered, non-close-packed monolayers of silica nanoparticles (137 ± 4 nm diameter) with adjustable interparticle distances is presented, which is based on a simple self-assembly procedure using aqueous dispersion with different ionic strengths. It is shown that these structures can be successfully transferred to air without suffering from aggregation. Scanning electron microscopy (SEM) is used to characterize the structures after transfer into the atmosphere. These investigations were combined with a quartz crystal microbalance with dissipation (QCM-D) experiments to follow the self-assembly process in solution. The nearest-neighbor distance distribution reveals a monotonous decrease of the average nearest-neighbor distance from 290 to 200 nm with increasing ionic strength from 0.05 to 1 mM, which indicates an increased shielding of the electrostatic interaction with increasing ionic strength. The observed saturation coverages for all studied ionic strengths are well explained with an effective hard-sphere model in which the saturation coverage is limited by Coulomb repulsion. However, at ionic strengths above 1 mM, significant amounts of aggregates are found in the dried samples, suggesting that the observed aggregates at high ionic strengths are formed during the drying process caused by capillary forces between the particles. Tuning the barrier for lateral diffusion, e.g., by changing the surface morphology or functionalization of the particles will offer a route to further extend the range of particle distances. The present approach can be easily expanded to a broad range of colloidal materials on surfaces, while it only requires low-cost laboratory equipment.

Lysosomal Dysfunction Caused by Cellular Accumulation of Silica Nanoparticles.

Nanoparticles (NPs) are widely used as components of drugs or cosmetics and hold great promise for biomedicine, yet their effects on cell physiology remain poorly understood. Here we demonstrate that clathrin-independent dynamin 2-mediated caveolar uptake of surface-functionalized silica nanoparticles (SiNPs) impairs cell viability due to lysosomal dysfunction. We show that internalized SiNPs accumulate in lysosomes resulting in inhibition of autophagy-mediated protein turnover and impaired degradation of internalized epidermal growth factor, whereas endosomal recycling proceeds unperturbed. This phenotype is caused by perturbed delivery of cargo via autophagosomes and late endosomes to SiNP-filled cathepsin B/L-containing lysosomes rather than elevated lysosomal pH or altered mTOR activity. Given the importance of autophagy and lysosomal protein degradation for cellular proteostasis and clearance of aggregated proteins, these results raise the question of beneficial use of NPs in biomedicine and beyond.

Structural Characterization of Ordered, Non-Close-Packed Functionalized Silica Nanoparticles on Gold Surfaces.

Nanostructured surfaces play an important role in modern science and technology. In particular, ordered arrangements of nonclose-packed nanoparticles created by self-assembly offer a versatile route to prepare systems, which can be used in various applications such as sensing, plasmonic devices or antireflection coatings. Self-assembly based systems are particularly appealing as preparation is rather simple. The ability of nanoparticle systems to form nonclosed packed monolayers by self-assembly depends on the balance of various energetic contributions in particular the adsorption energy, the lateral barrier for diffusion and the repulsion between particles. Even for simple model systems such as the monodispersed silica particles adsorbed on a bare gold surface investigated here, none of these quantities is easy to determine experimentally. To this end, we will report on a detailed characterization of the adsorption in particular with respect to the structural properties of the above-mentioned model system. Based on experimental results obtained by using quartz crystal microbalance with dissipation monitoring (QCM-D) as well as scanning electron microscopy (SEM) it is possible to determine the electrostatic pair potential from the lateral arrangement of the nano particles in the limit of low coverage.

Ordered Structures of Functionalized Silica Nanoparticles on Gold Surfaces: Correlation of Quartz Crystal Microbalance with Structural Characterization.

Quartz crystal microbalance (QCM) is frequently used to investigate adsorption of nanometer-sized objects such as proteins, viruses, or organic as well as inorganic nanoparticles from solution. The interpretation of the data obtained for heterogeneous adsorbate layers is not straightforward in particular if the systems exhibit sizable amounts of dissipation. In this study we investigate the deposition of monodisperse, amine functionalized silica nanoparticles on gold surfaces using QCM with dissipation (QCM-D) to obtain frequency and dissipation changes during adsorption from the liquid phase. These investigations are combined with ex situ scanning electron microscopy (SEM) measurements to study both coverage as well as lateral arrangement of the particles. An ordered layer of particles is found at saturation coverage due to the charged particle surface resulting in a repulsive interaction between the particles. The repulsion ensures a minimal distance between the particles, which leads to a saturation coverage of 15% for particles of 137 nm diameter. The frequency shift is shown to be a linear function of coverage which is a behavior expected for an elastic medium according to the Sauerbrey equation. However, the system shows a strong dependence of the normalized frequency shift on the overtones as well as a large dissipation, which is a clear indication for a system with viscoelastic properties. The analysis of the data show that a reliable determination of the adsorbed mass solely on the basis of QCM-D results is not possible, but additional information as determined by SEM in the present case is required to determine the coverage. From a correlation of the QCM-D results with the structural characterization it is possible to infer that the dissipation is a long ranged phenomenon. A lower boundary of the interaction length could be derived being twice the particle diameter for the particles studied here. In contrast to that the frequency response behaves like local phenomenon.

Controlling the Interaction and Non-Close-Packed Arrangement of Nanoparticles on Large Areas.

In light of the importance of nanostructured surfaces for a variety of technological applications, the quest for simple and reliable preparation methods of ordered, nanometer ranged structures is ongoing. Herein, a versatile method to prepare ordered, non-close-packed arrangements of nanoparticles on centimeter sized surfaces by self-assembly is described using monodisperse (118-162 nm Ø), amino-functionalized silica nanoparticles as an exploratory example. It is shown that the arrangement of the particles is governed by the interplay between the electrostatic repulsion between the particles and the interaction between particles and surfaces. The latter is tuned by the properties of the particles such as their surface roughness as well as the chemistry of the linkage. Weak dispersive interactions between amino groups and gold surfaces are compared to a covalent amide linkage of the amino groups with carboxylic acid functionalized self-assembled monolayers. It was shown that the order of the former systems may suffer from capillary forces between particles during the drying process, while the covalently bonded systems do not. In turn, covalently bonded systems can be dried quickly, while the van der Waals bonded systems require a slow drying process to minimize aggregation. These highly ordered structures can be used as templates for the formation of a second, ordered, non-close-packed layer of nanoparticles exemplified for larger polystyrene particles (Ø 368 ± 14 nm), which highlights the prospect of this approach as a simple preparation method for ordered arrays of nanoparticles with tunable properties.

Kinetics of aggregation and growth processes of PEG-stabilised mono- and multivalent gold nanoparticles in highly concentrated halide solutions.

5-6 nm gold nanoparticles were prepared by hydrolytic decomposition of [NMe4][Au(CF3)2] and functionalized in situ with mono- and multivalent thiolated PEG ligands. Time-dependent changes of the nanoparticles were monitored in aqueous NaCl, NaBr, and NaI solutions by UV-Vis spectroscopy, TEM, and HRTEM. The purely sterically protected particles are stable in ≤1 M NaCl and NaBr solutions, regardless of the valence of the ligands. At higher concentrations (≥2 M), the monovalent stabilized particles show minor reaction limited colloidal aggregation. In NaBr but not in NaCl solutions a minor Ostwald ripening also occurs. The divalent stabilized particles remain colloidally stable in both halide solutions, even if the temperature is raised or the concentration is increased above 2 M. In ≤1 M aqueous NaI solutions the particles remain stable. Above, the monovalent stabilized particles undergo an oxidative reaction, resulting in a time-dependent shift and broadening of the absorbance spectrum. Finally, this process slows down while the width of the spectra slightly narrows. The kinetics of this process can be described by a two-step sigmoidal process, comprising a slow induction period where active species are formed, followed by a fast growth and aggregation process. The increasing concentration of fused structures from the aggregates during this process results in a narrowing of the size distributions. The divalent stabilized particles show only some minor broadening and a slight shift of the absorbance spectra in ≤3 M NaI solutions. These observations confirm the excellent stability of the multivalent stabilized particles from this chloride-free particle synthesis.